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DESCRIPTION
COMPOSITION FOR POLYURETHANE FOAM, PREPARATION FOR POLYURETHANE FOAM,
POLYMER POLYOL PREPARATION FOR POLYURETHANE FOAM, PRODUCTION
PROCESSES THEREFOR, AND POLYURETHANE FOAM
5
Technical Field
[0001]
The present invention relates to a composition for a polyurethane
foam, a preparation for a polyurethane foam, a polymer polyol
10 preparation for a polyurethane foam, production processes therefor,
and a polyurethane foam.
[0002]
More particularly, the present invention relates to a
preparation for a polyurethane foam and a polymer polyol preparation
15 for a polyurethane foam, each of which exhibits high coloration and
discoloration inhibition properties over a long period of time when
stored, andtoacompositionfor a polyurethane foam, which is excellent
in storage stability and is preferable as a resin premix.
20 Background Art
[0003]
Polyurethane foams have been widely used as heat insulating
materials for electric refrigerators, freezers, cold storages,
building material panels, etc. because of their excellent heat
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insulation performance, moldability and self-adhesion properties,
and they have been widely used for interior trim materials, such as
sheet cushions, sheet backs, headrests, armrests, instrument panels,
door trims and ceiling materials of vehicles such as automobiles,
5 bicycle saddles, air planes, sheet materials for railroad vehicles,
furniture, bedding, and office supplies, such as cushioning materials
of business chairs, because of their excellent cushioning properties.
[0004]
Polyurethane foams are obtained by preparing a resin premix
10 containing a polyol such as a polyoxyalkylene polyol or a polymer
polyol (polymer-dispersed polyol) , a catalyst for polyurethane foam
production, a blowing agent, etc. and allowing this resin premix to
react with a polyisocyanate. The polyoxyalkylene polyol is obtained
by, for example, addition polymerization of an alkylene oxide compound
15 onto an active hydrogen compound using a basic catalyst.
[0005]
To the polyoxyalkylene polyol, a stabilizer such as an
antioxidant is usually added for the purpose of preventing oxidation
deterioration of the polyol or in order not to form a peroxide that
20 inhibits reactivity of the catalyst for polyurethane foam production.
Such a stabilizer is, for example, a phenol-based compound (see, for
example, patent literature 1).
[0006]
When a catalyst or an acid derived from the polyol is contained
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in a resin premix for a long period of time, various problems such
that the resin premix is color-changed to yellow or brown with time,
the component contained in the resin premix is crystallized and
precipitated, and separation between an aqueous layer and an organic
5 layer occurs in the resin premix are usually liable to take place.
Further, when a large amount of the catalyst is contained in the resin
premix, the catalyst has influence on the urethanation reaction during
the production of a polyurethane foam, and as a result, there is a
fear of difficult control of the reaction time or a fear of evil influence
10 on the performance or the moldability of the foam.
[0007]
The phenol-based compound is widely used as an additive added
to a polyoxyalkylene polyol, but in general, it tends to be discolored
under the basic conditions, particularly in a resin premix or a
15 polyoxyalkylene polyol containing a basic catalyst used for
polymerization.
[0008]
On that account, in general, the polyoxyalkylene polyol
containing the catalyst is not used as it is in the resin premix,
20 and for example, it is commonly carried out to neutralize the catalyst
contained in the polyoxyalkylene polyol with an acid or the like and
to purify the polyoxyalkylene polyol to reduce the amount of the
catalyst, the acid component, etc. to a certain level or lower, prior
to use for the resin premix (patent literatures 2 to 5, etc.).
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•
[0009]
However, a removal step, a purification step, etc. are required,
and the process is extremely complicated.
[0010]
5 Therefore, development of a resin premix, which is capable of
producing a urethane foam without any problem even if it contains
a catalyst, an acid and a stabilizer such as an antioxidant and which
is excellent in long-term storage stability, has been desired.
10 Citation List
Patent Literature
[0011]
Patent literature 1: Japanese Patent Laid-Open Publication No.
2005-194362
15 Patent literature 2: Japanese Patent Laid-Open Publication No.
1976-101099
Patent literature 3: Japanese Patent Laid-Open Publication No.
1998-30023
Patent literature 4 : Japanese Patent Laid-Open Publication No.
20 2000-17070
Patent literature 5: Japanese Patent Laid-Open Publication No.
2001-106780
Siammary of Invention
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Technical Problem
[0012]
The present invention is intended to solve such problems
associated with the prior art as mentioned above, and it is an object
5 of the present invention to provide a preparation for a polyurethane
foam, a polymer polyol preparation for a polyurethane foam and a
composition for a polyurethane foam, each of which can be inhibited
from being colored or discolored over a long period of time when stored,
does not bring about precipitation of crystal and separation between
10 an aqueous layer and an organic layer, is excellent in storage stability
and is preferable for a resin premix, and production processes for
them.
Solution to Problem
15 [0013]
In order to solve the above problems, the present inventors
have earnestly studied, and as a result, they have found that since
a specific composition for a polyurethane foam, a specific preparation
for a polyurethane foam and a specific polymer polyol preparation
20 for a polyurethane foam exhibit high coloration and discoloration
inhibition properties over a long period of time when stored and are
excellent in storage stability, they can be each stored for a long
period of time as a resin premix that is prepared in the production
of a polyurethane foam. Thus, the present inventors have accomplished
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the present invention.
[0014]
That is to say, the composition for a polyurethane foam of the
present invention is characterized by comprising:
5 (i) at least one polyol selected from a polyoxyalkylene polyol
and a polymer polyol wherein polymer fine particles obtained by
polymerizing a compound having an unsaturated bond are dispersed in
the polyoxyalkylene polyol,
(ii) a compound having a P=N bond,
10 (iii) an antioxidant having a hydroxyphenyl group,
(iv) at least one acid selected from the group consisting of
an acyclic aliphatic monocarboxylic acid of 2 to 25 carbon atoms,
a hydroxycarboxylic acid of 2 to 25 carbon atoms, a polycarboxylic
acid of 20 to 60 carbon atoms, an aromatic monocarboxylic acid
15 represented by the following formula (1), a sulfonic acid and an acid
having a sulfuric acid ester group, or its salt,
(v) a catalyst for polyurethane foam production, and
(vi) a blowing agent.
20
[0015]
[Chem. 1]
^COOH
( 1 )
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[0016]
wherein B} is a hydrocarbon group, andm represents a number of hydrogen
atoms of a benzene ring having been replaced with R^ and is any one
of 0 to 5.
5 [0017]
The production process for a composition for a polyurethane
foam is characterized by comprising a step which comprises adding,
to a polyol (i) containing a polyoxyalkylene polyol (p) obtained by
addition polymerization of an alkylene oxide compound onto an active
10 hydrogen compound using the aforesaid compound (ii) as a catalyst,
and the compound (ii) having been used for the production of the polyol
(P),
the aforesaid antioxidant (iii) and the aforesaid acid or its
salt (iv) in such an amount that the molar ratio (a/b) of the acid
15 or its salt (iv) (a) to the compound (ii) (b) having a P=N bond becomes
not less than 0.3 but not more than 25, to obtain a preparation (c)
for a polyurethane foam and then adding the aforesaid catalyst (V)
for production and the aforesaid blowing agent (vi) to the preparation
(c) .
20 [0018]
It is preferable that the production process for a composition
for a polyurethane foam further comprises a step of preparing a polymer
polyol in the preparation (c), and the polymer polyol is obtained
by dispersing polymer fine particles obtained by polymerizing a
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compound having an unsaturated bond, in the preparation (c).
[0019]
The polyurethane foam of the present invention is characterized
by being obtained by the use of the composition for a polyurethane
5 foam of the present invention.
Advantageous Effects of Invention
[0020]
According to the present invention, a composition for a
10 polyurethane foam, which can be inhibited from being colored or
discolored over a long period of time when stored, does not bring
about precipitation of crystal and separation between an aqueous layer
and an organic layer and is excellent in storage stability, can be
obtained. The composition can be stored over a long period of time
15 as a resin premix that is prepared in the production of a polyurethane
foam.
[0021]
Further, inthe resinpremix, deterioration of a polyoxyalkylene
polyol is inhibited, and a polyurethane foam obtained by the use of
20 the composition for a polyurethane foam of the present invention can
maintain its favorable properties over a long period of time.
Furthermore, a peroxide that inhibits reactivity of a catalyst for
polyurethane foam production is rarely formed, and therefore,
urethanation reactivity can be properly controlled in the production
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of a polyurethane foam. Moreover, the resulting polyurethane foam
rarely causes a problem of yellowing or the like.
[0022]
Moreover, when the composition of the present invention is
5 produced, a crude polyol obtained by the use of a compound having
a P=Nbondas a catalyst canbe used without purification, and therefore,
the steps can be drastically omitted. On that account, environmental
burden can be reduced, and the production cost can be also significantly
reduced.
10 [0023]
In addition, the preparation for a polyurethane foam and the
polymer polyol preparation for a polyurethane foam exhibit high
coloration and discoloration inhibition properties over a long period
of time when stored and are excellent in storage stability.
15
Description of Embodiments
[0024]
[Composition for polyurethane foam, preparation for
polyurethane foam and polymer polyol preparation for polyurethane
20 foam]
The composition for a polyurethane foam of the present invention
contains at least (i) a specific polyol, (ii) a compound having a
P=N bond, (iii) an antioxidant having a hydroxyphenyl group, (iv)
a specific acid or its salt, (v) a catalyst for polyurethane foam
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production and (vi) a blowing agent, and contains other assistants
when needed. The composition is preferable as a resin premix that
is prepared in the production of a polyurethane foam.
[0025]
5 The preparation for a polyurethane foam of the present invention
(also referred to as a "preparation (c)") contains at least (p) a
specific polyoxyalkylene polyol and/or a polymer polyol wherein
polymer fine particles obtained by polymerizing a compound having
an unsaturated bond are dispersed in the polyol, (ii) a compound having
10 a P=N bond, which has been used for the production of the polyol (p),
(iii) an antioxidant having a hydroxyphenyl group and (iv) a specific
acidor its salt. The preparation (c) is preferable for the composition
for a polyurethane foam.
[0026]
15 The polymer polyol preparation for a polyurethane foam of the
present invention (also referred to as a "preparation (pc) ") contains
the components contained in the preparation (c) of the present
invention, and further contains a polymer polyol wherein polymer fine
particles obtained by polymerizing a compound having an unsaturated
20 bond are dispersed in the preparation (c) . The preparation (pc) is
preferable for the composition for a polyurethane foam.
[0027]
<(i) Polyol>
In the composition for a polyurethane foam of the present
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%
invention, at least one polyol selected from the later-described
polyoxyalkylene polyol and polymer-dispersed polyol is contained,
and if necessary, other polyols may be contained.
[0028]
5 In the present invention, the polyol (i) may contain a catalyst
having been used for the production of a polyoxyalkylene polyol.
[0029]
The amount of all the polyols contained in the composition for
a polyurethane foam is usually 80 to 98% by mass, preferably 82 to
10 97% by mass, more preferably 85 to 96% by mass, based on 100% by mass
of the composition.
[0030]
The amount of the polyol (i) contained in the preparation (c)
or the preparation (pc) is not specifically restricted as far as the
15 effects of the present invention are exerted, but the amount thereof
is usually 80.00 to 99.99% by mass, preferably 80.00 to 99.98% by
mass, more preferably 90 to 99.98% by mass, based on 100% by mass
of the preparation (c) or the preparation (pc).
[0031]
20 (Polyoxyalkylene polyol)
The polyoxyalkylene polyol related to the present invention
is obtained by addition polymerization of an alkylene oxide compound
onto an active hydrogen compound using a catalyst, such as the later
described compound having a P=N bond, potassium hydroxide, cesium
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hydroxide or rubidium hydroxide. As the catalyst, the compound having
a P=N bond is preferable from the viewpoints that the total degree
of unsaturation at the time of completion of the addition
polymerization can be more reduced and a polyoxyalkylene polyol can
5 be efficiently produced and from the viewpoints that a small catalytic
amount required for the polymerization is enough because of high
activity per mol and the amount of the acid added can be decreased.
[0032]
The polyoxyalkylene polyol is also preferably a polyol (p)
10 obtained by the use of the acid or its salt (iv) in such an amount
that the molar ratio (a/b) of the acid or its salt (iv) (a) to the
compound (ii) (b) becomes a specific value and by the use of the
antioxidant (iii) and the compound (ii) as a catalyst.
[0033]
15 Although the hydroxyl value of the polyoxyalkylene polyol is
not specifically restricted, it is preferably 10 to 80 mgKOH/g, more
preferably 15 to 60 mgKOH/g, most preferably 18 to 40 mgKOH/g. A
hydroxyl value of the above range is preferable because a polyurethane
foam having optimum hardness, flexibility, mechanical strength,
20 impact resilience, etc. and having optimum balance among them is
obtained.
[0034]
The total degree of unsaturation of the polyoxyalkylene polyol
is not specifically restricted, but from the viewpoint of obtaining
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a general polyurethane foam, it is preferably not more than 0.050
meq/g, more preferably not more than 0. 040 meq/g, still more preferably
not more than 0.030 meq/g. Although the lower limit of the total
degree of unsaturation is not specifically restricted, it is, for
5 example, 0.001 meq/g. A total degree of unsaturation of the above
range is preferable because the resulting polyurethane foam has good
impact resilience and good wet heat peimanent set (wet set).
[0035]
Examples of the active hydrogen compounds include alcohols,
10 phenols, polyamine, alkanolamine and thioalcohols. Specific
examples thereof include:
water, dihydric alcohols, such as ethylene glycol, diethylene
glycol, triethylene glycol, propylene glycol, dipropylene glycol,
tripropylene glycol, 1,5-pentanediol, neopentyl glycol,
15 2-methyl-l,5-pentanediol, 2-ethyl-l,4-butanediol,
1,4-dimethylolcyclohexane, 1,3-propanediol, 1,4-cyclohexanediol,
1,3-butanediol, 1,4-butanediol, 1,6-hexanediol and
1,4-cyclohexanediol,
alkanolamines, such as monoethanolamine, diethanolamine and
20 triethanolamine,
polyhydric alcohols, such as glycerol, diglycerol, triglycerol,
tetraglycerol, trimethylolpropane, trimethylolethane,
trimethylolbutane, ditrimethylolpropane, pentaerythritol,
dipentaerythritol and tripentaerythritol.
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%
saccharides or their derivatives, such as glucose, sorbitol,
dextrose, fructose, sucrose and methyl glycoside,
aliphatic amines, such as ethylenediamine,
di(2-aminoethyl)amine and hexamethylenediamine, aromatic amines,
5 such as toluylenediamine and diphenylmethanediamine,
phenol compounds, such as bisphenol A, bisphenol F, bisphenol
S, novolak, resol and resorcin,
dihydric thioalcohols, such as ethylene thioglycol, propylene
thioglycol, trimethylene thioglycol and butanedithiol, and
10 alkylene thioglycols, such as diethylene thioglycol and
triethylene thioglycol.
[0036]
These active hydrogen compounds can be also used in combination
of two or more kinds. Further, compounds obtained by addition
15 polymerization of alkylene oxide compounds onto these active hydrogen
compounds through a hitherto publicly known method can be also used.
[0037]
Of these compounds, most preferable are dihydric alcohols,
compounds having a number-average molecular weight of up to 2,000
20 obtained by addition polymerization of alkylene oxides onto dihydric
alcohols, trihydric alcohols, compounds having a number-average
molecular weight of up to 2,000 obtained by addition polymerization
of alkylene oxides onto trihydric alcohols, tetrahydric alcohols,
and compounds having a number-average molecular weight of up to 3, 000
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obtained by addition polymerization of alkylene oxides onto
tetrahydric alcohols. Compounds having a number-average molecular
weight of more than 2,000 after the addition of alkylene oxides onto
dihydric alcohols or trihydric alcohols and compounds having a
5 number-average molecular weight of more than 3, 000 after the addition
of alkylene oxides onto tetrahydric alcohols are undesirable because
the amount of monools as by-products is increased.
[0038]
Examples of the alkylene oxide compounds subjected to addition
10 polymerization onto the active hydrogen compounds include propylene
oxide, ethylene oxide, 1,2-butylene oxide, 2,3-butylene oxide,
styrene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin,
methyl glycidyl ether, allyl glycidyl ether and glycidol. These
compounds may be used singly or in combination of two or more kinds.
15 [0039]
Of these, preferable are propylene oxide, ethylene oxide,
1,2-butylene oxide, 2,3-butylene oxide and styrene oxide. More
preferable are propylene oxide and ethylene oxide.
[0040]
20 The temperature for the addition polymerization of the alkylene
oxide compound onto the active hydrogen compound is preferably 15
to 150°C, more preferably 40 to 130°C, still more preferably 50 to
125°C.
[0041]
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J^
The maximum pressure for the addition polymerization reaction
of the alkylene oxide compound is preferably not more than 882 kPa.
The addition polymerization of the alkylene oxide compound is carried
out usually in a pressure reactor. The reaction of the alkylene oxide
5 compound may be initiated under reduced pressure or may be initiated
at atmospheric pressure. When the reaction is initiated at
atmospheric pressure, the reaction is desirably carried out in the
presence of an inert gas, such as nitrogen or helium. If the maximum
reaction pressure for the reaction of the alkylene oxide compound
10 exceeds 882 kPa, the amount of monools as by-products is liable to
be increased.
[0042]
As a method to feed an epoxide compound to the polymerization
system, a method comprising feeding a part of the necessary amount
15 of the alkylene oxide compound at once and feeding the residue
continuously, a method of feeding all of the alkylene oxide compound
continuously, or the like is used. In the method comprising feeding
a part of the necessary amount of the alkylene oxide compound at once,
it is preferable that the reaction temperature in the initial stage
20 of the polymerization reaction of the alkylene oxide compound is set
to a lower temperature in the aforesaid temperature range, and after
feeding of the alkylene oxide compound, the reaction temperature is
gradually raised.
