TECHNICAL FIELD
[0001]
The present invention relates to a polyisocyanate composition, polyurethane resin
composed of the polyisocyanate composition, and a coating including the polyurethane resin.
BACKGROUND ART
[0002]
It has been known that when producing polyurethane resin, use of polyisocyanate
derived from hexamethylenediisocyanate allows for production of polyurethane resin with
excellent weatherability.
[0003]
For such polyisocyanate, for example, Patent Document 1 has proposed a
polyisocyanate composition derived from a hexamethylenediisocyanate monomer and isobutanol,
having an isocyanurate trimer concentration of 60 mass% under conditions where
hexarnethylenediisocyanate monomer and a solvent are not included, having 1% or more and
less than 5% of a ratio of the number of the allophanate group/isocyanurate group derived from
isobutanol, having a uretdione dimer concentration of 12 mass%, and having a viscosity at 25°C
of 620 mPa·s (for example, see Example 1 ).
Citation List
Patent Document
[0004]
Patent Document 1: Japanese Unexamined Patent Publication No. 2007-112936
SUMMARY OF THE INVENTION
PROBLEM TO BE SOLVED BY THE INVENTION
[0005]
However, the polyurethane resin obtained from the polyisocyanate composition of
Patent Document 1 has insufficient hardness and chemical resistance depending on the industrial
fields to which it is applied.
l/65
[0006]
Furthermore, examination by the present inventors has revealed that, for example, in
usage for a coating, there is a trade-off relationship between hardness and surface smoothness,
and it is necessary to achieve sufficient surface smoothness even with improvement in hardness.
[0007]
Thus, an object of the present invention is to provide a polyisocyanate composition that
allows for production of polyurethane resin with improved hardness and chemical resistance, and
for well-balanced improvement in hardness, chemical resistance, and surface smoothness.
MEANS FOR SOLVING THE PROBLEM
[0008]
The present invention [1] includes a polyisocyanate composition including at least a
pentamethylenediisocyanate derivative, wherein 5 mass% or more and 95 mass% or less of a
uretdione derivative composed of an isocyanate bimolecular-product of
pentamethylenediisocyanate is contained.
[0009]
The present invention [2] includes the polyisocyanate composition of [1] above,
containing 10 mass% or more and 95 mass% or less of the uretdione derivative composed of the
isocyanate bimolecular-product of pentamethylenediisocyanate.
[0010]
The present invention [3] includes the polyisocyanate composition of [ 1] or [2] above,
wherein in a chromatogram of the polyisocyanate composition in gel permeation chromatograph
measurement, the ratio of the peak area having a peak top between 280 to 490 of polyethylene
glycol-based molecular weight relative to a total peak area is 50% or more and 80% or less.
[0011]
The present invention [ 4] includes the polyisocyanate composition of any one of [ 1] to
[3] above, containing 3 mass% or more and 20 mass% or less of an isocyanate quadmolecularproduct
of pentamethylenediisocyanate.
[0012]
The present invention [5] includes the polyisocyanate composition of any one of [ 1] to
[ 4] above, containing 10 mass% or more and 55 mass% or less of an isocyanate trimolecular-
2/65
product of pentamethylenediisocyanate.
[00 13]
The present invention [ 6] includes polyurethane resin of a reaction product of the
polyisocyanate composition of any one of [ 1] to [ 5] and an active hydrogen group-containing
compound.
[0014]
The present invention [7] includes a method for producing polyurethane resin, the
method including allowing the polyisocyanate composition of any one of [1] to [5] to react with
an active hydrogen group-containing compound.
[0015]
The present invention [8] includes a coating including the polyurethane resin of [ 6]
above.
EFFECTS OF THE INVENTION
[00 16]
The polyisocyanate composition of the present invention includes at least a
pentamethylenediisocyanate derivative, wherein 5 mass% or more and 95 mass% or less of a
uretdione derivative composed of an isocyanate bimolecular-product of
pentamethylenediisocyanate is contained.
[0017]
Therefore, the polyurethane resin produced from the polyisocyanate composition and
the coating containing the polyurethane resin allows for improvement in hardness and chemical
resistance, and for improvement in hardness, chemical resistance, and surface smoothness in
well-balanced manner.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018]
FIG. 1 is a chromatogram of gel permeation chromatograph measurement of the polyisocyanate
composition of Example 2.
FIG. 2 is a chromatogram of gel permeation chromatograph measurement of the polyisocyanate
composition of Example 4.
FIG. 3 is a chromatogram of gel permeation chromatograph measurement of the polyisocyanate
3/65
composition of Example 9.
DESCRIPTION OF EMBODIMENTS
[00 19]
The polyisocyanate composition of the present invention contains at least a
pentamethylenediisocyanate derivative, and preferably, the polyisocyanate composition of the
present invention consists essentially of the pentamethylenediisocyanate derivative. In the
polyisocyanate composition of the present invention, essentially means that impurities other than
the pentamethylenediisocyanate derivative are 1.0 mass% or less relative to a total amount of the
polyisocyanate composition.
[0020]
Examples of the pentamethylenediisocyanate include, for example, 1, 2-
pentamethylenediisocyanate, 1, 3-pentamethylenediisocyanate, 1, 4-pentamethylenediisocyanate,
1, 5-pentamethylenediisocyanate, 2, 3-pentamethylenediisocyanate, 2, 4-
pentamethylenediisocyanate, and a mixture thereof. Preferably, 1, 5-
pentamethylenediisocyanate is used.
[0021]
In the following, in the present invention, pentamethylenediisocyanate (hereinafter may
be referred to as PDI) is 1, 5-pentamethylenediisocyanate unless otherwise noted.
[0022]
The pentamethylenediisocyanate is not particularly limited, and for example, it can be
produced in accordance with Example 1 of DESCRIPTION ofWO 2012/121291.
[0023]
The polyisocyanate composition of the present invention contains, as an essential
component, a uretdione derivative of pentamethylenediisocyanate, and may contain, as optional
components, for example, an isocyanurate derivative and an allophanate derivative of
pentamethylenediisocyanate.
[0024]
Examples of the uretdione derivative of pentamethylenediisocyanate include uretdione
multimolecular-product ofpentamethylenediisocyanate such as, for example, uretdione
bimolecular-product (to be specific, a compound in which two isocyanate groups at one end of
4/65
two pentamethylenediisocyanates form one uretdione ring, and the other two isocyanate groups
of the pentamethylenediisocyanates remain (pentamethylenediisocyanate bimolecular-product
having one uretdione ring)), uretdione trimolecular-product (to be specific,
pentamethylenediisocyanate trimolecular-product having two uretdione rings), uretdione
quadmolecular-product (to be specific, pentamethylenediisocyanate quadmolecular-product
having three uretdione rings), uretdione pentamolecular-product (to be specific,
pentamethylenediisocyanate pentamolecular-product having four uretdione rings),-··, and
uretdione n-molecular-product (to be specific, pentamethylenediisocyanate n-molecular-product
having (n-1) uretdione ring)) of pentamethylenediisocyanate, and preferably includes uretdione
bimolecular-product, uretdione trimolecular-product, and uretdione quadmolecular-product of
pentamethylenediisocyanate.
[0025]
Examples of the isocyanurate derivative of pentamethylenediisocyanate include
isocyanurate multimolecular-product ofpentamethylenediisocyanate such as, for example,
isocyanurate trimolecular-product (to be specific, a compound in which three isocyanate groups
at one end of three pentamethylenediisocyanates form one isocyanurate ring, and the other three
isocyanate groups of the pentamethylenediisocyanates remain (pentamethylenediisocyanate
trimolecular-product having one isocyanurate ring)), isocyanurate pentamolecular-product (to be
specific, pentamethylenediisocyanate pentamolecular-product having two isocyanurate rings),···,
and isocyanurate n-molecular-product (pentamethylenediisocyanate having n-molecular-product
((n-1 )/2) isocyanurate ring) of pentamethylenediisocyanate, and preferably includes isocyanurate
trimolecular-product of pentamethylenediisocyanate.
