SPECIFICATION
AQUEOUS POLYURETHANE RESIN DISPERSION AND PREPARATION
PROCESS FOR THE SAME
5
TECHNICAL FIELD
[OOO 11
The present invention relates to an aqueous urethane resin dispersion
comprising at least a polyurethane resin and a radically polymerizable compound, and a
10 preparation process for the same, and a use thereof.
BACKGROUND ART
[0002]
Polycarbonate polyol is a usehl compound as a raw material for preparing, by
15 reaction with an isocyanate compound, a polyurethane resin which is used for a rigid
foam, flexible foam, paint, adhesive, synthetic leather, ink binder and the like.
Furthermore, a paint film obtained by coating an aqueous polyurethane resin dispersion
in which polycarbonate polyol is used as a raw material, is known to be excellent in
light resistance, heat resistance, hydrolysis resistance and oil resistance (see Patent .
20 Document 1).
[0003]
Among them, a paint film obtained by coating an aqueous urethane resin
dispersion in which an aliphatic polycarbonate polyol is used, is known to be used as an
undercoating agent because adhesion to a substrate and blocking resistance are
25 improved thereby (see Patent Document 2). When an aliphatic polycarbonate polyol
was solely used as a raw material, however, there occurred a problem that the hardness
of the paint films obtained from an aqueous polyurethane resin dispersion was not
sufficient in the field of paint or in the field of coating agents for outer panels etc. of
aircrafts/automobiles and external wall surfaces, flooring materials, etc. of houses.
30 [0004]
In order to improve the hardness of paint films, aqueous polyurethane resin
dispersions in which a polycarbonate polyol having an alicyclic structure is used are
generally proposed (see Patent Documents 3, 4 and 5), but when a polycarbonate polyol
having an alicyclic structure is used, dispersibility in an aqueous medium is poor, which,
35 in turn, results in the problem that handleability and stability of the resultant aqueous
polyurethane resin dispersions are affeced. Although there exist examples of aqueous
polyurethane resin dispersions in which a polycarbonate polyol having an alicyclic
structure was used, like, for example, Patent Document 3, no influence on hardness was
clarified in this document, and dispersibility in an aqueous medium was also not
satisfactory.
5 [0005]
Furthermore, aqueous polyurethane resin dispersions in which polycarbonate
diol having an alicyclic structure was used, were poor in drying property, and there was
a problem that hardness was not enough depending on the drying conditions.
Furthermore, when drying hours were prolonged, there occurred the problem that the
10 entire painting step was prolonged, and when the drying temperature was raised, there
occurred the problem that there were cases where substrates were affected.
[0006]
As a method to lower the drying temperature of aqueous polyurethane resin
dispersions, there is known a method of forming a paint film at a low drying
15 temperature comprising introducing a photo-curable component in urethane, and
photocuring the mixture. Some examples have been reported where this technique was
applied to an aqueous polyurethane resin dispersion derived from polycarbonate. The
first method is a method of reacting a compound containing at least one isocyanate
reactive group with at least one free-radically polymerizable unsaturated group so as to
20 introduce a polymerizable unsaturated bond to an urethane terminal during synthesis of
polyurethane (see Patent Document 6). The aqueous polyurethane resin dispersion
obtained by this method, however, has the defects that the molecular weight was small
and that the physical properties of the paint film before photoirradiation were low.
[0007]
2 5 The second method is a method of obtaining a water dispersion by dispersing a
compound containing a free-radically polymerizable unsaturated group into an aqueous
polyurethane resin dispersion having a high molecular weight, using a surfactant (see
Patent Document 7). Since radically polymerizable compounds also exhibit excellent
curing property in the other methods than heating, they are generally recognized as
30 advantageous also in terms of productivity and energy conservation, and in the light of
such properties, they are used as an active component for various coatings including
metal paints, overcoating agents for various plastic films, wood paints and printing inks
as well as adhesives. In this method as well, adhesion, chemical resistance,
contamination resistance and elasticity in these applications are improved. In specific
3 5 combinations, however, there was a problem that hardness after curing of such
compositions was not sufficient, and since a surfactant was used, there was also a
problem that the surfactant remaining in a paint film was able to lower the paint film
performance.
[0008]
[Patent Documents 11 Japanese Laid-open Patent [Kokai] Publication No. Hei
5 10-120757
[Patent Documents 21 Japanese Laid-open Patent [Kokai] Publication No. 2005-281544
[Patent Documents 31 Japanese Laid-open Patent [Kokai] Publication No. Hei 6-248046
[Patent Documents 41 Patent Application No. 2008-140474
[Patent Documents 51 Patent Application No. 2008-1 80856
10 [Patent Documents 61 Japanese Laid-open Patent [Kohyo] Publication 2008-534710
[Patent Documents 71 Japanese Laid-open Patent [Kokai] Publication No. 2008-248014
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
15 [0009]
The object of the invention is to obtain an aqueous polyurethane resin
dispersion having a good dispersibility in an aqueous medium and being capable of
forming a paint film excellent in strength when cured by ultraviolet light. Furthermore,
the object of the invention is to obtain an aqueous polyurethane resin dispersion capable
20 of providing a paint film being excellent in drying property and having a high hardness
and a scratch resistance.
Means for Solving the Problem
[OO lo]
25 As a result of intensive and extensive studies for overcoming the
aforementioned problems in conventional techniques, the inventors have found that the
objects can be achieved by an aqueous polyurethane resin dispersion containing a
polyurethane resin and a radically polymerizable compound, wherein a polycarbonate
polyol was used as a raw material of the polyurethane resin.
30 [OOll]
The invention (1) relates to an aqueous polyurethane resin dispersion
containing at least a polyurethane resin and a radically polymerizable compound (C),
wherein the polyurethane resin is a polyurethane resin obtained by reacting at
least a polycarbonate polyol (a); an acidic group-containing polyol (b); and an optional
35 polyol (c) other than (a) and (b), with a polyisocyanate (d), and optionally hrther
reacting with a chain extender (El).
The invention (2) relates to an aqueous polyurethane resin dispersion of the
invention (I), wherein the polycarbonate polyol (a) includes a polycarbonate polyol
having an alicyclic structure in the main chain (al).
The invention (3) relates to an aqueous polyurethane resin dispersion of the
5 invention (2), wherein the content percentage of the alicyclic structure in the
polycarbonate polyol (a) is 20 to 65 wt %.
The invention (4) relates to an aqueous polyurethane resin dispersion of any of
the inventions (1) to (3), wherein the radically polymerizable compound (C) is a
(meth)acrylate compound.
10 The invention (5) relates to an aqueous polyurethane resin dispersion of any of
the inventions (I) to (4), wherein the radically polymerizable compound (C) includes a
compound having a polyalkylene glycol structure.
The invention (6) relates to an aqueous polyurethane resin dispersion of any of
the inventions (1) to (5), wherein the radically polymerizable compound (C) includes a
15 bifunctional (meth)acrylate compound (Cl) and a tri- or more-functional (meth)acrylate
compound (C2).
The invention (7) relates to an aqueous polyurethane resin dispersion of any of
the inventions (1) to (6), wherein the content of the radically polymerizable compound
(C) is 10 to 50 wt % based on 100 wt % of the total solid content of the aqueous
20 polyurethane resin dispersion.
The invention (8) relates to an aqueous polyurethane resin dispersion of any of
the inventions (1) to (7), substantially containing no protective colloid, emulsifier, nor
surfactant.
The invention (9) relates to an aqueous polyurethane resin dispersion of any of
25 the inventions (1) to (8), wherein the polyurethane resin is a polyurethane resin obtained
by reacting at least a polycarbonate polyol (a); an acidic group-containing polyol (b);
and an optional polyol (c) other than (a) and (b), with a polyisocyanate (d) to afford a
polyurethane prepolymer having no free-radically polymerizable unsaturated group, and
further reacting with a chain extender (B).
30 The invention (10) relates to an aqueous polyurethane resin dispersion of any
of the inventions (1) to (1 O), further containing a photo-initiator.
The invention (1 1) relates to a paint composition, containing an aqueous
polyurethane resin dispersion of any of the inventions (1) to (10).
The invention (12) relates to a coating agent composition, containing an
35 aqueous polyurethane resin dispersion of any of the inventions (1) to (10).
The invention (13) relates to a process for preparing an aqueous polyurethane
resin dispersion of any of the inventions (I) to (10) comprising:
the step (al) of reacting a polycarbonate polyol (a), an acidic group-containing
polyol (b), and an optional polyol (c) other than (a) and (b), with a polyisocyanate (d) to
afford a polyurethane prepolymer (A),
5 the step (j3) of neutralizing the acidic group of the polyurethane prepolymer
(A),
the step (y) of dispersing the polyurethane prepolymer (A) and a radically
polymerizable compound (C) in an aqueous medium, and
the step (6) of reacting the polyurethane prepolymer (A) with a chain extender
10 (B) which is reactive to the isocyanate groups of the polyurethane prepolymer (A) to
afford an aqueous polyurethane resin.
Effect of the Invention
[OO 1 21
15 According to the present invention, provided are an aqueous polyurethane resin
dispersion having a good dispersibility in an aqueous medium and being capable of
forming a paint film excellent in strength when cured by ultraviolet light, and a
preparation process of the same. Furthermore, according to the present invention, an
aqueous polyurethane resin dispersion being capable of providing a paint film being
20 excellent in drying property, having a high hardness and a scratch resistance as well as a
preparation process of the same are provided. The aqueous polyurethane resin
dispersion of the invention can be a raw material for a paint, a coating agent and a paint
composition.
25 BEST MODE FOR CARRYING OUT THE INVENTION
[00 131
The invention relates to an aqueous polyurethane resin dispersion containing at
least a polyurethane resin and a radically polymerizable compound,
wherein the polyurethane resin is a polyurethane resin obtained by reacting at
30 least a polycarbonate polyol (a), an acidic group-containing polyol (b) with a
polyisocyanate (d), and optionally fbrther reacting with a chain extender,
and the invention relates to the aqueous polyurethane resin dispersion, wherein
the polyurethane resin is a polyurethane resin obtained by reacting at least a
polycarbonate polyol (a); an acidic group-containing polyol (b); and a polyol (c) other
35 than (a) and (b) with a polyisocyanate (d), and optionally fbrther reacting with a chain
extender (B).
[00 141
I. Polycarbonate polyol (a)
The polycarbonate polyol (a) (hereinafter also referred to as "(a)") used in the
invention is not particularly limited, and it is obtained by carbonate-binding a polyol
5 with a polyol, and it may contain in its molecule an ester bond and the like. The
number average molecular weight of the polycarbonate polyol (a) is not particularly
limited, and the number average molecular weight is preferably 400 to 8000. When
the number average molecular weight is in this range, suitable viscosity and favorable
handleability can easily be attained. Furthermore, performance as a soft segment can
10 easily be ensured, and when a paint film is formed using a resultant aqueous
polyurethane resin dispersion, occurrence of cracking can easily be inhibited, and
firtherrnore, the polycarbonate polyol (a) is filly reactive to an isocyanate compound
(c) to produce an urethane prepolymer efficiently. The number average molecular
weight of the polycarbonate polyol (a) is more preferably 400 to 4000.
15 [0015]
In the invention, the number average molecular weight refers to a number
average molecular weight calculated based on a hydroxyl value measured according to
JIS K 1577. Specifically, a hydroxyl value is measured, and then the number average
molecular weight is calculated according to a terminal-group analysis using (56.1 x
20 1000 x valence)/hydroxyl value (mgKOWg). In this formula, valence refers to the
number of hydroxyl groups in one molecule, and when the polycarbonate polyol is
polycarbonate diol, the valence is 2.
[OO 161
The polycarbonate polyol (a) can be obtained, for example, by reacting one or
25 more polyols with a carbonic acid ester or phosgene. Polycarbonate polyols obtained
by reacting one or more polyols with a carbonic acid ester are preferable because of
easiness in production and no subgeneration of terminal chlorinated product.
[OO 171
The polyol is not particularly limited and includes, for example, aliphatic
30 polyols, polyols having an alicyclic structure, aromatic polyols, polyester polyols and
polyetherpolyols. Herein, the alicyclic structure includes those having a heteroatom
such as oxygen atom and nitrogen atom in the ring.
[OO 1 81
The aliphatic polyol is not particularly limited and includes, for example,
35 aliphatic polyols having a carbon number of 3 to 12. Specifically, it includes linear
aliphatic diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,
1,7-heptanediol, 1,s-octanediol and 1,9-nonanediol; branched aliphatic diols such as
2-methyl-1,3-propanediol, 2-methyl-1,5-pentanediol,3- methyl-1,5-pentanediol,a nd
2-methyl-1,9-nonanediol; and tri-or more fbnctional polyalcohols such as
1,1,1 -trimethylolpropane and pentaerythritol.
5 [0019]
The polyol having an alicyclic structure is not particularly limited and includes,
for example, polyols having in the main chain an alicyclic group with a carbon number
of 5 to 12. Specifically, there can be mentioned diols having an alicyclic structure in
the main chain such as structural isomers or mixtures thereof of 1,4-cyclohexane
10 dimethanol, 1,3-cyclohexane dimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol,
1,4-cycloheptanediol, 2,5-bis(hydroxymethy1)-1,4-dioxane, 2,7-norbornanediol,
tetrahydrofbrandimethanol, 1,4-bis(hydroxyethoxy)cyclohexane, and
tricyclodecanedimethanols represented by tricyclo[5.2.1 .~~>~]decanedimethanol.
Among them, 1,4-cyclohexane dimethanol is preferable because of availability.
15 [0020]
The aromatic polyol is not particularly limited and includes, for example,
1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol,
4,4'-naphthalendimethanol and 3,4'-naphthalendimethanol.
[002 11
20 The polyester polyol is not particularly limited 'and includes, for example,
polyester polyols of a hydroxy carboxylic acid and a diol, such as a polyester polyol of
6-hydroxy caproic acid and hexanediol, and polyester polyols of a dicarboxylic acid and
a diol such as a polyester polyol of adipic acid and hexanediol.
[0022]
25 The polyether polyol is not particularly limited and includes, for example,
polyethylene glycols (e.g., diethylene glycol, triethylene glycol and tetraethylene
glycol) and polyalkylene glycols such as polypropylene glycol and polytetramethylene
glycol.
100231
3 0 The carbonic acid ester is not particularly limited and includes, for example,
aliphatic carbonic acid esters such as dimethyl carbonate and diethyl carbonate;
aromatic carbonic acid esters such as diphenyl carbonate; cyclic carbonic acid esters
such as ethylene carbonate. In addition, phosgene and the like capable of producing a
polycarbonate polyol can also be used. Among them, aliphatic carbonic acid ester is
35 preferable and dimethyl carbonate is particularly preferable because of easiness in
production of the polycarbonate polyols.
[0024]
As the process for producing a polycarbonate polyol from the polyol and
carbonic acid ester, there can be mentioned, for example, a method comprising adding
in a reactor a carbonic acid ester and a polyol of an excessive mole number with respect
5 to the mole number of the carbonic acid ester, reacting them at a temperature of 160 to
200°C and at a pressure of around 50 mmHg for 5 to 6 hours, and hrther at a pressure
of several mmHg or less at 200 to 220°C for several hours. In the reaction, it is
preferred that the reaction be carried out while subgenerated alcohol is being taken out
from the system. At this time, if carbonic acid ester is gone out of the system by an
10 azetropic reaction with subgenerated alcohol, an excessive amount of carbonic acid
ester may be added. Furthermore, a catalyst such as titanium tetrabutoxide may be
used in the reaction.
[0025]
It is preferred that a polycarbonate polyol having an alicyclic structure in the
15 main chain (al) (hereinafter also referred to as "polycarbonate polyol (al)" or "(al)") be
used as a polycarbonate polyol (a), since a resultant paint film is excellent in drying
property and has a high hardness. Among them, the polycarbonate polyol having an
alicyclic structure in the main chain (al) preferably has a number average molecular
weight of 400 to 3000, more preferably 400 to 2000, and particularly preferably 500 to
20 1000.
[0026]
The polycarbonate polyol having an alicyclic structure in the main chain (al)
includes, for example, a polycarbonate polyol obtained by reacting a polyol having an
alicyclic structure in the main chain with a carbonic acid ester; and a copolymerized
25 polycarbonate polyol obtained by reacting a polyol having an alicyclic structure in the
main chain and another polyol (a polyol having no alicyclic structure in the main chain)
with a carbonic acid ester. In view of dispersibility of the aqueous dispersion, a
copolymerized polycarbonate polyol in which the polyol having no alicyclic structure in
the main chain is used in combination is preferable. As the the polyol having no
30 alicyclic structure in the main chain, an aliphatic polyol, an aromatic polyol, a polyester
polyol and a polyether polyol may be used, and the above-mentioned specific examples
are applicable. Among them, combinations of a polyol having an alicyclic structure in
the main chain and an aliphatic polyol are preferable, and a copolymerized
polycarbonate polyol obtained by using 1,4-cyclohexanedimethanol and 1,6-hexanediol
35 in combination is particularly preferable.