[0043]
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In the addition polymerization reaction of the alkylene oxide
compound, a solvent can be used when needed. Examples of the solvents
include aliphatic hydrocarbons, such as pentane, hexane and heptane,
ethers, such as diethyl ether, tetrahydrofurananddioxane, andaprotic
5 polar solvents, such as dimethyl sulfoxide andN,N-dimethylformamide.
When a solvent is used, the solvent is desirably recovered and reused
after the production in order not to increase the production cost
of the polyoxyalkylene polyol.
[0044]
10 (Polymer polyol)
The polymer polyol (also referred to as a "polymer-dispersed
polyol") related to the present invention can be obtained as a
dispersion wherein vinyl polymer particles are dispersed in a
polyoxyalkylene polyol by subjecting a compound having an unsaturated
15 bond to dispersion polymerization in the polyoxyalkylene polyol using
a radical initiator such as an azo compound or a peroxide. Although
these vinyl polymer particles may be vinyl polymer particles made
of a polymer of the compound having an unsaturated bond, they are
preferably polymer particles wherein at least a part of the compound
20 having an unsaturated bond is grafted on a specific polyol that is
a dispersion medium during the dispersion polymerization.
[0045]
Examples of the azo compounds include
2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile),
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41
2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(isobutyronitrile)
and dimethyl-2,2'-azobis(2-methyl propionate). Examples of the
peroxides include benzoyl peroxide, t-butyl peroxide and di-t-butyl
peroxide. Of these, the azo compounds are preferable, and
5 2,2'-azobis(isobutyronitrile) and dimethyl-2,2'-azobis(2-methyl
propionate) are more preferable.
[0046]
The compound having an unsaturated bond is a compound having
an unsaturated bond in a molecule, and examples thereof include:
10 cyano group-containing monomers, such as acrylonitrile and
methacrylonitrile,
methacrylic acid ester-basedmonomers, such as methyl acrylate,
butyl acrylate, stearyl acrylate, hydroxyethyl acrylate,
hydroxymethyl methacrylate, hydroxyethyl methacrylate,
15 hydroxypropyl methacrylate, dimethylaminoethyl acrylate and
dimethylaminopropyl methacrylate,
carboxyl group-containing monomers, such as acrylic acid,
methacrylic acid, itaconic acid, maleic acid and fumaric acid,
acid anhydride group-containing monomers, such as maleic
20 anhydride and itaconic anhydride,
hydrocarbon-based monomers, such as butadiene, isoprene and
1,4-pentadiene,
aromatic hydrocarbon-based monomers, such as styrene,
a-methylstyrene, phenylstyrene and chlorostyrene.
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halogen-containing monomers, such as vinyl chloride and
vinylidene chloride,
vinyl ethers, such as vinyl ethyl ether and vinyl butyl ether,
vinyl ketones, such as vinyl ethyl ketone,
5 vinyl esters, such as vinyl acetate,
acrylamides, such as acrylamide, N,N-dimethylacrylamide,
N-isopropylacrylamide, N,N-dimethylaminopropylacrylamide and
methylenebisacrylamide, and methacrylamides, such as
N,N-dimethylmethacrylamide.
10 [0047]
Of these, acrylonitrile, styrene, methyl acrylate and
hydroxyethyl methacrylate are preferable.
[0048]
These compounds having an unsaturated bond can be used singly
15 or as a mixture of two or more kinds.
[0049]
In the production of the polymer polyol, a dispersion stabilizer,
a chain transfer agent, etc. may be added in addition to the compound
having an unsaturated bond.
20 [0050]
Although the hydroxyl value of the polymer polyol is not
specifically restricted, it is preferably 10 to 80 mgKOH/g, more
preferably 15 to 60 mgKOH/g, most preferably 18 to 4 0 mgKOH/g. A
hydroxyl value of the above range is preferable because a polyurethane
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foam having good flexibility and impact resilience is obtained.
[0051]
When a polymer polyol is contained in the present invention,
the total amount of the polymer polyol is usually 2 to 100% by mass,
5 preferably 2 to 95% by mass, more preferably 5 to 80% by mass, based
on 100% by mass of the total amount of all the polyol components.
Although the content of the vinyl polymer particles in the polymer
polyol is not specifically restricted, it is preferably 3 to 60% by
mass, more preferably 5 to 50% by mass, still more preferably 8 to
10 45% by mass, based on 100% by mass of the total amount of the polymer
polyol.
[0052]
The polymer polyol can be also prepared by directly polymerizing
the compound having an unsaturated bond in the preparation (c) of
15 the present invention using the polyoxyalkylene polyol (p) contained
in the preparation (c) and thereby dispersing the polymer fine
particles. In this case, at least the compound (ii) having been used
for the production of the polyol (p) , the antioxidant (iii) and the
acidor its salt (iv) are contained in the preparation (c), and therefore,
20 the resulting preparation (pc) can be also inhibited frombeing colored
or discolored over a long period of time when stored.
[0053]
In the production of the polymer polyol, polymerization reaction
is carried out using the polyoxyalkylene polyol, the compound having
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an unsaturated bond, the radical initiator, and if necessary, a chain
transfer agent and a dispersion stabilizer. The polymerization
reaction can be carried out batchwise or continuously. Although the
polymerization temperature is determined according to the type of
5 the polymerization initiator, it is not lower than the decomposition
temperature of the polymerization initiator, preferably in the range
of 60 to 200°C, more preferably 90 to 150°C. The polymerization
reaction can be carried out under pressure or at atmospheric pressure.
Although the polymerization reaction can be carried out in the absence
10 of a solvent, the reaction can be also carried out in the presence
of at least one solvent selected from water and an organic solvent,
or a mixture of water and an organic solvent. Examples of the organic
solvents include toluene, xylene, acetonitrile, hexane, heptane,
dioxane, ethylene glycol dimethyl ether, N,N-dimethylformamide,
15 methanol, butanol and isopropanol.
[0054]
After the polymerization reaction is completed, the polymer
polyol obtained can be used as it is as a raw material of polyurethane,
but the polymer polyol is preferably used after the compound having
20 an unsaturated bond, a decomposition product of the radical initiator,
the chain transfer agent, the solvent, etc. are distilled off under
reduced pressure.
[0055]
The mean particle diameter of the polymer contained in the
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polymer polyol of the present invention is preferably 0.01 to 10 ]m.
from the viewpoints of dispersion stability of the polymer and
influence on the properties of the polyurethane. Such a particle
diameter can be obtained by appropriately controlling the types and
5 the amounts of the chain transfer agent, the dispersion stabilizer
and the solvent, a weight composition ratio of the ethylenically
unsaturated monomer, etc.
[0056]
(Other polyols)
10 In the composition for a polyurethane foam of the present
invention, other polyols generally used for producing polyurethane
foams may be contained when needed, in addition to the polyoxyalkylene
polyol and/or the polymer polyol. Examples of other polyols include
polyester polyol, polyether ester polyol and polycarbonate polyol.
15 [0057]
Examples of the polyester polyols include condensates of
low-molecular polyols and carboxylic acids, lactone-based polyols,
such as e-caprolactone ring-opened polymer and
p-methyl-5-valerolactone ring-opened polymer, andhydroxycarboxylic
20 acid-based polyols, such as polylactic acid and polyricinoleic acid.
[0058]
Examples of the low-molecular polyols include dihydric alcohols
of 2 to 10 carbon atoms, such as ethylene glycol and propylene glycol,
trihydric alcohols of 2 to 10 carbon atoms, such as glycerol.
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trimethylolpropaneandtrimethylolethane, tetrahydric alcohols, such
as pentaerythritol and diglycerol, and saccharides, such as sorbitol
and sucrose.
[0059]
5 Examples of the carboxylic acids include dicarboxylic acids
of 2 to 10 carbon atoms, such as succinic acid, adipic acid, maleic
acid, fumaric acid, phthalic acid and isophthalic acid, and acid
anhydrides of 2 to 10 carbon atoms, such as succinic anhydride, maleic
anhydride and phthalic anhydride.
10 [0060]
When other polyols are contained in the present invention, the
content thereof is preferably less than 80% by mass, more preferably
not more than 50% by mass, particularly preferably not more than 30%
by mass, based on 100% by mass of all the polyol components.
15 [0061]
<(ii) Compound having P=N bond>
The compound having a P=N bond (also referred to as a "compound
(ii) ") related to the present invention is not specifically restricted
provided that it can be used as a catalyst for producing a
20 polyoxyalkylene polyol contained in the polyol, and examples of such
compounds include a phosphazenium compound, aphosphine oxide compound
and a phosphazene compound.
[0062]
In the present invention, the content ratio of the compound
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(ii) contained in the polyol (p) is not specifically restricted as
far as the effects of the present invention are exerted, but when
the content ratio is calculated from the charge of each component,
the lower limit is preferably 150 ppm, more preferably 200 ppm, still
5 more preferably 300 ppm, and the upper limit is preferably 5000 ppm,
more preferably 3000 ppm, still more preferably 2000 ppm,
[0063]
In the present invention, the content ratio of the compound
(ii) contained in the preparation (c) for a polyurethane foam is not
10 specifically restricted as far as the effects of the present invention
are exerted, but when the content ratio is calculated from the charge
of each component, the lower limit is preferably 50 ppm, more preferably
lOOppm, stillmore preferably 200 ppm, andtheupper limit is preferably
3000 ppm, more preferably 2500 ppm, still more preferably 2000 ppm.
15 [0064]
In the present invention, the content ratio of the compound
(ii) contained in the composition for a polyurethane foam is not
specifically restricted as far as the effects of the present invention
are exerted, but when the content ratio is calculated from the charge
20 of each component, the lower limit is preferably 50 ppm, more preferably
lOOppm, stillmorepreferably 200ppm, andtheupper limit is preferably
3000 ppm, more preferably 2500 ppm, still more preferably 2000 ppm.
[0065]
The content ratio of the compound (ii) contained in the polyol
SF-2542
25 n
(p) or the preparation (c) for a polyurethane foam or the composition
for a polyurethane foam can be also determined by a capillary
electrophoresis method, amethodusing a trace total nitrogen analyzer,
a IH-NMR method or the like.
5 [0066]
The upper limit of the ratio (a/b) of the total number of moles
(a) of the later-described acid or its salt to the number of moles
(b) of the compound (ii) having a P=N bond is preferably 25, more
preferably 15, still more preferably 10, most preferably 8, and the
10 lower limit thereof is preferably 0.3, more preferably 0.5, still
more preferably 0.8, because coloration and discoloration inhibition
properties of the polyoxyalkylene polyol composition are good and
the reactivity of the urethanation reaction is stabilized. The
compound (ii) is preferably contained in the composition for a
15 polyurethane foam or the preparation (c or pc) in such an amount that
the above-mentioned ratio is obtained.
[0067]
When an aliphatic carboxylic acid is used as the acid or its
salt (iv) , the molar ratio (a/b) is preferably 5 to 25, more preferably
20 8 to 23, still more preferably 10 to 22. In the case of an acid other
than the aliphatic carboxylic acid, the molar ratio (a/b) is preferably
0.3 to 13, more preferably 0.5 to 11, still more preferably 0.8 to
[0068]
SF-2542
Jp
26
In the present invention, the polyol (i) containing the polyol
(p) and the compound (ii) can be used for the preparation (c) for
a polyurethane foam, as it is, without removing the compound (ii)
having been used for the production of the polyoxyalkylene polyl (p) .
5 In this case, as the molar ratio (a/b), the ratio of the number of
moles of the acid or its salt (iv) added to the preparation (c) to
the number of moles of the compound (ii) having been used for the
production of the polyol (p) is preferably in the above range,
[0069]
10 Examples of the phosphazenium compounds include a compound
represented by the following chemical formula (2) and a compound
represented by the following chemical formula (3).
[0070]
[Chem. 2]
NRa
A.
II
R,N N NR,
i Yd 1
R»N'4P = NVpt-{N = PVNR,
I x-U I
R,N N NRa
11
RzN-P-NR,
NR.
Q-
15
( 2 )
[0071]
f
SF-2542
27
In the formula (2), a, b, c and d are each a positive number
of 0 to 3 but there is no case where all of a, b, c and d become 0
at the same time. Each R is the same or different hydrocarbon group
of 1 to 10 carbon atoms, and two R on the same nitrogen atom may be
5 bonded to each other to foinn a cyclic structure. Q~ represents a
hydroxyl anion, an alkoxy anion, an aryloxy anion or a carboxy anion.
[0072]
[Chem. 3]
15
NR,
A.
R,N-P—NR,
II
RJ^f N NR,
I ^ d I
I /4-s I
RaN N NR,
II
R,N-P-NR.
NRa
r-
10 [0073]
(3)
In the formula (3), a, b, c and d are each a positive number
of 0 to 3 but there is no case where all of a, b, c and d become 0
at the same time. Each R is the same or different hydrocarbon group
of 1 to 10 carbon atoms, and two Ron the same nitrogen atom are sometimes
bonded to each other to form a cyclic structure, r is an integer
of 1 to 3 and represents a number of phosphazenium cations. T^"
represents an inorganic anion having a valence of r.
[0074]
SF-2542
28
f
Of these, the compound represented by the chemical fojnnula (2)
is preferable.
[0075]
In the phosphazenium cation represented by the chemical formula
5 (2) or the chemical formula (3), a, b, c and d are each a positive
number of 0 to 3. However, there is no case where all of a, b, c
and d become 0 at the same time. They are each preferably an integer
of 0 to 2. More preferable are numbers in a combination of (2, 1,
1, 1), (1, 1, 1, 1), (0, 1, 1, 1), (0, 0, 1, 1) or (0, 0, 0, 1), regardless
10 of the order of a, b, c and d. Still more preferable are numbers
in a combination of (1, 1, 1, 1), (0, 1, 1, 1), (0, 0, 1, 1) or (0,
0, 0, 1).
[0076]
In the phosphazenium cation represented by the chemical formula
15 (2) or the chemical formula (3), each R is the same or different
hydrocarbon group of 1 to 10 carbon atoms. Examples of R include
aliphatic or aromatic hydrocarbon groups, such as methyl, ethyl,
n-propyl, isopropyl, allyl, n-butyl, sec-butyl, tert-butyl,
2-butenyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-l-butyl, isopentyl,
20 tert-pentyl, 3-methyl-2-butyl, neopentyl, n-hexyl,
4-methyl-2-pentyl, cyclopentyl, cyclohexyl, 1-heptyl, 3-heptyl,
1-octyl, 2-octyl, 2-ethyl-l-hexyl, 1,l-dimethyl-3,3-dimethylbutyl
(tert-octyl), nonyl, decyl, phenyl, 4-toluyl, benzyl, 1-phenylethyl
and 2-phenylethyl. Of these, preferable are aliphatic hydrocarbon
SF-2542
29
groups of 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl,
isopropyl, tert-butyl, tert-pentyl and tert-octyl. More preferable
is a methyl group or an ethyl group.
[0077]
5 When two R on the same nitrogen atom in the phosphazenium cation
are bonded to each other to form a cyclic structure, the divalent
hydrocarbon group on the nitrogen atom is a divalent hydrocarbon group
having a main chain constituted of 4 to 6 carbon atoms (the ring becomes
5- to 7-membered ring containing nitrogen atom). Preferable are,
10 for example, tetramethylene, pentamethylene and hexamethylene. More
preferable is a tetramethylene or pentamethylene group. A group
wherein a main chain of the above group is substituted by an alkyl
group such as methyl or ethyl is also available. All or a part of
possible nitrogen atoms in the phosphazenium cation may take such
15 a cyclic structure as above.
[0078]
In the chemical formula (3), T^' represents an inorganic anion
having a valence of r. r is an integer of 1 to 3. Examples of such
inorganic anions include inorganic anions of boric acid, tetraf luoric
20 acid, hydrocyanic acid, thiocyanic acid, hydrohalogenic acid, such
as hydrofluoric acid, hydrochloric acid or hydrobromic acid, nitric
acid, sulfuric acid, phosphoric acid, phosphorous acid,
hexaf luorophosphoric acid, carbonic acid, hexaf luoroantimonic acid,
hexafluorothallium acid and perchloric acid, and inorganic anions
SF-2542
30
such as HS04~ and HCO3". These inorganic anions can exchange each other
through ion exchange reaction. Of these inorganic anions, preferable
are anions of inorganic acids, such as boric acid, tetrafluoroboric
acid, hydrohalogenic acid, phosphoric acid, hexafluorophosphoric
5 acid and perchloric acid, and more preferable is chlorine anion.
[0079]
When the phosphazenium compound of the chemical formula (3)
is used as a catalyst, it is necessary to prepare an alkali metal
or alkaline earth metal salt of an active hydrogen compound in advance.
10 The preparation process for the salt may be a publicly known process.
The alkali metal or alkaline earth metal salt of an active hydrogen
compound, which is allowed to coexist with the compound represented
by the chemical formula (3), is a salt wherein active hydrogen of
the active hydrogen compound dissociates into a hydrogen ion and the
15 hydrogen ion is replaced with an alkali metal or alkaline earth metal
ion.
[0080]
Examples of preferred forms of the compounds represented by
the chemical formula (2) include
20 tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium
hydroxide,
tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium
methoxide,
tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium
^
SF-2542
31
ethoxide, and
tetrakis[tri(pyrrolidin-1-yl)phosphoranylideneamino]phosphonium
tert-butoxide.
[0081]
The phosphine oxide compound is, for example, a compound
represented by the following chemical formula (4).
