JP2003226735A - Water-dispersion of acrylic-urethane copolymer and paint and adhesive containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-dispersion of an acrylic-urethane copolymer to form a coating film having excellent adhesion to a substrate having difficult adhesiveness such as a plastic, good for thermal resistance, water-resistance, abrasion resistance, flexibility resistance and especially excellent in weather resistance, and to provide a paint and an adhesive containing the water- dispersion. <P>SOLUTION: The water-dispersion of an acrylic-urethane copolymer is obtained from chain-elongating of (a) a polyisocyanate compound, (b) a high molecular weight polyol containing an acrylic polyol having a hydroxyl value of 5-200 mgKOH/g which is obtained by copolymerizing an ultraviolet absorbing aromatic monomer with an aliphatic monomer having one ethylenic unsaturated bond and hydroxyl groups, and (c) a neutralized material of an isocyanate group-terminal prepolymer obtained from a compound having an anionic hydrophilic group and two or more active hydrogen, in water using (d) at least one selected from the group consisting of a water-soluble polyamine, hydrazine and these derivatives, and a paint and an adhesive comprises the water- dispersion. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an acrylic-urethane copolymer water dispersion, and a coating agent and an adhesive containing the water dispersion. More specifically, the present invention relates to an acrylic-urethane copolymer aqueous dispersion which forms a coating film having excellent adhesion, heat resistance, water resistance, abrasion resistance, and bending resistance, and particularly excellent weather resistance, and the dispersion. The present invention relates to a coating agent and an adhesive containing.

[0002]

2. Description of the Related Art Conventionally, organic solvent-based resins have been mainly used in the field of various adhesives and various coating agents such as paints and printing inks. It is being replaced by an aqueous resin for reasons such as environmental improvement. Furthermore, high quality, diversification of coating substrate,
With the use in new applications, such water-based resins are required to be highly functional.For example, in the coating field such as outer walls, roofs and structures in the construction field, durability performance under more severe conditions is required. ing. As an aqueous resin for such applications, an acrylic polymer is inexpensive and has excellent weather resistance, light resistance, and toughness, and is therefore used in a wide range of fields such as architectural interiors, leather, metals, and wooden floors. . However, it is difficult to achieve both softness and hardness with acrylic resin alone, and soft ones generally have poor water resistance and alkali resistance.On the other hand, hard ones have poor film-forming properties, crack resistance, flex resistance, etc. Due to the inferiority, a problem such as peeling of the coating film occurs when the base material expands and contracts due to the temperature difference of the outside air. In addition, water-based urethane resin is mainly used as a coating agent for woodworking products and flooring materials because of its excellent elasticity, abrasion resistance, and bending resistance. It has the drawback of being inferior. In order to improve such a drawback, by blending, compounding or copolymerizing an aqueous acrylic resin and an aqueous urethane resin,
Various water-based resins have been developed that have both the advantageous properties of urethane resin and the advantageous properties of acrylic resin, and water-based resins having excellent adhesion to various substrates, water resistance, bending resistance, etc. have been obtained. However, in terms of long-term weather resistance, sufficient performance cannot be obtained, and further improvement is required.

[0003]

DISCLOSURE OF THE INVENTION The present invention has excellent adhesiveness even to substrates having poor adhesion such as plastics, urethane elastomers and concrete materials, and has excellent heat resistance, water resistance, abrasion resistance, An acrylic-urethane copolymer water dispersion that forms a coating film having excellent flex resistance and particularly excellent weather resistance, and a coating agent and an adhesive containing the water dispersion, which are made for the purpose of providing the same. is there.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has found that a polyisocyanate compound and an ultraviolet absorbing aromatic monomer are copolymerized to give a hydroxyl value of 5 to 5. A neutralized product of an isocyanate group-terminated prepolymer obtained from the reaction of a high molecular weight polyol containing 200 mgKOH / g of an acrylic polyol and a compound having an anionic hydrophilic group and two or more active hydrogens,
Aqueous dispersion of acrylic-urethane copolymer obtained by chain extension in water has excellent adhesion even to difficult-to-adhere substrates, and heat resistance, water resistance, abrasion resistance, and bending resistance. Excellent,
It was found that a coating film having particularly excellent weather resistance was formed, and the present invention was completed based on this finding. That is, the present invention provides (1) (a) a polyisocyanate compound,
(b) The hydroxyl value based on the aliphatic monomer obtained by copolymerizing the ultraviolet absorbing aromatic monomer and the aliphatic monomer having one ethylenically unsaturated bond and a hydroxyl group is A high molecular weight polyol containing 5 to 200 mg KOH / g of an acrylic polyol and (c) an anionic hydrophilic group and 2
A neutralized product of an isocyanate group-terminated prepolymer obtained from a compound having one or more active hydrogens is prepared by using at least one selected from the group consisting of (d) water-soluble polyamine, hydrazine and derivatives thereof in water. Acrylic characterized by being an aqueous dispersion obtained by chain extension
Urethane copolymer water dispersion, (2) UV-absorbing aromatic monomer is an acrylic-urethane copolymer water dispersion according to item 1, which is a compound represented by the general formula [1],