[0027]
When the polycarbonate polyol having an alicyclic structure in the main chain
(al) is used, the alicyclic structure-content percentage in the polycarbonate polyol (a) is
preferably 20 to 65 wt %. As long as it is in this range, because of the presence of the
alicyclic structure, a paint film excellent in hardness can easily be obtained, while
5 situations where the alicyclic structure-content percentage is too large and the viscosity
of the prepolymer at the time of manufacture of the aqueous polyurethane resin
dispersion is too high, resulting in difficulty in handling, are likely to be avoided. The
alicyclic structure-content percentage is more preferably 30 to 55 wt %.
[0028]
10 Here, the "alicyclic structure-content percentage" refers to the weight
proportion of an alicyclic group in the polycarbonate polyol (a). It refers to a value
calculated based, for instance, on a cycloalkane residue such as a cyclohexane residue
(in the case of 1,4-hexanedimethanol, the portion of cyclohexane from which two
hydrogens atoms are removed), or on an unsaturated heterocycle residue such as a
15 tetrahydrofuran residue (in the case of tetrahydrofurandimethanol, the portion of
tetrahydrofuran from which two hydrogens atoms are removed).
[0029]
The polycarbonate polyol (a) may be used alone or as a combination of plural
types thereof. For example, a polycarbonate polyol having an alicyclic structure in the
20 main chain (al) may be used alone, or a polycarbonate polyol having an alicyclic
structure in the main chain (al) and a polycarbonate polyol other than that may be used
in combination.
[0030]
The above-mentioned polycarbonate polyol other than (al) which can be used
25 in combination with a polycarbonate polyol having an alicyclic structure in the main
chain (al) is not particularly limited, and specifically mentioned are an aliphatic
polycarbonate diol such as polytetramethylene carbonatediol, polypentamethylene
carbonatediol and polyhexamethylene carbonatediol; an aromatic polycarbonate diol
such as poly 1,4-xylylene carbonatediol; a polycarbonate diol as a reaction product of
30 plural types of aliphatic diols with a carbonic acid ester; a copolymerized polycarbonate
diol of a polycarbonate diol as a reaction product of an aliphatic diol, an aromatic diol
with a carbonic acid ester, and a polycarbonate diol as a reaction product of an aliphatic
diol, a dimer diol with a carbonic acid ester; and the like. For example, a combination
use of a polycarbonate polyol having an alicyclic structure in the main chain (al) and an
35 aliphatic polycarbonate polyol may be mentioned.
[003 11
11. Acidic group-containing polyol (b)
The acidic group-containing polyol (b) (hereinafter also referred to as "(b)")
used in the invention is not particularly limited, as long as it contains two or more
hydroxyl groups and one or more acidic groups in a molecule. As the acidic group,
5 carboxy groups, sulfone acid groups, phosphate groups and phenolic hydroxyl groups
may be metnioned. In particular, as the acidic group-containing polyol (b), those
containing a compound having two hydroxyl groups and one carboxy group in a
molecule are preferable. The acidic group-containing polyol (b) may be used alone or
as a combination of plural types thereof.
10 [0032]
As the acidic group-containing polyol (b), specifically mentioned are: dialkanol
alkane acids including dimethylol alkane acids such as 2,2-dimethylolpropionic acid
and 2,2-dimethylol butanoic acid; N,N-bishydroxyethyl glycine, N,N-bishydroxyethyl
alanine, 3,4-dihydroxy butane sulfonic acid, 3,6-dihydroxy-2-toluene sulfonic acid,
15 acidic group-containing polyether polyols and acidic group-containing polyester polyols.
Among them, in view of availability, dialkanol alkane acids containing two alkanol
groups are preferable, and alkane acids having a carbon number of 4 to 12 and
containing two methyl01 groups (dimethylol alkane acid) are more preferable, and
among the dimethylol alkane acid, 2,2-dimethylolpropionic acid is particularly
20 preferable.
[0033]
111. Polyol (c) (a polyol other than (a) and (b))
In addition to the polycarbonate polyol (a) and the acidic group-containing
polyol (b), a polyol (c) (hereinafter also referred to as "polyol (c)" or "(c)") can be used.
25 As the polyol (c), a high molecular polyol such as a polymeric polyol and a low
molecular polyol can be mentioned. As the high molecular polyol, those having a
number average molecular weight of 400 to 4000 are included. The polyol may be a
diol or a trivalent or more polyalcohol. The polyol (c) may be used alone or as a
combination of plural types thereof. In view of the fact that the hardness of the paint
30 film is greater, a low molecular polyol is preferable, and among them, a low molecular
diol is preferable.
[0034]
The polymer polyol is not particularly limited, and polyester polyol, polyether
polyol, acryl polyol and polydiene polyol can suitably be used.
35 [0035]
The polyester polyol is not particularly limited and includes, for example,
polyethylene adipate polyol, polybutylene adipate polyol, polyethylene butylene adipate
polyol, polyhexamethylene isophthalate adipate polyol, polyethylene succinate polyol,
polybutylene succinate polyol, polyethylene sebacate polyol, polybutylene sebacate
polyol, poly-s-caprolactone polyol, poly(3-methyl- 1,5-pentylene adipate)polyol, and a
5 polycondensate of 1,6-hexanediol and a dimer acid.
[003 61
The polyether polyol is not particularly limited and includes, for example,
polyethylene glycol, polypropylene glycol, polytetramethylene glycol, random
copolymers and block copolymers of ethylene oxide and propylene oxide, and ethylene
10 oxide and butylene oxide. Furthermore, polyether polyester polyol having an ether
bond and an ester bond, and the like can be used.
[003 71
The polydiene polyol is not particularly limited and includes polydiene polyols
containing a unit derived from butadiene, isoprene, 1,3-pentadiene, chloroprene,
15 cyclopentadiene or the like. Specific examples of the polydiene polyol includes, for
example, hydroxyl group-terminated liquid polybutadiene ("Poly bd" manufactured by
Idemitsu Kosan Co., Ltd.), bifunctional hydroxyl group-terminated liquid polybutadiene
("KRASOL" manufactured by Idemitsu Kosan Co., Ltd.), hydroxyl group-terminated
liquid polyisoprene ("Poly ip" manufactured by Idemitsu Kosan Co., Ltd.), and
20 hydroxyl group-terminated liquid polyolefin ("Epol" manufactured by Idemitsu Kosan
Co., Ltd.).
[003 81
The polyacryl polyol is not particularly limited and includes, for example,
polyacryl polyols obtained by polymerizing
25 one selected from the group consisting of
acrylates having an active hydrogen such as 2-hydroxyethyl acrylate,
2-hydroxypropyl acrylate and 2-hydroxybutyl acrylate; or acryl acid monoester or
methacrylic acid monoester of glycerine; acryl acid monoester or methacrylic acid
monoester of trimethylolpropane; or a mixture thereof;
3 0 and
one selected from the group consisting of
acrylates such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl
acrylate and 2-ethylhexyl acrylate; methacrylates having an active hydrogen such as
2-hydroxyethyl methacrylate, Zhydroxypropyl methacrylate, 2-hydroxybutyl
35 methacrylate, 3-hydroxypropyl methacrylate and 4-hydroxybutyl methacrylate; or
methacrylates such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate,
n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate and lauryl
methacrylate; or a mixture thereof,
in the presence or absence of one selected from the group consisting of
unsaturated carboxylic acid such as acryl acid, methacrylic acid, maleic acid
5 and itaconic acid;
unsaturated arnide such as acrylamide, N-methylolacrylamide and diacetone
acrylamide; and the other polymerizable monomers such as glycidyl methacrylate,
styrene, vinyl toluene, vinyl acetate, acrylonitrile and dibutyl fbmarate; or a mixture
thereof. As the polymerization method, emulsion polymerization, suspension
10 polymerization, dispersion polymerization, solution polymerization and the like can be
mentioned. In emulsion polymerization, polymerization can be made in a stepwise
manner.
[0039]
The low molecular polyol is not particularly limited and includes those having
15 a number average molecular weight of 60 or more and less than 400. For example,
there can be mentioned aliphatic diols having a carbon number of 2 to 9 such as
ethylene glycol, 1,3-propanediol, 2-methyl- l,3-propanediol,
2,2-dimethyl- 1,3 -propanediol, 2-butyl-2-ethyl- 1,3 -propanediol, 1,4-butanediol,
1,5-pentanediol, 3- methyl-1,5-pentanediol,1 ,6-hexanediol, 1,9-nonanediol,
20 2-methyl-1,s-octanediold, iethylene glycol, triethylene glycol and tetraethylene glycol;
diols having a carbon number of 6 to 12 and an alicyclic structure such as
1,4-cyclohexane dimethanol, 1,3 -cyclohexane dimethanol, 1,4-cyclohexanediol,
1,4-bis(hydroxyethyl)cyclohexane, 2,7-norbornanediol, tetrahydrofurandimethanol and
2,5-bis(hydroxymethy1)- 1,4-dioxane; and aromatic diols such as 1,4-benzene methanol,
25 1,3-benzene methanol and 1,4-dihydroxybenzene. Furthermore, as the low molecular
weight polyol, a low molecular weight polyalcohol such as trimethylolpropane,
pentaerythritol and sorbitol may be used.
[0040]
The ratio of a polyol (c) to a polycarbonate polyol (a) is preferably 40 wt % or
30 less. As long as it is in this range, problems including insufficient hardness of the
resultant paint film or difficulty in preparing a polyurethane resin water dispersion are
likely to be avoided. The proportion of a polyol (c) is more preferably 20 wt % or less.
IV. Hydroxyl equivalent of polyol component
[0041]
3 5 In the invention, the hydroxyl equivalent number in total of a polycarbonate
polyol (a), an acidic group-containing polyol (b) and an optional polyol (c) is preferably
100 to 500. As long as the hydroxyl equivalent number is in this range, the
manufacture of the aqueous polyurethane resin dispersion is easy, and a favorable
storage stability of the aqueous polyurethane resin dispersion and a paint film excellent
in hardness can easily be obtained. In view of hardness of the paint film, the hydroxyl
5 equivalent number is preferably 150 to 400, more preferably 180 to 300, and
particularly preferably 200 to 270.
[0042]
The hydroxyl equivalent number can be calculated using the following
formulae (1) and (2).
10 Hydroxyl equivalent number of each polyol = Molecular weight of each
polyol/Number of hydroxyl group of each polyol . . . (1)
Total hydroxyl equivalent number of polyols = Mltotal mole number of
polyols . . . (2)
In formula (2), M represents [{hydroxyl equivalent number of polycarbonate
15 polyol (a) x mole number of polycarbonate polyol (a)) + {hydroxyl equivalent number
of acidic group-containing polyol (b) x mole number of acidic group-containing polyol
(b)) + {hydroxyl equivalent number of a polyol (c) xmole number of a polyol (c))].
[0043]
V. Polyisocyanate (d)
20 The polyisocyanate (d) that can be used in the invention is not particularly
limited, and an aromatic polyisocyanate, an aliphatic polyisocyanate, an alicyclic
polyisocyanate and the like can be mentioned.
[0044]
As the aromatic polyisocyanate, specifically included are 1,3-phenylene
25 diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylenediisocyanate (TDI),
2,6-tolylenediisocyanate, 4,4'-diphenylmethane diisocyanate (MDI),
2,4-diphenylmethane diisocyanate, 4,4'-diisocyanate biphenyl,
3,3'-dimethyl-4,4'-diisocyanate biphenyl, 3,3'-dimethyl-4,4'-diisocyanate
diphenylmethane, 1,5-naphthylene diisocyanate, 4,4',4"-triphenylmethane triisocyanate,
30 m-isocyanate phenylsulfonyl isocyanate, and p-isocyanate phenylsulfonyl isocyanate.
[0045]
As the aliphatic polyisocyanate, specifically included are ethylene diisocyanate,
tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodeca methylene
diisocyanate, 1,6,11 -undecane triisocyanate, 2,2,4-trimethyl hexamethylene
35 diisocyanate, lysine diisocyanate, 2,6-diisocyanate methyl caproate, bis(2-isocyanate
ethyl)hmarate, bis(2-isocyanate ethy1)carbonate and 2-isocyanate
ethyl-2,6-diisocyanate hexanoate.
[0046]
As the alicyclic polyisocyanate, specifically included are isophorone
diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI),
5 cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenation TDI),
bis(2-isocyanate ethyl)-4-cyclohexene-1,2-dicarboxylate,2 ,5-norbornane diisocyanate,
2,6-norbornane diisocyanate.
[0047]
These polyisocyanate may be used alone or as a combination of plural types
10 thereof.
[0048]
While the aforementioned polyisocyanate typically has two isocyanate groups
per molecule, a polyisocyanate having three or more isocyanate groups such as
triphenylmethane triisocyanate may be used within the range where the polyurethane
15 resin in the invention does not gelate.
[0049]
Among the aforementioned polyisocyanates, in view of control of reaction,
provision of great hardness and strength, etc., 4,4'-diphenylenemethane diisocyanate
O I ) , isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate
20 (hydrogenated MDI) are preferable.
[0050]
VI. Polyurethane resin or polyurethane prepolymer (A)
The polyurethane resin in the invention is either a polyurethane resin obtained
by reacting at least a polycarbonate polyol (a), an acidic group-containing polyol (b)
25 with a polyisocyanate (d); or a polyurethane resin obtained by reacting a polycarbonate
polyol (a), an acidic group-containing polyol (b) with a polyisocyanate (d) to obtain a
polyurethane prepolymer (A), and further reacting this with a chain extender (B). The
polyurethane resin or polyurethane prepolymer (A) may be a polyurethane resin
obtained by reacting the polycarbonate polyol (a), the acidic group-containing polyol
30 (b), a polyol (c) with the polyisocyanate (d); or a polyurethane resin obtained by
reacting the polycarbonate polyol (a), the acidic group-containing polyol (b), a polyol
(c) with the polyisocyanate (d) to obtain a polyurethane prepolymer (A), and further
reacting this with a chain extender (B). In the case where a polyurethane resin is
obtained by reacting the polyurethane prepolymer (A) with the chain extender (B), the
35 reaction temperature of the polyurethane prepolymer (A) with the chain extender (B) is,
for example, 0 to 80°C, and preferably 0 to 60°C.
[005 11
When the polyurethane resin or polyurethane prepolymer (A) is prepared,
assuming that the polycarbonate polyol (a), the acidic group-containing polyol (b) and
an optional polyol (c) in total are 100 parts by weight, the ratio of the polycarbonate
5 polyol (a) is preferably 50 to 95 parts by weight, more preferably 70 to 92 parts by
weight, and particularly preferably 80 to 90 parts by weight; the ratio of the acidic
group-containing polyol (b) is preferably 5 to 25 parts by weight, more preferably 10 to
20 parts by weight, and particularly preferably 12 to 18 parts by weight; and the ratio of
the polyol (c) is preferably 0 to 40 parts by weight, more preferably 0 to 30 parts by
10 weight and particularly preferably 0 to 20 parts by weight. As long as the ratio of the
polycarbonate polyol (a) is in the above-mentioned range, reduction in hardness of the
resultant paint film can be inhibited, and a favorable film forming property can easily be
attained. As long as the ratio of the acidic group-containing polyol (b) is in the
above-mentioned range, the dispersibilit y of the resultant aqueous polyurethane resin
15 into an aqueous medium is favorable and a sufficient water resistance of the paint film
can easily be attained. As long as the ratio of the polyol (c) is in the above-mentioned
range, the ratio of the polycarbonate polyol (a) to the total polyol component will not be
relatively too small, or the ratio of the acidic group-containing polyol compound (b)
will not be relatively too small, and a favorable hardness of the paint film and
20 dispersibility of the aqueous polyurethane resin can easily be attained.
[0052]
When the polyurethane resin or polyurethane prepolymer (A) is prepared, the
ratio of the mole number of the isocyanate groups of the polyisocyanate (d) to the mole
number of the total hydroxyl groups of the polyol component consisting of the
25 polycarbonate polyol (a) and the acidic group-containing polyol (b), or the polyol
component consisting of the polycarbonate polyol (a), the acidic group-containing
polyol (b) and the polyol (c), is preferably 1.01 to 2.5. As long as it is in this range,
the following problems are likely to be avoided: because of the mole number of
hydroxyl groups of the polyol component being too large, polyurethane prepolymer (A)
30 having no isocyanate group at a molecular terminal is too much, and molecules which
do not react with a chain extender (B) are too many, causing reduction in strength of the
paint film obtained by coating the resultant aqueous polyurethane resin dispersion, and
also, because of the mole number of hydroxyl groups of the polyol component being too
small, a great amount of unreacted polyisocyanate (d) may remain in the reaction
35 system, and may react with a chain extender or with water to cause a molecular
elongation, with the result that the paint film obtained by coating the resultant aqueous
polyurethane resin dispersion has an uneven surface. The ratio of the mole number of
isocyanate groups of the polyisocyanate (d) with respect to the mole number of total
hydroxyl groups of the polyol component preferably is 1.2 to 2.2, and particularly
preferably 1.2 to 2.0.