[0082]
[Chem. 4]
NR2
I
RN-P~NR2
II
NR2 N
I 1
R 2 N - P = N - P = 0 • xCHiO)
NR2 N
II
R2N-P-NR2
NR2 . . . (4)
10 [0083]
In the chemical formula (4), each R is the same or different
hydrocarbon group of 1 to 10 carbon atoms. Examples of R include
aliphatic or aromatic hydrocarbon groups, such as methyl, ethyl,
n-propyl, isopropyl, allyl, n-butyl, sec-butyl, tert-butyl,
15 2-butenyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-l-butyl, isopentyl,
tert-pentyl, 3-methyl-2-butyl, neopentyl, n-hexyl,
4-methyl-2-pentyl, cyclopentyl, cyclohexyl, 1-heptyl, 3-heptyl,
1-octyl, 2-octyl, 2-ethyl-l-hexyl, 1,l-dimethyl-3,3-dimethylbutyl
SF-2542
32
l|
(common name: tert-octyl), nonyl, decyl, phenyl, 4-toluyl, benzyl,
1-phenylethyl and2-phenylethyl. Rmaybe in the form of a pyrrolidine
group or a piperidino group. Of these R, preferable are the same
or different aliphatic hydrocarbon groups of 1 to 8 carbon atoms,
5 such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, tert-pentyl
and 1,l-dimethyl-3,3-dimethylbutyl. More preferable is a methyl
group or an ethyl group.
[0084]
The phosphine oxide compound represented by the chemical formula
10 (4) can be synthesized by the method described in "Journal of general
chemistry of the USSR", 55, 1453 (1985) or a method analogous thereto.
The phosphine oxide compound represented by the chemical foinnnula (4)
usually has hygroscopicity and tends to become a water-containing
substance or a hydrate, x representing the amount of water molecules
15 contained in the phosphine oxide compound is indicated by a molar
ratio to the phosphine oxide compound, and x is 0 to 5, preferably
0 to 2. As a preferred foinn of the phosphine oxide compound,
tris[tris(dimethylamino]phosphoranylideneamino]phosphine oxide or
tris[tris(diethylamino)phosphoranylideneamino]phosphine oxide can
20 be mentioned,
[0085]
The phosphazene compound is, for example, a compound described
in Japanese Patent Laid-Open Publication No. 1998-36499, and is
specifically a compound represented by the following chemical formula
SF-2542
33
^
(5).
[0086]
[Chem. 5]
Q
I
D N D
D N D
H
D-P-D
D • • • (5)
5 [0087]
In the chemical formula (5), 1, m and n are each a positive
integer of 0 to 3.
[0088]
In the chemical formula (5) , Q is a hydrocarbon group of 1 to
10 20 carbon atoms, and examples thereof include:
alkyl groups, such as methyl, ethyl, propyl, isopropyl, n-butyl,
isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl,
octyl, tert-octyl, nonyl and decyl,
alkyl groups having an unsaturated bond or an aromatic group,
15 such as allyl, 2-methylallyl, benzyl, phenethyl, o-anisyl,
1-phenylethyl, diphenylmethyl, triphenylmethyl and cinnamyl,
alicyclic groups, such as cyclopentyl, cyclohexyl,
4-methylcyclohexyl, 3-propylcyclohexyl, 4-phenylcyclohexyl,
cycloheptyl and 1-cyclohexenyl,
SF-2542
34
#
alkenyl groups, such as vinyl, styryl, propenyl, isopropenyl,
2-methyl-l-propenyl and 1,3-butadienyl,
alkynyl groups, such as ethynyl and 2-propynyl, and
aromatic groups, such as phenyl, o-tolyl, m-tolyl, p-tolyl,
5 2,3-xylyl, 2,4-xylyl, 3,4-xylyl, mesityl, o-cumenyl, m-cumenyl,
p-cumenyl, 1-naphthyl, 2-naphthyl and p-methoxyphenyl.
[0089]
In the chemical formula (5) , each D is the same or different
hydrocarbon group of 1 to 20 carbon atoms, an alkoxy group, a phenoxy
10 group, a thiol residue, a thiophenol residue, a mono-substituted amino
group, a di-substituted amino group or a cyclic amino group of a 5-
to 6-membered ring.
[0090]
Examples of the hydrocarbon groups of 1 to 20 carbon atoms as
15 D include:
alkyl groups, such as methyl, ethyl, propyl, isopropyl, n-butyl,
isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl,
octyl, tert-octyl, nonyl and decyl,
alkyl groups having an unsaturated bond or an aromatic group,
20 such as allyl, 2-methylallyl, benzyl, phenethyl, o-anisyl,
1-phenylethyl, diphenylmethyl, triphenylmethyl and cinnamyl,
alicyclic groups, such as cyclopentyl, cyclohexyl,
4-methylcyclohexyl, 3-propylcyclohexyl, 4-phenylcyclohexyl,
cycloheptyl and 1-cyclohexenyl,
SF-2542
35
#
alkenyl groups, such as vinyl, styryl, propenyl, isopropenyl,
2-inethyl-l-propenyl and 1, 3-butadienyl,
alkynyl groups, such as ethynyl and 2-propynyl, and
aromatic groups, such as phenyl, o-tolyl, m-tolyl, p-tolyl,
5 2,3-xylyl, 2,4-xylyl, 3,4-xylyl, mesityl, o-cumenyl, m-cumenyl,
p-cumenyl, 1-naphthyl, 2-naphthyl and p-methoxyphenyl.
[0091]
Examples of the alkoxy groups as D include alkoxy groups
containing 1 to 20 carbon atoms, such as methoxy, ethoxy, propoxy,
10 isopropoxy, butoxy, pentyloxy, allyloxy, cyclohexyloxy and
benzyloxy.
Examples of the phenoxy groups as D include phenoxy groups
containing 6 to 20 carbon atoms, such as phenoxy, 4-methylphenoxy,
3-propylphenoxy and 1-naphthyloxy.
15 Examples of the thiol residues as D include thiol residues
containing 1 to 20 carbon atoms, such as methylthio, ethylthio,
propylthio, isopropylthio, butylthio, isobutylthio, tert-butylthio,
pentylthio, hexylthio, heptylthio, octylthio, tert-octylthio,
nonylthio and decylthio.
20 [0092]
Examples of the thiophenol residues as D include thiophenol
residues containing 6 to 20 carbon atoms, such as phenylthio,
o-toluylthio, m-toluylthio, p-toluylthio, 2,3-xylylthio,
2, 4-xylylthio, 3, 4-xylylthio, 4-ethylphenylthio and 2-naphthylthio.
SF-2542
36
Examples of the mono-substituted amino groups as D include
mono-substituted amino groups containing 1 to 20 carbon atoms, such
asmethylamino, ethylamino, propylamine, isopropylamino, butylamino,
isobutylamino, tert-butylamino, pentylamino, hexylamino,
5 heptylamino, octylamino, tert-octylamino, nonylamino, decylamino,
1-ethylpropylamino, 1-ethylbutylamino, anilino, o-toluylamino,
m-toluylamino, p-toluylamino, 2,3-xylylinoamino, 2,4-xylylinoamino
and 3,4-xylylinoamino.
[0093]
10 Examples of the di-substituted amino groups as D include amino
groups di-substituted by the same or different hydrocarbon groups
of 1 to 20 carbon atoms, such as dimethylamino, diethylamino,
methylethylamino, dipropylamino, methylpropylamino,
diisopropylamino, dibutylamino, methylbutylamino, diisobutylamino,
15 di-sec-butylamino, dipentylamino, dihexylamino, ethylhexylamino,
diheptylamino, dioctylamino, di-tert-octylamino,
ethyl-tert-octylamino, dinonylamino, didecylamino, diphenylamino,
methylphenylamino, ethylphenylamino, di-o-toluylamino,
di-2,3-xylylamino and phenyltoluylamino.
20 Examples of the cyclic amino groups of a 5- to 6-membered ring
as D include 1-pyrrolidinyl, 3-methyl-l-pyrrolidinyl, 1-pyrrolyl,
3-ethyl-l-pyrrolyl, 1-indolyl, 1-piperidyl, 3-methyl-l-piperidyl,
1-piperazinyl, 4-methyl-l-piperazinyl, 1-imidazolidinyl and
4-morpholinyl.
SF-2542
37
#
[0094]
All or a part of possible bonds foinned by bonding of two D on
the same phosphorus atom or on two different phosphorus atoms to each
other may fo2:m a cyclic structure. As the divalent group (D-D) on
5 the phosphorus atom in this case, a saturated or unsaturated aliphatic
divalent hydrocarbon group, such as ethylene, vinylene, propylene,
1,2-cyclohexanylene, 1,2-phenylene, trimethylene, propenylene,
tetramethylene, 2,2'-biphenylene, 1-butenylene, 2-butenylene or
pentamethylene, can be mentioned.
10 [0095]
Further, there can be mentioned a divalent group wherein into
one or both of bonds between both ends of the above divalent group
and phosphorus atoms is inserted arbitrary one or two atoms selected
from the group consisting an oxygen atom, a sulfur atom and a nitrogen
15 atom to which a hydrogen atom or an aliphatic or aromatic hydrocarbon
group, such as methyl group, ethyl group, butyl group, cyclohexyl
group, benzyl group or phenyl group, is bonded. Specific examples
of such divalent groups include groups of methyleneoxy, ethylene-2-oxy,
trimethylene-3-oxy, methylenedioxy, ethylenedioxy,
20 trimethylene-l,3-dioxy, cyclohexane-l,2-dioxy, benzene-l,2-dioxy,
methylenethio, ethylene-2-thio, trimethylene-3-thio,
tetramethylene-4-thio, methylenedithio, ethylenedithio,
trimethylene-1,3-dithio, iminomethylene, 2-iminoethylene,
3-iminotrimethylene, 4-iminotetramethylene, N-ethyliminomethylene,
SF-2542
38
N-cyclohexyl-2-iminoethylene, N-methyl-3-iminotrimethylene,
N-benzyl-4-iminotetramethylene, diiminomethylene,
1,2-diiminoethylene, 1, 2-diiminovinylene, 1, 3-diiminotrimethylene,
N,N' -dimethyldiiminomethylene, N,N' -diphenyl-l,2-diiminoethylene,
5 N,N'-dimethyl-l,2-diiminoethylene,
N-methyl-N'-ethyl-1,3-diiminotrimethylene,
N,N'-diethyl-1,4-diiminotetramethylene and
N-methyl-1,3-diiminotrimethylene.
[0096]
10 All or a part of possible bonds formed by bonding of D and Q
to each other may form a cyclic structure, and as the divalent group
(D-Q) to connect a nitrogen atom to a phosphorus atom in this case,
there can be mentioned the same saturated or unsaturated aliphatic
divalent hydrocarbon group as the aforesaid divalent group on the
15 phosphorus atom or a divalent group wherein arbitrary one atom selected
from the group consisting an oxygen atom, a sulfur atom and a nitrogen
atom to which a hydrogen atom or an aliphatic or aromatic hydrocarbon
group, such as methyl group, ethyl group, butyl group, cyclohexyl
group, benzyl group or phenyl group, is bonded is inserted into the
20 bond between the above divalent hydrocarbon group and the phosphorus
atom. Specific examples of such divalent groups include groups of
methyleneoxy, ethylene-2-oxy, methylenethio, ethylene-2-thio,
iminomethylene, 2-iminoethylene, N-methyliminomethylene,
N-ethyl-2-iminoethylene, N-methyl-3-iminotrimethylene and
SF-2542
39
N-phenyl-2-iminoethylene.
[0097]
Specific examples of the phosphazene compounds having a
structure represented by the chemical formula (5) wherein each D is
5 the same or different alkyl group include
l-tert-butyl-2,2,2-trimethylphosphazene and
1-(1,1,3,3-tetramethylbutyl)-2,2,4,4,4-pentaisopropyl-2A^, 4A^-cat
enadi(phosphazene).
[0098]
10 Examples of the compounds wherein D is an alkyl group having
an unsaturated bond or an aromatic group include
l-tert-butyl-2,2,2-triallylphosphazene,
l-cyclohexyl-2,2, 4,4, 4-pentaallyl-2A^, 4A^-catenadi (phosphazene)
and
15 l-ethyl-2,4,4,4-tribenzyl-2-tribenzylphosphoranylideneamino-2A^,
4A^-catenadi(phosphazene).
[0099]
Examples of the compounds wherein D is an alicyclic group include
l-methyl-2,2,2-tricyclopentylphosphazene and
20 l-propyl-2,2, 4, 4, 4-cyclohexyl-2A^, 4A^-catenadi (phosphazene) .
[0100]
Examples of the compounds wherein D is an alkenyl group include
l-butyl-2,2,2-trivinylphophazene and
l-tert-buty-2, 2,4,4, 4-pentastyryl-2A^, 4A^-catenadi (phosphazene) .
SF-2542
40
#
[0101]
Examples of the compounds wherein D is an alkynyl group include
l-tert-butyl-2,2,2-tri(2-phenylethynyl)phosphazene. Examples of
the compounds wherein D is an aromatic group include
5 l-isopropyl-2,4,4,4-tetraphenyl-2-triphenylphosphoranylideneamin
o-2A^, 4A^-catenadi (phosphazene) .
[0102]
Examples of the compounds wherein D is an alkoxy group include
l-tert-butyl-2,2,2-trimethoxyphosphazene,
10 1-(1,1,3,3-tetramethylbutyl)-2,2,4,4,4-pentaisopropoxy-2A^, 4A^-ca
tenadi(phosphazene) and
l-phenyl-2, 2, 4, 4, 4-pentabenzyloxy-2A^, 4A^-catenadi (phosphazene) .
[0103]
Examples of the compounds wherein D is a phenoxy group include
15 l-methyl-2,2,2-triphenoxyphosphazene and
l-tert-butyl-2,2,4,4,4-penta(1-naphthyloxy)-
2A^, 4A^-catenadi (phosphazene) .
[0104]
Examples of the compounds wherein D is a di-substituted amino
20 group include l-tert-butyl-2,2,2-tris(dimethylamino)phosphazene,
1-(1,1,3,3-tetramethylbutyl)-2,2,2-tris(dimethylamino)phosphazen
e, l-ethyl-2,2,4,4,4-pentakis(dimethylamino)-
2A^,4A^-catenadi(phosphazene),
l-tert-butyl-2,4,4, 4-tetrakis(dimethylamino)-2-tris(dimethylamin
SF-2542
41
o)phosphoranylideneamino-2A^, 4X^-catenadi (phosphazene) ,
l-tert-butyl-2,4,4,4-tetrakis(diisopropylamino)-2-tris(diisoprop
ylamino)phosphoranylideneamino-2A^, 4A^-catenadi (phosphazene),
l-tert-butyl-2,4,4,4-tetrakis(di-n-butylamino)-2-tris(di-n-butyl
5 amino) phosphoranylideneamino-2X^, 4X^-catenadi (phosphazene) ,
l-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamin
o)phosphoranylideneamino]- 2A^,4X^-catenadi(phosphazene),
1-(1,1,3,3-tetramethylbutyl)-4,4,4-tris(dimethylamino)-2,2-bis[t
ris (dimethylamino) phosphoranylideneamino] -2A^, 4X^-catenadi (phosph
10 azene),
1-(1,1,3,3-tetramethylbutyl)-4,4,4-tris(methylethylamino)-2,2-bi
s[tris(methylethylamino)phosphoranylideneamino]-
2A^, 4A^-catenadi (phosphazene) ,
l-tert-butyl-4,4,4-tris(diethylamino)-2,2-bis[tris(diethylamino)
15 phosphoranylideneamino] -2A^, 4A^-catenadi (phosphazene) ,
l-tert-butyl-4,4,4-tris(diisopropylamino)-2,2-bis[tris(diisoprop
ylamino) phosphoranylideneamino] -2A^, 4A^-catenadi (phosphazene),
l-tert-butyl-4,4,4-tris(di-n-butylamino)-2,2-bis[tris(di-n-butyl
amino) phosphoranylideneamino] -2A^, 4A^-catenadi (phosphazene),
20 l-tert-butyl-4,4,6,6,6-pentakis(dimethylamino)-2,2-bis[tris(dime
thylamino)phosphoranylideneamino]-2A^, 4A^, 6A^-catenatri(phosphaze
ne) ,
l-tert-butyl-4,4,6,6,6-pentakis(diethylamino)-2,2-bis[tris(dieth
ylamino)phosphoranylideneamino]-2A^, 4A^, 6A^-catenatri(phosphazene
SF-2542
42
#
l-tert-butyl-4,4,6,6,6-pentakis(diisopropylamino)-2,2-bis[tris(d
iisopropylamino)phosphoranylideneamino]-2A^, 4A^, 6A^-catenatri(pho
sphazene),
5 l-tert-butyl-4,4,6,6,6-pentakis(di-n-butylamino)-2,2-bis[tris(di
-n-butylamino)phosphoranylideneamino]-2A^, 4A^, 6A^-catenatri(phosp
hazene),
l-tert-butyl-4,4,6,6,6-pentakis(dimethylamino)-2-[2,2,2-tris(dim
ethylamino)phosphazen-l-yl]-2-[2,2,4,4,4-pentakis(dimethylamino)
10 -2A^, 4A^-catenadi (phosphazen) -1-yl] -2A^, 4A^, 6A^-catenatri (phosphaz
ene) and
l-phenyl-2,2-bis(dimethylamino)-4,4-dimethoxy-4-phenylamino-2A^,
4A^-catenadi(phosphazene).
[0105]
15 Examples of the compounds wherein two D on the same phosphorus
atom or on two different phosphorus atoms are bonded to each other
to form a cyclic structure include
2-(tert-butylimino)-2-dimethylamino-l,3-dimethyl-l,3-diaza-2A^-p
hosphinane.
20 [0106]
Examples of preferred forms of the phosphazene compounds include
l-tert-butyl-2,2,2-tris(dimethylamino)phosphazene,
1- (1,1,3,3-tetramethylbutyl)-2,2,2-tris(dimethylamino)phosphazen
e.
SF-2542
43
^^^
l-ethyl-2,2, 4, 4, 4-pentakis (dimethylamino) -2A^, 4A^-catenadi (phosph
azene),
l-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamin
o) phosphoranylideneamino] -2A^, 4X^-catenadi (phosphazene) ,
5 1-(1,1,3,3-tetramethylbutyl)-4,4,4-tris(dimethylamino)-2,2-bis[t
ris (dimethylamino) phosphoranylideneamino] -2A^, 4A^-catenadi (phosph
azene), l-tert-butyl-2,2,2-tri(1-pyrrolidinyl)phosphazene and
7-ethyl-5,11-dimethyl-l, 5, 7, ll-tetraaza-6A^-phosphaspiro [5, 5] und
ec-1(6)-ene.