[0026]
Examples of the allophanate derivative of pentamethylenediisocyanate include
allophanate multimolecular-product of pentamethylenediisocyanate such as, for example,
allophanate bimolecular-product (to be specific, a compound in which an allophanate group is
formed by reaction of a urethane group, which is formed by reaction between one isocyanate
group of one pentamethylenediisocyanate and a hydroxy group of monohydric alcohol
(described later), with one isocyanate group of another pentamethylenediisocyanate, and other
two isocyanate groups remain (pentamethylenediisocyanate bimolecular-product having one
5/65
allophanate group)), allophanate quadmolecular-product (to be specific, a compound in which
two allophanate groups are formed by reaction of two urethane groups, which are formed by
reaction between two isocyanate groups at one end of two pentamethylenediisocyanates and two
hydroxy groups of dihydric alcohol (described later), with two isocyanate groups at one end of
other two pentamethylenediisocyanates, and other four isocyanate groups remain
(pentamethylenediisocyanate quadmolecular-product having two allophanate groups)), and
allophanate of pentamethylenediisocyanate obtained by further allowing the above-described
allophanate bimolecular-product or allophanate quadmolecular-product to react with
pentamethylenediisocyanate and/or alcohol, and preferably include allophanate bimolecularproduct
and quadmolecular-product of pentamethylenediisocyanate, more preferably include
allophanate bimolecular-product of pentamethylenediisocyanate.
[0027]
The polyisocyanate composition of the present invention contains, as an essential
component, a uretdione derivative composed of isocyanate bimolecular-product of
pentarnethylenediisocyanate (in the following, referred to as uretdione bimolecular-product), and
preferably contains, as an optional component, isocyanate trimolecular-product (mainly contains
isocyanurate trimolecular-product and uretdione trimolecular-product, also may include
iminooxadiazinedione trimolecular-product (structural isomers ofisocyanurate trimolecularproduct))
and isocyanate quadmolecular-product (mainly contains uretdione quadmolecularproduct
and allophanate quadmolecular-product) of pentamethylenediisocyanate. More
preferably, as an optional component, isocyanate trimolecular-product, isocyanate
quadmolecular-product, and allophanate bimolecular-product of pentamethylenediisocyanate are
contained.
[0028]
The derivative content of pentamethylenediisocyanate relative to a total amount of the
polyisocyanate composition can be determined by gel permeation chromatography (GPC) in
accordance with Examples to be described later.
[0029]
To be specific, the polyisocyanate composition is subjected to measurement with gel
permeation chromatograph equipped with a refractive index detector (RID), and in the
6/65
chromatogram, the ratio ofthe peak area having a polyethylene glycol-based molecular weight
peak top in a specific range relative to a total peak area corresponds to the derivative content of
pentamethyl enediisocyanate (mass-based).
[0030]
The derivative having a polyethylene glycol-based molecular weight peak top in a
specific range measured with a chromatogram of gel permeation chromatograph is identified
with lH-NMR method or 13C-NMR method, after separating the derivative of each peak in
fraction gel permeation chromatograph.
[0031]
The pentamethylenediisocyanate uretdione bimolecular-product content corresponds to,
in a chromatogram of the polyisocyanate composition subjected to gel permeation
chromatograph measurement, an area ratio of a peak area having a peak top between 280 or more
and 350 or less, preferably 290 or more and 330 or less of polyethylene glycol-based molecular
weight relative to a total peak area.
[0032]
The pentamethylenediisocyanate uretdione bimolecular-product content relative to a
total amount of the polyisocyanate composition is, 5 mass% or more and 95 mass% or less,
preferably 60 mass% or less, more preferably 50 mass% or less, further preferably 40 mass% or
less, even more preferably 30 mass% or less, even more preferably 20 mass% or less, even more
preferably 10 mass% or less, and particularly preferably 7 mass% or less.
[0033]
When the pentamethylenediisocyanate uretdione bimolecular-product content is within
the above-described range, a polyisocyanate composition that allows for improvement in
hardness and chemical resistance of polyurethane resin (described later) can be produced.
[0034]
In view of smoothness of polyurethane resin (described later),
pentamethylenediisocyanate uretdione bimolecular-product content relative to a total amount of
the polyisocyanate composition is, for example, 5 mass% or more, preferably 10 mass% or more,
more preferably 20 mass% or more, even more preferably 29 mass% or more, even more
preferably 50 mass% or more, even more preferably 60 mass% or more, and particularly
7/65
preferably 80 mass% or more, and for example, 95 mass% or less.
[0035]
The pentamethylenediisocyanate allophanate bimolecular-product content corresponds
to the ratio of a peak area having a peak top between more than 350 and 410 or less, preferably
360 or more and 400 or less of the polyethylene glycol-based molecular weight relative to a total
peak area in a chromatogram of the polyisocyanate composition subjected to gel permeation
chromatograph measurement.
[0036]
The pentamethylenediisocyanate allophanate bimolecular-product content relative to a
total amount of the polyisocyanate composition is, for example, 1 mass% or more, preferably 5
mass% or more, more preferably 15 mass% or more, and for example, 50 mass% or less,
preferably 30 mass% or less, more preferably 20 mass% or less.
[0037]
When the pentamethylenediisocyanate allophanate bimolecular-product content is
within the above-described range, a polyisocyanate composition that allows for improvement in
bending resistance and elongation at break in tensile test of polyurethane resin to be produced
(described later) can be produced.
[0038]
The isocyanate trimolecular-product of pentamethylenediisocyanate content corresponds
to the ratio of a peak area having a peak top between more than 410 and 490 or less, preferably
430 or more and 480 or less of the polyethylene glycol-based molecular weight relative to a total
peak area in a chromatogram of the polyisocyanate composition subjected to gel permeation
chromatograph measurement. The isocyanate trimolecular-product of
pentamethylenediisocyanate content corresponds to, mainly, a total amount of the
pentamethylenediisocyanate isocyanurate trimolecular-product content and the
pentamethylenediisocyanate uretdione trimolecular-product content.
[0039]
The isocyanate trimolecular-product of pentamethylenediisocyanate content relative to a
total amount of the polyisocyanate composition is, for example, 1 mass% or more, preferably 10
mass% or more, more preferably 20 mass% or more, even more preferably 30 mass% or more,
8/65
even more preferably 35 mass% or more, even more preferably 40 mass% or more, particularly
preferably 42 mass% or more, and for example, 55 mass% or less, preferably 45 mass% or less.
[0040]
When the isocyanate trimolecular-product of pentamethylenediisocyanate content is
within the above-described range, a polyisocyanate composition that allows for improvement in
hardness and chemical resistance of polyurethane resin to be produced (described later) can be
produced.
[0041]
The pentamethylenediisocyanate isocyanate quadmolecular-product content corresponds
to, in a chromatogram of the polyisocyanate composition subjected to gel permeation
chromatograph measurement, a ratio of a peak area having a peak top between 580 or more and
730 or less, preferably 590 or more and 720 or less of polyethylene glycol-based molecular
weight relative to a total peak area. The pentamethylenediisocyanate isocyanate
quadmolecular-product content corresponds to a total amount of the pentamethylenediisocyanate
uretdione quadmolecular-product content and the pentamethylenediisocyanate allophanate
quadmolecular-product content.
[0042]
The pentamethylenediisocyanate quadmolecular-product content relative to a total
amount of the polyisocyanate composition is, for example, 1 mass% or more, preferably 3
mass% or more, and for example, 20 mass% or less, preferably 15 mass% or less, more
preferably, 10 mass% or less, even more preferably 6 mass% or less.
[0043]
When the pentamethylenediisocyanate isocyanate quadmolecular-product content is
within the above-described range, a polyisocyanate composition that allows for improvement in
hardness and chemical resistance of polyurethane resin to be produced (described later) can be
produced.