5 [0053]
When the polyurethane resin or urethane prepolymer (A) is prepared, the
reaction of the polyol component comprising the polycarbonate polyol (a), the acidic
group-containing polyol (b), and a polyol (c) as needed, with the polyisocyanate (d),
may be conducted by reacting (a), (b) and (c) in any order with (d), or the plural types
10 of polyols may be mixed and then reacted with (d).
[0054]
When the polycarbonate polyol (a) and the acidic group-containing polyol (b)
and, the polyol (c) as needed are reacted with the polyisocyanate (d), a catalyst can be
used.
15 [0055]
The catalyst is not particularly limited and includes, for example, metals and
organic and inorganic acid salts such as tin-based catalysts (trimethyl tin laurate,
dibutyltin dilaurate or the like) or lead-based catalysts (lead octoate or the like), as well
as organometallic derivati~es~amine-basecda talysts (triethylamine, N-ethyl morpholin,
20 triethylene diamine and the like), and diazabicyclo undecene-based catalysts. Among
them, in view of reactivity, dibutyltin dilaurate are preferable.
[0056]
While the reaction temperature when reacting the polyol component with the
polyisocyanate is not particularly limited, 40 to 150°C are preferable. When the
25 reaction temperature is too low, the raw materials may not dissolve, and the viscosity of
the resultant urethane prepolymer (A) can be too high to stir sufficiently. When the
reaction temperature is too high, defects such as side reactions can occur. The reaction
temperature is more preferably 60 to 120°C.
[0057]
30 The reaction between the polycarbonate polyol (a) and the acidic
group-containing polyol (b) and the polyol (c) as needed, with the polyisocyanate (d),
can be made with no solvent or with an organic solvent. As the organic solvent,
acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofbran, dioxane,
dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N-ethyl pyrrolidone,
35 ethyl acetate and the like can be mentioned. Among them, acetone, methyl ethyl
ketone and ethyl acetate are preferable since they can be removed by heating and
decompression after dispersion of polyurethane prepolymer in water and a chain
extension reaction. Also, N-methylpyrrolidone and N-ethyl pyrrolidone are preferable
since they work as a film formation auxiliary when a paint film is prepared from the
resultant aqueous polyurethane resin dispersion. The amount of the organic solvent
5 added is preferably 0.1 to 2.0 times, and more preferably 0.15 to 0.7 times of the total
amount of the polycarbonate polyol (a), the acidic group-containing polyol (b), and the
polyol (c) as needed in terms of weight.
[0058]
In the invention, the acid value of the polyurethane resin or polyurethane
10 prepolymer (A) is preferably 10 to 55 mgKOWg. As long as it is in this range, a
favorable dispersibility in an aqueous medium and water resistance of the resultant paint
film can easily be attained. The acid value is more preferably 14 to 42 mgKOWg, and
even more preferably 18 to 35 mgKOWg.
[0059]
15 In particular, the acid value of the polyurethane resin or polyurethane
prepolymer (A) is an average content of acidic groups in a solid content excluding a
solvent used in preparing a polyurethane resin or polyurethane prepolymer (A) as well
as a neutralizer for dispersing the polyurethane prepolymer (A) in an aqueous medium,
and is determined by the weight of the polyolcarbonate polyol (a), the polyisocyanate
20 (d) and the acidic group-containing polyol (c), as well as the acidic groups contained in
the acidic group-containing polyol (c), and can be calculated by the formula below.
When an aqueous polyurethane resin dispersion of the invention is prepared by reacting
a polycarbonate polyol (a) and a polyisocyanate (d) with an acidic group-containing
polyol (c) to obtain a polyurethane prepolymer (A), followed by dispersing the
25 polyurethane prepolymer (A) in a water system solvent and causing a chain extension
using a chain extender (B), the above-mentioned acid value is a synonym of the acid
value of the polyurethane prepolymer (A).
[Mathematical Formula I]
Millimole number of Acid group-containing polyol compound x Molecular weight of KOH (56.1)
Acid value =
Total weight [g] of (a), (b), (c) and (d)
[0060]
30 In the invention, the polyurethane prepolymer (A) preferably has no
free-radically polymerizable unsaturated group because of the physical properties of the
resultant paint film before photoirradiation, in particularl, the tackfree time being short,
and preparation of urethane prepolymer being easy.
[006 11
VII. Chain extender (B)
The chain extender (B) of the invention is reactive to the isocyanate group of
the polyurethane prepolymer (A). As the chain extender, there can be mentioned, for
example, amine compounds such as ethylenediamine, 1,4-tetramethylenediamine,
5 2-methyl- 1 ,Spentanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine,
1,4-hexamethylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine,
1,3-bis(aminomethyl)cyclohexane, xylylenediamine, piperazine, 2,5-dimethylpiperazine,
hydrazine, adipoyldihydrazide, diethylenetriamine and triethylenetetramine; diol
compounds such as ethylene glycol, propylene glycol, 1,4-butanediol and
10 1,6-hexanediol; polyalkylene glycols represented by polyethylene glycol; and water,
and among them, preferred is primary diamine compounds. These may be used alone
or as a combination of plural types thereof
[0062]
The amount of the chain extender (B) is preferably an equivalent or less of the
15 isocyanate group which becomes the starting point of chain extension in the resultant
polyurethane prepolymer (A), and more preferably 0.7 to 0.99 equivalent of the
isocyanate group. When the chain extender (B) was added exceeding the equivalnent
of the isocyanate group, the molecular weight of the polyurethane polymer (A) after
chain extension decreases, and the strength of the paint film formed by coating the
20 resultant aqueous polyurethane resin dispersion decreases. The chain extender (B)
may be added after dispersion of the polyurethane prepolymer into water, or may be
added during the dispersion. The chain extension may be carried out with water. In
this case, water as a dispersion medium also functions as a chain extender.
[0063]
25 VIII. Radically polymerizable compound
While the radically polymerizable compound in the invention is not
particularly limited as long as it is polymerized in the copresence of a photoradical
generator or in the copresence of a thermal radical generator, it is preferable to use a
compound which does not react with an isocyanate group at 25"C, and a (meth)acrylate
30 compound is particularly preferable. The (meth)acrylate compound includes
(meth)acrylate compounds as a monomer, polyurethane (meth)acrylate compounds,
polyester (meth)acrylate based compounds, and polyalkylene (meth)acrylate based
compounds. (Meth)acrylate herein refers to acrylate and/or methacrylate.
[0064]
3 5 As the (meth)acrylate compounds as a monomer, mono(meth)acrylates and
poly(meth)acrylates such as mono(meth)acrylates; and di(meth)acrylates,
tri(meth)acrylates, tetra(meth)acrylates, penta(meth)acrylates and hexa(meth)acrylates
can be used.
100651
As the mono(meth)acrylates, for example, acryloyl morpholin,
5 2-ethylhexyl(meth)acrylate, styrene, methyl(meth)acrylate,
tetrahydrofUrfUryl(meth)acrylate, dodecyl(meth)acrylate, cyclohexyl(meth)acrylate,
dicyclopentenyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, dicyclopentenyloxy
ethyl(meth)acrylate, phenoxyethyl(meth)acrylate, isobornyl(meth)acrylate and
N-vinyl-2-pyrrolidone can be mentioned.
10 100661
As the di(meth)acrylates, for example, alkylene glycol di(meth)acrylate such as
ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol
di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate,
tricyclodecanedimethanol di(meth)acrylate and bisphenol A di(meth)acrylate; polyether
15 di(meth)acrylate such as polyethylene glycol di(meth)acrylate and polypropylene glycol
di(meth)acrylate; alkylene oxide-modified di(meth)acrylate such as bisphenol A
ethylene oxide-modified di(meth)acrylate, bisphenol A propylene oxide-modified
di(meth)acrylate, neopentyl glycol ethylene oxide-modified di(meth)acrylate and
neopentyl glycol propylene oxide-modified di(meth)acrylate; and epoxy
20 di(meth)acrylate such as 1,6-hexanediol epoxy di(meth)acrylate, neopentyl glycol
epoxy di(meth)acrylate, bisphenol A epoxy di(meth)acrylate, bisphenol A propylene
oxide-modified epoxy di(meth)acrylate, phthalic acid epoxy di(meth)acrylate,
polyethylene glycol epoxy di(meth)acrylate and polypropylene glycol epoxy
di(meth)acrylate can be mentioned.
25 100671
As the tri(meth)acrylates, for example, trimethylolpropane triacrylate, ethylene
oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified
trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate can be
mentioned.
30 [0068]
As the tetra(meth)acrylates, for example, pentaerythritol tetra(meth)acrylate
can be mentioned.
As the penta(meth)acrylates, for example, dipentaerythritol
penta(meth)acrylate can be mentioned.
3 5 As the hexa(meth)acrylates, for example, dipentaerythritol hexa(meth)acrylate
can be mentioned.
[0069]
Among these (meth)acrylate compounds as a monomer, in view of hardness,
poly(meth)acrylate such as di(meth)acrylate, tri(meth)acrylate, tetra(meth)acrylate,
penta(meth)acrylate and hexa(meth)acrylate are preferable. This is because as a result
5 of having a plurality of (meth)acryloyl groups in a molecule, a higher molecular weight
can easily be attained compared with the case of mono(meth)acrylates.
[0070]
Furthermore, as the (meth)acrylate compounds as a polymer, those publicly
known can be used. In particular, compounds having a polyalkylene glycol structure
10 in a molecule are preferable, and compounds having a polyalkylene glycol structure
represented by the following general formula (I) in a molecule are particularly
preferable. As a result of having a polyalkylene glycol structure in a molecule,
(meth)acrylate compounds as a polymer more easily disperse in an aqueous medium,
which enhances the storage stability of the resultant aqueous polyurethane dispersion.
15 Furthermore, when the polyalkylene glycol structure is a structure represented by the
following general formula (I), the storage stability of the (meth)acrylate compounds as
a polymer per se is high, and the dispersibility in an aqueous medium is high, and thus it
is particularly preferred that the polyalkylene glycol structure be the one represented by
the following general formula (1):
20 [Chemical formula 11
(wherein R represents a linear or branched alkyl group having a carbon number of 2 to 5
which may have a substituent, and n represents an integer of 1 to 10).
[007 11
25 The (meth)acrylate compounds as a polymer having a polyalkylene glycol
structure in a molecule include, in addition to mono(meth)acrylates, poly(meth)acrylates
such as di(meth)acrylates, tri(meth)acrylates and tetra(meth)acrylates.
[0072]
As the mono(meth)acrylates, for example, polyethylene glycol
30 mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene
glycol-polypropylene glycol mono(meth)acrylate, poly(ethy1ene glycol-tetra methylene
glycol)mono(meth)acrylate, poly(propy1ene glycol-tetramethylene
glycol)mono(meth)acrylate, methoxy polyethylene glycol mono(meth)acrylate, octoxy
polyethylene glycol-polypropylene glycol mono(meth)acrylate, lauroxy polyethylene
glycol mono(meth)acrylate, stearoxy polyethylene glycol mono(meth)acrylate,
nonylphenoxy polyethylene glycol mono(meth)acrylate, and nonylphenoxy
polypropylene glycol polyethylene glycol mono(meth)acrylate can be mentioned.
[0073]
5 As the poly(meth)acrylates, for example, polyethylene glycol di(meth)acrylate,
polypropylene glycol di(meth)acrylate, polyethylene glycol-polypropylene glycol
di(meth)acrylate, poly(ethy1ene glycol-tetra methylene glycol)di(meth)acrylate,
poly(propy1ene glycol-tetra methylene glycol)di(meth)acrylate, methoxy polyethylene
glycol di(meth)acrylate, octoxy polyethylene glycol-polypropylene glycol
10 di(meth)acrylate, lauroxy polyethylene glycol di(meth)acrylate, stearoxy polyethylene
glycol di(meth)acrylate, nonylphenoxy polyethylene glycol di(meth)acrylate,
nonylphenoxy polypropylene glycol polyethylene glycol di(meth)acrylate, alkylene
oxide-modified trimethylolpropane triacrylate (Laromer (Registered Trademark) P033F
manufactured by BASF) such as ethylene oxide (6 mole) modified trimethylolpropane
15 triacrylate (Laromer (Registered Trademark) LR8863 manufactured by BASF) can be
mentioned.
[0074]
Furthermore, as the radically polymerizable compounds, those commercially
available may be used as they are. As such commercially available products, for
20 example, Blenmer series manufactured by NOF Corporation and various grades of
Laromer (Registered Trademark) manufactured by BASF can be mentioned.
[0075]
As (meth)acrylates as a polymer other than the compounds having a
polyalkylene glycol structure, for example, acryl-based polymers having a
25 polymerizable unsaturated bond at a molecular terminal can be used.
As the acryl-based polymers having a polymerizable unsaturated bond at a
molecular terminal, for example, polybutylacrylate ("Actflow BGV-100T"
manufactured by Soken Chemical & Engineering Co.,Ltd.) having a polymerizable
double bond at one of molecular terminals, and polybutylacrylate ("Actflow"
30 manufactured by Soken Chemical & Engineering Co., Ltd.) having a polymerizable
double bond at both molecular terminals, can be mentioned.
[0076]
The radically polymerizable compound (C) may be used alone or as a
combination of plural types thereof.
35 [0077]
The ratio of the radically polymerizable compound (C) is preferably 10 to 50
wt % based on 100 wt % of the total solid content of the aqueous polyurethane resin
dispersion (including a radically polymerizable compound). As long as it is in this
range, the drying property of the resultant paint film is excellent, and a high hardness of
the resultant paint film can easily be attained, and furthermore, a favorable storage
5 stability of the aqueous polyurethane resin dispersion can easily be attained. The ratio
of the radically polymerizable compound (C) is more preferably 15 to 40 wt %, and
particularly preferably 20 to 40 wt %.
[0078]
The (meth)acryl equivalent of the radically polymerizable compound (C) is
10 preferably 90 to 300. As long as it is in this range, the storage stability of the aqueous
polyurethane resin dispersion is favorable, and a paint film with a favorable light
resistance and hardness can easily be attained. The (meth)acryl equivalent of the
radically polymerizable compound (C) is more preferably 90 to 150. When a plurality
of radically polymerizable compounds are used in combination, the sum of the
15 (meth)acryl equivalents of the respective radically polymerizable compounds multiplied
by the ratio of the respective radically polymerizable compounds to the total radically
polymerizable compounds represents the (meth)acryl equivalent of the radically
polymerizable compounds. Furthermore, (meth)acryl equivalent as used herein refers
to methacryl equivalent and acryl equivalent, and represented by the following formula.
20 (Meth)acryl equivalent = (the molecular weight of radically polymerizable
compound)/(the number of (meth)acryloyl groups in a molecule)
[0079]
In the invention, as a radically polymerizable compound (C), a bifunctional
(meth)acrylate compound (C 1) and a tri- or more-functional (meth)acrylate compound
25 (C2) are preferably used in combination. Here, a "bifunctional (meth)acrylate
compound" represents a compound having two (meth)acryloyl groups in one molecule,
and a "tri- or more-functional (meth)acrylate compound" refers to a compound having
three or more (meth)acryloyl groups in one molecule.