10 [0107]
Of the compounds (ii) , preferable are phosphazenium compounds,
more preferable are compounds represented by the chemical formula
(2), and still more preferable is
tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium
15 hydroxide in the present invention, from the viewpoints of long-term
storage stability of a resin premix, coloration and discoloration
inhibition properties of a resin premix during storage, and
industrially effective utilization of a catalyst.
[0108]
20 <(iii) Antioxidant having hydroxyphenyl group>
In the composition of the present invention, an antioxidant
having a hydroxyphenyl group is contained for the purpose of preventing
deterioration of polyols such as polyoxyalkylene polyol and polymer
polyol. In the present invention, this antioxidant is sometimes
SF-2542
44
l »
referred to as an "antioxidant (iii)",
[0109]
When an antioxidant having a hydroxyphenyl group, such as BHT,
is used in the production of a general polyoxyalkylene polyol, there
5 is usually a problem that an antioxidant itself is liable to undergo
structural change under the basic conditions to cause coloration and
discoloration.
[0110]
However, it has been found that even if the composition for
10 a polyurethane foam contains a polyol and a compound having a P=N
bond, the reactivity of the composition does not change even in the
storage of the composition for a long time and the storage stability
becomes good in the present invention, particularly by the use of
the antioxidant together with the later-described acid or its salt
15 related to the present invention. Although the reason is not clear,
it is presumed that by the use of a combination of specific acid and
antioxidant or by the use of specific acid, antioxidant, polyol and
compound having a P=N bond, the compounds in the composition for a
polyurethane foam are stably present and the maintenance of reactivity
20 of the composition for a polyurethane foam over a long period of time
has succeeded.
[0111]
It has been further found that even in the case of the preparation
for a urethane foam of the present invention, coloration and
SF-2542
45
^
discoloration during storage can be inhibited over a long time, and
even when a resin premix is prepared by adding various additives related
to urethane foams after storage of the preparation, the resin premix
can be stably stored.
5 [0112]
The content ratio of the antioxidant (iii) contained in the
polyol (p) of the present invention is not specifically restricted
as far as the effects of the present invention are exerted, but when
the content ratio is calculated from the charge of each component,
10 the lower limit is 100 ppm, preferably 200 ppm, and the upper limit
is 20000 ppm, preferably 15000 ppm.
[0113]
The content ratio of the antioxidant (iii) contained in the
preparation (c) of the present invention is not specifically restricted
15 as far as the effects of the present invention are exerted, but when
the content ratio is calculated from the charge of each component,
it is preferably 100 to 15000 ppm, more preferably 200 to 10000 ppm,
still more preferably 250 to 6000 ppm.
[0114]
20 The content ratio of the antioxidant (iii) contained in the
composition of the present invention is not specifically restricted
as far as the effects of the present invention are exerted, but when
the content ratio is calculated from the charge of each component,
it is preferably 100 to 15000 ppm, more preferably 200 to 10000 ppm.
SF-2542
46
*
still more preferably 250 to 6000 ppm.
[0115]
It is also possible to determine the content ratio of the
antioxidant (iii) contained in the polyol (p) , the preparation (c)
5 or the composition of the present invention by properly combining
NMR method, gas chromatography, liquid chromatography and mass
spectrometry.
[0116]
Examples of the antioxidants include BHT
10 (3,5-di-tert-butyl-4-hydroxytoluene),
pentaerythrityl-tetrakis-3-(3,5-di-tert-butyl-4-hydroxypheyl)pro
pionate (also referred to as "Irganox 1010"),
octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (also
referred to as "Irganox 1076"), 2-tert-butyl-4-ethylphenol,
15 2,6-di-tert-butyl-4-ethylphenol, triethylene
glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate],
stearyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,
2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propion
ate] , isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (also
20 referred to as "Irganox 1135"),
1,3,5-trimethyl-2,4,6-tris[(3,5-di-t-butyl-4-hydroxyphenyl)methy
l]benzene, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenyl)methyl
isocyanurate,
1,3,5-tris[(4-t-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]
SF-2542
47
#
isocyanurate,
1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane,
2,2'-methylenebis(4-methyl-6-t-butylphenol) and
3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-l
5 ,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane. Of these,
antioxidants having t-butyl group-substituted hydroxyphenyl group
are preferable, and for the reason of solubility in the composition
for a polyurethane fcam, antioxidant performance, etc., BHT, Irganox
1010, Irganox 1076 and Irganox 1135 are more preferable.
10 [0117]
These antioxidants may be used singly or in combination of two
or more kinds.
[0118]
<{iv) Acid or its salt>
15 In the composition of the present invention, at least one acid
selected from the group consisting of an acyclic aliphatic
monocarboxylic acid of 2 to 25 carbon atoms, a hydroxycarboxylic acid
of 2 to 25 carbon atoms, a polycarboxylic acid of 20 to 60 carbon
atoms, an aromatic monocarboxylic acid represented by the aforesaid
20 formula (1) , a sulfonic acid and an acid having a sulfuric acid ester
group, or its salt is contained. In the present invention, these
are sometimes referred to as "acids or their salts (iv)")
[0119]
When inorganic acids (mineral acids) , such as hydrochloric acid.
SF-2542
48
A
nitric acid, nitrous acid, sulfuric acid, boric acid, hydrofluoric
acid, phosphoric acid, phosphorous acid, hypophosphorous acid and
pyrophosphoric acid, or their salts are contained in a resin premix
for a long period of time, crystals are usually liable to be precipitated,
5 and the possibility of inhibiting the production of a polyurethane
foam is high. Further, when the acids or their salts are used in
the form of an aqueous solution or when a resin premix is prepared
using water as the later-described blowing agent, they are usually
liable to be separated in water, together with the compound having
10 a P=N bond and hydrophilic components such as a catalyst for
polyurethane foam production, and therefore, it is difficult to obtain
a resin premix having storage stability.
[0120]
In the case of the composition for a polyurethane foam of the
15 present invention, however, crystals are not precipitated, andbesides,
a resin premix can have storage stability over a long period of time
without bringing about separation between an aqueous layer and an
organic layer. Moreover, it has been found that by the use of the
acid or its salt together with the antioxidant related to the present
20 invention, reactivity of the composition for a polyurethane foam does
not change even when the composition is stored for a long time, and
the storage stability of the composition becomes good, as previously
described. Although the reason for them is not clear, it is presumed
that by virtue of a combination of specific acid and antioxidant.
SF-2542
49
#
the compounds in the composition for a polyurethane foam are stably
present and the maintenance of reactivity of the composition over
a long period of time has succeeded.
[0121]
5 It is preferable that the acid or its salt (iv) of the present
invention satisfies the ratio (a/b) thereof to the number of moles
of the compound having a P=N bond, as previously described.
[0122]
Examples of the acyclic aliphatic monocarboxylic acids of 2
10 to 25 carbon atoms, preferably 2 to 20 carbon atoms, and their salts
include acetic acid, propionic acid, butyric acid, valeric acid,
caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric
acid, lauric acid, myristic acid, palmitic acid, stearic acid, and
their salts.
15 [0123]
Examples of the hydroxycarboxylic acids of 2 to 25 carbon atoms,
preferably 2 to 20 carbon atoms, and their salts include lactic acid,
malic acid, tartaric acid, citric acid, ricinoleic acid, and their
salts.
20 [0124]
Examples of the polycarboxylic acids of 20 to 60 carbon atoms,
preferably 25 to 55 carbon atoms, and their salts include dimer acids
(dimers of carboxylic acids of 18 carbon atoms) (Pripol 1009, Pripol
1006 and Pripol 1013 available from Croda Japan K.K.) and their salts.
SF-2542
50
^
The dimer acids can be produced on the basis of, for example, the
description of Japanese Patent Laid-Open Publication No. 2005-2085.
[0125]
Examples of the aromatic monocarboxylic acids represented by
5 the aforesaid formula (1) and their salts include benzoic acid,
decylbenzoic acid, dodecylbenzoic acid, and their salts. In the
formula (1), R"^ represents a hydrocarbon group. Examples of the
hydrocarbon groups include methyl group, ethyl group, propyl group,
isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
10 t-butyl group, n-pentyl group, isopentyl group, t-pentyl group,
neopentyl group, hexyl group, isohexyl group, heptyl group, octyl
group, nonyl group, decyl group and dodecyl group. R""" is preferably
a decyl group or a dodecyl group, m represents a number of hydrogen
atoms of the benzene ring having been replaced with R''", and is any
15 one of 0 to 5, preferably 0 to 2.
[0126]
Examples of the sulfonic acids and their salts include
p-toluenesulfonic acid, alkylbenzenesulfonic acids such as
dodecylbenzenesulfonic acid (including straight-chain type or
20 branched type), benzenesulfonic acid, methanesulfonic acid,
camphorsulfonic acid, and their salts.
[0127]
Examples of the acids having sulfuric acid ester group and their
salts include polyoxyalkylene alkenyl ether ammonium sulfate (Latemul
SF-2542
51
%
PD-105 available fromKao Corporation) andpolyoxyethylene styrenated
phenyl ether ammonium sulfate (Latemul E-IOOOA available from Kao
Corporation).
[0128]
5 The salt is not specifically restricted as far as it can be
neutralized with an acid and exerts the effects of the present invention.
However, there can be mentioned, for example, alkali metal salts,
such as lithium salt, sodium salt and potassium salt, alkaline earth
metal salts, such as calcium salt, magnesium salt and barium salt,
10 weakly basic salts, such as ammonium salt, amine salt and pyridinium
salt, metal salts, such as copper salt and silver salt, and complex
salts with copper. Preferable are weakly basic salts, such as ammonium
salt, amine salt and pyridinium salt.
[0129]
15 These acids may be in the form of acid anhydrides or hydrates
as far as they exert the effects of the present invention.
[0130]
Of these, preferable are lactic acid, malic acid, tartaric acid,
citric acid, dimer acid, benzoic acid, decylbenzoic acid,
20 dodecylbenzoic acid, p-toluenesulfonic acid, alkylbenzenesulfonic
acids such as dodecylbenzenesulfonic acid (including straight-chain
type or branched type), benzenesulfonic acid, methanesulfonic acid,
camphorsulfonic acid, polyoxyalkylene alkenyl ether ammonium sulfate
and polyoxyethylene styrenated phenyl ether ammonium sulfate, and
#
SF-2542
52
more preferable are p-toluenesulfonic acid, alkylbenzenesulfonic
acids such as dodecylbenzenesulfonic acid (including straight-chain
type or branched type) , benzenesulfonic acid, methanesulfonic acid
and camphorsulfonic acid, because the ratio (a/b) of the total number
5 of moles (a) of the acid or its salt to the number of moles (b) of
the compound having a P=N bond necessary to obtain coloration and
discoloration inhibition properties is small, that is, coloration
and discoloration can be efficiently inhibited by the addition of
a small amount of the acid, and there is no odor of the acid, etc.
10 [0131]
These acids and their salts may be used singly or in combination
or two or more kinds.
[0132]
<(v) Catalyst for polyurethane foam production>
15 The catalyst for polyurethane foam production (also referred
to as a "catalyst (v) for production") related to the present invention
is not specifically restricted provided that it can be used for the
reaction of a polyol with a polyisocyanate, and a hitherto publicly
known catalyst can be used.
20 [0133]
Although the amount of the catalyst (v) for production is not
specifically restricted, it is preferably 0.1 to 10 parts by mass,
more preferably 0.2 to 5 parts by mass, based on 100 parts by mass
of all the polyol components.
SF-2542
53
[0134]
As the catalysts (v) for production, aliphatic amines, such
as triethylenediamine, bis(2-dimethylaminoethyl)ether,
l-isobutyl-2-methylimidazole and morpholines, organotin compounds,
5 such as tin octanoate and dibutyltin dilaurate, etc. can be preferably
used.
[0135]
These catalysts can be used singly or in combination of two
or more kinds.
10 [0136]
<(vi) Blowing agent>
As the blowing agents, water and physical blowing agents, such
as hydroxyfluorocarbons (HFC-245fa, etc.) which were developed for
the purpose of global environmental protection, hydrocarbons
15 (cyclopentane, etc.) , carbonic acid gas and liquefied carbonic acid
gas, can be used. Of these, water, carbonic acid gas and liquefied
carbonic acid gas are preferable from the viewpoint of reduction of
environmental burden.
[0137]
20 As the blowing agent related to the present invention, a physical
blowing agent such as liquefied carbonic acid gas is employable, but
it is desirable to use water.
[0138]
When water is used as the blowing agent, the amount of water
#
SF-2542
54
is preferably 1.3 to 6.5 parts by mass, more preferably 1.8 to 6.0
parts by mass, still more preferably 2.0 to 5.5 parts by mass,
particularly preferably 2.0 to 5.0 parts by mass, based on 100 parts
by mass of all the polyol components. By the use of water as the
5 blowing agent in the above amount, foaming is stabilized and
effectively carried out.
[0139]
As the blowing agent, a physical blowing agent can be used in
combination with water. Of the physical blowing agents, carbon acid
10 gas and liquefied carbonic acid gas are preferable from the viewpoint
of reduction of environmental burden.
[0140]

In the composition for a polyurethane foam, the preparation
15 for a polyurethane foam and the polymer polyol preparation for a
polyurethane foam of the present invention, a foam stabilizer, a chain
extender, a crosslinking agent, an interconnecting agent, an
antifoaming agent, and as other assistants, additives generally used
for producing polyurethane foams or polyurethane resins, such as flame
20 retardant, pigment and ultraviolet light absorber, can be used in
addition to the above components, within limits not detrimental to
the objects of the present invention.
[0141]
As the foam stabilizer, a hitherto publicly known foam stabilizer
^
SF-2542
55
can be used, and there is no specific limitation. However, it is
preferable to use an organosilicon-based surface active agent.
[0142]
For example, FV-1-1013-16, SRX-274C, SF-2969, SF-2961, SF-2962,
5 L-3601, SZ-1325 and SZ-1328 available from Dow Corning Toray Silicone
Co., Ltd., L-5309, L-5307, L-3600, L-5366 and Y-10366 available from
Momentive Performance Materials Inc., DC-2525 and DC-6070 available
from Air Products Japan, Inc., B-8715 andB-8742 available fromEvonik
Industries AG, etc. can be preferably used. The amount of the foam
10 stabilizer used is preferably 0.1 to 10 parts by mass, more preferably
0.5 to 5 parts by mass, based on 100 parts by mass of all the polyol
components.
[0143]
As the additives, there can be mentioned additives described
15 in "Polyurethane" edited by Nobutaka Matsudaira and Tetsuro Maeda,
8th issue, Maki Shoten (1964) pp. 134-137, and "Functional
Polyurethane" editedbyHitoshiMatsuo, NobuakiKuniiandSeishiTanabe,
1st issue, CMC Publishing Co., Ltd. (1989) pp. 54-68.
[0144]
20 In the composition for a polyurethane foam of the present
invention, a crosslinking agent can be also used. When a crosslinking
agent is used, a compound having a hydroxyl value of 200 to 1800 mgKOH/g
is preferably used as the crosslinking agent.
[0145]
4
SF-2542
56
Examples of such crosslinking agents include aliphatic
polyhydric alcohols, such as glycerol, and alkanolamines, such as
diethanolamine and triethanolamine.
[0146]
5 Further, a polyoxyalkylene polyol having a hydroxyl value of
200 to 1800 mgKOH/g can be also used as the crosslinking agent, and
furthermore, a hitherto publicly known crosslinking agent can be also
used.
[0147]
10 When such a crosslinking agent is used, it is preferably used
in an amount of not more than 10 parts by mass based on 100 parts
by mass of all the polyol components.
[0148]

15 The polyisocyanate for use in the present invention is not
specifically restricted, and for example, hitherto publicly known
polyisocyanates described in "Polyurethane Resin Handbook" edited
by Keiji Iwata, 1st issue. The Nikkan Kogyo Shimbun, Ltd. (1987) pp.
71-98, etc. can be mentioned. Of these, toluylene diisocyanate
20 (isomer ratio of 2,4-form, 2,6-form, etc. is not specifically
restricted, but toluylene diisocyanate having a 2,4-form/2,6-form
ratio of 80/20 is preferable) (e.g., COSMONATE (trademark) T-80
available from Mitsui Chemicals, Inc.), polymethylene polyphenyl
polyisocyanate (e.g., COSMONATE (trademark) M-200 available from
SF-2542
57
Mitsui Chemicals, Inc.) or its urethane derivative, or a mixture
thereof can be preferably used in order to obtain a foamed product.
[0149]
When the polyisocyanate is a mixture of toluylene diisocyanate
5 and another polyisocyanate, the amount of the toluylene diisocyanate
contained is desired to be preferably 50 to 99% by mass, more preferably
70 to 90% by mass, particularly preferably 75 to 85% by mass, based
on the total amount of the polyisocyanate, from the viewpoint of a
balance between durability and mechanical strength of the foam.
10 [0150]
As the polyisocyanate for use in the present invention, an
isocyanate-terminated prepolymer obtained by allowing a polyol to
react with a polyisocyanate through a hitherto publicly known method
may be used instead of the aforesaid polyisocyanate.
15 [0151]
As the polyisocyanate for use in the present invention, a
combination of a polyisocyanate and an isocyanate-terminated
prepolymer may be used.
[0152]
20 In the present invention, it is desirable to use the components
so that the NCO index may preferably become 0. 70 to 1. 30, more preferably
0.80 to 1.20. When the NCO index is in the above range, a polyurethane
foam having appropriate hardness and mechanical strength and having
proper impact resilience, elongation andmoldability can be obtained.
SF-2542
58
#
In the present invention, the NCO index means a value obtained by
dividing the total number of isocyanate groups in the polyisocyanate
by the total number of active hydrogen atoms that react with an
isocyanate group, such as a hydroxyl group of a polyol, an amino group
5 of a crosslinking agent and water. That is to say, when the number
of active hydrogen atoms that react with an isocyanate group is
stoichiometrically equal to the number of isocyanate groups in the
polyisocyanate, the NCO index becomes 1.0.