[0044]
In view ofbalance between smoothness, hardness, and chemical resistance of
polyurethane resin (described later), the pentamethylenediisocyanate quadmolecular-product
content relative to a total amount of the polyisocyanate composition is, for example, 1 mass% or
9/65
more, preferably 3 mass% or more, more preferably 6 mass% or more, even more preferably l 0
mass% or more, particularly preferably 15 mass% or more, and for example, 20 mass% or less.
[0045]
In the present invention, in a chromatogram of the polyisocyanate composition in gel
permeation chromatograph measurement, the ratio of a peak area having a peak top between 280
or more and 490 or less, preferably 290 or more and 480 or less of the polyethylene glycol-based
molecular weight relative to a total peak area (in the following, referred to as bimolecularproduct
and trimolecular-product area ratio) is, for example, 40 mass% or more, preferably 50
mass% or more, more preferably, 60 mass% or more, and for example, 80 mass% or less,
preferably 70 mass% or less, more preferably 65 mass% or less.
[0046]
The area ratio of the pentamethylenediisocyanate bimolecular-product and trimolecularproduct
mainly corresponds to a total amount of pentamethylenediisocyanate uretdione
bimolecular-product, allophanate bimolecular-product, and isocyanate trimolecular-product
(isocyanurate trimolecular-product and uretdione trimolecular-product) contents.
[0047]
When the bimolecular-product and trimolecular-product area ratio is within the abovedescribed
range, a polyisocyanate composition that allows for production of polyurethane resin
(described later) having well-balanced smoothness, hardness, and chemical resistance can be
produced.
[0048]
In a chromatogram of the polyisocyanate composition subjected to gel permeation
chromatograph measurement, the peak top of the polyethylene glycol-based molecular weight
corresponding to the peak top of the isocyanate quadmolecular-product or more corresponds to
the derivative with high-molecular weight of isocyanurate pentamolecular-product, uretdione
pentamolecular-product or more.
[0049]
The ratio (uretdione bimolecular-product/isocyanate trimolecular-product) of the
pentamethylenediisocyanate uretdione bimolecular-product relative to the isocyanate
trimolecular-product of pentamethylenediisocyanate can be calculated based on their area ratios
10/65
as described above, and for example, the ratio is 0.10 or more, preferably 0.20 or more, more
preferably 0.30 or more, even more preferably 0.80 or more, and for example, 10 or less,
preferably 3.00 or less, more preferably 2.00 or less, even more preferably 1.50 or less,
particularly preferably 1.00 or less.
[0050]
When the above-described ratio of the pentamethylenediisocyanate uretdione
bimolecular-product to the pentamethylenediisocyanate-trimolecular-product is within the abovedescribed
range, a polyisocyanate composition that allows for production of polyurethane resin
(described later) having well-balanced smoothness, hardness, and chemical resistance can be
produced.
[0051]
The polyisocyanate composition has a pentamethylenediisocyanate
(pentamethylenediisocyanate monomer) concentration (measured in accordance with Examples
to be described later) relative to a total amount of the polyisocyanate composition of, generally
less than the detection limit, and when it has a pentamethylenediisocyanate
(pentamethylenediisocyanate monomer) concentration of the detection limit or more, the
pentamethylenediisocyanate (pentamethylenediisocyanate monomer) concentration is, for
example, 0.1 mass% or more, and for example, 1.0 mass% or less, preferably 0.5 mass% or less,
more preferably 0.2 mass% or less.
[0052]
The polyisocyanate composition has an isocyanate group content (measured in
accordance with Examples to be described later) relative to a total amount of the polyisocyanate
composition of, 20.0 mass% or more, preferably 22.0 mass% or more, more preferably, 23.0
mass% or more, even more preferably 24.0 mass% or more, and for example, 27.0 mass% or less,
preferably 26.0 mass% or less, more preferably, 25.0 mass% or less, even more preferably 24.5
mass% or less.
[0053]
In the polyisocyanate composition, the average functionality of the isocyanate group is,
for example, 1.8 or more, preferably 2.0 or more, and for example, 4.0 or less, preferably 3.0 or
less.
11/65
[0054]
The polyisocyanate composition has a viscosity at 25°C (measured in accordance with
Examples to be described later) of, for example, 23 mPa·s or more, preferably 70 mPa·s or more,
more preferably 100 mPa·s or more, and for example, 2000 mPa·s or less, preferably 1500 mPa·s
or less, more preferably 1200 mPa·s or less, even more preferably 1000 mPa·s or less, even more
preferably 600 mPa·s or less, even more preferably 400 mPa·s or less, even more preferably 300
mPa·s or less, even more preferably 200 mPa·s or less, particularly preferably 180 mPa·s or less.
[0055]
When the polyisocyanate composition has a viscosity within the above-described range,
smoothness of the polyurethane resin to be produced (described later) can be improved.
[0056]
Next, a method for producing a polyisocyanate composition of the present invention is
described.
[0057]
To produce the polyisocyanate composition of the present invention, inactive gas such
as nitrogen is introduced into pentamethylenediisocyanate, and after allowing the atmosphere to
be an inactive gas atmosphere, reaction is caused to form a derivative.
[0058]
To produce a polyisocyanate composition (containing a small amount of, or not
containing a derivative other than the uretdione derivative) containing a uretdione derivative of
pentamethylenediisocyanate as an essential component, pentamethylenediisocyanate is heated in
an inactive gas atmosphere to cause uretdione-formation reaction.
[0059]
To be specific, to produce a polyisocyanate composition (to be specific, a
polyisocyanate composition containing 80% or more of the uretdione derivative (in particular,
uretdione bimolecular-product)) containing uretdione derivative ofpentamethylenediisocyanate
(in particular, uretdione bimolecular-product) in a larger amount relative to other derivatives, for
example, the following conditions are applied: under atmosphere of inactive gas such as nitrogen
gas and normal pressure (atmospheric pressure), reaction temperature of, for example, 1 oooc or
more, preferably 130°C or more, and for example, 200°C or less, preferably 170°C or less, the
12/65
reaction time of, for example, 0.5 hours or more, preferably 3 hours or more, and for example, 20
hours or less, preferably 15 hours or less.
[0060]
blended.
[0061]
In the above reaction, as necessary, a known uretdione-formation catalyst can be
Examples of the uretdione-formation catalyst include trivalent phosphorus compounds
such as triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine,
triisobutylphosphine, tritertiarybutylphosphine, tri-n-hexylphosphine, tricyclohexylphosphine,
tri-n-octylphosphine, tribenzylphosphine, and benzyldimethylphosphine, and Lewis acids such as
boron trifluoride and zinc trichloride.
[0062]
The uretdione-formation catalyst can be used singly, or can be used in combination of
two or more.
[0063]
When the uretdione-formation catalyst is blended, for example, 1 ppm or more,
preferably 10 ppm or more, generally 1000 ppm or less, preferably 500 ppm or less of the
catalyst is blended relative to pentamethylenediisocyanate, based on mass.
[0064]
When the uretdione-formation catalyst is blended, the reaction temperature is, for
example, 25°C or more, preferably 40°C or more, more preferably, 60°C or more, and for
example, l20°C or less, preferably 100°C or less.
[0065]
In this manner, a reaction mixture containing the uretdione derivative of
pentamethylenediisocyanate in a larger amount relative to other derivative can be produced.
[0066]
In the derivative-formation reaction, to produce a polyisocyanate composition
containing isocyanurate derivative and uretdione derivative of pentamethylenediisocyanate,
pentamethylenediisocyanate is subjected to isocyanurate-formation reaction and uretdioneformation
reaction.
13/65
[0067]
Upon producing the polyisocyanate composition containing isocyanurate derivative and
uretdione derivative ofpentamethylenediisocyanate, to produce a polyisocyanate composition
containing 20 mass% or less of the uretdione derivative relative to a total amount of the
polyisocyanate composition (to be specific, the ratio of the uretdione derivative (in particular,
uretdione bimolecular-product) relative to the isocyanurate derivative (in particular, isocyanate
trimolecular-product) is 0.6 or less), pentamethylenediisocyanate is first subjected to
isocyanurate-formation reaction, and thereafter, subjected to uretdione-formation reaction.