[Chemical 3] (However, in the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ² is an alkylene group having 1 to 6 carbon atoms, R ³ is a hydrogen atom or a methyl group, and X is A hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a cyano group or a nitro group), and (3) an acrylic polyol are represented by the general formula [2]. An acrylic-urethane copolymer aqueous dispersion according to claim 1, wherein the ultraviolet-stable monomer and / or the ultraviolet-stable monomer represented by the general formula [3] is copolymerized.

[Chemical 4] (However, in the formula, R ⁴ is a hydrogen atom or a cyano group,
R ⁵ and R ⁶ are each independently a hydrogen atom, a methyl group or an ethyl group, R ⁷ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and Y is an oxygen atom or an imino group. ) And (4) in the acrylic polyol, a UV absorbing aromatic monomer used for copolymerization, a UV stable monomer represented by the general formula [2] and a UV stability represented by the general formula [3] Acrylic-urethane copolymer aqueous dispersion according to claim 1 or 3, wherein the total weight of the monomers is 1 to 30% by weight of all the monomers used for the copolymerization, and (5) containing the acrylic polyol. The amount is 5 of the total weight of (b) high molecular weight polyol.
The acrylic-urethane copolymer aqueous dispersion according to the first item, which is ˜60% by weight, and (6) the high molecular weight polyol is selected from polyester polyol, polycarbonate polyol, polyether polyol and dimer diol, in addition to acrylic polyol. Acrylic-urethane copolymer water dispersion according to claim 1, containing at least one kind,
(7) (c) In the compound having an anionic hydrophilic group and two or more active hydrogens, the anionic hydrophilic group is a carboxyl group, and the content of the carboxyl group in the acrylic-urethane copolymer is 0.3 to 2.5 of the total weight of the polymer
The acrylic-urethane copolymer water dispersion according to the first aspect, which is the weight%, and (8) the acrylic-urethane copolymer water dispersion according to any of the first to seventh aspects. And an adhesive containing the acrylic-urethane copolymer water dispersion according to any one of (1) to (7). Furthermore, as a preferred embodiment of the present invention, (10) the acrylic-urethane copolymer aqueous dispersion according to item 1, wherein the acrylic polyol has a glass transition temperature (Tg) of −25 to 100 ° C.
(11) The weight average molecular weight of the acrylic polyol is 1,
Acrylic according to item 1, which is 000 to 500,000
The urethane-copolymer aqueous dispersion, and (12) the acrylic-urethane-copolymer aqueous dispersion, wherein the high molecular weight polyol contains 1 to 30% by weight of dimer diol,
Can be mentioned.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The acrylic-urethane copolymer aqueous dispersion of the present invention comprises (a) a polyisocyanate compound and (b)
UV absorbing aromatic monomer and ethylenically unsaturated bond 1
And a high molecular weight polyol containing an acrylic polyol having a hydroxyl value of 5 to 200 mgKOH / g based on the aliphatic monomer obtained by copolymerizing an aliphatic monomer having a hydroxyl group and a hydroxyl group, and (c) anion A neutralized product of an isocyanate group-terminated prepolymer obtained from a compound having a hydrophilic hydrophilic group and two or more active hydrogens, using (d) at least one selected from water-soluble polyamines, hydrazine and derivatives thereof, It is an aqueous acrylic-urethane copolymer aqueous dispersion obtained by chain extension in water. There is no particular limitation on the (a) polyisocyanate compound used in the present invention. Examples thereof include aromatic diisocyanates such as cyclic diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, and xylylene diisocyanate. These polyisocyanate compounds can be used alone or in combination of two or more. Among these,
Aliphatic diisocyanates and alicyclic diisocyanates are preferable because they give a non-yellowing-modified coating film, and isophorone diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate and hexamethylene diisocyanate can be particularly preferably used.