[0153]
10 [Production processes for preparation for polyurethane foam,
polymer polyol preparation for polyurethane foam and composition for
polyurethane foam]
The production process for the composition for a polyurethane
foam of the present invention is not specifically restricted as far
15 as the effects of the present invention are exerted, and the composition
can be produced by a process publicly known in the polyurethane field.
[0154]
For example, there is a process wherein given amounts of raw
materials are placed in a mixing tank equipped with a stirring device
20 and mixed by the stirring device. In this case, it is preferable
to use a mixing tank capable of being closed so that the water content
in the composition for a polyurethane foam should not be changed,
and it is more preferable to mix them in dry air or nitrogen. In
the mixing, the temperature may be ordinary temperature, but in order
^^B
SF-2542
59
to improve mixing stirring performance, the temperature may be raised
within limits that do not exert evil influence on the production of
a polyurethane foam.
[0155]
5 In another general process, the composition can be produced
by guiding the raw materials introduced in the tank to a piping system
by means of a pump or the like and mixing them by a mixing machine
installed in the piping system.
[0156]
10 The composition for a polyurethane foam of the present invention
exhibits high coloration and discoloration inhibition properties over
a long period of time when stored and has excellent storage stability,
and therefore, even if the compound having a P=N bond and having been
used in the production of a polyoxyalkylene polyol, the acid or its
15 salt, etc. are not removed, the composition can be also produced by
using a crude polyoxyalkylene polyol. That is to say, in the foresaid
process, the composition can be also produced by adding the antioxidant
related to the present invention, the acid or its salt in an amount
satisfying the given molar ratio(a/b), and if necessary, other
20 additives to a polyol (i) containing a crude polyoxyalkylene polyol
(p) having been obtained by addition polymerization of an alkylene
oxide compound onto an active hydrogen compound using a compound having
a P=N bond as a catalyst to obtain a preparation (c) for a polyurethane
foam, which contains the polyol, the compound having a P=N bond, the
SF-2542
60
#
antioxidant, the acid or its salt, etc., and then carrying out a step
of adding a catalyst forpolyurethane foam production, a blowing agent,
and if necessary, other assistants directly to the preparation.
[0157]
5 In the aforesaid process, the composition can be also produced
by adding the antioxidant related to the present invention and the
acid or its salt in an amount satisfying the given molar ratio (a/b)
to a crude polyoxyalkylene polyol (p) having been obtained by addition
polymerization of an alkylene oxide compound onto an active hydrogen
10 compound using a compound having a P=N bond as a catalyst to obtain
a preparation (c) for a polyurethane foam, which contains the polyol,
the compound having a P=N bond, the antioxidant, the acid or its salt,
etc., and then carrying out a step of adding a polyol (i) , a catalyst
for polyurethane foam production, a blowing agent, and if necessary,
15 other assistants to the preparation.
[0158]
After the preparation (c) is obtained, a polymer polyol
preparation (pc) for a polyurethane foam containing a given amount
of a polymer polyol wherein polymer fine particles obtained by
20 polymerizing a compound having an unsaturated bond in the preparation
(c) are dispersed, preferably containing a given amount of a polymer
polyol wherein polymer fine particles obtained by polymerizing a
compound having an unsaturated bond are dispersed in a polyoxyalkylene
polyol (p) contained in the preparation (c), is obtained, and this
SF-2542
61
#
preparation (pc) can be used for the composition for a polyurethane
foam. In this case, a polymer polyol may be previously contained
in the preparation (c), but when efficiency is taken into consideration,
the preparation (c) preferably contains no polymer polyol.
5 [0159]
In the aforesaid process, to a polymer polyol wherein polymer
fine particles obtained by polymerizing a compound having an
unsaturated bond are dispersed, preferably to a polymer polyol wherein
polymer fine particles obtained by polymerizing a compound having
10 an unsaturated bond are dispersed in a crude polyoxyalkylene polyol
(p) having been obtained by addition polymerization of an alkylene
oxide compound onto an active hydrogen compound using a compound having
a P=N bond as a catalyst, the antioxidant related to the present
invention and the acid or its salt in an amount satisfying the given
15 molar ratio(a/b) are added to obtain a polymer polyol preparation
(pc2) for a polyurethane foam, and this preparation (pc2) can be used
for the composition for a polyurethane foam.
[0160]
According to such production processes, steps can be omitted.
20 Therefore, environmental burden can be reduced, and the production
cost can be also significantly reduced. Moreover, since the steps
are simple, the quality is stabilized and the yield is improved, so
that such processes are preferable.
[0161]
SF-2542
62
#
In the production process for a preparation for a polyurethane
foam, the acid or its salt (iv) and the antioxidant (iii) are added
in given amounts usually at 50 to 130°C. In this case, water or an
inert organic solvent may be added in order to improve solubility,
5 dispersibility and handling properties. The water thus added may
be used as it is as a blowing agent contained in the resin premix.
On the other hand, for the purpose of mainly treating the organic
solvent, water may be removed by heat treatment, reduced pressure
treatment or reduced pressure heating treatment to such an extent
10 that no influence is exerted on the production of a polyurethane foam.
The acid or its salt and the antioxidant may be added at the same
time, but it is preferable to add the antioxidant after the acid or
its salt is added. Although the antioxidant may be added immediately
after the addition of the acid or its salt, it is preferable to add
15 the antioxidant usually after 3 to 120 minutes. Further, it is
preferable to add the acid or its salt in such an amount that the
ratio (a/b) of the total number of moles (a) of the acid or its salt
to the number of moles (b) of the compound having a P=N bond becomes
a value of the aforesaid range, because the coloration and
20 discoloration inhibition properties are high over a long time and
the storage stability is also high.
[0162]
Also in the preparation (c) of the present invention, the acid
or its salt and the antioxidant may be added at the same time, but
SF-2542
63
it is preferable to add the antioxidant (iii) after the acid or its
salt (iv) is added. Addition of the acid or its salt (iv) to the
crude polyol (i) containing the polyol (p) may be carried out at room
temperature, but taking stirring properties into consideration, the
5 temperature may be raised up to about 120°C. Particularly when the
antioxidant is a solid, the temperature is preferably raised to not
lower than 60°C during the addition of the antioxidant, taking
solubility into consideration. The addition is preferably carried
out at normal pressure or under pressure, and is preferably carried
10 out in a nitrogen atmosphere.
[0163]
[Polyurethane foam and production process therefor]
The composition for a polyurethane foam, the preparation for
a polyurethane foam and the polymer polyol preparation for a
15 polyurethane foam of the present invention can be used as raw materials
of polyurethane foams, particularly those of soft polyurethane foams.
[0164]
The production process for the polyurethane foam of the present
invention is not specifically restricted, and a publicly known
20 production process can be properly adopted. Specifically, any of
a slab foaming process, a hot-cure mold foaming process and a cold-cure
mold foaming process can be adopted.
[0165]
For producing the polyurethane foam by a cold-cure mold foaming
SF-2542
64
%
process, a publicly known cold-cure mold foaming process can be adopted.
A resin premix obtained from the composition for a polyurethane foam
of the present invention and a polyisocyanate are mixed usually by
the use of a high-pressure foaming machine or a low-pressure foaming
5 machine so that the NCO index may become a given value, and this mixture
is injected into a mold and subjected to reaction, foaming and curing
to obtain a polyurethane foam of a given shape.
[0166]
The curing time is usually 30 seconds to 30 minutes, the mold
10 temperature is usually room temperature to about 80°C, and the curing
temperature is preferably room temperature to about 150°C. After
curing, the cured product may be heated at a temperature of 80 to
180°C within limits not detrimental to the objects and the effects
of the present invention.
15 [0167]
The resin premix is usually mixed with a polyisocyanate by a
high-pressure foaming machine or a low-pressure foaming machine, and
in the case where a compound exhibiting hydrolyzability such as an
organotin catalyst is used as a catalyst and water is used as a blowing
20 agent, it is preferable that the water component and the organotin
catalyst component are injected into the foaming machine through
different pathways in order to avoid contact of the catalyst with
water, and they are mixed using a mixing head of the foaming machine.
From the viewpoints of mixing properties in the foaming machine and
SF-2542
65 •
moldability of the foam, the viscosity of the resin premix used is
preferably not more than 4000 mPa -s (value obtained by using Brookfield
type viscometer in JIS K1557-5 (2007)) at 25°C.
[0168]
5 Properties (e.g., impact resilience, hardness, durability,
etc.) of the polyurethane foam of the present invention can be properly
determined according to the use purpose of the polyurethane foam,
and for example, automobile interior trim materials such as sheet
cushions and sheet backs for vehicles (e.g., automobiles), furniture,
10 beddings, office supplies, etc. can be preferably produced.
Examples
[0169]
The present invention is described below in more detail with
15 reference to the following examples, but it should be construed that
the present invention is in no way limited to those examples. In
the examples, "part (s) " and "%" mean "part (s) by mass" and "% by mass",
respectively.
[0170]
20 Analysis and measurement in the examples and the comparative
examples were carried out in accordance with the following methods.
[0171]
[Measurement and evaluation method]
(1) Hydroxyl value (OHV)
SF-2542
66
#
Measurement was carried out in accordance with the method
described in the B method of JIS K-1557-1 (2007).
[0172]
(2) Total degree of unsaturation
5 Measurement was carried out in accordance with the method
described in JIS K-1557-3 (2007).
[0173]
(3) Content ratio (% by mass) of oxyethylene end group
The content ratio (% by mass) of an oxyethylene end group in
10 a polyol was calculated from the charge of each component using the
following calculation formula.
[0174]
(Amount of ethylene oxide) / (amount of active hydrogen compound
+ amount of alkylene oxide + amounts of other components) x 100
15 The content ratio (% by mass) can be measured also by the use
of ^H-NMR.
[0175]
(4) Content ratio (ppm) of compound having P=N bond
In the examples, the content ratio of the compound having a
20 P=N bond in a polyol was calculated from the charge of each component.
The calculation formula is shown below.
[0176]
(Amount of compound having P=N bond) / (amount of compound having
P=N bond + amount of active hydrogen compound + amount of alkylene
SF-2542
67
#
oxide + amounts of other components ) x lOOOOOO
Measurement of the content ratio of the compound having a P=N
bond in a polyol was carried out by the use of a capillary electrophoresis
method using a fully automatic CIA system manufactured by Waters
5 Corporation. To a polyol, a hydrochloric acid aqueous solution was
added, and using a shaker, extraction of the compound having a P=N
bond from the hydrochloric acid aqueous solution was carried out.
Thereafter, standstill liquid separation was carried out to separate
an aqueous layer, and using a capillary electrophoresis analyzer,
10 determination of phosphazenium cation was carried out.
[0177]
On the other hand, when the solubility of the polyol was high,
nitrogen atoms remaining in the polyol were determined, whereby the
content ratio of phosphazenium cation was calculated back. For the
15 analysis of nitrogen contained in the polyol, a trace total nitrogen
analyzer (model: TN-100) manufactured by Mitsubishi Chemical
Corporation and an element analyzer (model: PE2400) manufactured by
Perkin Elmer, Inc. were used.
[0178]
20 The content ratio of the compound having a P=N bond can be
determined also by carrying out ^H-NMR measurement using a nuclear
magnetic resonance apparatus AL-400 manufactured by JOEL Ltd.,
referring to the method of Japanese Patent Laid-Open Publication No.
2000-344881.
SF-2542
68
#
[0179]
For example, the chemical shift of proton of a methyl group
of tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium
is in the vicinity of 2.7 ppm, and the content ratio can be also calculated
5 by comparing it with
tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium of
a known concentration.
[0180]
(5) Molar ratio (a/b) of acid/compound having P=N bond
10 With respect to the acid having a sulfuric acid ester group,
titration was carried out using sodium hydroxide, and from the
titration value obtained, the molar ratio was calculated.
[0181]
With respect to other acids, the number of moles was calculated
15 from the molecular weight, and the molar ratio was calculated.
[0182]
(6) Coloring property test of composition (resin premix) for
polyurethane foam.
The composition for a polyurethane foam was portioned in a glass
20 bottle containing nitrogen, and stored for 7 days at room temperature.
After the storage, the composition was placed in a colorless and
transparent cell having an optical path length of 2 cm, and the
appearance (degree of discoloration) was visually observed.
[0183]
SF-2542
69
#
(7) Evaluation of storage stability of composition for
polyurethane foam
When polyurethane foams were prepared using the composition
for a polyurethane foam given immediately after preparation and the
5 composition stored for 7 days at room temperature after preparation,
a rise time (RT, second(s)) was measured. A difference (RTb-RTa)
between the rise time after 7 days (RTb) and the rise time immediately
after preparation (RTa) was calculated, and the resulting value was
compared with a value (RTb-RTa: 40 seconds) obtained in Reference
10 Example 1 in which no acid was added, whereby storage stability of
the resulting composition for a polyurethane foam was evaluated.
[0184]
The rise time indicates a time taken for a foamed reaction mixture
to reach a maximum height from the beginning of mixing of a resin
15 premix with a polyisocyanate. A smaller difference (RTb-RTa)
indicates that the urethanation reaction is more stable without a
change with time, so that the reactivity can be properly controlled,
and a urethane foam can be stably obtained.
[0185]
20 (8) Coloringproperty test of preparation for polyurethane foam
The resulting preparation for a polyurethane foam was portioned
in a glass bottle containing nitrogen and stored for 28 days at 50°C
or 24 hours at 100°C. After the preparation or after the storage,
the composition was placed in a colorless and transparent cell having
SF-2542
70
J^
an optical path length of 2 cm, and the appearance (degree of
discoloration) was visually observed.
[0186]
[Raw materials]
5
(Polyol a)
In an autoclave equipped with a stirring device, a thermometer
and a manometer, glycerol and
tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium
10 hydroxide (PZN) in an amount of 0.18 mol%/molOH based on the hydroxyl
group of glycerol, as a compound having a P=N bond, were placed, then
vacuum dehydration was carried out at 100°C for 6hours, and thereafter,
propylene oxide was continuously fed at a reaction temperature of
80°C and a maximum reaction pressure of 3. 8 kg/cm^ to perform addition
15 polymerization. Subsequently, ethylene oxide was continuously fed
at a reaction temperature of 100°C and a maximum reaction pressure
of 3.8 kg/cm^ to perform addition polymerization, whereby a polyol
a was obtained.
[0187]
20 The total degree of unsaturation of this polyol was 0.018 meq/g,
the hydroxyl value thereof was 34 mgKOH/g, and the content ratio of
the oxyethylene end group was 15% by mass. The content ratio of the
compound having a P=N bond to the polyol a was calculated to be 800
ppm from the charge of the compound.
SF-2542
71
[0188]
(Polyol b)
In an autoclave equipped with a stirring device, a thermometer
and a manometer, glycerol and
5 tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium
hydroxide in an amount of 0.18 mol%/molOH based on the hydroxyl group
of glycerol, as a compound having a P=N bond, were placed, then vacuum
dehydration was carried out at 100°C for 6 hours, and thereafter,
propylene oxide was continuously fed at a reaction temperature of
10 80°C and a maximum reaction pressure of 3. 8 kg/cm^ to perform addition
polymerization. Subsequently, ethylene oxide was continuously fed
at a reaction temperature of 100°C and a maximum reaction pressure
of 3.8 kg/cm^ to perform addition polymerization, whereby a polyol
b was obtained,
15 [0189]
The total degree of unsaturation of this polyol was 0. 025 meq/g,
the hydroxyl value thereof was 24 mgKOH/g, and the content ratio of
the oxyethylene end group was 14.5% by mass. The content ratio of
the compound having a P=N bond to the polyol b was calculated from
20 the charge of the compound, similarly to the polyol (a), and as a
result, it was 580 ppm.
[0190]
(Polyol c)
In an autoclave equipped with a stirring device, a thermometer
SF-2542
72 •
and a manometer, 1 mol of pentaerythritol, 0.03 mol of glycerol and
tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium
hydroxide in an amount of 0.07 mol%/molOH based on the total amount
of the hydroxyl groups of pentaerythritol and glycerol, as a compound
5 having a P=N bond, were placed, and thereafter, propylene oxide was
continuously fed at a reaction temperature of 107°C and a maximum
reaction pressure of 2.9 kg/cm^ to perform addition polymerization.
Subsequently, ethylene oxide was continuously fed at a reaction
temperature of 120°C and a maximum reaction pressure of 2.9 kg/cm^
10 to perform addition polymerization, whereby a polyol c was obtained.
[0191]
The total degree of unsaturation of this polyol was 0. 025 meq/g,
the hydroxyl value thereof was 34 mgKOH/g, and the content ratio of
the oxyethylene end group was 15% by mass. The content ratio of the
15 compound having a P=N bond to the polyol c was calculated from the
charge of the compound, similarly to the polyol (a) , and as a result,
it was 300 ppm.
[0192]
(Polyol d)
20 In an autoclave, the polyol a was placed, then the system was
set in a nitrogen atmosphere, and thereafter, the temperature was
raised to 80°C. Subsequently, to 100 parts by weight of the polyol
a, 4 parts by weight of ion-exchanged water were added, then BHT in
an amount of 300 ppmbased on the polyol a was introduced, and thereafter,
SF-2542
73
«
0.5 part by weight of an adsorbent KW-700 (available f romKyowa Chemical
Industry Co., Ltd.) was introduced. After stirring at 100°C for 3
hours, dehydration was carried out under reducedpressure, and finally,
with passing nitrogen into the liquid phase, nitrogen bubbling under
5 reduced pressure was carried out for 4 hours under the conditions
of 110°C and 30 mm Hgabs. (3990 Pa) . After the pressure was returned
to atmospheric pressure from reduced pressure using nitrogen, vacuum
filtration was carried out through a 5C filter paper (retention
particle diameter: 1 ym) manufactured by ADVANTEC Toyo Kaisha, Ltd.
10 to perform purification of the polyol.