[OOSO]
30 (Bifunctional(meth)acrylate compound (Cl))
In the invention, the bifunctional(meth)acrylate compound (Cl) is not
particularly limited and includes, for example, alkylene glycol di(meth)acrylate such as
ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol
di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate,
35 tricyclodecane dimethanol di(meth)acrylate, and bisphenol A di(meth)acrylate;
polyether di(meth)acrylate such as polyethylene glycol di(meth)acrylate and
polypropylene glycol di(meth)acrylate; alkylene oxide-modified di(meth)acrylate such
as bisphenol A ethylene oxide-modified di(meth)acrylate, bisphenol A propylene
oxide-modified di(meth)acrylate, neopentyl glycol ethylene oxide-modified
di(meth)acrylate and neopentyl glycolpropylene oxide-modified di(meth)acrylate;
5 epoxy di(meth)acrylate such as 1,6-hexanediol epoxy di(meth)acrylate, neopentyl
glycol epoxy di(meth)acrylate, bisphenol A epoxy di(meth)acrylate, bisphenol A
propylene oxide-modified epoxy di(meth)acrylate, phthalic acid epoxy di(meth)acrylate,
polyethylene glycol epoxy di(meth)acrylate and polypropylene glycol epoxy
di(meth)acrylate. Among the bifinctional(meth)acrylate compounds, because of
10 availability, and high rate of consumption of acryloyl groups by photoirradiation
resulting in light resistance of the resultant paint film, alkylene glycol di(meth)acrylate
and polyethers di(meth)acrylate are preferable, polyether di(meth)acrylate is more
preferable, and polypropylene glycol di(meth)acrylate is particularly preferable. These
bifinctional(meth)acrylate compounds may be used alone or as a combination of plural
15 types thereof
[008 11
As the polypropylene glycol di(meth)acrylate, for example, dipropylene glycol
diacrylate (number average molecular weight of 242, e.g. APG-100 manufactured by
Shin Nakamura Chemical Co., Ltd.; DPGDA manufactured by DAICEL-CYTEC
20 Company Ltd.), tripropylene glycol diacrylate (number average molecular weight of
300, e.g. Aronix M-220 manufactured by Toagosei Co., Ltd.; APG-200 manufactured
by Shin Nakamura Chemical Co., Ltd.; TPGDA manufactured by DAICEL-CYTEC
Company Ltd. and the like), heptapropylene glycol diacrylate (number average
molecular weight of 536, e.g. Aronix M-225 manufactured by Toagosei Co., Ltd.;
25 APG-400 manufactured by Shin Nakamura Chemical Co., Ltd. and the like; FA-P240A
manufactured by Hitachi Chemical Co., Ltd.), undecapropylene glycol diacrylate
(number average molecular weight of 808, e.g. Aronix M-270 manufactured by
Toagosei Co., Ltd.; APG-700 manufactured by Shin Nakamura Chemical Co., Ltd.;
FA-P270A manufactured by Hitachi Chemical Co., Ltd. and the like) can be mentioned.
30 While the number average molecular weight of the polypropylene glycol
di(meth)acrylate is not particularly limited, 500 or less is preferable since a hard paint
film is obtainable.
[0082]
Among them, dipropylene glycol diacrylate and tripropylene glycol diacrylate
35 are preferable in view of stability of the polyurethane resin water dispersion, and
tripropylene glycol diacrylate is more preferable in view of skin stimulation of the
polyurethane resin water dispersion.
[0083]
(Tri- or more-functional (meth)acrylate compound (C2))
As the tri- or more-functional (meth)acrylate compound (C2), for example,
5 tri(meth)acrylate compounds such as trirnethylolpropane triacrylate, ethylene
oxide-modified trirnethylolpropane tri(meth)acrylate, propylene oxide-modified
trirnethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate and
tris(acryloy1oxy ethy1)isocyanurate; tetra(meth)acrylate compounds such as
pentaerythritol tetra(meth)acrylate; penta(meth)acrylate compounds such as
10 dipentaerythritol penta(meth)acrylate; and hexa(meth)acrylate compounds such as
dipentaerythritol hexa(meth)acrylate can be mentioned. Among the tri- or
more-functional (meth)acrylates, in view of the stability of the polyurethane resin water
dispersion, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate and
pentaerythritol tetra (meth)acrylate are preferable, and in view of the amount of
15 consumption of the acryloyl groups when irradiated with ultraviolet light,
trirnethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate
are more preferable. These tri- or more-functional (meth)acrylate compounds may be
used alone or as a combination of plural types thereof. For example, tri(meth)acrylate
compounds and tetra(meth)acrylate compounds used in combination can be mentioned.
20 [0084]
As the tri- or more-functional (meth)acrylate compound (C2), in view of
availability and a high hardness of the resultant paint film, tri- or more-functional
(meth)acrylate compounds not having two or more ether linkage on average in a
molecule are preferable, and tri-functional (meth)acrylate compounds having no ether
25 linkage in a molecule and/or tetra-functional (meth)acrylate compounds having no ether
linkage in a molecule are more preferable, and tri(meth)acrylates having no ether
linkage in a molecule are particularly preferable. Among the trio1 triacrylates, in view
of availability, trirnethylolpropane triacrylate and/or trirnethylolpropane trimethacrylate
are preferable.
30 [0085]
When a bifunctional(meth)acryloyl compound (Cl) and a tri- or
more-functional (meth)acryloyl compound (C2) are used in combination, the ratio by
weight is preferably 5:95 to 95:5. As long as the ratio is in this range, a paint film
excellent in hardness and light resistance can easily be obtained. The ratio is more
35 preferably 90: 10 to 20:80, and even more preferably 80:20 to 40:60.
[0086]
IX. Aqueous medium
In the invention, the polyurethane resin is dispersed in an aqueous medium.
As the aqueous medium, water or a mixture medium of water and a hydrophilic organic
solvent, or the like can be mentioned.
5 [0087]
As the water, for example, tap water, ion exchanged water, distilled water,
extra pure water can be mentioned. Among them, in view of availability and the fact
of particles becoming unstable under the influence of salts, use of ion exchanged water
is preferable.
10 [OOSS]
As the hydrophilic organic solvent, lower monohydric alcohols such as
methanol, ethanol and propanol; polyalcohols such as ethylene glycol and glycerine;
and aprotic hydrophilic organic solvents such as N-methyl morpholin, dimethyl
sulfoxide, dimethylformamide and N-methylpyrrolidone can be mentioned. As the
15 amount of the hydrophilic organic solvent in the aqueous medium, 0 to 20 wt % is
preferable.
[0089]
X. Process for preparing aqueous polyurethane resin dispersion
Next, the preparation process of the aqueous polyurethane resin dispersion will
20 be explained.
The process for preparing the aqueous polyurethane resin dispersion of the
invention can comprise:
the step (al) of reacting a polycarbonate polyol (a), an acidic group-containing
polyol (b) with a polyisocyanate (d) to obtain a polyurethane prepolymer (B);
25 the step (p) of neutralizing the acidic group of the polyurethane prepolymer
(A) ;
the step (y) of dispersing the polyurethane prepolymer (A) and a radically
polymerizable compound (C) in an aqueous medium; and
the step (6) of reacting the polyurethane prepolymer (A) with the chain
30 extender (B) which is reactive to the isocyanate group of the polyurethane prepolymer
(A) to obtain an aqueous polyurethane resin.
[0090]
Furthermore, the process can comprise the step (a2) of reacting a
polycarbonate polyol (a), an acidic group-containing polyol (b), a polyol (c) other than
35 (a) and (b) with a polyisocyanate (d) to obtain a polyurethane prepolymer (A);
the step (p) of neutralizing the acidic group of the polyurethane prepolymer
(A);
the step (y) of dispersing the polyurethane prepolymer (A) and a radically
polymerizable compound (C) in an aqueous medium; and
the step (6) of reacting the polyurethane prepolymer (A) with a chain extender
5 (B) which is reactive to the isocyanate group of the polyurethane prepolymer (A) to
obtain an aqueous polyurethane resin.
[0091]
The step (al) or (a2) of obtaining a polyurethane prepolymer (A) may be
carried out in an inert gas atmosphere, or in an atmospheric atmosphere.
10 [0092]
Furthermore, as an acidic group neutralizer used in the step (P) of neutralizing
the acidic group of the polyurethane prepolymer (A), organic amines such as
trimethylamine, triethylamine, triisopropylamine, tributylarnine, triethanolamine,
N-methyl diethanolamine, N-phenyl diethanolamine, dimethyl ethanolamine, diethyl
15 ethanolamine, N-methyl morpholin and pyridine; inorganic alkalies such as sodium
hydroxide and potassium hydroxide; ammonia; and the like can be mentioned. Among
them, organic amines can preferably be used, and more preferably tertiary amines can
be used, and most preferably triethylamine can be used.
Here, the acidic group of the polyurethane prepolymer (A) refers to a
20 carboxylic acid group, a sulfone acid group or the like.
[0093]
In the step (y) of dispersing the polyurethane prepolymer (A) and the radically
polymerizable compound (C) in an aqueous medium, while the method and the handling
order and the like are not particularly limited as long as (A) and (C) can be dispersed in
25 an aqueous medium, for example, a method of adding (C) to (A) and dispersing the
mixture in an aqueous medium; a method of adding (A) to (C) and dispersing the
mixture in an aqueous medium; a method of dispersing (A) in an aqueous medium, and
then mixing and dispersing (C) in the medium; a method of dispersing (C) in an
aqueous medium, and then mixing and dispersing (A) in the medium; and a method of
30 dispersing (A) and (C) separately in an aqueous medium and then mixing the two media
can be mentioned.
[0094]
For the mixing, stirring and dispersng, publicly known stirring devices such as
homomixer and homogenizer can be used. Furthermore, for the purpose of viscosity
35 adjustment, workability improvement and dispersibility improvement, the
above-mentioned hydrophilic organic solvent, water or the like may be added in
advance to the polyurethane prepolymer (A) or the radically polymerizable compound
(C) before mixing.
[0095]
Furthermore, it is preferred that the step (y) of mixing the polyurethane
5 prepolymer (A) with the radically polymerizable compound (C) be carried out in the
presence of oxygen in order to avoid unnecessary consumption of double bonds of the
radically polymerizable compound (C). Furthermore, if necessary, a
polymerization-inhibitor may be added. The temperature when mixing the
polyurethane prepolymer (A) with the radically polymerizable compound (C) can be 0
10 to 100°C in order to avoid unnecessary polymerization of radically polymerizable
compounds. The reaction is preferably carried out at 0 to 80°C. For example, it can
be set at 0 to 70°C and preferably at 50 to 70°C.
[0096]
In the preparation process of the invention, the step (P) of neutralizing the
15 acidic group of the polyurethane prepolymer (A), and the step (y) of dispersing the
polyurethane prepolymer (A) and the radically polymerizable compound (C) in an
aqueous medium, may be carried out in any order, or the two steps can be carried out
simultaneously. In this case, (A), (C), an aqueous medium and an acidic
group-neutralizer may be mixed at one time, or the acidic group-neutralizer may be
20 mixed with an aqueous medium or (C) beforehand, and then the mixture and (A) may
be mixed.
[0097]
The step (y) of dispersing the polyurethane prepolymer (A) and the radically
polymerizable compound (C) in an aqueous medium, and the step (6) of reacting the
25 polyurethane prepolymer (A) with a chain extender (B) to obtain an aqueous
polyurethane resin, can be carried out simultaneously.
In this case, (A), (B), (C) and an aqueous medium may be mixed at one time,
or (B) may be mixed in an aqueous medium beforehand, and then the mixture may be
mixed with (A) and (C).
30 [0098]
The step (P) of neutralizing the acidic group of the polyurethane prepolymer
(A), the step (y) of dispersing the polyurethane prepolymer (A) and the radically
polymerizable compound (C) in an aqueous medium, and the step (6) of reacting the
polyurethane prepolymer (A) with a chain extender (B) to obtain an aqueous
35 polyurethane resin, can be carried out simultaneously. In this case, (A), (B), (C), the
acidic group-neutralizer and an aqueous medium may be mixed at one time, or (B) and
the acidic group-neutralizer may be mixed in an aqueous medium or (C) beforehand,
and then the mixture may be mixed with (A) and (C).
[0099]
In the step (6) of reacting the polyurethane prepolymer (A) with the chain
5 extender (B) which is reactive to the isocyanate group of the polyurethane prepolymer
(A) to obtain an aqueous polyurethane resin, the reaction may be carried out slowly
while cooling, or in some cases, the reaction may be accelerated under a heating
condition of 60°C or less. The reaction time while cooling can be about 0.5 to 24
hours, and reation time under a heating condition of 60°C or less is about 0.1 to 6 hours.
10 [OlOO]
The ratio of the polyurethane resin in the aqueous polyurethane resin
dispersion is preferably 5 to 60 wt %, more preferably 20 to 50 wt %, and even more
preferably 15 to 20 wt %. Furthermore, the number average molecular weight can be
set at 10,000 to 1,000,000.
15 [OlOl]
XI. Photo-initiator
A photo-initiator can be added to the aqueous polyurethane resin dispersion of
the invention.
As the photo-initiator, commonly used ones can be used, for example, a
20 photo-fragmentation type in which cleavage easily occurs by ultraviolet irradiation to
produce two radicals and/or a hydrogen abstraction type, or a mixture of these can be
used. As these compounds, for example, acetophenone, 2,2-diethoxy acetophenone,
p-dimethylamino acetophenone, benzophenone, 2-chlorobenzophenone, p,pY-bis
diethylamino benzophenone, benzoin ethyl ether, benzoin n-propyl ether, benzoin
25 isopropyl ether, benzoin isobutyl ether, benzoin n-butyl ether, benzoin dimethyl ketal,
thioxanthone, p-isopropyl-a-hydroxy isobutyl phenone, 2,2-dimethoxy-2-phenyl
acetophenone, 1 -hydroxy cyclocyclohexyl p henyl ketone,
2-methyl- 1 [4-(methy1thio)phenyll-2-morpholinopropan- 1 -one,
2-hydroxy-2-methyl-1-phenyl propan-1-one, 2,4,6,-trimethyl benzophenone, 4-methyl
30 benzophenone, 2,2-dimethoxy-1,2-diphenyelt hanone can be mentioned. Preferably,
hydroxycyclohexyl phenyl ketone can be mentioned.
[O 1 021
When the photo-initiator is added, it is preferably added after the step (6) of
reacting the polyurethane prepolymer (A) with the chain extender (E3) which is reactive
35 to the isocyanate group of the polyurethane prepolymer (A) to obtain an aqueous
polyurethane resin.
The amount of the photo-initiator is preferably 0.5 wt % to 5 wt % based on the
total solid content of the aqueous polyurethane resin dispersion (including a radically
polymerizable compound).
[0103]
5 XII. Additives
Furthermore, additives can be added, if necessary, to the aqueous polyurethane
resin dispersion of the invention and such additives include a thickener, a
photosensitizer, a curing catalyst, an ultraviolet absorber, a photostabilizer, an
antifoamer, a plasticizer, a surface conditioner, and an antisettling agent. Such
10 additives may be used alone or as a combination of plural types. It is preferred that the
aqueous polyurethane resin dispersion of the invention contain substantially no
protective colloid, emulsifier nor surfactant in view of hardness and chemical resistance
of the resultant paint film.
[0 1 041
15 The paint composition and coating agent of the invention are a paint
composition and coating agent containing the aqueous polyurethane resin dispersion.
In addition to the aqueous polyurethane resin dispersion, other resins can be
added to the paint composition and coating agent of the invention. As the other resins,
polyester resin, acryl resin, polyethers resin, polycarbonate resin, polyurethane resin,
20 epoxy resin, alkyd resin, polyolefin resin and the like can be mentioned. These may be
used alone or as a combination of plural types thereof
Furthermore, the other resins preferably have one kind or more hydrophilic
groups. As the hydrophilic groups, hydroxyl groups, carboxy groups, sulfone acid
groups, polyethylene glycol groups and the like can be mentioned.
25 [0105]
As the other resins, at least one type selected from the group consisting of
polyester resin, acryl resin and polyolefin resin is preferable.
[0 1061
The polyester resin can typically produced by esterification or
30 transesterification of an acid component with an alcohol component.
As the acid component, a compound typically used as an acid component in
producing a polyester resin can be used. As the acid component, for example,
aliphatic polybasic acid, alicyclic polybasic acid, aromatic polybasic acid and the like
can be used.
3 5 The hydroxyl value of the polyester resin is preferably about 10 to 300
mgKOWg, more preferably about 50 to 250 mgKOWg, and even more preferably about
80 to 180 mgKOWg. The acid value of the polyester resin is preferably about 1 to 200
mgKOWg, more preferably about 15 to 100 mgKOWg, and even more preferably about
25 to 60 mgKOWg.
The weight average molecular weight of the polyester resin is preferably 500 to
5 500,000, more preferably 1,000 to 300,000, and even more preferably 1,500 to 200,000.
[0 1071
As the acryl resin, a hydroxyl group-containing acryl resin is preferable. The
hydroxyl group-containing acryl resin can be prepared by copolymerizing a hydroxyl
group-containing polymerizable unsaturated monomer with another polymerizable
10 unsaturated monomer which is copolymerizable with the hydroxyl group-containing
polymerizable unsaturated monomer by a well-known method, for example, a solution
polymerization method in an organic solvent or an emulsion polymerization method in
water.
The hydroxyl group-containing polymerizable unsaturated monomer is a
15 compound having one or more hydroxyl groups and one or more polymerizable
unsaturated bonds in a molecule. For example, a monoesterified compound of a
dihydric alcohol having a carbon number of 2 to 8 and a (meth)acryl acid such as
2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate,
3-hydroxypropyl(meth)acrylate and 4-hydroxybutyl(meth)acrylate; an E-caprolactone
20 modified product of these monoesterified compounds;
N-hydroxymethyl(meth)acrylamide; an ally1 alcohol; and a (meth)acrylate having a
polyoxyethylene chain whose molecular terminal is a hydroxyl group, can be
mentioned.