[0068]
To cause isocyanurate-formation reaction, adding an isocyanurate-formation catalyst
and heating will suffice, but going through urethane-forming reaction allows formation of an
isocyanurate ring easily, and therefore preferably alcohol is blended to subject
pentamethylenediisocyanate and alcohol to urethane-forming reaction.
[0069]
Examples of the alcohol include monohydric alcohol and dihydric alcohol.
[0070]
Examples of the monohydric alcohol include straight chain monohydric alcohol and
branched monohydric alcohol.
[0071]
Examples of the straight chain monohydric alcohol include C (number of carbon, the
same applies in the following) 1 to 20 straight chain monohydric alcohol such as methanol,
ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, ndecanol,
n-undecanol, n-dodecanol (laurylalcohol), n-tridecanol, n-tetradecanol, n-pentadecanol,
n-hexadecanol, n-heptadecanol, n-octadecanol (stearyl alcohol), n-nonadecanol, and eicosanol.
[0072]
Examples of the branched monohydric alcohol include C3 to 20 branched monohydric
alcohols such as isopropanol, isobutanol (isobutylalcohol), sec-butanol, tert-butanol, isopentanol,
isohexanol, isoheptanol, isooctanol, 2-ethylhexane-1-ol, isononanol, isodecanol, 5-ethyl-2-
nonanol, trimethylnonylalcohol, 2-hexyldecanol, 3, 9-diethyl-6-tridecanol, 2-isoheptyl
isoundecanol, 2-octyldodecanol, and other branched alkanol (C5 to 20).
14/65
[0073]
Examples of the dihydric alcohol include C2 to 20 dihydric alcohols such as straight
chain dihydric alcohol including ethylene glycol, 1, 3-propanediol, 1, 4-butanediol ( 1, 4-
butyleneglycol), 1, 5-pentanediol, 1, 6-hexanediol, 1, 4-dihydroxy-2-butene, diethylene glycol,
triethylene glycol, dipropylene glycol, and other straight chain alkane (C7 to 20) diols; branched
dihydric alcohols including 1, 2-propanediol, 1, 3-butanediol (1, 3-butyleneglycol), 1, 2-
butanediol (1, 2-butyleneglycol), neopentyl glycol, 3-methyl-1, 5-pentanediol, 2, 2, 2-
trimethylpentanediol, 3, 3-dimethylolheptane, 2, 6-dimethyl-1-octene-3, 8-diol, and other
branched alkane (C7 to 20) diols; 1, 3-or 1, 4-cyclohexanedimethanol and a mixture thereof, 1,
3- or 1, 4-cyclohexanediol and a mixture thereof, hydrogenated bisphenol A, and bisphenol A.
[0074)
For alcohol, a compound having both a hydrophilic group and an active hydrogen group
to be described later (in the following, referred to as hydrophilic group-containing active
hydrogen compound) can also be used.
[0075)
These alcohols can be used singly, or can be used in combination of two or more.
[0076)
For the alcohol, preferably, Cl to 20 straight chain monohydric alcohol, C3 to 20
branched monohydric alcohol are used. Even more preferably, C3 to 20 branched monohydric
alcohol is used, and particularly preferably, isobutylalcohol is used.
[0077]
In this reaction, alcohol is blended, and therefore to be described later, except for the
case where the allophanate derivative is produced intentionally, a small amount of allophanate
derivative is by-produced and remains relative to the isocyanurate derivative.
[0078]
When the allophanate derivative is not produced intentionally, alcohol is blended
relative to 100 parts by mass ofpentamethylenediisocyanate, in an amount of, for example, 0.01
parts by mass or more, preferably 0.05 parts by mass or more, and for example, 1.0 part by mass
or less, preferably 0.8 parts by mass or less.
[0079]
15/65
When the allophanate derivative is not produced intentionally, the allophanate derivative
content relative to a total amount of the polyisocyanate composition is, for example, 0.1 mass%
or more, and for example, 10 mass% or less, preferably 5 mass% or less.
[0080]
The urethane-forming reaction conditions are as follows: for example, under atmosphere
of inactive gas such as nitrogen gas and normal pressure (atmospheric pressure), reaction
temperature of, for example, room temperature (for example, 25°C) or more, preferably 40°C or
more, for example, 1 00°C or less, preferably 90°C or less. The reaction time is, for example,
0.5 hours or more, preferably 1 hour or more, and for example, 10 hours or less, preferably 6
hours or less, more preferably, 3 hours or less.
[0081 J
In the urethane-forming reaction described above, a known urethane-forming catalyst
(for example, amines, organic metal compound, etc) can be blended.
[0082]
In this manner, pentamethylenediisocyanate that went through urethane-formation can
be produced.
[0083]
To cause isocyanurate-formation reaction, then, pentamethylenediisocyanate that went
through urethane-formation and pentamethylenediisocyanate are subjected to isocyanurate ringformation
reaction in the presence of a derivative-formation catalyst (isocyanurate-formation
catalyst) that accelerates isocyanurate formation.
[0084]
Examples of the isocyanurate-formation catalyst include hydroxide of
tetraalkylammonium such as tetramethylammonium, tetraethylammonium, tetrabutylammonium,
trimethylbenzylammonium, and tributylbenzylammonium or their organic salt of weak acid;
hydroxide oftrialkylhydroxyalkylammonium such as trimethylhydroxypropylammonium (also
called: N-(2-hydroxypropyl)-N ,N ,N -trimethylammonium ), trimethylhydroxyethylammonium,
triethylhydroxypropylammonium, and triethylhydroxyethylammonium or their organic salt of
weak acid (for example, N-(2-hydroxypropyl)-N,N,N-trimethylammonium-2-ethylhexanoate,
etc); metal salt (for example, alkali metal salt, magnesium salt, tin salt, zinc salt, lead salt, etc) of
16/65
alkylcarboxylic acid such as acetic acid, caproic acid, octylic acid, myristic acid, and naphthenic
acid; metal chelate compounds of ~-diketone such as aluminum acetylacetone and lithium
acetylacetone; Friedel-Crafts catalysts such as aluminum chloride and boron trifluoride; various
organic metal compounds such as titaniumtetrabutyrate and tributylantimonyoxide; and
aminosilyl group-containing compounds such as hexamethylsilazane.
[0085]
These isocyanurate-formation catalysts can be used singly, or can be used in
combination of two or more.
[0086]
These isocyanurate-formation catalysts accelerate isocyanurate formation, but do not
accelerate uretdione formation.
[0087]
For the isocyanurate-formation catalyst, preferably, organic salt of weak acid of
trialkylhydroxyalkylammonium is used, more preferably, N-(2-hydroxypropyl)-N,N,Ntrimethylammonium-
2-ethylhexanoate is used.
[0088]
The isocyanurate-formation catalyst (based on active component 100%) is blended in an
amount relative to 100 parts by mass of pentamethylenediisocyanate of, for example, 0.002 parts
by mass or more, preferably 0.005 parts by mass or more, and for example, 0.1 parts by mass or
less, preferably 0.05 parts by mass or less.
[0089]
In the isocyanurate ring-formation reaction, reaction conditions are as follows: for
example, under atmosphere of inactive gas such as nitrogen gas and normal pressure
(atmospheric pressure), reaction temperature of, for example, 50°C or more, preferably 70°C or
more, more preferably 80°C or more, and for example, l20°C or less, preferably 100°C or less.
The reaction time is, for example, 10 minutes or more, preferably 20 minutes or more, and for
example, 120 minutes or less, preferably 60 minutes or less.