[0193]
After the purification operation, the hydroxyl value of the
polyol d was 34 mgKOH/g, and the total degree of unsaturation thereof
was 0.018 meq./g. The content ratio of the compound having a P=N
15 bond to the polyol d was measured to be 17 ppm by the use of ^H-NMR.
[0194]
(Polyol e)
In an autoclave equipped with a stirring device, a thermometer
and a manometer, glycerol and
20 tris[tris(dimethylamino)phosphoranylideneamino]phosphine oxide
(PZO) in an amount of 0.18 mol%/molOH based on the hydroxyl group
of glycerol, as a compound having a P=N bond, were placed, then vacuum
dehydration was carried out at 100°C for 6 hours, and thereafter,
propylene oxide was continuously fed at a reaction temperature of
SF-2542
74
#
80°C and a maximum reaction pressure of 3. 8 kg/cm^ to perfoirm addition
polymerization. Subsequently, ethylene oxide was continuously fed
at a reaction temperature of 100°C and a maximum reaction pressure
of 3.8 kg/cm^ to perform addition polymerization, whereby a polyol
5 e was obtained.
[0195]
The total degree of unsaturation of this polyol was 0. 018 meq/g,
the hydroxyl value thereof was 34 mgKOH/g, and the content ratio of
the oxyethylene end group was 15% by mass. The content ratio of the
10 compound having a P=N bond to the polyol e was calculated to be 612
ppm from the charge of the compound. The appearance was slightly
white opaque.
[0196]
(Polymer polyol a)
15 In an autoclave equipped with a stirring device, a thermometer
and a manometer, glycerol and potassium hydroxide were placed, then
vacuum dehydration was carried out at 100 °C for 6 hours, and thereafter,
propylene oxide was continuously fed at a reaction temperature of
120 °C and a maximum reaction pressure of 3. 8 kg/cm^ to perform addition
20 polymerization. Subsequently, ethylene oxide was continuously fed
at a reaction temperature of 110°C and a maximum reaction pressure
of 3.8 kg/cm^ to perform addition polymerization, whereby a polyol
f was obtained.
[0197]
SF-2542
75
#
Subsequently, to the polyol f, water and one equivalent of
phosphoric acid based on KOH were added, and they were stirred for
30 minutes. Further, an adsorbent (available from Tomita
Pharmaceutical Co., Ltd., trade name: AD-600) and 300 ppm of BHT were
5 added, and dehydration drying was carried out for 3 hours under the
conditions of 100°C and 1330 Pa. Thereafter, solids were removed
by filtration to obtain a polyol g. The hydroxyl value of this polyol
g was 34 mgKOH/g, and the content ratio of the oxyethylene end group
was 15% by mass.
10 [0198]
In an autoclave equipped with a stirring device, a thermometer,
a manometer and a liquid feeding device, the polyol g was introduced
to a full liquid level, and the temperature was raised to 120°C with
stirring. To the autoclave, a mixture of the polyol g,
15 2,2'-azobis(isobutyronitrile), acrylonitrile and styrene was
continuously introduced. The initial reaction solution continuously
obtained through a discharge port was discarded, and the subsequent
reaction solution was used in the next step. The reaction was carried
out under the reaction conditions of a reaction temperature of 120°C
20 and a reaction pressure of 440 kPa, and the residence time was 50
minutes. To the resulting reaction solution, BHT in an amount of
300 ppm based on the reaction solution was added, and thereafter,
a reduced pressure heating treatment was carried out for 3 hours under
the conditions of 120 °C and not more than 655 Pa to remove an unreacted
SF-2542
76
ethylenically unsaturated monomer and a decomposed product of the
polymerization initiator, whereby a polymer polyol a was obtained.
[0199]
The hydroxyl value of this polymer polyol a was 21 mgKOH/g,
5 the content ratio of a component derived from the polyol g was 61.5%
by mass, the content ratio of a polymer component derived from
acrylonitrile was 30.8% by mass, and the content ratio of a polymer
component derived from styrene was 7.7% by mass. These content ratios
were calculated from the charges of the components and the amount
10 of the unreacted monomer determined by gas chromatography. Since
the compound having a P=N bond was not used in the preparation of
the polymer polyol a, the content ratio of the compound was 0 ppm.
[0200]
(Polymer polyol b)
15 In a four-neck flask equipped with a stirring device, a nitrogen
feed pipe and a thermometer, to the polyol b was added DBSA-L in such
an amount that the molar ratio (acid (a)/compound (b) ) became 4.0,
and they were heated at 100°C for 2 hours. Thereafter, an antioxidant
(BHT) was added in an amount of 300 ppm based on the polyol b, and
20 the mixture was heated at 100°C for 1 hour to obtain a polyol h. The
mixing was entirely carried out in a closed state. On the assumption
that the compound having a P=N bond was derived from the polyol b
and was not eliminated during the preparation, the content ratio of
the compound having a P=N bond to the polyol h was taken to be 580
SF-2542
77
ppm. Further, on the assumption that DBSA-L and BHT were not eliminated
either during the preparation, the content ratios of them to the polyol
h were calculated to be 1000 ppm and 300 ppm, respectively.
[0201]
5 A polymer polyol b was obtained by carrying out the same
operations as those of the production of the polymer polyol a, except
that the solution of the polyol h was used instead of the polyol g,
and acrylonitrile was used while changing the amounts of acrylonitrile
and styrene.
10 [0202]
The hydroxyl value of this polymer polyol b was 19 mgKOH/g,
the content ratio of a component derived from the polyol h was 80%
by mass, and the content ratio of a polymer component derived from
acrylonitrile was 20% by mass. On the assumption that the compound
15 having a P=N bond was derived from the polyol h and was not eliminated
during the step of dispersing the polymer, the content ratio of the
compound having a P=N bond to the polymer polyol b was calculated
to be 464 ppm.
[0203]
20 (Polymer polyol d)
A polymer polyol c was obtained by carrying out the same
operations as those of the production of the polymer polyol a, except
that the amounts of acrylonitrile and styrene were changed, and the
polyol g was replaced with the polyol c.
SF-2542
78
•
[0204]
The hydroxyl value of this polymer polyol c was 22.3 mgKOH/g,
the content ratio of a component derived from the polyol c was 60%
by mass, the content ratio of a polymer component derived from
5 acrylonitrile was 12.3% by mass, and the content ratio of a polymer
component derived from styrene was 27.7% by mass.
[0205]
In a four-neck flask equipped with a stirring device, a nitrogen
feed pipe and a thermometer, to the polymer polyol c was added DBSA-L
10 in such an amount that the molar ratio (acid (a) /compound (b)) became
4.0, and they were heated at 100°C for 2 hours. Thereafter, an
antioxidant (BHT) was added in an amount of 300 ppmbased on the polymer
polyol c, and the mixture was heated at 100°C for 1 hour to obtain
a polymer polyol d. The mixing was entirely carried out in a closed
15 state. On the assumption that the compound having a P=N bond was
derived from the polyol c and was not eliminated during the preparation,
the content ratio of the compound having a P=N bond to the polymer
polyol d was taken to be 180 ppm. Further, on the assumption that
DBSA-L and BHT were not eliminated either during the preparation,
20 the content ratios of them to the polymer polyol d were calculated
to be 310 ppm and 300 ppm, respectively.
[0206]
(Polymer polyol e)
In a four-neck flask equipped with a stirring device, a nitrogen
SF-2542
79
feed pipe and a thermometer, to the polyol a was added DBSA-L in such
an amount that the molar ratio (acid (a)/compound (b) ) became 2.3,
and they were heated at 100°C for 2 hours. Thereafter, an antioxidant
(BHT) was added in an amount of 300 ppm based on the polyol a, and
5 the mixture was heated at 100°C for 1 hour to obtain a polyol i. The
mixing was entirely carried out in a closed state. On the assumption
that the compound having a P=N bond was derived from the polyol a
and was not eliminated during the preparation, the content ratio of
the compound having a P=N bond to the polyol i was taken to be 800
10 ppm. Further, on the assumption that DBSA-L and BHT were not eliminated
either during the preparation, the content ratios of them to the polyol
i were calculated to be 800 ppm and 300 ppm, respectively.
[0207]
A polymer polyol e was obtained by carrying out the same
15 operations as those of the production of the polymer polyol a, except
that the solution of the polyol i was used instead of the polyol g,
and acrylonitrile and styrene were used while changing the amounts
of acrylonitrile and styrene.
[0208]
20 The hydroxyl value of this polymer polyol e was 19.9 mgKOH/g,
the content ratio of a component derived from the polyol i was 61%
by mass, the content ratio of a polymer component derived from
acrylonitrile was 15.6% by mass, and the content ratio of a polymer
component derived from styrene was 23.4% by mass. On the assumption
SF-2542
80
H
that the compound having a P=N bond was derived from the polyol i
and was not eliminated during the step of dispersing the polymer,
the content ratio of the compound having a P=N bond to the polymer
polyol e was calculated to be 488 ppm.
5 [0209]
(Polymer polyol f)
A polyol j was obtained by carrying out the same operations
as those of the preparation of the polyol g, except that BHT was not
added. Thereafter, a polymer polyol f was obtained by carrying out
10 the same operations as those of the production of the polymer polyol
a, except that the polyol j was used and BHT was not used.
[0210]
The hydroxyl value of this polymer polyol f was 21 mgKOH/g,
the content ratio of a component derived from the polyol j was 61.5%
15 by mass, the content ratio of a polymer component derived from
acrylonitrile was 30.8% by mass, and the content ratio of a polymer
component derived from styrene was 7.7% by mass. These content ratios
were calculated from the charges of the components and the amount
of the unreacted monomer determined by gas chromatography. Since
20 the compound having a P=N bond was not used in the preparation of
the polymer polyol f, the content ratio of the compound was 0 ppm.
[0211]

(Antioxidant a)
SF-2542
81
41
•BHT (available from Junsei Chemical Co., Ltd.)
(Antioxidant b)
•Irganox 1010 (available from BASF Japan Ltd.)
(Antioxidant c)
5 -Irganox 1076 (available from BASF Japan Ltd.)
(Antioxidant d)
•Irganox 1135 (available from BASF Japan Ltd.)

(Antioxidant e)
10 -Tris (2-ethylhexyl phosphite) (JP-308E available from Johoku
Chemical Co., Ltd.)
(Antioxidant f)
•Bis (tridecyl) pentaerythritol diphosphite (JPP-13R available
from Johoku Chemical Co., Ltd.)
15 [0212]

(Acyclic aliphatic monocarboxylic acid of 2 to 25 carbon atoms
or its salt>
•Acetic acid (available from Wako Pure Chemical Industries,
20 Ltd.)
•Heptanoic acid (available from Wako Pure Chemical Industries,
Ltd.)
•Palmitic acid (available from Wako Pure Chemical Industries,
Ltd.)
SF-2542
82
(Hydroxycarboxylic acid of 2 to 25 carbon atoms or its salt)
•Lactic acid (available from Wako Pure Chemical Industries,
Ltd.)
(Polycarboxylic acid of 20 to 60 carbon atoms or its salt)
5 -Dimer acid (Pripol 1009 available from Croda Japan K.K.)
(Aromatic monocarboxylic acid represented by the formula (1)
or its salt or its salt)
•Decylbenzoic acid (DCA available from Wako Pure Chemical
Industries, Ltd.)
10 -Benzoic acid (available from Wako Pure Chemical Industries,
Ltd.)
(Sulfonic acid or its salt)
•p-Toluenesulfonicacid (PTSA available from Wako Pure Chemical
Industries, Ltd.)
15 -Camphorsulfonic acid (CSA available from Wako Pure Chemical
Industries, Ltd.)
-Dodecylbenzenesulfonic acid (DBSA-L (straight-chain type):
NEOPELEX GS available from Kao Corporation)
•Dodecylbenzenesulfonic acid (DBSA-B (branched type): Lipon
20 LH-900 available from Lion Corporation)
(Acid having sulfuric acid ester group or its salt)
•Polyoxyethylene styrenated phenyl ether ammonium sulfate
(Latemul E-IOOOA available from Kao Corporation)
•Polyoxyalkylene alkenyl ether ammonium sulfate (Latemul
SF-2542
83
•
PD-105 available from Kao Corporation)
(Others)
•Oxalic acid (available from Wako Pure Chemical Industries,
Ltd.)
5 -Suberic acid (available from Wako Pure Chemical Industries,
Ltd.)
•Phosphoric acid (available from Wako Pure Chemical Industries,
Ltd.)
[0213]
10
(Catalyst a)
•Amine catalyst of Minico L-1020 (trade name, 33% diethylene
glycol solution of triethylenediamine) available from
Katsuzai-Chemical Corporation
15 (Catalyst b)
•Amine catalyst of bis (2-dimethylaminoethyl) ether (tradename:
Minico TMDA) available from Katsuzai-Chemical Corporation

•Water
20
(Interconnecting agent a)
•Polyether polyol of ACTOCOL EP-505S (trade name, hydroxyl
value: 52 mgKOH/g) available from Mitsui Chemicals, Inc.
(Crosslinking agent a)
SF-2542
84
«
•Amine-based crosslinking agent of ACTOCOL KL-210 (trade name,
hydroxyl value: 840 mgKOH/g) available from Mitsui Chemicals, Inc.
(Crosslinking agent b)
•Purified glycerol (hydroxyl value: 1830 mgKOH/g)
5 (Foam stabilizer a)
•Silicone foam stabilizer of DC-6070 (trade name) available
from Air Products Japan, Inc.
(Foam stabilizer b)
•Silicone foam stabilizer of DC-2525 (trade name) available
10 from Air Products Japan, Inc.
[0214]

(Example 1)
15 In a four-neck flask equipped with a stirring device, a nitrogen
feed pipe and a thermometer, to the polyol a was added acetic acid
in such an amount that the molar ratio (a/b) became 20.5, and they
were heated at 100°C for 2 hours. Thereafter, an antioxidant (BHT)
was added in an amount of 300 ppm based on the polyol a, and the mixture
20 was heated at 100 °C for 1 hour to prepare a preparation for a polyurethane
foam. The mixing was entirely carried out in a closed state. On the
assiomption that the compound having a P=N bond was derived from the
polyol a and was not eliminated during the preparation, the content
ratio of the compound having a P=N bond to the polyol a was taken
SF-2542
85
to be 800 ppm. Further, on the assumption that acetic acid and BHT
were not eliminated either during the preparation, the content ratios
of them to the polyol a were calculated to be 1300 ppm and 300 ppm,
respectively.
5 [0215]
60 Parts of the preparation for a polyurethane foam, 40 parts
of the polymer polyol (a), 0.4 part of the catalyst (a), 0.1 part
of the catalyst (b), 4.0 parts of water, 1. 5 parts of the interconnecting
agent (a), 2.5 parts of the crosslinking agent (a), 0.2 part of the
10 crosslinking agent (b), 0.3 part of the foam stabilizer (a) and 0.7
part of the foam stabilizer (b) were mixed to prepare a composition
(resin premix) for a polyurethane foam. As the compound having a
P=N bond (catalyst), the compound contained in the preparation for
a polyurethane foam was used as it was, and therefore, the content
15 ratio of the compound having a P=N bond in the resin premix was calculated
to be 438 ppm. The content ratios of acetic acid and BHT in the resin
premix were calculated to be 711 ppm and 273 ppm, respectively. Using
the resulting resin premix, a coloring property evaluation test was
carried out. The results are set forth in Table 1. The resin premix
20 was not discolored even after storage for 7 days.
[0216]
Subsequently, 100 parts by mass of the resin premix were
temperature-controlled to 22±1 °C in advance, then to the resin premix,
46 parts of a polyisocyanate (COSMONATE (trademark) TM-20 available
SF-2542
8 6
•
from Mitsui Chemicals, Inc.) (NCO index: 1.00) having been
temperature-controlled to 22±1 °C were added, and they were immediately
vigorously stirred at 5000 rpm for 5 seconds using a homogenizer.
Thereafter, the mixed liquid was introduced into a polypropylene
5 containerof 150mm (diameter) x 300 mm (height) to obtain a polyurethane
foam. During foaming, a rise time (RTg) was measured in an environment
of 22+1°C by the use of a laser sensor manufactured by Keyence
Corporation, and the foam height was also recorded for 5 minutes.
[0217]
10 Using the composition after storage for 7 days at room
temperature, a rise time (RTb) was measured in the same manner as
that for the composition immediately after preparation, and storage
stability of the resin premix was evaluated. The results are set
forth in Table 1.
15 [0218]
Each of the urethane foams obtained by the use of the composition
immediately after preparation and the composition after storage for
7 days was not yellowed and had proper impact resilience, moldability
and durability.
20 [0219]
(Examples 2 to 24 and 27, Comparative Examples 1 to 5)
Resin premixes and polyurethane foams (Examples 2 to 24 and
27, Comparative Examples 1 to 5) were obtained in the same manner
as in Example 1, except that the charges of the polyols (a to e) ,
SF-2542
87
the polymer polyols (a, b, e and f) , the antioxidants (a to f) , the
acid or its salt, the catalysts (a and b) , water, the interconnecting
agent (a), the crosslinking agents (a and b) and the foam stabilizers
(a and b) were changed in accordance with Tables 1 to 4. The results
5 are set forth in Tables 1 to 4.
[0220]
(Example 25)
40 Parts of the polymer polyol (b) as the preparation (c) for
a polyurethane foam, 60 parts of the polyol (d), 0.4part of the catalyst
10 (a), 0.1 part of the catalyst (b), 3.9 parts of water, 1.0 part of
the interconnecting agent (a), 1.5 parts of the crosslinking agent
(a), 0.2 part of the crosslinking agent (b) and 1.0 part of the foam
stabilizer (b) were mixed to prepare a composition (resin premix)
for a polyurethane foam. The compound having a P=N bond (catalyst)
15 was contained in the polyol (d) and the polymer polyol (b) , and therefore,
the content ratio of the compound having a P=N bond in the resin premix
was calculated to be 222 ppm. The content ratios of DBSA-L and BHT
in the resin premix were calculated to be 370 ppm and 278 ppm,
respectively. Using the resulting resin premix, a coloring property
20 evaluation test was carried out.