[0 1081
25 It is preferred that the hydroxyl group-containing acryl resin have a cationic
functional group.
The hydroxyl group-containing acryl resin having a cationic functional group
can be produced by, for example, using a polymerizable unsaturated monomer having a
cationic functional group such as a tertiary amino group and a quarternary ammonium
30 salt group as one of the polymerizable unsaturated monomers.
The hydroxyl value of the hydroxyl group-containing acryl resin is, in view of
the storage stability of the aqueous polyurethane resin dispersion and water resistance of
the resultant paint film, etc., preferably about 1 to 200 mgKOWg, more preferably
about 2 to 100 mgKOWg and even more preferably 3 to 60 mgKOWg.
3 5 Furthermore, when the hydroxyl group-containing acryl resin has an acid group
such as a carboxyl group, the acid value of the hydroxyl group-containing acryl resin is,
in view of water resistance of the resultant paint film etc., preferably about 1 to 200
mgKOWg, more preferably about 2 to 150 mgKOH/g and even more preferably about 5
to 100 mgKOH1g.
The weight average molecular weight of the hydroxyl group-containing acryl
5 resin is preferably within the range of 1,000 to 200,000, more preferably 2,000 to
100,000 and even more preferably 3,000 to 50,000.
[0 1 091
As the polyethers resin, polymers or copolymers having an ether linkage can be
mentioned, and, for example, polyethers derived from aromatic polyhydroxy
10 compounds such as polyoxyethylene-based polyethers, polyoxypropylene-based
polyethers, polyoxybutylene-based polyethers, bisphenol A or bisphenol F can be
mentioned.
As the polycarbonate resin, polymers prepared from bisphenol compounds can
be mentioned, and, for example, bisphenol A polycarbonate can be mentioned.
15 As the polyurethane resin, resins having an urethane bond obtained by reacting
various polyol components such as acryl, polyester, polyether and polycarbonate with
polyisocyanate can be mentioned.
[Ol lo]
As the epoxy resin, resins obtained by reacting a bisphenol compound with an
20 epichlorohydrin and the like can be mentioned. As the bisphenol, for example,
bisphenol A and bisphenol F can be mentioned.
As the alkyd resin, alkyd resins obtained by reacting a polybasic acid such as
phthalic acid, terephthalic acid and succinic acid with a polyalcohol, and hrther with a
modifier such as oilloil fatty acid (soybean oil, linseed oil, coconut oil, stearic acid, etc.)
25 and natural resin (rosin, succinite, etc.) can be mentioned.
[Olll]
As the polyolefin resin, resins obtained by water-dispersing, using an
emulsifier, a polyolefin resin obtained by polymerizing or copolymerizing an
olefin-based monomer suitably with another monomer by a common polymerization
30 method, or by emulsion-polymerizing an olefin-based monomer suitably with another
monomer, can be mentioned. Furthermore, optionally, a so-called chlorinated
polyolefin-modified resin obtained by chlorinating the polyolefin resin may be used.
As the olefin-based monomer, for example, a-olefins such as ethylene,
propylene, 1 -butene, 3-methyl- 1-butene, 4-methyl- 1 -pentene, 3 -methyl-1 -pentene,
3 5 1 -heptene, 1 -hexene, 1 -decene and 1 -dodecen; and conjugated dienes or non-conjugated
dienes such as butadiene, ethylidene norbornane, dicyclo pentadiene, 1,5-hexadiene and
styrenes can be mentioned, and these monomers may be used alone or as a combination
of plural types thereof.
As the monomer copolymerizable with an olefin-based monomer, for example,
acetic acid vinyl, vinyl alcohol, maleic acid, citraconic acid, itaconic acid, maleic acid
5 anhydride, citraconic acid anhydride and itaconic acid anhydride can be mentioned, and
these monomers may be used alone or as a combination of plural types thereof.
[0112]
By causing the paint composition and coating agent of the invention to contain
a curing agent, it is possible to enhance water resistance etc. of a paint film or
10 multi-layer paint film or coating film in which the paint composition or the coating
agent is used.
[0113]
As the curing agent, for example, amino resin, polyisocyanate, blocked
polyisocyanate, melamine resin and carbodiimide may be used. Only one type curing
15 agent may be used, or a plural types may be used in combination.
[0114]
As the amino resin, for example, a partially or completely methyloled amino
resin obtained by reacting an amino component and an aldehyde component can be
mentioned. As the amino component, for example, melamine, ureas, benzoguanamine,
20 acetoguanamine, steroguanamine, spyroguanamine and dicyandiamide can be
mentioned. As the aldehyde component, for example, formaldehyde,
paraformaldehyde, acetaldehyde and benzaldehyde can be mentioned.
[0115]
As the polyisocyanate, for example, compounds having two or more isocyanate
25 groups in a molecule can be mentioned, and for example, hexamethylene diisocyanate
and trimethyl hexamethylene diisocyanate can be mentioned.
[0116]
As the blocked polyisocyanate, those obtained by adding a blocking agent to
the polyisocyanate group of the above-mentioned polyisocyanate can be mentioned, and
30 as the blocking agent, those including phenol-based blocking agents such as phenol and
cresol; aliphatic alcohol-based blocking agents such as methanol and ethanol; active
methylene-based blocking agents such as dimethyl malonate and acetyl acetone;
mercaptan-based blocking agents such as butyl mercaptan and dodecyl mercaptan; acid
amide-based blocking agents such as acetanilide and acetic acid amide; lactam-based
35 blocking agents such as E-caprolactam and 6-valerolactam; acid imide-based blocking
agents such as succinimide and maleimide; oxime-based blocking agents such as
acetaldoxime, acetone oxime and methylethylketoxime; and amine-based blocking
agents such as diphenyl aniline, aniline and ethyleneimine, can be mentioned.
[0117]
As the melamine resin, for example, methylolmelamines such as dimethylol
5 melamine and trimethylolmelamine; alkyl etherified products or condensation products
of these methylolmelamines; condensation products of alkyl etherified products of
methylolmelamines and the like can be mentioned.
[0118]
As the paint composition and coating agent of the invention, a coloring
10 pigment, an extender pigment and a lustrous pigment can be added.
As the coloring pigment, for example, titanium oxide, zinc white, carbon black,
molybdenum red, prussian blue, cobalt blue, azo pigment, phthalocyanine'pigment,
quinacridone pigment, isoindoline pigment, threne-based pigment and perylene pigment
can be mentioned. These may be used alone or as a combination of plural types
15 thereof. In particular, it is preferred that titanium oxide and/or carbon black be used as
a coloring pigment.
As the extender pigment, for example, clay, kaolin, barium sulfate, barium
carbonate, calcium carbonate, talc, silica and alumina white can be mentioned. These
may be used alone or as a combination of plural types thereof. In particular, as the
20 extender pigment, barium sulfate and/or talc is preferably used, and barium sulfate is
more preferably used.
As the lustrous pigment, for example, aluminium, copper, zinc, brass, nickel,
aluminium oxide, mica, aluminium oxide coated with titanium oxide or iron oxide, and
mica coated with titanium oxide or iron oxide can be used.
25 [0119]
The paint composition and coating agent of the invention can contain, if
necessary, commonly used additives for paint such as a thickener, a curing catalyst, an
ultraviolet absorber, a photostabilizer, an antifoamer, a plasticizer, a surface conditioner,
and an antisettling agent. These may be used alone or as a combination of plural types
30 thereof.
The preparation process of the paint composition and coating agent of the
invention is not particularly limited, and a publicly known preparation process can be
used. Typically, the paint composition and the coating agent is prepared by mixing the
aqueous polyurethane resin dispersion with the above-mentioned various additives,
35 adding an aqueous medium, and adjusting the viscosity according to the particular
coating method.
[O 1201
As the subject material to be painted by the paint composition or as the subject
material to be coated by the coating agent, metal, plastic, inorganic matter, wood and
the like can be mentioned.
5 As the painting method of the paint composition or the coating method of the
coating agent, bell coating, spray coating, roll coating, shower coating, dipping coating
and the like can be mentioned.
[Exampl el
[O 12 11
10 Next, the invention will be explained in more details by way of Examples and
Comparative Examples.
[O 1221
[Example 11
(Preparation of the aqueous polyurethane resin dispersion)
15 To a reactor equipped with a stirrer and a heater were added 136.3 g (0.149
mole) of ETERNACOLL (Registered Trademark) "UM-90 (311)" (a polycarbonate diol
prepared using 1,6-hexanediol, 1,4-cyclohexane dimethanol and a carbonic acid ester as
raw materials, molar mass: 915 glmol, hydroxyl valu'e: 122.5 mgKOWg) manufactured
by Ube Industries, Ltd. and 1 17.7 g of NMP (N-methyl-2-pyrrolidone) while
20 introducing nitrogen. Then stirred at 70°C. Next, 130.8 g (0.499 mole) of
hydrogenated MDI was stirred at 80°C for 1.5 hours. Then, 20.6 g (0.154 mole) of
dimethylolpropionic acid and 0.3 g of dibutyltin dilaurate as a catalyst were added and
reacted at 90°C for 5 hours to produce a prepolymer (at this time, the amount of the
carboxylic acid group contained in the prepolymer was 2.45 wt % and the hydroxyl
25 equivalent number was 259). After completion of the urethanation reaction, the
reaction mixture was cooled to 70°C, and to this was added 14.8 g (0.146 mole) of
triethylamine and 38.1 g of Laromer LR8863 (a radically polymerizable compound
manufactured by BASF) to obtain a prepolymer before water dispersion. This mixture
was added under vigorous stirring into 428.4 g of water. Then, 46.6 g (0.140 mole) of
30 a 3 5 wt % aqueous 2-methyl- l,5-pentanediamine solution was added to cause a chain
extension reaction to obtain an aqueous polyurethane resin dispersion.
[0123]
[Example 21
To the aqueous polyurethane dispersion synthesized in Example 1 was added 2
3 5 wt %/solid content of a polymerization initiator (IRGACURE 8 19, manufactured by
Ciba Specialty Co., Ltd.), and stirred well to obtain a coating agent. This was coated
on a glass plate, dried at 60°C for 30 minutes, and then the plate was passed under a
SOW metal halide lamp (lamp height: 10 cm, transportation velocity: 2.2 mrnlmin, one
time irradiation, ultraviolet radiation intensity: 1300 rn~lcms~o) as to cure the coated
surface to obtain a coated film of 27 pm.
5 [0124]
[Comparative Example 11
To a glass separable flask having an inner volume of 1 1 and eqipped with a
stirrer and a thermometer were added 300 g (0.300 mole) of ETERNACOLL
(Registered Trademark) "UH- 100" (a polycarbonate diol prepared using 1,6-hexanediol
10 and a carbonic acid ester as raw materials, molar mass: 1000 g/mol, hydroxyl value:
112.2 mgKOHtg) manufactured by Ube Industries, Ltd. and 257 g of
N-methylpyrrolidone, and stirred at a bath temperature of 60°C, and then, at the same
temperature, 259.47 g (0.989 mole) of Desmojule W (Registered Trademark)
(4,4'-diisocyanatedicyclohexylmethane) manufactured by Sumika Bayer Urethane Co.,
15 Ltd. was added and the temperature was elevated to 90°C while stirring, and the mixture
was stirred at the same temperature for 90 minutes (internal temperature: 80°C to 85°C).
Then, 40.2 g (0.300 mole) of dimethylolpropionic acid and 0.69 g of dibutyltin dilaurate
were added and the temperature was elevated to 95°C while stirring (internal
temperature: 90°C to 95°C). After 3 hours, the mixture was cooled to 80°C, and 30.3
20 g (0.299 mole) of triethylamine was added to neutralize to obtain a polyurethane
prepolymer.
This polyurethane prepolymer solution was slowly added to water to disperse,
and to this dispersion liquid was slowly added 122.88 g (0.370 mole) of aqueous
2-methylpentane-1,5-diamine solution at a concentration of 35% to cause a chain
25 extension reaction to obtain an aqueous polyurethane resin dispersion.
[0 1251
[Comparative Example 21
The aqueous polyurethane dispersion synthesized in Comparative Example 1
was coated on a glass plate as it is, and after drying at 60°C for 30 minutes, the plate
30 was fired at 120°C for 3 hours to obtain a coated film of 50 ym.
[0 1261
(Hardness evaluation)
The hardness of the paint films prepared in Example 2 and Comparative
Example 2 were evaluated by pendulum hardness. The results are shown in the
35 following Table.
[0 1271
[Table 11
Example 2 I Comparative Example 2
I Pendulum hardness (second) / 26 1 I 168 I
[0 1281
The polyurethane resin aqueous dispersion of the invention is excellent in
5 dispersibility in an aqueous medium and in strength of the resultant paint film obtained
by coating and drying the dispersion. Furthermore, since it has hydrolysis resistance,
durability, heat resistance and wear resistance and is particularly excellent in hardness,
it is usehl as a raw material for a coating agent or a paint composition. Furthermore,
according to the preparation process of the invention, it is possible to efficiently
10 produce a polyurethane resin aqueous dispersion having the above-mentioned
properties.
[0129]
[Example 31
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
15 Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
molecular weight: 91 6; hydroxyl value: 122 mgKOH1g; 350 g of a polycarbonate diol
obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
between the polyol components is 1,4-cyclohexane dimethanol: 1,6-hexanediol = 3: l),
2,2-dimethylolpropionic acid (62.6 g) and isophorone diisocyanate (336 g) were heated
20 in N-ethyl pyrrolidone (3 15 g) in the presence of dibutyltin dilaurate (0.6 g) under
nitrogen atmosphere at 80 to 90°C for 3. 5 hours. The content of NCO group when the
urethanation reaction was completed was 5.27 wt %. The reaction mixture was cooled
to 80°C, and to this was added and mixed triethylamine (47.1 g). The reaction mixture
(1 9 1 g) and a mixed solution of trimethylolpropane triacrylate (TMPTA) and
25 tripropylene glycol diacrylate (TPGDA) (weight ratio 1 : 1, 57.3 g) were mixed, and
added to water (375 g) under vigorous stirring. Then, a 35 wt % aqueous
2-methyl-1,5-pentanediamines olution (32.3 g) was added to obtain an aqueous
polyurethane resin dispersion.
The acryl equivalent of the radically polymerizable compound (a mixture of
30 TMPTA and TPGDA) in Example 3 was 1 19.
[0130]
[Example 41 .
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
molecular weight: 916; hydroxyl value: 122 mgKOWg; 350 g of a polycarbonate diol
obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
between the polyol components is 1,4-cyclohexane dimethanol: 1,6-hexanediol = 3 : l),
2,2-dimethylolpropionic acid (62.4 g) and isophorone diisocyanate (335 g) were heated
5 in N-ethyl pyrrolidone (317 g) in the presence of dibutyltin dilaurate (0.6 g) under
nitrogen atmosphere at 80 to 90°C for 3.5 hours. The content of NCO group when the
urethanation reaction was completed was 5.23 wt %. The reaction mixture was cooled
to 80°C, and to this was added and mixed triethylamine (47.2 g). The reaction mixture
(210 g) and a mixed solution of trimethylolpropane triacrylate (TMPTA) and
10 polypropylene glycol diacrylate (PPGDA, the molecular weight of propylene glycol
portion is approximately 400) (weight ratio 1: 1, 34.5 g) were mixed and added to water
(352 g) under vigorous stirring. Then, a 35 wt % aqueous
2-methyl- 1, 5-pentanediamine solution (3 5.5 g) was added to obtain an aqueous
polyurethane resin dispersion.
15 The acryl equivalent of the radically polymerizable compound (a mixture of
TMPTA and PPGDA) in Example 4 was 144.
[013 11
[Example 51
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
20 Trademark) UM90(1/1) (manufactured by Ube Industries, Ltd.; number average
molecular weight: 914; hydroxyl value: 123 mgKOWg; 75.1 g of a polycarbonate diol
obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
between the polyol components is 1,4-cyclohexane dimethanol: 1,6-hexanediol = 1 :I),
2,2-dimethylolpropionic acid (13.4 g) and isophorone diisocyanate (72.9 g) were heated
25 in N-ethyl pyrrolidone (67.1 g) in the presence of dibutyltin dilaurate (0.1 g) under
nitrogen atmosphere at 80 to 90°C for 3.5 hours. The content of NCO group when the
urethanation reaction was completed was 4.84 wt %. The reaction mixture was cooled
to 80°C, and to this was added and mixed triethylamine (9.9 g). The reaction mixture
(189 g) and a mixed solution of trimethylolpropane triacrylate (TMPTA) and
30 tripropylene glycol diacrylate (TPGDA) (weight ratio 1: 1, 55.2 g) were mixed and
added to water (373 g) under vigorous stirring. Then, a 35 wt % aqueous
2-methyl-1,5-pentanediamine solution (32.8 g) was added to obtain an aqueous
polyurethane resin dispersion.