[0090]
In the isocyanurate ring-formation reaction, at the point when the reaction rate of the
isocyanate group (the reaction rate of the isocyanate group and the urethane group relative to a
17/65
total amount of the isocyanate group and the urethane group when the isocyanate group and the
urethane group of the pentamethylenediisocyanate after completion of the urethane-forming
reaction are allowed to react and converted to the uretdione group, isocyanurate group, and
allophanate group) or conversion rate of the isocyanate group (the reaction rate of the isocyanate
group relative to a total amount of the isocyanate group when the isocyanate group of the
pentamethylenediisocyanate is allowed to react and converted to the uretdione group,
isocyanurate group, urethane group, and allophanate group) reaches a predetermined ratio to be
described later, for example, a reaction terminator such as phosphoric acid, monochloroacetic
acid, benzoyl chloride, dodecylbenzenesulfonic acid, toluenesulfonic acid ( o- or ptoluenesulfonic
acid) and a derivative thereof (for example, o- or p-toluenesulfonic acid methyl,
etc), and toluenesulfonamide (o- or p-toluenesulfonamide) is added to the reaction liquid to
deactivate the catalyst and to terminate the isocyanurate-formation reaction. In this case, the
isocyanurate-formation reaction can also be terminated by adding an adsorbent that adsorbs
catalysts such as chelate resin and ion-exchange resin.
[0091 J
The reaction rate of the isocyanate group is, for example, 5 mass% or more, preferably
10 mass% or more, and for example, 35 mass% or less, preferably 25 mass% or less.
[0092]
When the reaction rate of the isocyanate group is more than the above-described range,
the produced isocyanurate derivative of pentamethylenediisocyanate further goes through
reaction, which may reduce solubility, compatibility, and the isocyanate group concentration, and
may increase viscosity. The reaction rate of the isocyanate group can be measured by, for
example, titrimetry such as the one in Examples to be described later.
[0093]
The isocyanate group conversion rate relative to a total amount of the polyisocyanate
composition is, for example, 10 mass% or more, preferably 20 mass% or more, more preferably
25 mass% or more, even more preferably 35 mass% or more, and for example, 70 mass% or less,
preferably 50 mass% or less.
[0094]
The isocyanate group conversion rate can be measured by a method, for example, such
18/65
as the one using GPC a device, as in Examples to be described later.
[0095]
In this manner, pentamethylenediisocyanate can be subjected to isocyanurate-formation
reaction.
[0096]
Thereafter, the reaction liquid produced by the isocyanurate-formation reaction is
subjected to heat treatment, thereby subjecting the reaction liquid to uretdione-formation reaction.
[0097]
The heat treatment conditions are the same as those in the above-described uretdioneformation
reaction, and to be specific, the heat treatment temperature is, for example, 1 oooc to
200°C, preferably 150°C to 170°C, and the heat treatment time is, 0.5 hours to 5 hours, 1 hour to
3 hours.
[0098]
In this manner, the uretdione-formation reaction can be performed, and as a result, a
reaction mixture containing an isocyanurate derivative and a uretdione derivative, and containing
20 mass% or less of the uretdione derivative relative to the isocyanurate derivative can be
produced.
[0099]
Upon producing the polyisocyanate composition containing isocyanurate derivative and
uretdione derivative of pentamethylenediisocyanate, when producing a polyisocyanate
composition (to be specific, more than 0.6 ofuretdione derivative (in particular, uretdione
bimolecular-product) relative to isocyanurate derivative (in particular, isocyanate trimolecularproduct))
containing more than 20 mass% ofthe uretdione derivative relative to a total amount of
the polyisocyanate composition, the isocyanurate-formation reaction and uretdione-formation
reaction of the pentamethylenediisocyanate are performed simultaneously.
[0100]
To perform the isocyanurate-formation reaction and uretdione-formation reaction
simultaneously, first, in the same manner as described above, pentamethylenediisocyanate and
alcohol are subjected to urethane-forming reaction.
[0 101]
19/65
In this reaction, the alcohol blended is, for example, in view of accelerating the
isocyanurate ring-formation reaction by alcohols and catalysts, preferably dihydric alcohol, more
preferably, 1, 3-propanediol (1, 3-PG), 1, 3-butanediol (1, 3-BG), 1, 4-butanediol (1, 4-BG), even
more preferably 1, 3-butanediol (1, 3-BG) is used.
[0102]
To perform the isocyanurate-formation reaction and the uretdione-formation reaction
simultaneously, next, in the presence of a derivative-formation catalyst that can work as both the
uretdione-formation catalyst and the isocyanurate-formation catalyst, the
pentamethylenediisocyanate that went through urethane-forming reaction and
pentamethylenediisocyanate are subjected to isocyanurate ring-formation reaction, and also
pentamethylenediisocyanate is subjected to uretdione-formation reaction.
[0103]
Examples of the derivative-formation catalyst that works as both the uretdioneformation
catalyst and the isocyanurate-fmmation catalyst include, for example, the abovedescribed
trivalent phosphorus compound, and preferably tri-n-butylphosphine is used.
[0104]
These derivative-formation catalysts that work as both the uretdione-formation catalyst
and the isocyanurate-formation catalyst accelerate isocyanurate formation as well as uretdione
formation. It also may accelerate iminooxadiazinedione-formation.
[0105]
The derivative-formation catalyst that works as both the uretdione-formation catalyst
and the isocyanurate-formation catalyst is blended in an amount of, for example, relative to 100
parts by mass of pentamethylenediisocyanate, for example, 0.1 parts by mass or more, preferably
0.3 parts by mass or more, and for example, 1.0 part by mass or less, preferably 0.5 parts by
mass or less.
[0106]
To perform the isocyanurate-formation reaction and the uretdione-formation reaction
simultaneously, the reaction conditions are as follows, for example, under atmosphere of inactive
gas such as nitrogen gas and normal pressure (atmospheric pressure), reaction temperature of, for
example, 25°C or more, preferably 40°C or more, more preferably 60°C or more, and for
20/65
example, 1 00°C or less, preferably 70°C or less. The reaction time is, for example, 1 hour or
more, preferably 2 hours or more, and for example, 4 hours or less, preferably 3 hours or less.
[0 1 07]
In the isocyanurate ring-formation reaction and the uretdione-formation reaction, in the
same manner as described above, when the reaction rate and the conversion rate of the
isocyanate group reaches a predetermined rate, the above-described reaction terminator is added
to the reaction liquid to deactivate the catalyst and terminate the reaction.
[01 08]
In this manner, pentamethylenediisocyanate can be subjected to isocyanurate-forrnation
reaction and uretdione-formation reaction, and as a result, a reaction mixture containing
isocyanurate derivative and uretdione derivative, and containing more than 20 mass% of the
uretdione derivative relative to the isocyanurate derivative can be produced.
[0109]
Thereafter, the above-described isocyanurate-formation catalyst and/or a known
allophanate-formation catalyst are added at, for example, 80 to 120°C, and the temperature is
kept for, for example, 1 to 10 hours, which allows for increase in the isocyanurate derivative
and/or allophanate derivative contents of the reaction mixture.
[0110]
In the above-described isocyanurate ring-formation reaction, the allophanate derivative
can be produced intentionally.
[0111]
When the allophanate derivative is produced intentionally, alcohol (in particular, to
produce allophanate bimolecular-product intentionally, monohydric alcohol) is blended in an
amount relative to 100 parts by mass ofpentamethylenediisocyanate, for example, 1.0 part by
mass or more, preferably 1.2 parts by mass or more, for example, 5.0 parts by mass or less,
preferably 2.0 parts by mass or less.
[0112]
When the alcohol is blended in an amount within the above-described range when the
allophanate derivative is produced intentionally, when in reaction with an active hydrogen groupcontaining
compound (described later), compatibility with the active hydrogen group-containing
21165
compound (described later) increases, and pot life of the polyisocyanate composition can be
made longer.
[0113]
To adjust the uretdione formation and isocyanurate ring-formation in the abovedescribed
uretdione-formation reaction and isocyanurate-formation reaction, for example,
organic phosphite such as the one described in Japanese Unexamined Patent Publication No.Sho
61-129173 can be blended as a promoter.
[0114]
Examples of the organic phosphite include organic phosphorous acid diester and organic
phosphorous acid triester, and to be specific, for example, monophosphites such as
triethylphosphite, tributylphosphite, tris (tridecyl) phosphite, triphenylphosphite, tris
(nonylphenyl) phosphite, tris (2, 4-di-t-butylphenyl) phosphite, and diphenyl (tridecyl)
phosphite; and di, tri, or tetraphosphites derived from polyhydric alcohol such as distearyl·penta
erythrityl·diphosphite, tripentaerythritol·triphosphite, and tetraphenyl·dipropylene
glycol·diphosphite.