[0221]
Further, the same operations as in Example 1 were carried out
to obtain a polyurethane foam, and storage stability of the resin
premix was evaluated. The results are set forth in Table 3.
SF-2542
88
[0222]
The urethane foams obtained by the use of the composition
immediately after preparation and the composition after storage for
7 days were evaluated, and as a result, each of them was not yellowed
5 and had proper impact resilience, moldability and durability.
[0223]
(Example 26)
A resin premix and a polyurethane foam were obtained by carrying
out the same operations as in Example 25, except that the amount of
10 thepolyol (d) mixed was changed and the polymer polyol (b) was replaced
with the polymer polyol (e). The results are set forth in Table 3.
[0224]
The urethane foams obtained by the use of the composition
immediately after preparation and the composition after storage for
15 7 days were evaluated, and as a result, each of them was not yellowed
and had proper impact resilience, moldability and durability.
[0225]
(Reference Example 1)
In a four-neck flask equipped with a stirring device, a nitrogen
20 feed pipe and a thermometer, to the polyol a was added an antioxidant
(BHT) in an amount of 300 ppm based on the polyol a, and they were
heated at 100°C for 1 hour. The mixing was entirely carried out in
a closed state. On the assumption that the compound having a P=N
bond was derived from the polyol a and was not eliminated during the
SF-2542
89
#
preparation, the content ratio of the compound having a P=N bond to
the polyol a was taken to be 800 ppm. Further, on the assumption
that BHT was not eliminated either during the preparation, the content
ratio of BHT to the polyol a was calculated to be 300 ppm.
5 [0226]
Using 60 parts of the preparation for a polyurethane foam, 40
parts of the polymer polyol (a), 0.4 part of the catalyst (a), 0.1
part of the catalyst (b), 3.9 parts of water, 1.0 part of the
interconnecting agent (a), 1.5 parts of the crosslinking agent (a),
10 0.2part of the crosslinking agent (b) and 1. Opart of the foam stabilizer
(b), the same operations as in Example 1 were carried out, whereby
a resin premix and a polyurethane foam were obtained, and they were
evaluated.
[0227]
15 The results are set forth in Table 4.
[0228]
(Reference Examples 2 and 3)
Resin premixes and polyurethane foams (Reference Examples 2
and 3) were obtained in the same manner as in Reference Example 1,
20 except that the polyol (a or d), water, the interconnecting agent
(a), the crosslinking agent (a) and the foam stabilizers (a and b)
were changed in accordance with Table 4. Then, they were evaluated.
[0229]
The results are set forth in Table 4.
'"^WIWWWMMtMii
SF-2542
[0230] [Table 1]
90
Table 1
,. * 1 1 1
Resin premix
Content in resin premix (part(s) by mass)
Polyol a
Polyol b
Polyol d
Polymer polyol a
Content ratio (xlO^) of compound having P=N
bond to polyol in preparation (c)
Content ratio (xlQ^) of compound having P=N
bond to resin premix
Content ratio (xlO^) of antioxidant a to
polyol in preparation (c)
Content ratio (xlO^) of antioxidant a to
resin premix
Acid species
Content ratio (xlO^) of acid to polyol in
preparation (c)
Content ratio (xlQ^) of acid to resin premix
Catalyst a
Catalyst b
Water
Interconnecting agent a
Example
1
60
40
800
438
300
273
acetic
acid
1300
711
0.4
0.1
4.0
1.5
2
60
40
800
438
300
273
heptanoic
acid
2000
1094
0.4
0.1
4.0
1.5
3
60
40
800
438
300
273
palmitic
acid
3000
1641
0.4
0.1
4.0
1.5
4
45
15
40
604
330
300
273
dimer
acid
1200
656
0.4
0.1
4.0
1.5
5
60
40
800
438
300
273
DCA
1100
602
0.4
0.1
4.0
1.5
6
60
40
800
438
300
273
PTSA
250
137
0.4
0.1
4.0
1.5
7
60
40
800
438
300
273
CSA
370
202
0.4
0.1
4.0
1.5
8
60
40
800
438
300
273
lactic
acid
300
164
0.4
0.1
4.0
1.5
9
60
40
800
438
300
273
benzoic
acid
700
383
0.4
0.1
4.0
1.5
10
60
40
580
322
300
278
DBSA-L
1000
555
0.4
0.1
3.9
1.0
IP^SHSBPBSBIPPB
^mmtmtttHii
SF-2542
[Table 1] (continued)
91
Table 1
Resin premix
Crosslinking agent a
Crosslinking agent b
Foam stabilizer a
Foam stabilizer b
Acid/compound having P=N bond (mol/mol)
Polyisocyanate
Coloring property test
Immediately after preparation
7 days after preparation
Evaluation of storage stability
Immediately after preparation
RTa (sec)
7 days after preparation
RTb (sec)
RTb-RTa
Example
1
2.5
0.2
0.3
0.7
20.5
TM-20
cream
color
cream
color
133
136
3
2
2.5
0.2
0.3
0.7
14.5
TM-20
cream color
cream color
119
123
4
3
2.5
0.2
0.3
0.7
11.1
TM-20
cream
color
cream
color
119
117
-2
4
2.5
0.2
0.3
0.7
2.7
TM-20
cream
color
cream
color
104
115
11
5
2.5
0.2
0.3
0.7
4.0
TM-20
cream
color
cream
color
108
115
7
6
2.5
0.2
0.3
0.7
1.2
TM-20
cream
color
cream
color
107
116
9
7
2.5
0.2
0.3
0.7
1.5
TM-20
cream
color
cream
color
113
120
7
8
2.5
0.2
0.3
0.7
3.2
TM-20
cream
color
cream
color
113
125
12
9
2.5
0.2
0.3
0.7
5,4
TM-20
cream
color
cream
color
106
127
21
10
1.5
0.2
1.0
4.0
TM-20
cream
color
cream
color
113
117
4
(1) Each content ratio was calculated from the charge.
llliSllfllfJIIJjppMIJIIIlBI! plWPJItWMiWipWIII!!
•«Ml^.ft««»<»rimaif<«WW-'-«lgWfh'-Ht'lr«
SF-2542
92 0
[0231] [Table 2]
Table 2
Resin premix
Content in resin premix (part(s) by mass)
Polyol a
Polyol b
Polymer polyol a
Content ratio (xlO^) of ccxtpound having P=N bond
to polyol in preparation (c)
Content ratio (xlO*) of ccnpound having P=N bond
to resin premix
Content ratio (xlO^) of antioxidant a to polyol
in preparation (c)
Content ratio (xlO*) of antioxidant a to resin
premix
Content ratio (xlO^) of antioxidant b to polyol
in preparation (c)
Content ratio (xlO^) of antioxidant b to resin
premix
Content ratio (xlO^) of antioxidant c to polyol
in preparation (c)
Content ratio (xlO^) of antioxidant c to resin
premix
Content ratio (xlO^) of antioxidant d to polyol
in preparation (c)
Content ratio (xio') of antioxidant d to resin
premix
Exaitple
11
60
40
580
322
300
278
12
60
40
800
438
300
273
13
60
40
800
438
109
300
164
14
60
40
800
438
109
300
164
15
60
40
800
438
109
300
164
16
60
40
800
438
10,000
5,579
17
60
40
580
322
300
278
18
60
40
800
438
300
273
19
60
40
800
438
300
273
20
60
40
800
438
300
273
21
60
40
580
322
300
278
mmmim''ivm'mmmmmmm'mm!mimmmumMmmmmmmmm»>m •iWiWIWB»tW»w»WII'l»ii»WiM!lWWIif»lWW"l!mil
*"*'WII»l^»¥(»W'H{lWWiW
SF-2542
93 m
[Table 2] (continued) Table 2
Resin premix
Acid species
Content ratio (xlO*) of acid to polyol in
preparation (c)
Content ratio (xlO^) of acid to resin premix
Catalyst a
Catalyst b
Water
Interconnecting agent a
Crosslinking agent a
Crosslinking agent b
Foam stabilizer a
Foam stabilizer b
Acid/ccnpound having P=N bond (mol/mol)
Polyisocyanate
Coloring property test
Immediately after preparation
7 days after preparation
Evaluation of storage stability
Iitmediately after preparation
RTa (sec)
7 days after preparation
RTb (sec)
RTb-RTa
Exanple
11
DBSA-B
500
278
0.4
0.1
3.9
1.0
1.5
0.2
1.0
2.0
TM-20
cream
color
cream
color
102
108
6
12
DBSA-L
100
55
0.4
0.1
4.0
1.5
2.5
0.2
0.3
0.7
0.3
TM-20
cream
color
cream
color
96
107
11
13
DBSA-L
1030
563
0.4
0.1
4.0
1.5
2.5
0.2
0.3
0.7
3.0
TM-20
cream
color
cream
color
102
108
6
14
DBSA-L
1030
563
0.4
0.1
4.0
1.5
2.5
0.2
0.3
0.7
3.0
TM-20
cream
color
cream
color
112
118
6
15
DBSA-L
1030
563
0.4
0.1
4.0
1.5
2.5
0.2
0.3
0.7
3.0
TM-20
cream
color
cream
color
114
123
9
16
DBSA-L
1030
563
0.4
0.1
4.0
1.5
2.5
0.2
0.3
0.7
3.0
TM-20
cream
color
cream
color
110
119
9
17
Latemul
E-IOOOA
3000
1665
0.4
0.1
3.9
1.0
1.5
0.2
1.0
1.3
TM-20
cream
color
cream
color
110
114
4
18
Latemul
PD-105
2000
1094
0.4
0.1
4.0
1.5
2.5
0.2
0.3
0.7
1.5
TM-20
cream
color
cream
color
104
110
6
19
DBSA-L
10300
5634
0.4
0.1
4.0
1.5
2.5
0.2
0.3^
0.7
29.8
TM-20
cream
color
cream
color
No foam
obtained
20
DBSA-L
70
38
0.4
0.1
4.0
1.5
2.5
0.2
0.3
0.7
0.2
TM-20
cream
color
orange
color
96
107
11
21
DBSA-L
1375
763
0.4
0.1
3.9
1.0
1.5
0.2
1.0
5.5
TM-20
cream
color
cream
color
135
141
6
(1) Each content ratio was calculated from the charge.
wywKpippiJiiaB pwpwiipipipipjiiiiiiwip IIWfflWWHIIWWWPJtIiliWglWilBiaill
mmtmummmmt
SF-2542
94 4^^
[0232][Table 3]
Table 3
Resin premix
Content in resin premix (part{s) by mass)
Polyol a
Polyol d
Polyol e
Polymer polyol a
Polymer polyol b
Polymer polyol e
Content ratio (xlO*) of compound having P=N bond to polyol in preparation (c)
Content ratio (xlO^) of compound having P=N bond to polymer polyol in preparation (c)
Content ratio (xlO^) of compound having P=N bond to resin premix
Content ratio (xlO^) of antioxidant a to polyol in preparation (c)
Content ratio (xlO^) of antioxidant a to resin premix
Acid species
Content ratio (xlO^) of acid to polyol in preparation (c)
Content ratio (xlO^) of acid to polymer polyol in preparation (c)
Content ratio (xlO^) of acid to resin premix
Catalyst a
Catalyst b
Water
Interconnecting agent a
Crosslinking agent a
Crosslinking agent b
Example
22
60
40
800
444
300
249
DBSA-L
3106
1724
0.4
0.1
3.9
1.0
1.5
0.2
23
60
40''
800
444
300
249
DBSA-L
4142
2299
0.4
0.1
3.9
1.0
' 1.5
0.2
24
60
40
800
444
300
249
DBSA-L
5176
2873
0.4
0.1
3.9
1.0
1.5
0.2
25
50
50
17
464
222
300
278
DBSA-L
800
370
0.4
0.1
^ 3.9
1.0
1.5
0.2
26
60
40
17
488
190
300
278
DBSA-L
488
181
0.4
0.1
3.9
1.0
1.5
0.2
27
60
40
612
340
300
278
DBSA-L
400
148
0.4
0.1
3.9
1.0
1.5
0.2
M*»t»nJI>HWai»lit»lMi»M<
SF-2542
[Table 3] (continued)
Table 3
95
Resin premix
Foam stabilizer a
Foam stabilizer b
Acid/coinpound having P=N bond (mol/mol)
Polyisocyanate
Coloring property test
Immediately after preparation
7 days after preparation
Evaluation of storage stability
Immediately after preparation
RTa (sec)
7 days after preparation
RTb (sec)
RTb-RTa
Example
22
1.0
9.0
TM-20
cream
color
cream
color
156
156
0
23
1.0
12.0
TM-20
cream
color
cream
color
184
188
4
24
1.0
15.0
TM-20
cream
color
cream
color
237
241
4
25
1.0
4.0
TM-20
cream
color
cream
color
127
123
-4
26
1.0
2.3
TM-20
white
color
white
color
117
118
1
27
1.0
1.2
TM-20
cream
color
cream
color
113
119
6
(1) Each content ratio was calculated from the charge.
l|y^,»^lWWi»IWPipj«ll!liWlB;iWi>im>«l'WJiH»»'l"p»^^^^
mummmmammt^smm
SF-2542
96 #
[0233][Table 4]
Table 4
Resin prettiix
Content in resin premix (part(s) by mass)
Polyol a
Polyol c
Polyol d
Polymer polyol a
Polymer polyol f
Content ratio (xlO^) of cortpound having P=N
bond to polyol in preparation (c)
Content ratio (xio'') of cortpound having P=N
bond to resin premix
Content ratio (xlO^) of antioxidant a to polyol
in preparation (c)
Content ratio (xlO^) of antioxidant a to resin
premix
Content ratio (xlO*) of antioxidant e to polyol
in preparation (c)
Content ratio (xlO^) of antioxidant e to resin
premix
Content ratio (xlO^) of antioxidant f to polyol
in preparation (c)
Content ratio (xlO^) of antioxidant f to resin
premix
Ccirparative Exanple
1
37.5
22.5
40
506
277
300
273
2
22.5
37.5
40
311
170
300
273
3
60
40
300
164
300
273
4
60
40
800
438
10,000
5,469
5
60
40
800
438
10,000
5,469
Reference Exartple
1
60
40
800
444
300
278
2
60
40
800
438
0
109
3
60
40
17
9
300
273
WllHI|liiM«ltlW|li||.WIW
rnrfftir-Mii-iMaiMliinitillttMin'a il'iifiafiSi ffiiiiiiifflhffiittrt
SF-2542
97
[Table 4] (continued)
Table 4
Resin premix
Acid species
Content ratio (xlO^) of acid to polyol in
preparation (c)
Content ratio (xlO^) of acid to resin premix
Catalyst a
Catalyst b
Water
Interconnecting agent a
Crosslinking agent a
Crosslinking agent b
Foam stabilizer a
Foam stabilizer b
Acid/cortpound having P=N bond (mol/mol)
Polyisocyanate
Coloring property test
Iiimediately after preparation
7 days after preparation
Evaluation of storage stability
Immediately after preparation
RTa (sec)
7 days after preparation
RTb (sec)
RTb-RTa
Ccnparative Exanple
1
oxalic acid
120
66
0.4
0.1
4.0
1.5
2.5
0.2
0.3
0.7
2.0
TM-20
cream color
cream color
104
174
70
2
siiberic acid
210
115
0.4
0.1
4.0
1.5
2.5
0.2
0.3
0.7
2.9
TM-20
cream color
cream color
105
199
94
3
phosphoric
acid
100
55
0.4
0.1
4.0
1.5
2.5
0.2
0.3
0.7
2.6
TM-20
cream color
cream color
109
184
75
4
DBSA-L
1030
563
0.4
0.1
4.0
1.5
2.5
0.2
0.3
0.7
3.0
TM-20
cream color
cream color
107
147
40
5
DBSA-L
1030
563
0.4
0.1
4.0
1.5
2.5
0.2
0.3
0.7
3.0
TM-20
cream color
cream color
119
165
46
Reference Exanple
1
0
0
0.4
0.1
3.9
1.0
1.5
0.2
1.0
-
TM-20
pink color
pink color
100
140
40
2
0
0
0.4
0.1
4.0
1.5
2.5
0.2
0.3
0.7
-
TM-20
cream color
orange color
91
125
34
3
0
0
0.4
0.1
4.0
1.5
2.5
0.2
0.3
0.7
-
TM-20
cream color
cream color
105
113
8
(1) Each content ratio was calculated from the charge.
PSBS«W|!«ipiBi«i!Wlipp«i»! llllP.II.MlliWWiWWIIIIHmMiH.
SF-2542
98
#
[0234]
(Observation of change of polyurethane foam with time)
Appearances of the polyurethane foams obtained in Examples 10,
11, 17, and 22 to 27 were visually observed. The appearance 5 minutes
5 after foaming and the appearance 10 minutes after foaming were compared,
and a polyurethane foam whose appearance shrinkage had been observed
was evaluated as "X". Likewise, a polyurethane foam whose appearance
shrinkage had been observed one hour after foaming was evaluated as
"A", and a polyurethane foam whose appearance shrinkage had not been
10 observed even one hour after foaming was evaluated as "0".
[0235]
The results are set forth in Table 5.
fmmmmmmssaa^m attaanaBaaaicBiiaaj ^»aAmmMiim6tnimmmimsKM
SF-2542
99 w"
[0236][Table 5]
Table 5
Example
Acid species
Compound having P=N bond
Acid/compound having P=N bond
(mol/mol)
J^pearance
10
DBSA-L
PZN
4.0
0
11
DBSA-B
PZN
2.0
0
17
Latemul E-IOOOA
PZN
1.3
0
22
DBSA-L
PZN
9.0
0
23
DBSA-L
PZN
12.0
A
24
DBSA-L
PZN
15.0
X
25
DBSA-L
PZN
4.0
0
26
DBSA-L
PZN
2.3
0
27
DBSA-L
PZO
1.2
0
!wpwwww»wwiw-fg»»w»*wwipw«^^ Bjlfip«|jHlj.llHIBlH«!!