In the present invention, the high molecular weight polyol (b) is obtained by copolymerizing an ultraviolet absorbing aromatic monomer with an aliphatic monomer having one ethylenically unsaturated bond and a hydroxyl group. It contains an acrylic polyol having a hydroxyl number of 5 to 200 mg KOH / g based on said aliphatic monomer. The ultraviolet absorbing aromatic monomer is 300 to 40.
It is a monomer having an ultraviolet absorbing ability in the wavelength region of 0 nm, and for example, 2-ethylhexyl-2-cyano-3,3
-Diphenyl acrylate, ethyl-2-cyano-3,
Examples thereof include cyanoacrylate-based UV absorbing aromatic monomers such as 3-diphenyl acrylate and benzotriazole-based UV absorbing aromatic monomers.
Among these, the ultraviolet absorbing aromatic monomer is preferably a compound represented by the general formula [1].

[Chemical 5] In the general formula [1], R ¹ is a hydrogen atom or a carbon number of 1 to 1.
8 is an alkyl group, R ² is an alkylene group having 1 to 6 carbon atoms, R ³ is a hydrogen atom or a methyl group, X is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms,
It is an alkoxyl group having 1 to 4 carbon atoms, a cyano group or a nitro group. The alkyl group having 1 to 8 carbon atoms represented by R ¹ is
It may be linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an amyl group and an octyl group. Can be mentioned. The alkylene group having 1 to 6 carbon atoms represented by R ² may be linear or branched and includes, for example, a methylene group, an ethylene group,
Examples thereof include a propylene group, a trimethylene group, a butylene group and a hexamethylene group. Examples of the halogen atom represented by X include a chlorine atom and a bromine atom. The alkyl group having 1 to 8 carbon atoms represented by X may be linear or branched,
Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an amyl group and an octyl group. The alkoxyl group having 1 to 4 carbon atoms represented by X may be linear or branched, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group and a butoxy group. Can be mentioned.

As the compound represented by the general formula [1],
For example, 2- [2'-hydroxy-5 '-(methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyethyl) phenyl] -2H-benzotriazole,
2- [2'-hydroxy-5 '-(methacryloyloxypropyl) phenyl] -2H-benzotriazole, 2
-[2'-Hydroxy-5 '-(methacryloyloxyhexyl) phenyl] -2H-benzotriazole, 2-
[2'-Hydroxy-3'-t-butyl-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-t-butyl-
3 '-(methacryloyloxyethyl) phenyl] -2H
-Benzotriazole, 2- [2'-hydroxy-5'-
(Methacryloyloxymethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxymethyl) phenyl] -5
-Methoxy-2H-benzotriazole, 2- [2'-
Hydroxy-5 '-(methacryloyloxymethyl) phenyl] -5-cyano-2H-benzotriazole, 2-
[2'-hydroxy-5 '-(methacryloyloxymethyl) phenyl] -5-nitro-2H-benzotriazole and the like can be mentioned. These ultraviolet absorbing aromatic monomers may be used alone or in combination of two or more. Examples of the aliphatic monomer having one ethylenically unsaturated bond and a hydroxyl group used in the present invention include 2-hydroxyl ethyl (meth) acrylate, 2-hydroxyl propyl (meth) acrylate and 2-hydroxybutyl ( (Meth) acrylate, 3-chloro-2-hydroxybutyl
(Meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 5,6-dihydroxyhexyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate, mono (meth) acrylate of polyester diol obtained from phthalic acid and propylene glycol (Meth) acrylate having a hydroxyl group such as Here, (meth) acrylate is
Means acrylate and methacrylate. These monomers can be used alone, or
It is also possible to use two or more types in combination.

The acrylic polyol used in the present invention is further copolymerized with a UV stable monomer represented by the general formula [2] and / or a UV stable monomer represented by the general formula [3]. Preferably.

[Chemical 6] In the general formulas [2] and [3], R ⁴ is a hydrogen atom or a cyano group, R ⁵ and R ⁶ are each independently a hydrogen atom, a methyl group or an ethyl group, and R ⁷ is a hydrogen atom. Alternatively, it is an alkyl group having 1 to 18 carbon atoms, and Y is an oxygen atom or an imino group. 1 to 18 carbon atoms represented by R ⁷
The alkyl group of may be linear or branched, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group. Group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group,
Examples thereof include tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group and octadecyl group. Examples of the UV stable monomer represented by the general formula [2] include 4- (meth) acryloyloxy-2,2,
6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine,
4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine,
4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-
Examples thereof include tetramethylpiperidine. These ultraviolet stable monomers can be used alone or in combination of two or more. Examples of the UV stable monomer represented by the general formula [3] include 1- (meth) acryloyl-4- (meth).
Acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4-
(Meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine and the like can be mentioned. These UV stable monomers are 1
The seeds may be used alone, or two or more kinds may be used in combination. The above (meth) acryloyl means acryloyl and methacryloyl. In producing an acrylic polyol, a UV-absorbing aromatic monomer, a UV-stable monomer represented by the general formula [2] and / or a UV-stable monomer represented by the general formula [3] By further copolymerizing with the polymer, the ultraviolet stability of the coating film obtained from the acrylic-urethane copolymer aqueous dispersion is improved, and excellent weather resistance is exhibited.