[0115]
These organic phosphites can be used singly, or can be used in combination of two or
more.
[0116]
For the organic phosphite, preferably, monophosphites are used, more preferably, tris
(tridecyl) phosphite is used.
[0117]
The organic phosphite is blended in an amount of, relative to 100 parts by mass of
pentamethylenediisocyanate, for example, 0.01 parts by mass or more, preferably 0.05 parts by
mass or more, and for example, 1.0 part by mass or less, preferably 0.1 parts by mass or less.
[0118]
In the above-described uretdione-formation reaction and isocyanurate ring-formation
reaction, as necessary, a reaction stabilizer such as a hindered phenol antioxidant, for example, 2,
6-di (tert-butyl)-4-methylphenol, IRGANOX 1010, IRGANOX 1076, IRGANOX 1135,
IRGANOX 245 (all manufactured by BASF Japan, trade name) can be blended.
22/65
[0119]
The reaction stabilizer is blended in an amount of, relative to 1 00 parts by mass of
pentamethylenediisocyanate, for example, 0.01 parts by mass or more, preferably 0.05 parts by
mass or more, and for example, 1.0 part by mass or less, preferably 0.1 parts by mass or less.
[0120]
The above-described promoter and reaction stabilizer can be added at the time of the
above-described urethane-forming reaction.
[0121]
In the above-described derivative-formation reaction, as necessary, a known reaction
solvent can be blended.
[0122]
Then, after termination of reaction, from the reaction mixture obtained, unreacted
pentamethylenediisocyanate (when catalyst, reaction solvent and/or catalyst inactivator are
blended, including the catalyst, reaction solvent and/or catalyst inactivator) is removed by a
known method such as, for example, distillation such as thin-film distillation (Smith distillation)
and extraction, thereby producing a polyisocyanate composition.
[0123]
After removal of the unreacted pentamethylenediisocyanate, the above-described
reaction terminator can be added as a stabilizer to the produced polyisocyanate composition in an
arbitrary amount.
[0124]
In this manner, a polyisocyanate composition of the present invention containing a
uretdione derivative of pentamethylenediisocyanate as an essential component, and isocyanurate
derivative and allophanate derivative of pentamethylenediisocyanate as optional components can
be produced.
[0125]
In the polyisocyanate composition of the present invention, two types or more of the
polyisocyanate compositions prepared as described above can be blended.
[0126]
In the present invention, in the isocyanurate-fotmation reaction, isocyanurate-formation
23/65
reaction is caused by blending alcohol, but isocyanurate formation can be caused without
blending alcohol.
[0127]
The polyisocyanate composition of the present invention can be mixed with a uretdione
derivative, isocyanurate derivative, and allophanate derivative of aliphatic polyisocyanate
(excluding pentamethylenediisocyanate ).
[0128]
For the aliphatic polyisocyanate (excluding pentamethylenediisocyanate ), aliphatic
diisocyanates such as trimethylenediisocyanate, 1, 2-propylenediisocyanate,
butylenediisocyanate (tetramethylenediisocyanate, 1, 2-butylenediisocyanate, 2, 3-
butylenediisocyanate, 1, 3-butylenediisocyanate), hexamethylenediisocyanate (HDI, for example,
1, 6-hexamethylenediisocyanate, etc), 2, 4, 4- or 2, 2, 4-trimethylhexamethylenediisocyanate, 2,
6-diisocyanatemethyl caproate are used.
[0 129]
These aliphatic polyisocyanates (excluding pentamethylenediisocyanate) can be used
singly, or can be used in combination of two or more.
[0130]
The polyisocyanate composition of the present invention includes at least a
pentamethylenediisocyanate derivative, and contains 5 mass% or more and 95 mass% or less of a
uretdione derivative composed of isocyanate bimolecular-product of pentamethylenediisocyanate.
[0 131 J
Therefore, hardness and chemical resistance of polyurethane resin in which the
polyisocyanate composition of the present invention is used can be improved.
[0132]
The polyisocyanate composition thus produced does not include a solvent, and can be
used in a coating, adhesive, and other various industrial use without being diluted with a solvent,
but as necessary, it can be dissolved in an organic solvent to be diluted and used.
[0133]
Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone,
methyl isobutyl ketone, and cyclohexanone; nitriles such as acetonitrile; alkyl esters such as
24/65
methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate; aliphatic hydrocarbons such as
n-hexane, n-heptane, and octane; alicyclic hydrocarbons such as cyclohexane and
methylcyclohexane; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; glycol
ether esters such as methyl cellosolve acetate, ethyl cellosolve acetate, methyl carbitol acetate,
ethyl carbitol acetate, ethylene glycol ethylether acetate, propylene glycol methylether acetate, 3-
methyl-3-methoxybutyl acetate, and ethyl-3-ethoxypropionate; ethers such as diethylether,
tetrahydrofuran, and dioxane; halogenated aliphatic hydrocarbons such as methyl chloride,
methylene chloride, chloroform, carbon tetrachloride, methyl bromide, methylene iodide, and
dichloroethane; polar aprotic solvents such as N-methyl pyrrolidone, dimethylformamide, N,N'dimethylacetamide,
dimethyl sulfoxide, and hexamethyl phosphoramide.
[0134]
Examples of the organic solvent fu1iher include nonpolar solvents (nonpolar organic
solvent), and examples of nonpolar solvents include those nonpolar organic solvents having an
aniline point of, for example, 10 to 70°C, preferably 12 to 65°C and having low toxicity and
solvency, such as aliphatic, naphthene hydrocarbon organic solvent; and vegetable oils typically
represented by turpentine oil.
[0135]
The nonpolar organic solvents can be obtained from commercially available products,
and examples of those commercially available products include petroleum hydrocarbon organic
solvents such as Haws (manufactured by Shell Chemicals, aniline point l5°C), Swasol310
(manufactured by Maruzen Petrochemical, aniline point l6°C), Esso Naphtha No.6
(manufactured by Exxon Mobil Chemical, aniline point 43°C), Laws (manufactured by Shell
Chemicals, aniline point 43°C), Esso Naphtha No.5 (manufactured by Exxon Mobil Corporation,
aniline point 55°C), and pegasol 3040 (manufactured by Exxon Mobil Corporation, aniline point
55°C); and also turpentine oils such as methylcyclohexane (aniline point 40°C),
ethylcyclohexane (aniline point 44°C), and gum turpentine N (manufactured by YASUHARA
CHEMICAL CO.,LTD., aniline point 27°C).
[0136]
The polyisocyanate composition of the present invention can be mixed with these
organic solvents at an arbitrary ratio.
25/65
[0137]
When the polyisocyanate composition of the present invention is diluted with an organic
solvent, the polyisocyanate composition concentration relative to a total amount of the liquid
mixture in which the polyisocyanate composition is diluted with the organic solvent is, for
example, 20 mass% or more, preferably 30 mass% or more, and for example, 95 mass% or less,
preferably 90 mass% or less.
[0138]
In such a case, the viscosity at 25°C is adjusted to be, for example, 10 mPa·s or more,
preferably 20 mPa·s or more, and for example, 10000 mPa·s or less, preferably 5000 mPa·s or
less.
[0139]
To the polyisocyanate composition, as necessary, a known additive, for example, a
storage stabilizer (o-toluenesulfonamide, p-toluenesulfonamide, etc), plasticizer, anti-blocking
agent, heat-resistant stabilizer, light stabilizer, antioxidant, releasing agent, catalyst, pigment, dye,
lubricant, filler, and hydrolysis inhibitor can be further added at a suitable ratio.
[0140]
Such a polyisocyanate composition is suitably produced by the above-described method
for producing a polyisocyanate composition.