The acryl equivalent of the radically polymerizable compound (a mixture of
35 TMPTA and TPGDA) in Example 5 was 1 19.
[0 1 321
[Example 61
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
molecular weight: 9 16; hydroxyl value: 122 mgKOWg; 350 g of a polycarbonate diol
5 obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
between the polyol components is 1,4-cyclohexane dimethanol: 1;6-hexanediol = 3: I),
2,2-dimethylolpropionic acid (62.4 g) and isophorone diisocyanate (335 g) were heated
in N-ethyl pyrrolidone (3 17 g) in the presence of dibutyltin dilaurate (0.6 g) under
nitrogen atmosphere at 80 to 90°C for 3.5 hours. The content of NCO group when the
10 urethanation reaction was completed was 5.24 wt %. The reaction mixture was cooled
to 80°C, and to this was added and mixed triethylamine (47.3 g). The reaction mixture
(195 g) and a mixed solution of trimethylolpropane triacrylate (TMPTA) and
dipropylene glycol diacrylate (DPGDA) (weight ratio 1: 1, 57.8 g) were mixed and
added to water (386 g) under vigorous stirring. Then, a 35 wt % aqueous
15 2-methyl- l,5-pentanediamine solution (33.0 g) was added to obtain an aqueous
polyurethane resin dispersion.
The acryl equivalent of the radically polymerizable compound (a mixture of
TMPTA and DPGDA) in Example 6 was 109.
[0133]
20 [Example 71
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
molecular weight: 91 6; hydroxyl value: 122 mgKOWg; 3 50 g of a polycarbonate diol
obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
25 between the polyol components is 1,4-cyclo hexane dimethanol: 1,6-hexanediol = 3 : I),
2,2-dimethylolpropionic acid (62.5 g) and isophorone diisocyanate (335 g) were heated
in N-ethyl pyrrolidone (3 17 g) in the presence of dibutyltin dilaurate (0.6 g) under
nitrogen atmosphere at 80 to 90°C for 3.5 hours. The content of NCO group when the
urethanation reaction was completed was 5.19 wt %. The reaction mixture was cooled
30 to 80°C, and to this was added and mixed triethylamine (47.0 g). The reaction mixture
(1 80 g) and a mixed solution of trimethylolpropane triacrylate (TMPTA) and triethylene
glycol diacrylate (TEGDA) (weight ratio 1 : 1,53.1 g) were mixed and added to water
(3 52 g) under vigorous stirring. Then, a 3 5 wt % aqueous
2-methyl-1,5-pentanediamine solution (30.2 g) was added to obtain an aqueous
35 polyurethane resin dispersion.
The acryl equivalent of the radically polymerizable compound (a mixture of
TMPTA and TEGDA) in Example 7 was 1 19.
[0 1341
[Example 81
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
5 Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
molecular weight: 916; hydroxyl value: 122 mgKOWg; 350 g of a polycarbonate diol
obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
between the polyol components is 1,4-cyclohexane dimethanol: 1,6-hexanediol = 3: I),
2,2-dimethylolpropionic acid (62.4 g) and isophorone diisocyanate (335 g) were heated
10 in N-ethyl pyrrolidone (3 17 g) in the presence of dibutyltin dilaurate (0.6 g) under
nitrogenatmosphere at 80 to 90°C for 3.5 hours. The content of NCO group when the
urethanation reaction was completed was 5.24 wt %. The reaction mixture was cooled
to 80°C, and to this was added and mixed triethylamine (47.3 g). The reaction mixture
(180 g) and a mixed solution of trimethylolpropane triacrylate (TMPTA) and butanediol
15 diacrylate (BGDA) (weight ratio 1: 1, 52.5 g) were mixed and added to water (357 g)
under vigorous stirring. Then, a 35 wt % aqueous 2-methyl-l,5-pentanediamine
solution (30.3 g) was added to obtain an aqueous polyurethane resin dispersion.
The acryl equivalent of the radically polymerizable compound (a mixture of
TMPTA and BGDA) in Example 8 was 99.
20 [0135]
[Example 91
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
molecular weight: 916; hydroxyl value: 122 mgKOWg; 350 g of a polycarbonate diol
25 obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
between the polyol components is 1,4-cyclohexane dimethanol: 1,6-hexanediol = 3: I),
2,2-dimethylolpropionic acid (62.5 g) and isophorone diisocyanate (335 g) were heated
in N-ethyl pyrrolidone (3 17 g) in the presence of dibutyltin dilaurate (0.6 g) under
nitrogen atmosphere at 80 to 90°C for 3.5 hours. The content of NCO group when the
30 urethanation reaction was completed was 5.19 wt %. The reaction mixture was cooled
to 80°C, and to this was added and mixed triethylamine (47.0 g). The reaction mixture
(170 g) and a mixed solution of trimethylolpropane triacrylate (TMPTA) and
hexanediol diacrylate (HDDA) (weight ratio 1: 1, 50.5 g) were mixed and added to water
(33 1 g) under vigorous stirring. Then, a 35 wt % aqueous
35 2-methyl-1,Spentanediamine solution (29.0 g) was added to obtain an aqueous
polyurethane resin dispersion.
The acryl equivalent of the radically polymerizable compound (a mixture of
TMPTA and HDDA) in Example 9 was 105.
[0136]
[Example 101
5 In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
molecular weight: 916; hydroxyl value: 122 mgKOWg; 350 g of a polycarbonate diol
obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
between the polyol components is 1,4-cyclohexane dimethanol: 1,6-hexanediol = 3 : I),
10 2,2-dimethylolpropionic acid (62.5 g) and isophorone diisocyanate (3 3 5 g) were heated
in N-ethyl pyrrolidone (3 17 g) in the presence of dibutyltin dilaurate (0.6 g) under
nitrogen atmosphere at 80 to 90°C for 3.5 hours. The content of NCO group when the
urethanation reaction was completed was 5.19 wt %. The reaction mixture was cooled
to 80°C, and to this was added and mixed triethylamine (47.0 g). The reaction mixture
15 (184 g) and a mixed solution of tripropylene glycol diacrylate (TPGDA) and Laromer
8863 (manufactured by BASF) (weight ratio 1 : 1, 53.5 g) were mixed and added to
water (363 g) under vigorous stirring. Then, a 35 wt % aqueous
2-methyl- l,5-pentanediamine solution (3 1.4 g) was added to obtain an aqueous
polyurethane resin dispersion.
20 The acryl equivalent of the radically polymerizable compound (a mixture of
TPGDA and Laromer 8863) in Example 10 was 146.
[0137]
[Example 111
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
25 Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
molecular weight: 9 16; hydroxyl value: 122 mgKOWg; 350 g of a polycarbonate diol
obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
between the polyol components is 1,4-cyclohexane dimethanol: 1,6-hexanediol = 3 : I),
2,2-dimethylolpropionic acid (62.5 g) and isophorone diisocyanate (335 g) were heated
30 in N-ethyl pyrrolidone (3 17 g) in the presence of dibutyltin dilaurate (0.6 g) under
nitrogen atmosphere at 80 to 90°C for 3.5 hours. The content of NCO group when the
urethanation reaction was completed was 5.19 wt %. The reaction mixture was cooled
to 80°C, and to this was added and mixed tiethylamine (47.0 g). The reaction mixture
(1 79 g) and a mixed solution of trimethylolpropane triacrylate (TMPTA) and
35 tripropylene glycol diacrylate (TPGDA) (weight ratio 1 :5, 53.0 g) were mixed and
added to water (355 g) under vigorous stirring. Then, a 35 wt % aqueous
2-methyl-1,5-pentanediamine solution (30.8 g) was added to obtain an aqueous
polyurethane resin dispersion.
The acryl equivalent of the radically polymerizable compound (a mixture of
TMPTA and TPGDA) in Example 1 1 was 13 8.
5 [0138]
[Example 121
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
molecular weight: 916; hydroxyl value: 122 mgKOWg; 350 g of a polycarbonate diol
10 obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
between the polyol components is 1,4-cyclohexane dimethanol: 1,6-hexanediol = 3: I),
2,2-dimethylolpropionic acid (62.6 g) and isophorone diisocyanate (336 g) were heated
in N-ethyl pyrrolidone (3 15 g) in the presence of dibutyltin dilaurate (0.6 g) under
nitrogen atmosphere at 80 to 90°C for 3.5 hours. The content of NCO group when the
15 urethanation reaction was completed was 5.27 wt %. The reaction mixture was cooled
to 80°C, and to this was added and mixed triethylamine (47.1 g). The reaction mixture
(191 g) and a mixed solution of trimethylolpropane triacrylate (TMPTA) and neopentyl
glycol diacrylate (NPGDA) (weight ratio 1:5, 57.3 g) were mixed and added to water
(3 75 g) under vigorous stirring. Then, a 3 5 wt % aqueous
20 2-methyl-l,5-pentanediamine solution (32.4 g) was added to obtain an aqueous
polyurethane resin dispersion.
The acryl equivalent of the radically polymerizable compound in Example 12
(a mixture of TMPTA and NPGDA) was 105.
[0139]
25 [Example 131
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
molecular weight: 916; hydroxyl value: 122 mgKOWg; 350 g of a polycarbonate diol
obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
30 between the polyol components is 1,4-cyclohexane dimethanol: 1,6-hexanediol = 3: I),
2,2-dimethylolpropionic acid (62.5 g) and isophorone diisocyanate (335 g) were heated
in N-ethyl pyrrolidone (3 17 g) in the presence of dibutyltin dilaurate (0.6 g) under
nitrogen atmosphere at 80 to 90°C for 3.5 hours. The content of NCO group when the
urethanation reaction was completed was 5.19 wt %. The reaction mixture was cooled
35 to 80°C, and to this was added and mixed triethylamine (47.0 g). The reaction mixture
(185 g) and a mixed solution of pentaerythritol tetraacrylate (PETA) and tripropylene
glycol diacrylate (TPGDA) (weight ratio 1 :5, 52.8 g) were mixed and added to water
(362 g) under vigorous stirring. Then, a 35 wt % aqueous
2-methyl-1,Spentanediamines olution (30.4 g) was added to obtain an aqueous
polyurethane resin dispersion.
5 The acryl equivalent of the radically polymerizable compound (a mixture of
PETA and TPGD A) in Example 1 3 was 143.
[0 1401
[Example 141
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
10 Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
molecular weight: 91 6; hydroxyl value: 122 mgKOWg; 350 g of a polycarbonate diol
obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
between the polyol components is 1,4-cyclohexane dimethanol: 1,6-hexanediol = 3 : l),
2,2-dimethylolpropionic acid (62.5 g) and isophorone diisocyanate (335 g) were heated
in NEP (3 17 g) in the presence of dibutyltin dilaurate (0.6 g) under nitrogen atmosphere
at 80 to 90°C for 3.5 hours. The content of NCO group when the urethanation reaction
was completed was 5.19 wt %. The reaction mixture was cooled to 80°C, and to this
was added and mixed triethylamine (47.0 g). The reaction mixture (189 g) and a
mixed solution of trimethylolpropane triacrylate (TMPTA) and polypropylene glycol
diacrylate (PPGDA, the molecular weight of propylene glycol portion is approximately
700) (weight ratio 1: 1, 55.3 g) were mixed and added to water (377 g) under vigorous
stirring. Then, a 35 wt % aqueous 2-methyl-1,5-pentanediamine solution (32.2 g) was
added to obtain an aqueous polyurethane resin dispersion.
The acryl equivalent of the radically polymerizable compound (a mixture of
25 TMPTA and PPGDA) in Example 14 was 159.
[0141]
[Comparative Example 31
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
30 molecular weight: 9 16; hydroxyl value: 122 mgKOWg; 16 1 g of a polycarbonate diol
obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
between the polyol components is 1,4-cyclohexane dimethanol: 1,6-hexanediol = 3 : l),
2,2-dimethylolpropionic acid (29.1 g) and isophorone diisocyanate (157 g) were heated
in N-ethyl pyrrolidone (15 1 g) in the presence of dibutyltin dilaurate (0.3 g) under
35 nitrogen atmosphere at 80 to 90°C for 3.5 hours. The content of NCO group when the
urethanation reaction was completed was 5.28 wt %. The reaction mixture was cooled
to 80°C, and to this was added and mixed triethylamine (21.9 g). The reaction mixture
(236 g) was added to water (306 g) under vigorous stirring. Then, a 35 wt % aqueous
2-methyl-l,5-pentanediamines olution (40.0 g) was added to obtain an aqueous
polyurethane resin dispersion.
5 [0142]
[Example 151
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
molecular weight: 916; hydroxyl value: 122 mgKOWg; 161 g of a polycarbonate diol
10 obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
between the polyol components is 1,4-cyclohexane dimethanol: 1,6-hexanediol = 3: I),
2,2-dimethylolpropionic acid (29.1 g) and isophorone diisocyanate (157 g) were heated
in N-ethyl pyrrolidone (15 1 g) in the presence of dibutyltin dilaurate (0.3 g) under
nitrogen atmosphere at 80 to 90°C for 3.5 hours. The content of NCO group when the
15 urethanation reaction was completed was 5.28 wt %. The reaction mixture was cooled
to 80°C, and to this was added and mixed triethylamine (21.9 g). The reaction mixture
(210 g) and a mixed solution of trimethylolpropane triacrylate (TMPTA) and
tripropylene glycol diacrylate (TPGDA) (weight ratio 1: 1, 7.8 g) were mixed and added
to water (283 g) under vigorous stirring. Then, a 35 wt % aqueous
20 2-methyl- 1,5-pentanediamine solution (35.9 g) was added to obtain an aqueous
polyurethane resin dispersion.
The acryl equivalent of the radically polymerizable compound (a mixture of
TMPTA and TPGDA) in Example 15 was 1 19.
[0 1431
25 [Example 161
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UHlOO (manufactured by Ube Industries, Ltd.; number average molecular
weight: 1004; hydroxyl value: 112 mgKOHlg; 60.1 g of a polycarbonate diol obtained
by reacting 1,6-hexanediol with a carbonic acid ester), 2,2-dimethylolpropionic acid
30 (8.1 g) and isophorone diisocyanate (57.7 g) were heated in N-ethyl pyrrolidone (53.5
g) in the presence of dibutyltin dilaurate (0.1 g) under nitrogen atmosphere at 80°C for 4
hours. The content of NCO group when the urethanation reaction was completed was
4.94 wt %. The reaction mixture was cooled to 80°C, and to this was added and mixed
triethylamine (8.1 g). The reaction mixture (1 74 g) and a mixed solution of
35 trimethylolpropane triacrylate (TMPTA) and tripropylene glycol diacrylate (TPGDA)
(weight ratio 1 : 1, 5 1.8 g) were mixed and added to water (349 g) under vigorous stirring.
Then, a 3 5 wt % aqueous 2-methyl-1,5-pentanediamine solution (28.6 g) was added to
obtain an aqueous polyurethane resin dispersion.
The acryl equivalent of the radically polymerizable compound (a mixture of
TMPTA and TPGDA) in Example 16 was 1 19.
5 [0144]
[Example 171
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
molecular weight: 9 16; hydroxyl value: 122 mgKOWg; 3 50 g of a polycarbonate diol
10 obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
between the polyol components is 1,4-cyclohexane dimethanol: 1,6-hexanediol = 3: I),
2,2-dimethylolpropionic acid (62.6 g) and isophorone diisocyanate (336 g) were heated
in N-ethyl pyrrolidone (3 15 g) in the presence of dibutyltin dilaurate (0.6 g) under
nitrogen atmosphere at 80 to, 90°C for 3.5 hours. The content of NCO group when the
15 urethanation reaction was completed was 5.27 wt %. The reaction mixture was cooled
to 80°C, and to this was added and mixed triethylamine (47.1 g). The reaction mixture
(191 g) and a mixed solution (weight ratio 1: 1, 347 g) of trimethylolpropane triacrylate
(TMPTA) and tripropylene glycol diacrylate (TPGDA) were mixed and added to water
(1053 g) under vigorous stirring. Then, a 35 wt % aqueous
20 2-methyl-1,5-pentanediamine solution (32.2 g) was added to obtain an aqueous
polyurethane resin dispersion.
The acryl equivalent of the radically polymerizable compound (a mixture of
TMPTA and TPGDA) in Example 17 was 1 19.
[0145]
25 [Example 181
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
molecular weight: 916; hydroxyl value: 122 mgKOWg; 165 g of a polycarbonate diol
obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
30 between the polyol components is 1,4-cyclohexane dimethanol: 1,6-hexanediol = 3 : I),
2,2-dimethylolpropionic acid (29.5 g) and isophorone diisocyanate (160 g) were heated
in N-ethyl pyrrolidone (151 g) in the presence of dibutyltin dilaurate (0.3 g) under
nitrogen atmosphere at 80 to 90°C for 3 hours. Subsequently, 0.5 g each of
2,6-di-t-butyl-4-methyl phenol and 4-methoxy phenol were added. Furthermore,
35 hydroxyethyl methacrylate (HEMA, 82.3g) was added and heated for 10 hours. The
content of NCO group when the urethanation reaction was completed was 0.24 wt %.