#
SF-2542
100
[0237]
(Properties of soft polyurethane foam)
The resin premixes obtained in Examples 10 and 11 were
temperature-controlled to 22±1°C in advance, then to each of the resin
5 premixes, a polyisocyanate (COSMONATE (trademark) TM-20 available
from Mitsui Chemicals, Inc.) (NCO index: 1.00) having been
temperature-controlled to 22+1 °C was added, and they were iinmediately
vigorously stirred at 5000 rpmfor 5 secondsby theuseof ahomogenizer.
The mixtures were each injected into an aluminum test mold (internal
10 size: 300x300x100 mm) of 65°C having been coated with a commercially
available release agent in advance, and thereafter, the mold was
covered with a lid and closed with a clamp to perform foaming/curing.
Five minutes after the beginning of stirring, the clamp of the test
mold was removed, then the cured soft polyurethane foam was released
15 from the mold, and subsequently, the thickness of the polyurethane
foam was compressed by 80% using a roller to completely interconnect
bubbles (crushing operation). Various properties of the soft
polyurethane foam obtained 24 hours after foaming were measured by
the methods described in JIS K-6400. The results are set forth in
20 Table 6.
mSmmiiiiMmm^t,MMiMitiitimmtiim
SF-2542
[0238][Table 6]
101
Table 6
Example
Hardness 25% ILD
(kgf/314 cm^)
Overall density
(kg/m^)
Wet heat durability
Wet set (%)
10
Immediately after preparation
188
42.7
11.6
7 days after preparation
185
41.4
11.5
11
Immediately after preparation
175
42.3
12.7
7 days after preparation
177
40.9
11.5
'mmmmmmmmii
»
SF-2542
102
[0239]
(Example 100)
In a four-neck flask equipped with a stirring device, a nitrogen
feed pipe and a thermometer, to 100 parts by weight of the polyol
5 a was added PTSA in such an amount that the molar ratio (a/b) became
1.2, and they were heated at 100°C for 2 hours. Thereafter, an
antioxidant (BHT) was added in an amount of 300 ppm based on the polyol
a, and the mixture was heated at 100 °C for 1 hour to obtain a preparation
for a polyurethane foam. The mixing was entirely carried out in a
10 closed state. On the assumption that the compound having a P=N bond
was derived from the polyol a and was not eliminated during the
preparation, the content ratio of the compound having a P=N bond to
the polyol a was taken to be 800 ppm. Further, on the assumption
that PTSA and BHT were not eliminated either during the preparation,
15 the content ratios of them to the polyol a were calculated to be 250
ppm and 300 ppm, respectively.
[0240]
The resulting preparation was subjected to a coloring property
test. The results are set forth in Table 7. The preparation for a
20 polyurethane foam was not discolored after the passage of 24 hours
at 100°C and even after storage for 28 days at 50°C.
[0241]
(Examples 101 to 106, Comparative Examples 100 and 101, Reference
Examples 100 and 101)
SF-2542
103
Preparations for polyurethane foam (Examples 101 to 106,
Comparative Examples 100 and 101, Reference Examples 100 and 101)
were obtained in the same manner as in Example 100, except that the
charges of the polyols (a, c, d), the antioxidants (a to c) and the
5 acid or its salt were changed in accordance with Table 7 or 8.
[0242]
Evaluation results of the preparations obtained are set forth
in Tables 7 and 8.
[0243]
10 (Examples 107 and 108)
Using the polymer polyol b or d as the preparation (c) for a
polyurethane foam, evaluation was carried out. The results are set
forth in Table 7.
w!»ti#wiwtt>aiiaiB
SF-2542
[0244][Table 7]
104
Table 7
Polyol
Blending quantity
{part(s) by mass)
Polyol a
Polymer polyol b
Polymer polyol d
Content ratio (xlO^) of
ccnpound having P=N bond to
polyol in preparation (c)
Content ratio (xlO*) of
ccnpound having P=N bond to
polymer polyol in
preparation (c)
Content ratio (xlO^) of
antioxidant a to polyol in
preparation (c)
Content ratio (xlO*) of
antioxidant a to polymer
polyol in preparation (c)
Content ratio (xlO^) of
antioxidant b to polymer
polyol in preparation (c)
Exaitple
100
100
800
300
101
100
800
300
102
100
800
300
103
100
800
300
104
100
800
300
105
100
800
300
106
100
800
107
100
464
300
108
100
180
300
l»g!H|!apiiMiiBlliBgWWiWpW)W^
iiiiiiiiWiiitij»«M'imii»ri'iH Ims/m
SF-2542
[Table 7] (continued)
105
Table 7
Polyol
Content ratio (xio') of
antioxidant c to polymer
polyol in preparation (c)
Acid species
Content ratio (xlO^) of acid
to polyol in preparation (c)
Content ratio (xio^) of acid
to polymer polyol in
preparation (c)
Acid/conpound having P=N
bond (mol/mol)
Coloring property test
First day of preparation
24 hours after preparation
(storage at 100°C)
28 days after preparation
(storage at 50°C)
Exaitple
100
PTSA
250
1.2
colorless and
transparent
colorless and
transparent
colorless and
transparent
101
CSA
370
1.5
colorless and
transparent
colorless and
transparent
colorless and
transparent
102
lactic acid
300
3.2
colorless and
transparent
colorless and
transparent
colorless and
transparent
103
benzoic acid
700
5.4
colorless and
transparent
colorless and
transparent
colorless and
transparent
104
DBSA-L
100
0.3
colorless and
transparent
colorless and
transparent
colorless and
transparent
105
DBSA-L
1030
3.0
colorless and
transparent
colorless and
transparent
colorless and
transparent
106
300
DBSA-L
1030
3.0
colorless and
transparent
colorless and
transparent
colorless and
transparent
107
DBSA-L
800
4.0
cream
color
cream
color
cream
color
108
DBSA-L
310
4.0
cream
color
cream
color
cream
color
(1) Each content ratio was calculated from the charge.
IWIIMWpWiWIBIiW«!W»W
SF-2542
[0245][Table 8]
106
Table 8
Polyol
Blending quantity (part{s) by mass)
Polyol a
Polyol c
Polyol d
Content ratio (xlO^) of compound having
P=N bond to polyol in preparation (c)
Content ratio (xlO^) of antioxidant a to
polyol in preparation (c)
Acid species
Content ratio (xlO^) of acid to polyol
in preparation (c)
Acid/compound having P=N bond (mol/mol)
Coloring property test
First day of preparation
24 hours after preparation
(storage at 100°C)
28 days after preparation
(storage at 50°C)
Comparative Example
100
100
580
300
DBSA-L
70
0.2
colorless and transparent
purple color and
transparent
purple color and
transparent
101
100
300
300
oxalic acid
50
1.4
colorless and transparent
purple color and
transparent
purple color and
transparent
Reference Example
100
100
800
300
-
colorless and transparent
purple color and
transparent
purple color and
transparent
101
100
17
300
-
colorless and transparent
colorless and transparent
colorless and transparent
(1) Each content r a t i o was calculated from the charge.
rnmmmmgmmmmmmmi'imm

»
SF-2542 ^"^
107
r^"^' reft l^^^
CLAIMS
1, A composition for a polyurethane foam, comprising:
(i) at least one polyol selected from a polyoxyalkylene polyol
and a polymer polyol wherein polymer fine particles obtained by
5 polymerizing a compound having an unsaturated bond are dispersed in
the polyoxyalkylene polyol,
(ii) a compound having a P=N bond,
(iii) an antioxidant having a hydroxyphenyl group,
(iv) at least one acid selected from the group consisting of
10 an acyclic aliphatic monocarboxylic acid of 2 to 25 carbon atoms,
a hydroxycarboxylic acid of 2 to 25 carbon atoms, a polycarboxylic
acid of 20 to 60 carbon atoms, an aromatic monocarboxylic acid
represented by the following foimula (1) , a sulfonic acid and an acid
having a sulfuric acid ester group, or its salt,
15 (v) a catalyst for polyurethane foam production, and
(vi) a blowing agent,
[Chem. 1]
COOH
(R^),. (1)
wherein R''' is a hydrocarbon group, and m represents a number of hydrogen
20 atoms of a benzene ring having been replaced with R^ and is any one
of 0 to 5.
SF-2542
108 .r^S'-'
.%^ V v^^ 1#
w^ ^.^•*
• 0 \ :^
2, The composition for a polyurethane foam as claimed in
claim 1, wherein the molar ratio (a/b) of the acid or its salt (iv)
(a) to the compound (ii) (b) is not less than 0.3 but not more than
25.
3. The composition for a polyurethane foam as claimed in
claim 1, wherein the compound (ii) is represented by the following
formula (2) :
[Chem. 2]
r A^
R,N-P-NR,
II
R,N N NR,
R,N-ZP=NVP^N=PVNR,
R,N N NR,
II
RaN-P-NR,
NRi
Q-
10
(2)
wherein a, b, c and d are each a positive number of 0 to 3 but there
is no case where all of a, b, c and d become 0 at the same time, each
R is the same or different hydrocarbon group of 1 to 10 carbon atoms
and two R on the same nitrogen atom may be bonded to each other to
15 form a cyclic structure, and Q~ represents a hydroxyl anion, an alkoxy
anion, an aryloxy anion or a carboxy anion.
4^
SF-2542 G •*'^'" L ^ ^
* I"
4. The composition for a polyurethane foam as claimed in
claim 1, wherein the polyol (i) comprises at least one polyol selected
from a polyoxyalkylene polyol (p) obtained by addition polymerization
of an alkylene oxide compound onto an active hydrogen compound using
5 the compound (ii) as a catalyst and a polymer polyol wherein polymer
fine particles obtained by polymerizing a compound having an
unsaturated bond are dispersed in the polyoxyalkylene polyol (p).
5. The composition for a polyurethane foam as claimed in
10 claim 4, which comprises a preparation (c) for a polyurethane foam,
the catalyst (v) and the blowing agent (vi), wherein:
the preparation (c) comprises the polyol (i) , the compound (ii)
having a P=N bond and having been used for the production of the polyol
(p), the antioxidant (iii) and the acid or its salt (iv), and
15 the preparation (c) is obtained by adding the acid or its salt
(iv) in such an amount that the molar ratio (a/b) of the acid or its
salt (iv) (a) to the compound (ii) (b) becomes not less than 0.3 but
not more than 25, and the antioxidant (iii) to the polyol (i).
20 6. The composition for a polyurethane foam as claimed in
claim 5, which comprises a polymer polyol wherein, by the use of the
preparation (c) obtained, polymer fine particles obtained by
polymerizing a compound having an unsaturated bond are dispersed in
the preparation (c) .
SF-2542 n ^ f £ ^ '^^^^
7. The composition for a polyurethane foam as claimed in
claim 4, wherein the content ratio of the compound (ii) to the polyol
(p) is 150 to 5000 ppm.
5 8. The composition for a polyurethane foam as claimed in
claim 1, wherein the content ratio of the antioxidant (iii) in the
composition for a polyurethane foam is 100 to 15000 ppm.
9. The composition for a polyurethane foam as claimed in
10 claim 1, wherein the hydroxyl value of the polyoxyalkylene polyol
is 10 to 80 mgKOH/g.
10, A production process for a composition for a polyurethane
foam, comprising a step which comprises adding, to a polyol (i)
15 containing a polyoxyalkylene polyol (p) obtained by addition
polymerization of an alkylene oxide compound onto an active hydrogen
compound using a compound (ii) having a P=N bond as a catalyst, and
the compound (ii) having been used for the production of the polyol
(p),
20 an antioxidant (iii) having a hydroxyphenyl group and an acid
or its salt (iv) in such an amount that the molar ratio (a/b) of the
acid or its salt (iv) (a) to the compound (ii) (b) having a P=N bond
becomes not less than 0. 3 but not more than 25, to obtain a preparation
(c) for a polyurethane foam and then adding a catalyst (v) for
SF-2542 Qj
111
polyurethane foam production and a blowing agent (vi) to the
preparation (c), wherein:
the acid or its salt (iv) is at least one substance selected
from the group consisting of an acyclic aliphatic monocarboxylic acid
5 of 2 to 25 carbon atoms, a hydroxycarboxylic acid of 2 to 25 carbon
atoms, a polycarboxylic acid of 20 to 60 carbon atoms, an aromatic
monocarboxylic acid represented by the following formula (1), a
sulfonic acid and an acid having a sulfuric acid ester group,
[Chem. 3]
-COOH
10
wherein R''' is a hydrocarbon group, and m represents a number of hydrogen
atoms of a benzene ring having been replaced with R'"' and is any one
of 0 to 5,
15 11. The production process for a composition for a
polyurethane foam as claimed in claim 10, which comprises a step of
preparing a polymer polyol in the preparation (c), wherein:
the polymer polyol is obtained by dispersing polymer fine
particles obtained by polymerizing a compound having an unsaturated
20 bond in the preparation (c).
12. A preparation for a polyurethane foam, which is a
SF-2542 r:r.lG^^^' 0 ^ f t^ ^^
preparation (c) for a polyurethane foam comprising a polyol (i) , a
compound (ii) having a P=N bond, an antioxidant (iii) having a
hydroxyphenyl group and an acid or its salt (iv), wherein:
the polyol (i) contains a polyoxyalkylene polyol (p) obtained
5 by addition polymerization of an alkylene oxide compound onto an active
hydrogen compound using the compound (ii) as a catalyst, and the
compound (ii) having been used for the production of the polyol (p),
the acid or its salt (iv) is at least one substance selected
from the group consisting of an acyclic aliphatic monocarboxylic acid
10 of 2 to 25 carbon atoms, a hydroxycarboxylic acid of 2 to 25 carbon
atoms, a polycarboxylic acid of 20 to 60 carbon atoms, an aromatic
monocarboxylic acid represented by the following formula (1), a
sulfonic acid and an acid having a sulfuric acid ester group,
the preparation (c) is obtained by adding the acid or its salt
15 (iv) in such an amount that the molar ratio (a/b) of the acid or its
salt (iv) (a) tothecompound (ii) (b) having been used for the production
of the polyol (p) becomes not less than 0.3 but not more than 25,
and the antioxidant (ii) to the polyol (i), and
the content ratio of the compound (ii) having been used for
20 the production of the polyol (p), to the polyol (p) is 150 to 5000
ppm.
SF-2542
113
[Chem. 4]
..>^
Ifc^
-_ lira' \iy^.
^ \ ' ^ •
V*
COOH
(R^). ( 1 )
wherein R'"' is a hydrocarbon group, and m represents a number of hydrogen
atoms of a benzene ring having been replaced with R''' and is any one
5 of 0 to 5,
10
13. The preparation for a polyurethane foam as claimed in
claim 12, wherein the compound (ii) is represented by the following
formula (2):
[Chem. 5]
NR.
A.
R,N~-P-NR,
II
RJM N NR,
I Yd I
R,N>(P=NVP'-^N=PVNR
I A^ I
R^N N NR,
11
1
L
RzN-P-NR,
Yb
NR,
Q-
( 2 )
wherein a, b, c and d are each a positive number of 0 to 3 but there
is no case where all of a, b, c and d become 0 at the same time, each
R is the same or different hydrocarbon group of 1 to 10 carbon atoms
SF-2542 rf>-Q-^^' 2\ftBM^*
and two R on the same nitrogen atom may be bonded to each other to
form a cyclic structure, and Q~ represents a hydroxyl anion, an alkoxy
anion, an aryloxy anion or a carboxy anion.
5 14. A polymer polyol preparation for a polyurethane foam,
comprising a polymer polyol wherein polymer fine particles obtained
by polymerizing a compound having a unsaturated bond are dispersed
in the preparation (c) for a polyurethane foam as claimed in claim
12 or 13,
10 the content of the vinyl polymer particles in said polymer polyol
being 3 to 60% by weight based on 100% by weight of the polyol component.
15. A production process for a preparation for a polyurethane
foam, comprising a step of adding, to a polyol (i) containing a
15 polyoxyalkylene polyol (p) obtained by addition polymerization of
an alkylene oxide compound onto an active hydrogen compound using
a compound (ii) having a P=N bond as a catalyst, and the compound
(ii) having been used for the preparation of the polyol (p),
an antioxidant (iii) having a hydroxyphenyl group and an acid
20 or its salt (iv) in such an amount that the molar ratio (a/b) of the
acid or its salt (iv) (a) to the compound (ii) (b) having a P=N bond
and having been used for the production of the polyol (p) becomes
not less than 0.3 but not more than 25,
the content ratio of said compound (ii) having been used for
SF-2542 rv«-"y*- o.ftB lOU I*
the production of the polyol (p), to the polyol (p) being 150 to 5000
ppm,
wherein:
the acid or its salt (iv) is at least one substance selected
5 from the group consisting of an acyclic aliphatic monocarboxylic acid
of 2 to 25 carbon atoms, a hydroxycarboxylic acid of 2 to 25 carbon
atoms, a polycarboxylic acid of 20 to 60 carbon atoms, an aromatic
monocarboxylic acid represented by the following formula (1), a
sulfonic acid and an acid having a sulfuric acid ester group,
10 [Chem. 6]
COOH
(R')m ... (1)
wherein R^ is a hydrocarbon group, andm represents a number of hydrogen
atoms of a benzene ring having been replaced with R^ and is any one
of 0 to 5.
15
16, A production process for a polymer polyol preparation
for a polyurethane foam, comprising a step of preparing a polymer
polyol using the preparation (c) for a polyurethane foam obtained
by the production process as claimed in claim 15, wherein:
20 thepolymer polyol is obtained by dispersing, in the preparation
(c), polymer fine particles obtained by polymerizing a compound having
an unsaturated bond, in such amounts that the content of the vinyl
i.'
SF-2542 '^'
,. _3„Hf.^^^^tB^S^
lib . •'t^\^m\%
polymer particles in the polymer polyol becomes 3 to 60% by weight
based on 100% by weight of the polyol component.
17 . A polyurethane foam obtained by the use of the composition
5 for a polyurethane foam as claimed in any one of claims 1 to 9.