[0141]
The polyisocyanate composition of the present invention can also be used as an aqueous
polyisocyanate composition by allowing it to react with a hydrophilic group-containing an active
hydrogen compound, preferably used as an aqueous polyisocyanate composition.
[0142]
The hydrophilic group-containing active hydrogen compound is a compound having
both of at least one hydrophilic group and at least one active hydrogen group, and examples of
the hydrophilic group include an anionic group (for example, carboxy group (carboxylic acid
group), etc), a cationic group, and a nonionic group (for example, polyoxyethylene group, etc).
Preferably, a nonionic group is used. The active hydrogen group is a group that reacts with an
isocyanate group, and examples thereof include a hydroxyl group, amino group, and epoxy
group. When the hydrophilic group-containing active hydrogen compound has both of the
26/65
hydroxyl group and the amino group, the hydroxyl group is the hydrophilic group and the amino
group is the active hydrogen group.
[0143]
For the hydrophilic group-containing active hydrogen compound, to be more specific, a
carboxylic acid group-containing active hydrogen compound, sulfonic acid group-containing
active hydrogen compound, hydroxyl group-containing active hydrogen compound, hydrophilic
group-containing polybasic acid, and polyoxyethylene group-containing active hydrogen
compound are used.
[0144]
For the carboxylic acid group-containing active hydrogen compound, for example,
dihydroxyl carboxylic acids such as 2, 2-dimethylol acetic acid, 2, 2-dimethylollactic acid, 2, 2-
dimethylol propionic acid (DMPA), 2, 2-dimethylol butanoic acid (DMBA), 2, 2-dimethylol
butyric acid, and 2, 2-dimethylol valerie acid; diaminocarboxylic acids such as lysine, and
arginine, or their metal salts or ammonium salts are used. Preferably, 2, 2-dimethylolpropionic
acid (DMPA) and 2, 2-dimethylolbutanoic acid (DMBA) are used.
[0145]
For the sulfonic acid group-containing active hydrogen compound, for example,
dihydroxybutanesulfonic acid and dihydroxypropane sulfonic acid that are obtained from
synthetic reaction between an epoxy group-containing compound and acid sulfite are used.
Examples also include N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid, N,N-bis(2-
hydroxyethyl)-2-aminobutanesulfonic acid, 1, 3-phenylenediamine-4, 6-disulfonic acid,
diaminobutanesulfonic acid, diaminopropane sulfonic acid, 3, 6-diamino-2-toluenesulfonic acid,
2, 4-diamino-5-toluenesulfonic acid, N-(2-aminoethyl)-2-aminoethanesulfonic acid, 2-
aminoethanesulfonic acid, N-(2-aminoethyl)-2-aminobutanesulfonic acid, and metal salts or
ammonium salts of these sulfonic acids.
[0146]
For the hydroxyl group-containing active hydrogen compound, for example, N-(2-
aminoethyl) ethanolamine is used.
[0147]
Examples of the hydrophilic group-containing polybasic acid include polybasic acid
27/65
containing sulfonic acid, to be more specific, 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-
sulfophthalic acid, 5-(p-sulfophenoxy) isophthalic acid, 5-(sulfopropoxy) isophthalic acid, 4-
sulfonaphthalene-2, 7-dicarboxylic acid, sulfopropylmalonic acid, sulfosuccinic acid, 2-
sulfobenzoic acid, 2, 3-sulfobenzoic acid, 5-sulfosalicylic acid, alkyl ester of those carboxylic
acids, and also metal salts and ammonium salts of those sulfonic acids. Preferably, sodium
salts of 5-sulfoisophthalic acid, and sodium salts of 5-sulfoisophthalic acid dimethyl ester are
used.
[0 148]
The polyoxyethylene group-containing active hydrogen compound is a compound
containing a polyoxyethylene group in the main chain or side chain, and having at least one
active hydrogen group.
[0149]
For the polyoxyethylene group-containing active hydrogen compound, for example,
polyethylene glycol (e.g., number average molecular weight 200 to 6000, preferably 300 to
3000), one-end-terminated polyoxyethylene glycol (e.g., alkoxyethylene glycol with its one end
capped with an alkyl group having 1 to 4 carbon atoms, number average molecular weight 200 to
6000, preferably 300 to 3000), and a polyoxyethylene side chain-containing polyol are used.
[0150]
The polyoxyethylene side chain-containing polyol is a compound containing a
polyoxyethylene group in its side chain and having two or more active hydrogen groups, and can
be synthesized in the following manner.
[0151]
Specifically, first, a urethane-forming reaction is performed by mixing diisocyanate
(described later) and a one-end-capped polyoxyethylene glycol (e.g., alkoxy ethylene glycol of
which the terminal is capped with an alkyl group of 1 to 4 carbon atoms, having a number
average molecular weight of200 to 6000, or preferably 300 to 3000) at such a ratio that the
amount of the isocyanate group in the diisocyanate (described later) exceeds the amount of the
hydroxyl group in the one-end-capped polyoxyethylene glycol, and, if necessary, unreacted
diisocyanate (described later) is removed from the mixture, to thereby obtain a polyoxyethylene
chain-containing monoisocyanate.
28/65
[0152]
Subsequently, a urea-forming reaction is performed by mixing the polyoxyethylene
chain-containing monoisocyanate and dialkanolamine (e.g., diethanolamine) at such a ratio that
the amount of the isocyanate group in the polyoxyethylene group-containing monoisocyanate is
nearly equal to the amount of the secondary amino group in the dialkanolamine.
[0153]
For the diisocyanate for producing a polyoxyethylene side chain-containing polyol, it is
not particularly limited, and a known diisocyanate may be used. Examples of the diisocyanate
include, to be more specific, aliphatic diisocyanates such as pentamethylenediisocyanate
(PDI)(including pentamethylenediisocyanate of the present invention), and hexamethylene
diisocyanate (HDI); and alicyclic diisocyanates such as 1, 4- or 1, 3-
bis(isocyanatomethyl)cyclohexane (H6XDI), 3-isocyanatomethyl-3, 5, 5-trimethyl
cyclohexylisocyanate (also known as isophorone diisocyanate (IPDI)), 4, 4'-methylene
bis(cyclohexylisocyanate) (H12MDI) and 2, 6-bis(isocyanatomethyl)norbornane (NBDI).
[0154]
For the polyoxyethylene group-containing active hydrogen compound, furthermore,
for example, monohydric alcohol to which ethylene oxide is added (e.g.,
polyoxyethylenelaurylether, polyoxyethyleneoleylether, polyoxyethylenestearylether, etc.),
polyoxyethylene-containing sorbitan esters (e.g., polyoxyethylenesorbitan oleate,
polyoxyethylenesorbitan ricinoleate, polyoxyethylenesorbitan oleate, etc.), polyoxyethylenecontaining
alkyl phenols (e.g., polyoxyethyleneoctylphenolether,
polyoxyethylenenonylphenolether, etc.), and polyethylene glycol-containing higher fatty acid
esters (e.g., polyethylene glycollaurate, polyethylene glycol oleate, polyethylene glycolstearate,
etc.) are used.
[0155]
The polyisocyanate composition of the present invention can also be used as a blocked
isocyanate in which free isocyanate groups contained in the molecule are blocked by a blocking
agent.
[0156]
The blocked isocyanate can be produced, for example, by allowing the polyisocyanate
29/65
composition to react with the blocking agent.
[0157]
Examples of the blocking agent include an oxime, phenol, alcohol, imine, amine,
carbamic acid, urea, imidazole, imide, mercaptan, active methylene, acid amide (lactam), and
bisulfites blocking agent.
[0158]
Examples of the oxime blocking agent include formaldoxime, acetaldoxime, methyl
ethyl ketone oxime, cyclohexanoneoxime, acetoxime, diacetyl monoxime, benzophenone oxime,
2, 2, 6, 6-tetramethylcyclohexanoneoxime, diisopropylketoneoxime, methyltertbutylketoneoxime,
diisobutylketoneoxime, methylisobutylketoneoxime,
methylisopropylketoneoxime, methyl 2, 4-dimethylpentylketoneoxime, methyl 3-
ethylheptylketoneoxime, methyl isoamyl ketoneoxime, n-amylketoneoxime, 2, 2, 4, 4-
tetramethyl-1, 3-cyclobutanedionemonoxime, 4, 4'-dimethoxybenzophenoneoxime, and 2-
heptanoneoxime.