To the reaction mixture, triethylamine (22.1 g) was added and mixed. A prepolymer
was obtained. The reaction mixture (550 g) and a mixed solution of
trimethylolpropane triacrylate (TMPTA) and tripropylene glycol diacrylate (TPGDA)
(weight ratio 1: 1, 161 g) were mixed and added under vigorous stirring to water (1 140
5 g) to obtain an aqueous polyurethane resin dispersion.
The acryl equivalent o'f the radically polymerizable compound (a mixture of
TMPTA and TPGDA) in Example 18 was 1 19.
[0 1461
(Hardness evaluation)
10 The pencil hardness and pendulum hardness of films were measured and
evaluated.
[0 1471
[Preparation of samples for pendulum hardness and pencil hardness]
To the respective aqueous polyurethane resin dispersions of Examples 3 to 18
15 and Comparative Example 3 was added 2 wt %/solid content of a polymerization
initiator (IRGACURESOO, manufactured by Ciba Specialty Co., Ltd.) and stirred well to
obtain coating agents. They were uniformly coated on a glass plate so as to have a
film thicknees of approximately 20 pm after drying. Then, drying at 60°C for 30
minutes, paint films (before UV irradiation) were obtained. After the resultant paint
20 films were subjected to evaluation according to pendulum hardness measurement, they
were passed under a 80 W metal halide lamp (one time irradiation, ultraviolet radiation
intensity: 1000 mJlcm2). The resultant polyurethane resin paint films were subjected
to pencil hardness measurement and pendulum hardness measurement.
[0 1481
25 [Pencil hardness measurement]
As scratch resistance evaluation, pencil hardness was measured.
On the respective resultant laminated bodies of the glass plates and
polyurethane resin paint films, the pencil hardnesses of the respective resin paint films
were measured by a method according to JIS K 5600-5-4.
30 [0149]
[Pendulum hardness]
On the respective resultant laminated bodies of the glass plates and
polyurethane resin paint films, the pencil hardnesses of the respective resin paint films
were measured using a pendulum hardness meter (a pendulum hardness tester
3 5 manufactured by BYK-Gardner GmbH) by measuring the amplitude attenuation time.
The greater the amplitude attenuation time, the greater the hardness.
[0150]
(Remaining percentage of volatile component)
Evaluation was made by measuring the weight of polyurethane resin films
when prepared.
5 [Evaluation of remaining percentage of volatile component]
The respective aqueous polyurethane resin dispersions of Examples 3 to 18 and
Comparative Example 3 were uniformly coated on a glass plate so as to have a film
thicknees of approximately 20 ym after drying. The weights of the coated aqueous
polyurethane resin dispersions were measured. Then, after drying at 60°C for 30
10 minutes, the weights of the resultant polyurethane resin films were measured, and the
remaining content of volatile component in the respective paint films were calculated
from the solid content concentration of the respective aqueous polyurethane resin
dispersions using the formula below.
Calculation formula of the weight of volatile component:
15 (Weight of volatile component) = (Weight of film after drying) - (Weight of coated
aqueous polyurethane resin dispersion) x (Solid content concentration (%)/loo)
Calculation formula of remaining percentage of volatile component:
(Remaining percentage of volatile component)=[(Weight of volatile
component)/(Weight of film after drying)] x 100
20 [0151]
[Table 21
Example
8
43
-
-
8
41
8
40
29
TMPTN
BGDA
111
0
3
0
88
3 67
H
uMgO(311) @art by weight)
uM90(111) (part by weight)
UHlOO (part by weight)
DMPA (part by weight)
IPDI (part by weight)
MPMD (part by weight)
Radically polymerizable compound
(part by weight)
Radically polymerizable compound
(wt %)
Radically polymerizable compound
Radically polymerizable compound
(ratio)
Storage stability (appearance)
Remaining percentage of volatile
component (%)
Tackfiee
Pendlum hardness (before irradiation,
s)
Pendlum hardness (after irradiation, s)
Pencil hardness
Example
3
43
-
-
8
4 1
8
29
TMPTN
TPGDA
0
0
12 1
366
H
Example
4
43
-
-
8
41
8
22
18
TMPTN
PPGDA
111
0
8
0
86
342
F
Example
6
43
-
-
8
4 1
8
41
29
W T N
DPGDA
111
0
3
0
85
362
H
Example
5 -
43
-
8
4 1
8
40
29
TMFTN
TPGDA
111
0
0
o
76
362
H
Example
7
43
-
-
8
41
8
40
29
TMPTN
TEGDA
111
0
3
0
88
367
H
[Table 31
...
Radically polymerizable compound
Radically polymerizable compound
(ratio)
UM90(3/1) (part by weight)
UM90(111) @art by weight)
UHlOO (part by weight)
Storage stability (appearance)
Remaining percentage of volatile
component (%)
Tackfree
Example 11
43
-
-
TMPTN
HDDA
111
Pendlum hardness (before irradiation, s)
Pendlum hardness (after irradiation, s)
pencil hardness
Example 9
43 -
-
o
3
o
[0 1531
[Table 41
Example 12
43
-
-
Example 10
43 -
-
Laromerl
TPGDA
111
75
365
H
--- -
Edically polymerizable compound
(part by weight)
Radically polymerizable compound (wt %)
Radcally polymerizable compound
Radically polymerizable compound (ratio)
Storage stability (appearance)
Remaining percentage of volatile
component (%)
- - -
o
3
o
Example 13
43 -
-
TMPTN
TPGDA
115
54
347
H
0
0
-
-
o
25
-
Example 14
43
-
-
o
3
o
75
358
F
5
5
TMPTN
TPGDA
111
o
22
Tackfree
Pendlum hardness (before irradiation, s)
Pendlum hardness (after irradiation, s)
Pencil hardness
TMPTN
PPGDA
111
TMPTN
NPGDA
115
o
3
o
o
65
323
B
PETPJ
TPGDA
1 I5
41
29
TMPTN
TPGDA
111
o
2
-- -
o
146
-
<6B
o
3
o
41
246
H
I
x
-
-
2H
o
147
252
B
o
3
o
182
379
H
x
23
333
H
248
7 1
TMPTPJ
TPGDA
111
X
1
-- -
76
360
F
36
26
TMPTPJ
TPGDA
111
o
1
[O 1541
Parts by weight in the Tables show the parts by weight of each compound
assuming that the total solid content in urethane resin is 100 parts by weight.
Wt % in the Tables shows the wt % of acryl compound assuming that the total
5 solid content in the resin is 100 wt %.
Storage stability in the Tables shows the result of observation of change in
appearance one week after production. Evaluation criteria are as follows.
o : No change
x : aggregates are observed
10 Tackfree in the Tables indicates the results touching the paint films with
fingers after drying at 60°C for 30 minutes. Evaluation criteria are as follows.
o : No change
x : Mark of fingers or fingerprints remained.
Pencil hardness "<6Bn in the Tables shows that the pencil hardness is 6B or
15 less, and scars are left even with a 6B pencil.
[0155]
As shown in Tables 2 to 4, Examples 3 to 18 were superior in pencil hardness
to Comparative Example 3 which contains no radically polymerizable compounds. In
particular, Examples 3 to 14 and Example 18 in which a polycarbonate polyol having an
20 alicyclic structure in a main chain is used and a radically polymerizable compound
accounts for 10 to 50 wt %, are excellent, and among them, Examples 3 to 14 had a low
remaining percentage of volatile components and were excellent in tackfree.
[0156]
[Example 191
25 In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UHlOO (manufactured by Ube Industries, Ltd.; number average molecular
weight: 1004; hydroxyl value: 1 12 mgKOWg; 60.1 g of a polycarbonate diol obtained
by reacting 1,6-hexanediol with a carbonic acid ester), 2,2-dimethylolpropionic acid
(8.1 g) and isophorone diisocyanate (57.7 g) were heated in N-ethyl pyrrolidone (53.5
30 g) in the presence of dibutyltin dilaurate (0.1 g) under nitrogen atmosphere at 80°C for 4
hours. The content of NCO group when the urethanation reaction was completed was
4.94 wt %. The reaction mixture was cooled to 80°C, and to this was added and mixed
triethylamine (8.1 g). The reaction mixture (174 g) and a mixed solution of
trimethylolpropane triacrylate (TMPTA) and tripropylene glycol diacrylate (TPGDA)
3 5 (weight ratio 1 : 1, 5 1.8 g) were mixed and added to water (349 g) under vigorous stirring.
Then, a 35 wt % aqueous 2-methyl-l,5-pentanediamine solution (28.6 g) was added to
obtain an aqueous polyurethane resin dispersion.
[O 1571
[Example 201
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
5 Trademark) UH200 (manufactured by Ube Industries, Ltd.; number average molecular
weight: 1993; hydroxyl value: 56.3 mgKOWg; 450 g of a polycarbonate diol obtained
by reacting 1,6-hexanediol as a polyol component with a carbonic acid ester),
2,2-dimethylolpropionic acid (66.7 g) and isophorone diisocyanate (289 g) were heated
in N-ethyl pyrrolidone (199 g) in the presence of dibutyltin dilaurate (0.7 g) under
10 nitrogen atmosphere at 80 to 90°C for 4 hours. The content of NCO group when the
urethanation reaction was completed was 4.76 wt %. The reaction mixture was cooled
to 80°C, and to this was added and mixed triethylamine (101 g). The reaction mixture
(185 g) and a mixed solution of trimethylolpropane triacrylate (TMPTA) and
tripropylene glycol diacrylate (TPGDA) (weight ratio 1:3, 60.5 g) were mixed and
15 added to water (457 g) under vigorous stirring. Then, a 35 wt % aqueous
2-methyl-l,5-pentanediamines olution (28.3 g) was added to obtain an aqueous
polyurethane resin dispersion.
[0 1 3-31
[Example 2 1 ]
20 In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
molecular weight: 916; hydroxyl value: 122 mgKOWg; 350 g of a polycarbonate diol
obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
between the polyol components is 1,4-cyclohexane dimethanol: l,6-hexanediol = 3 : I),
25 2,2-dimethylolpropionic acid (62.5 g) and isophorone diisocyanate (335 g) were heated
in N-ethyl pyrrolidone (3 17 g) in the presence of dibutyltin dilaurate (0.6 g) under
nitrogen atmosphere at 80 to 90°C for 3.5 hours. The content of NCO group when the
urethanation reaction was completed was 5.19 wt %. The reaction mixture was cooled
to 80°C, and to this was added and mixed triethylamine (47.0 g). The reaction mixture
30 (179 g) and a mixed solution of trimethylolpropane triacrylate (TMPTA) and
tripropylene glycol diacrylate (TPGDA) (weight ratio 1 :5, 53.0 g) were mixed and
added to water (355 g) under vigorous stirring. Then, a 35 wt % aqueous
2-methyl-1,5-pentanediamines olution (30.8 g) was added to obtain an aqueous
polyurethane resin dispersion.
35 [0159]
[Example 221
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
molecular weight: 916; hydroxyl value: 122 mgKOWg; 350 g of a polycarbonate diol
obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
5 between the polyol components is 1,4-cyclohexane dimethanol: 1,6-hexanediol = 3: l),
2,2-dimethylolpropionic acid (62.6 g) and isophorone diisocyanate (336 g) were heated
in N-ethyl pyrrolidone (3 15 g) in the presence of dibutyltin dilaurate (0.6 g) under
nitrogen atmosphere at 80 to 90°C for 3.5 hours. The content of NCO group when the
urethanation reaction was completed was 5.27 wt %. The reaction mixture was cooled
10 to 80°C, and to this was added and mixed triethylamine (47.1 g). The reaction mixture
(191 g) and a mixed solution of trimethylolpropane triacrylate (TMPTA) and
tripropylene glycol diacrylate (TPGDA) (weight ratio 1: 1, 57.3 g) were mixed and
added to water (375 g) under vigorous stirring. Then, a 35 wt % aqueous
2-methyl-1,5-pentanediamines olution (32.3 g) was added to obtain an aqueous
15 polyurethane resin dispersion.
[0 1601
[Example 231
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
20 molecular weight: 9 16; hydroxyl value: 122 mgKOWg; 3 50 g of a polycarbonate diol
obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
between the polyol components is 1,4-cyclohexane dimethanol: 1,6-hexanediol = 3: I),
2,2-dimethylolpropionic acid (62.4 g) and isophorone diisocyanate (335 g) were heated
in N-ethyl pyrrolidone (3 17 g) in the presence of dibutyltin dilaurate (0.6 g) under
25 nitrogen atmosphere at 80 to 90°C for 3.5 hours. The content ofNCO group when the
urethanation reaction was completed was 5.24 wt %. The reaction mixture was cooled
to 80°C, and to this was added and mixed triethylamine (47.3 g). The reaction mixture
(195 g) and a mixed solution of trimethylolpropane triacrylate (TMPTA) and
dipropylene glycol diacrylate (DPGDA) (weight ratio 1: 1, 57.8 g) were mixed and
30 added to water (3 86 g) under vigorous stirring. Then, a 3 5 wt % aqueous
2-methyl-1,5-pentanediamineso lution (33.0 g) was added to obtain an aqueous
polyurethane resin dispersion.
[0161]
[Example 241
3 5 In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
molecular weight: 916; hydroxyl value: 122 mgKOWg; 350 g of a polycarbonate diol
obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
between the polyol components is 1,4-cyclohexane dimethanol: 1,6-hexanediol = 3: I),
2,2-dimethylolpropionic acid (62.5 g) and isophorone diisocyanate (335 g) were heated
5 in N-ethyl pyrrolidone (3 17 g) in the presence of dibutyltin dilaurate (0.6 g) under
nitrogen atmosphere at 80 to 90°C for 3.5 hours. The content of NCO group when the
urethanation reaction was completed was 5.19 wt %. The reaction mixture was cooled
to 80°C, and to this was added and mixed triethylamine (47.0 g). The reaction mixture
(180 g) and a mixed solution of trimethylolpropane triacrylate (TMPTA) and triethylene
10 glycol diacrylate (TEGDA) (weight ratio 1: 1, 53.1 g) were mixed and added to water
(3 52 g) under vigorous stirring. Then, a 3 5 wt % aqueous
2-methyl-l,5-pentanediamines olution (30.2 g) was added to obtain an aqueous
polyurethane resin dispersion.
[0 1 621
15 [Example 251
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
molecular weight: 916; hydroxyl value: 122 mgKOWg; 350 g of a polycarbonate diol
obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
20 between the polyol components is 1,4-cyclohexane dimethanol: 1,6-hexanediol = 3: I),
2,2-dimethylolpropionic acid (62.4 g) and isophorone diisocyanate (335 g) were heated
in N-ethyl pyrrolidone (3 17 g) in the presence of dibutyltin dilaurate (0.6 g) under
nitrogen atmosphere at 80 to 90°C for 3.5 hours. The content of NCO group when the
urethanation reaction was completed was 5.24 wt %. The reaction mixture was cooled
25 to 80°C, and to this was added and mixed triethylamine (47.3 g). The reaction mixture
(180 g) and a mixed solution of trimethylolpropane triacrylate (TMPTA) and butanediol
diacrylate (BGDA) (weight ratio 1: 1, 52.5 g) were mixed and added to water (357 g)
under vigorous stirring. Then, a 35 wt % aqueous 2-methyl-1,Spentanediamine
solution (30.3 g) was added to obtain an aqueous polyurethane resin dispersion.
30 [0163]
[Example 261
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
molecular weight: 916; hydroxyl value: 122 mgKOWg; 350 g of a polycarbonate diol
35 obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
between the polyol components is 1,4-cyclohexane dimethanol: 1,6-hexanediol = 3: I),
2,2-dimethylolpropionic acid (62.5 g) and isophorone diisocyanate (335 g) were heated
in N-ethyl pyrrolidone (3 17 g) in the presence of dibutyltin dilaurate (0.6 g) under
nitrogen atmosphere at 80 to 90°C for 3.5 hours. The content of NCO group when the
urethanation reaction was completed was 5.19 wt %. The reaction mixture was cooled
5 to 80°C, and to this was added and mixed triethylamine (47.0 g). The reaction mixture
(170 g) and a mixed solution of trimethylolpropane triacrylate (TMPTA) and
hexanediol diacrylate (HDDA) (weight ratio 1 : 1, 50.5 g) were mixed and added to water
(33 1 g) under vigorous stirring. Then, a 3 5 wt % aqueous
2-methyl-1,s-pentanediamines olution (29.0 g) was added to obtain an aqueous
10 polyurethane resin dispersion.