[0159]
Examples of the phenol blocking agent include phenol, cresol, ethyl phenol, npropylphenol,
isopropylphenol, n-butylphenol, sec-butylphenol, tert-butylphenol, n-hexylphenol,
2-ethylhexylphenol, n-octylphenol, n-nonylphenol, di-n-propylphenol, diisopropylphenol,
isopropylcresol, di-n-butylphenol, di-sec-butylphenol, di-tert-butylphenol, di-n-octylphenol, di-
2-ethylhexylphenol, di-n-nonylphenol, nitrophenol, bromophenol, chlorophenol, fluorophenol,
dimethylphenol, styrenated phenol, methylsalicylate, 4-hydroxybenzoic acid methyl ester, 4-
hydroxybenzoic acid benzyl ester, hydroxybenzoic acid 2-ethylhexyl ester, 4-[(dimethylamino)
methyl]phenol, 4-[(dimethylamino) methyl]nonylphenol, bis(4-hydroxyphenyl) acetic acid,
pyridinol, 2- or 8-hydroxyquinoline, 2-chloro-3-pyridinol, and pyridine-2-thiol.
[0160]
Examples of the alcohol blocking agent include, for example, methanol, ethanol, 2-
propanol, n-butanol, sec-butanol, 2-ethylhexylalcohol, 1- or 2-octanol, cyclohexylalcohol,
ethylene glycol, benzylalcohol, 2, 2, 2-trifluoroethanol, 2, 2, 2-trichloroethanol, 2-
(hydroxyrnethyl) furan, 2-methoxyethanol, methoxypropanol, 2-ethoxyethanol, npropoxyethanol,
2-butoxyethanol, 2-ethoxyethoxyethanol, 2-ethoxybutoxyethanol,
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butoxyethoxyethanol, 2-ethylhexyloxyethanol, 2-butoxyethylethanol, 2-butoxyethoxyethanol,
N,N-dibutyl-2-hydroxyacetamido, N-hydroxysuccinimide, N-morpholine ethanol, 2, 2-dimethyl-
1, 3-dioxolane-4-methanol, 3-oxazolidine ethanol, 2-hydroxymethylpyridine, furfuryl alcohol,
12-hydroxystearic acid, triphenylsilanol, and methacrylic acid 2-hydroxyethyl ester.
[0161]
Examples of the imine blocking agent include ethyleneimine, polyethyleneimine, 1, 4, 5,
6-tetrahydropyrimidine, and guanidine.
[0162]
Examples of the amine blocking agent include dibutylamine, diphenylamine, aniline, Nmethylaniline,
carbazole, bis(2, 2, 6, 6-tetramethylpiperidinyl) amine, di-n-propylamine,
diisopropylamine, isopropylethylamine, 2, 2, 4-, or 2, 2, 5-trimethylhexamethyleneamine, Nisopropylcyclohexylamine,
dicyclohexylamine, bis(3, 5, 5-trimethylcyclohexyl) amine,
piperidine, 2, 6-dimethylpiperidine, 2, 2, 6, 6-tetramethy1piperidine, (dimethyl amino )-2, 2, 6, 6-
tetramethylpiperidine, 2, 2, 6, 6-tetramethyl-4-piperidine, 6-methyl-2-piperidine, and 6-
aminocaproic acid.
[0 163]
Examples of the carbamic acid blocking agent include N-phenylcarbamate phenyl.
[0164]
Examples of the urea blocking agent include urea, thiourea, and ethyleneurea.
[0 165]
Examples of the imidazole blocking agent include imidazole, 2-methylimidazole, 2-
ethyl-4-methylimidazole, 2-isopropyl imidazole, 2, 4-dimethylimidazole, 4-methylimidazole, 2-
phenylimidazole, 4-methyl-2-phenylimidazole, pyrazole, 3-methylpyrazole, 3, 5-
dimethylpyrazole, 1, 2, 4-triazole, and benzotriazole.
[0 166]
Examples of the imide blocking agent include succinimide, maleimide, and phthal imide.
[0167]
Examples of the mercaptan blocking agent include butyl mercaptan, dodecylmercaptan,
and hexylmercaptan.
[0168]
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Examples of the active methylene blocking agent include Meldrum's acid, malonic acid
dimethyl ester, methyl acetoacetate, ethyl acetoacetate, malonic acid di-tert-butyl ester, malonic
acid 1-tert-butyl 3-methyl ester, malonic acid diethyl ester, acetoacetic acid tert-butyl ester, 2-
acetoacetoxyethylmethacrylate, acetylacetone, and cyanoethyl acetate.
[0 169]
Examples of the acid amide (lactam) blocking agent include acetanilide, Nmethylacetamide,
acetic acidamide, s-caprolactam, 8-valerolactam, y-butyrolactam, pyrrolidone,
2, 5-piperazine dione, and laurolactam.
[0170]
The blocking agent is not limited to the above, and for example, other blocking agents
such as benzoxazolone, isatoic acid anhydride, and tetrabutylphosphonium·acetate can be used.
[0171]
These blocking agent can be used singly, or can be used in combination of two or more.
[0172]
As the blocking agent, those blocking agents that dissociate at preferably 200°C or less,
preferably 100 to 180°C are used. To be more specific, for example, active methylene
compounds such as ethyl acetoacetate, or oximes such as methyl ethyl ketone oxime are used.
[0173]
The blocked isocyanate can be obtained by blending a polyisocyanate composition with
a blocking agent at a proportion such that the blocking agent is excessive relative to the
isocyanate group in the polyisocyanate composition, and then allowing the mixture to react
under known conditions.
[0174]
The polyisocyanate composition of the present invention can be used as an aqueous
blocked isocyanate in which free isocyanate groups are blocked by a blocking agent, and which
is dispersed or dissolved in water.
[0175]
The method for producing the aqueous blocked isocyanate is not particularly limited,
but for example, the following method can be used: first, a polyisocyanate composition (in the
following, referred to as partly blocked isocyanate) is produced, in which a portion of the free
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isocyanate group is blocked by a blocking agent, and thereafter, the free isocyanate groups
(remained isocyanate group without being blocked by the blocking agent) of the partly blocked
isocyanate is allowed to react with the above-described hydrophilic group-containing active
hydrogen compound.

Claims
1. A polyisocyanate composition comprising at least a pentamethylenediisocyanate derivative,
wherein the polyisocyanate composition contains 5 mass% or more and 95 mass% or less of a
uretdione derivative composed of an isocyanate bimolecular-product of
pentamethylenediisocyanate.
2. The polyisocyanate composition of Claim I, containing 10 mass% or more and 95 mass% or
less of the uretdione derivative composed of an isocyanate bimolecular-product of the
pentamethylenediisocyanate,
3. The polyisocyanate composition of Claim 1, wherein in a cliromatogram of the
polyisocyanate composition in gel permeation chroinalograph measurement, the ratio of the peak
area having a peak top between 280 to 490 of polyethylene glycol-bascd molecular weight
relative to a total peak area is 50% or more 80% or less,
4. The polyisocyanate composition of Claim 1, containing 3 mass% or more and 20 mass% or
less of an isocyanate quadmolccular-product of the pentamethylenediisocyanate.
5. The polyisocyanate composition of Claim 1, containing 10 mass% or more and 55 mass% or
less of an isocyanate trimolecular-product of pentamethylenediisocyanate.
6. Polyurethane resin comprising a reaction product of the polyisocyanate composition of
Claim 1 and an active hydrogen group-containing compound.
7. A method for producing polyurethane resin, the method including allowing the
polyisocyanate composition of Claim 1 to react with an active hydrogen group-containing
compound,
8. A coating comprising the polyurethane resin of Claim 6.