[0 1641
[Example 271
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
15 molecular weight: 916; hydroxyl value: 122 mgKOWg; 3 50 g of a polycarbonate diol
obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
between the polyol components is 1,4-cyclohexane dimethanol: 1,6-hexanediol = 3 : I),
2,2-dimethylolpropionic acid (62.6 g) and isophorone diisocyanate (336 g) were heated
in N-ethyl pyrrolidone (3 15 g) in the presence of dibutyltin dilaurate (0.6 g) under
20 nitrogen atmosphere at 80 to 90°C for 3.5 hours. The content of NCO group when the
urethanation reaction was completed was 5.27 wt %. The reaction mixture was cooled
to 80°C, and to this was added and mixed triethylamine (47.1 g). The reaction mixture
(1 91 g) and a mixed solution of trimethylolpropane triacrylate (TMPTA) and neopentyl
glycol diacrylate (NPGDA) (weight ratio 1 :5, 57.3 g) were mixed and added to water
25 (375 g) under vigorous stirring. Then, a 35 wt % aqueous
2-methyl-1,Spentanediamine solution (32.4 g) was added to obtain an aqueous
polyurethane resin dispersion.
[0 1651
[Example 281
3 0 In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
molecular weight: 916; hydroxyl value: 122 mgKOWg; 3 50 g of a polycarbonate diol
obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
between the polyol components is 1,4-cyclohexane dimethanol: 1,6-hexanediol = 3 :I),
35 2,2-dimethylolpropionic acid (62.5 g) and isophorone diisocyanate (335 g) were heated
in N-ethyl pyrrolidone (3 17 g) in the presence of dibutyltin dilaurate (0.6 g) under
nitrogen atmosphere at 80 to 90°C for 3.5 hours. The content of NCO group when the
urethanation reaction was completed was 5.19 wt %. The reaction mixture was cooled
to 80°C, and to this was added and mixed triethylamine (47.0 g). The reaction mixture
(185 g) and a mixed solution of pentaerythritol tetraacrylate (PETA) and tripropylene
5 glycol diacrylate (TPGDA) (weight ratio 1.5, 52.8 g) were mixed and added to water
(362 g) under vigorous stirring. Then, a 35 wt % aqueous
2-methyl-l,5-pentanediamines olution (30.4 g) was added to obtain an aqueous
polyurethane resin dispersion.
[O 1661
1 0 [Example 291
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UHlOO (manufactured by Ube Industries, Ltd.; number average molecular
weight: 1004; hydroxyl value: 112 mgKOWg; 360 g of a polycarbonate diol obtained
by reacting 1,6-hexanediol with a carbonic acid ester), 2,2-dimethylolpropionic acid
15 (62.5 g) and isophorone diisocyanate (327 g) were heated in N-ethyl pyrrolidone (186
g) in the presence of dibutyltin dilaurate (0.6 g) under nitrogen atmosphere at 80°C for 4
hours. The content of NCO group when the urethanation reaction was completed was
5.57 wt %. To the reaction mixture was added and mixed triethylamine (46.9 g).
The reaction mixture (1 57 g) and a mixed solution of Laromer 8863 (manufactured by
20 BASF) and tripropylene glycol diacrylate (TPGDA) (weight ratio 1 : 1, 8 1.1 g) were
mixed and added to water (438 g) under vigorous stirring. Then, a 35 wt % aqueous
2-methyl-1,5-pentanediamine solution (29.4 g) was added to obtain an aqueous
polyurethane resin dispersion.
[0 1671
25 [Example 3 01
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UHlOO (manufactured by Ube Industries, Ltd.; number average molecular
weight: 1004; hydroxyl value: 112 mgKOWg; 360 g of a polycarbonate diol obtained
by reacting 1,6-hexanediol with a carbonic acid ester), 2,2-dimethylolpropionic acid
30 (62.5 g) and isophorone diisocyanate (327 g) were heated in N-ethyl pyrrolidone (186
g) in the presence of dibutyltin dilaurate (0.6 g) under nitrogen atmosphere at 80°C for 4
hours. The content of NCO group when the urethanation reaction was completed was
5.57 wt %. To the reaction mixture was added and mixed triethylamine (46.9 g).
The reaction mixture (166 g) and a mixed solution of Laromer 8863 (manufactured by
35 BASF) and tripropylene glycol diacrylate (TPGDA) (weight ratio 1.3, 84.3 g) were
mixed and added to water (463 g) under vigorous stirring. Then, a 35 wt % aqueous
2-methyl- l,5-pentanediamine solution (3 0.9 g) was added to obtain an aqueous
polyurethane resin dispersion.
[0 1681
[Example 3 11
5 In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UH200 (manufactured by Ube Industries, Ltd.; number average molecular
weight: 1993; hydroxyl value: 56.3 mgKOWg; 450 g of a polycarbonate diol obtained
by reacting 1,6-hexanediol as a polyol component with a carbonic acid ester),
2,2-dimethylolpropionic acid (66.7 g) and isophorone diisocyanate (289 g) were heated
10 in N-ethyl pyrrolidone (199 g) in the presence of dibutyltin dilaurate (0.7 g) under
nitrogen atmosphere at 80 to 90°C for 4 hours. The content of NCO group when the
urethanation reaction was completed was 4.76 wt %. The reaction mixture was cooled
to 80°C, and to this was added and mixed triethylamine (101 g). The reaction mixture
(168 g) and a mixed solution of Laromer 8863(BASF) and tripropylene glycol
15 diacrylate (TPGDA) (weight ratio 1.5, 56.1 g) were mixed and added to water (41 1 g)
under vigorous stirring. Then, a 3 5 wt % aqueous 2-methyl- 1 ,5-pentanediamine
solution (25.6 g) was added to obtain an aqueous polyurethane resin dispersion.
[0 1691
[Example 321
20 In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
molecular weight: 916; hydroxyl value: 122 mgKOWg; 350 g of a polycarbonate diol
obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
between the polyol components is 1,4-cyclohexane dimethanol: 1,6-hexanediol = 3: l),
25 2,2-dimethylolpropionic acid (62.5 g) and isophorone diisocyanate (335 g) were heated
in N-ethyl pyrrolidone (3 17 g) in the presence of dibutyltin dilaurate (0.6 g) under
nitrogen atmosphere at 80 to 90°C for 3.5 hours. The content of NCO group when the
urethanation reaction was completed was 5.19 wt %. The reaction mixture was cooled
to 80°C, and to this was added and mixed triethylamine (47.0 g). The reaction mixture
30 (183 g) and a mixed solution of trimethylolpropane triacrylate (TMPTA) and
polypropylene glycol diacrylate (PPGDA, the molecular weight of propylene glycol
portion: approximately 400) (weight ratio 1: 1, 54.0 g) were mixed and added to water
(356 g) under vigorous stirring. Then, a 35 wt % aqueous
2-methyl- 1 ,Spentanediamine solution (3 1.1 g) was added to obtain an aqueous
35 polyurethane resin dispersion.
[0 1 701
[Example 3 31
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
molecular weight: 916; hydroxyl value: 122 mgKOWg; 350 g of a polycarbonate diol
5 obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
between the polyol components is 1,4-cyclohexane dimethanol: 1,6-hexanediol = 3: I),
2,2-dimethylolpropionic acid (62.5 g) and isophorone diisocyanate (33 5 g) were heated
in N-ethyl pyrrolidone (3 17 g) in the presence of dibutyltin dilaurate (0.6 g) under
nitrogen atmosphere at 80 to 90°C for 3.5 hours. The content of NCO group when the
10 urethanation reaction was completed was 5.19 wt %. The reaction mixture was cooled
to 80°C, and to this was added and mixed triethylamine (47.0 g). The reaction mixture
(189 g) and a mixed solution of trimethylolpropane triacrylate (TMPTA) and
polypropylene glycol diacrylate (PPGDA, molecular weight of propylene glycol
portion: approximately 700) (weight ratio 1 : 1, 55.3 g) were mixed and added to water
15 (377 g) under vigorous stirring. Then, a 35 wt % aqueous
2-methyl-1,Spentanediamine solution (32.2 g) was added to obtain an aqueous
polyurethane resin dispersion.
[0171]
[Example 341
20 In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UM90(3/1) (manufactured by Ube Industries, Ltd.; number average
molecular weight: 9 16; hydroxyl value: 122 mgKOWg; 3 50 g of a polycarbonate diol
obtained by reacting a carbonic acid ester with a polyol mixture in which molar ratio
between the polyol components is 1,4-cyclohexane dimethanol: 1,6-hexanediol = 3: I),
25 2,2-dimethylolpropionic acid (62.5 g) and isophorone diisocyanate (335 g) were heated
in N-ethyl pyrrolidone (3 17 g) in the presence of dibutyltin dilaurate (0.6 g) under
nitrogen atmosphere at 80 to 90°C for 3.5 hours. The content of NCO group when the
urethanation reaction was completed was 5.19 wt %. The reaction mixture was cooled
to 80°C, and to this was added and mixed triethylamine (47.0 g). The reaction mixture
30 (1 84 g) and a mixed solution of tripropylene glycol diacrylate (TPGDA) and Laromer
8863 (manufactured by BASF) (weight ratio 1 : 1, 53.5 g) were mixed and added to
water (363 g) under vigorous stirring. Then, a 35 wt % aqueous
2-methyl-1,5-pentanediamine solution (3 1.4 g) was added to obtain an aqueous
polyurethane resin dispersion.
35 [0172]
[Example 3 51
In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UH100 (manufactured by Ube Industries, Ltd.; number average molecular
weight: 1004; hydroxyl value: 112 mgKOWg; 360 g of polycarbonate diol obtained by
reacting 1,6-hexanediol with a carbonic acid ester), 2,2-dimethylolpropionic acid (62.5
5 g) and isophorone diisocyanate (327 g) were heated in N-ethyl pyrrolidone (1 86 g) in
the presence of dibutyltin dilaurate (0.6 g) under nitrogen atmosphere at 80°C for 4
hours. The content of NCO group when the urethanation reaction was completed was
5.57 wt %. To the reaction mixture was added and mixed triethylamine (46.9 g). A
prepolymer was obtained. The reaction mixture (159 g) and Laromer 8863
10 (manufactured by BASF, 8 1.5 g) were mixed and added under vigorous stirring to water
(447 g). Then, a 35 wt % aqueous 2-methyl-1,5-pentanediamine solution (30.0 g) was
added to obtain an aqueous polyurethane resin dispersion.
[0173]
[Example 3 61
15 In a reactor equipped with a stirrer and a heater, ETERNACOLL (Registered
Trademark) UHl 00 (manufactured by Ube Industries, Ltd.; number average molecular
weight: 1004; hydroxyl value: 112 mgKOWg; 360 g of a polycarbonate diol obtained
by reacting 1,6-hexanediol with a carbonic acid ester), 2,2-dimethylolpropionic acid
(62.5 g) and isophorone diisocyanate (327 g) were heated in N-ethyl pyrrolidone (1 86
20 g) in the presence of dibutyltin dilaurate (0.6 g) under nitrogen atmosphere at 80°C for 4
hours. The content of NCO group when the urethanation reaction was completed was
5.57 wt %. To the reaction mixture was added and mixed triethylamine (46.9 g). A
prepolymer was obtained. The reaction mixture (166 g) and tripropylene glycol
diacrylate (TPGDA, 81.7 g) were mixed and added under vigorous stirring to water
25 (450 g). Then, a 35 wt % aqueous 2-methyl-1,5-pentanediamines olution (30.0 g) was
added to obtain an aqueous polyurethane resin dispersion.
[0 1 741
(Hardness evaluation)
Evaluation was made by measuring pendulum hardness.
30 [Preparation of samples for pendulum hardness]
To the respective aqueous polyurethane resin dispersions of Examples 19 to 36,
2 wt %/solid content of a polymerization initiator (lRGACURE500, manufactured by
Ciba Specialty Co., Ltd.) was added and stirred well to obtain a coating agent. They
were uniformly coated on a glass plate so as to have a film thicknees of approximately
35 20 pm after drying. Then, paint films (before W irradiation) were obtained by drying
at 60°C for 30 minutes. After the resultant paint films were subjected to evaluation
according to pendulum hardness measurement, the glass plates were passed under a
SOW metal halide lamp (one time irradiation, ultraviolet radiation intensity 1000
m~lcrn~). The resultant polyurethane resin paint films were subjected to the evaluation
of pendulum hardnessmeasurement.
[Pendulum hardness]
In the laiminate bodies of glass plates and polyurethane resin paint films, the
hardnesses of resin paint films were measured by determining the respective amplitude
attenuation times by a pendulum hardness meter (a pendulum hardness tester
10 manufactured by BYK-Gardner GmbH). The greater the amplitude attenuation time,
the greater the hardness.
[Table 51
[0 1 771
[Table 61
[0 1 781
Parts by weight in Table 5 and Table 6 show the parts by weight of each
compound assuming that the total solid content in the urethane resin (containing no
5 bifunctional(meth)acrylate compound and tri- or more-functional(meth)acrylate
compound) is 100 parts by weight.
Bifunctional: Tri(Tetra)fUnctional in Table 5 and Table 6 show the weight ratio
of bifunctional acrylate and tri(tetra)fLnctional acrylate.
[0 1 791
10 As shown in Tables 5 and 6, the paint films in Examples 19 to 36 each have
favorable hardness before and after irradiation, and in particular, fiom the comparison
between Example 29 and Examples 35 to 36, it is understood that when
bifunctional(meth)acrylate compounds and tri- or more-fUnctional(meth)acrylate
compounds are used in combination, excellent results can be obtained.
15 [Industrial Applicability]
[O 1 801
The aqueous polyurethane resin dispersion of the invention can be used widely
as a raw material or the like for paints and coating agents.
1. An aqueous polyurethane resin dispersion containing at least a polyurethane
resin and a radically polymerizable compound (C),
5 wherein the polyurethane resin is a polyurethane resin obtained by reacting at
least a polycarbonate polyol (a); an acidic group-containing polyol (b); and an optional
polyol (c) other than (a) and (b), with a polyisocyanate (d), and optionally further
reacting with a chain extender (B).
2. The aqueous polyurethane resin dispersion according to claim 1, wherein the
10 polycarbonate polyol (a) includes a polycarbonate polyol having an alicyclic structure in
a main chain (al).
3. The aqueous polyurethane resin dispersion according to claim 2, wherein a
content percentage of the alicyclic structure in the polycarbonate polyol (a) is 20 to 65
wt %.
15 4. The aqueous polyurethane resin dispersion according to any one of claims 1 to
3, wherein the radically polymerizable compound (C) is a (meth)acrylate compound.
5. The aqueous polyurethane resin dispersion according to any one of claims 1 to
4, wherein the radically polymerizable compound (C) includes a compound having a
polyalkylene glycol structure.
20 6. The aqueous polyurethane resin dispersion according to any one of claims 1 to
5, wherein the radically polymerizable compound (C) includes a bifunctional
(meth)acrylate compound (Cl) and a tri- or more-functional (meth)acrylate compound
(C2).
7. The aqueous polyurethane resin dispersion according to any one of claims 1 to
25 6, wherein a content of the radically polymerizable compound (C) is 10 to 50 wt %
based on 100 wt % of a total solid content of the aqueous polyurethane resin dispersion.
8. The aqueous polyurethane resin dispersion according to any one of claims 1 to
7, substantially containing no protective colloid, emulsifier, nor surfactant.
9. The aqueous polyurethane resin dispersion according to any one of claims 1 to
30 8, wherein the polyurethane resin is a polyurethane resin obtained by reacting at least a
polycarbonate polyol (a); an acidic group-containing polyol (b); and an optional polyol
(c) other than (a) and (b), with a polyisocyanate (d) to afford a polyurethane prepolymer
having no free-radically polymerizable unsaturated group, and further reacting with a
chain extender (B).
3 5 10. The aqueous polyurethane resin dispersion according to any one of claims 1 to
9, containing a photo-initiator.
11. A paint composition containing an aqueous polyurethane resin dispersion
according to any one of claims 1 to 10.
12. A coating agent composition containing an aqueous polyurethane resin
dispersion according to any one of claims 1 to 10.
5 13. A process for preparing an aqueous polyurethane resin dispersion according to
any one of claims 1 to 10 comprising:
a step (al) of reacting a polycarbonate polyol (a), an acidic group-containing
polyol (b), and an optional polyol (c) other than (a) and (b), with a polyisocyanate (d) to
afford a polyurethane prepolymer (A),
10 a step (0) of neutralizing the acidic group of the polyurethane prepolymer (A),
a step (y) of dispersing the polyurethane prepolymer (A) and a radically
polymerizable compound (C) in an aqueous medium, and
. .
I a step (6) of reacting the polyurethane prepolymer (A) with a chain extender
(B) which is reactive to an isocyanate group of the polyurethane prepolymer (A) to
.,,.-,.-, 15 afford an aqueous polyurethane resin.