In the present invention, a monomer copolymerizable with the above-mentioned monomer can be further copolymerized during the production of the acrylic polyol. As the copolymerizable monomer, for example, methyl (meth) acrylate, ethyl (meth)
Acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl
(Meth) acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth)
Acrylate, n-hexyl (meth) acrylate, 2-
Ethyl butyl (meth) acrylate, n-octyl (meth)
Acrylate, 2-ethylhexyl (meth) acrylate, 2-chloroethyl (meth) acrylate, trifluoroethyl (meth) acrylate, benzyl (meth) acrylate, hexafluoroisopropyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2 -N-
Butoxyethyl (meth) acrylate, 2-methoxybutyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-nitro-2-methylpropyl (meth) acrylate, furfuryl (meth) acrylate, cyclopentyl (meth) acrylate, Cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, te
rt-Butylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, tetrahydrofurfuryl
(Meth) acrylate, tetrahydropyranyl (meth) acrylate, benzyl (meth) acrylate, cinnamyl
(Meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-phenylethyl (meth) acrylate, phenyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid, vinylsulfonic acid, styrenesulfonic acid, sulfoethyl (Meth) acrylate, 2-
(Meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxypropyl acid phosphate, 2- (meth) acryloyloxy-3-chloropropyl acid phosphate, propyl acid phosphate, 2- (meth) acryloyloxyethyl phenyl phosphate , Vinyl chloride, vinylidene chloride, styrene,
Examples thereof include α-methylstyrene, vinyltoluene, (meth) acrylonitrile, vinyl acetate, vinylpyridine, vinylpyrrolidone, methylcrotonate, and maleic anhydride. These copolymerizable monomers can be used alone or in combination of two or more. Incidentally, (meth) acrylate means acrylate and methacrylate, (meth) acrylic acid means acrylic acid and methacrylic acid, (meth) acryloyl means acryloyl and methacryloyl, (meth) acrylonitrile and acrylonitrile and Methacrylonitrile is meant.

In the acrylic polyol used in the present invention, the proportion of each of the above-mentioned monomers is not particularly limited, but the UV-absorbing aromatic monomer used in the copolymerization, the UV-stability represented by the general formula [2]. The total weight of the polymerizable monomer and the UV stable monomer represented by the general formula [3] is preferably 1 to 30% by weight, and 2 to 20% by weight based on the total monomers used for the copolymerization. Is more preferable, and 3 to 15% by weight is further preferable. When the total weight of the UV-absorbing aromatic monomer and the UV-stable monomer is less than 1% by weight of the total monomers, the weather resistance of the coating film obtained from the acrylic-urethane copolymer aqueous dispersion is high. It may be insufficient. When the total weight of the UV-absorbing aromatic monomer and the UV-stable monomer exceeds 30% by weight of the total monomers, the gloss, solvent resistance and chemical resistance of the coating film may deteriorate. In the present invention, the method for producing an acrylic polyol is not particularly limited,
It can be produced by a conventionally known polymerization method, for example, a bulk polymerization method or a solution polymerization method. Acrylic polyol, the above monomers, polyester polyol, polycarbonate polyol, which is another polyol component,
It can also be obtained by polymerization using a polyether polyol or the like as a solvent. The acrylic polyol used in the present invention has a hydroxyl value of 5 to 20 based on an aliphatic monomer having one ethylenically unsaturated bond and a hydroxyl group.
0 mgKOH / g, more preferably 30 to 70 mgKOH / g
It is g. The hydroxyl number based on the aliphatic monomer is
It can be calculated from the composition of the monomers to be copolymerized. When the ultraviolet absorbing aromatic monomer has a hydroxyl group, it is obtained by copolymerizing an ultraviolet absorbing aromatic monomer and an aliphatic monomer having one ethylenically unsaturated bond and a hydroxyl group. The hydroxyl number of the resulting acrylic polyol is measured as the sum of the hydroxyl number based on the aromatic monomer and the hydroxyl number based on the aliphatic monomer. The hydroxyl value based on the aliphatic monomer is 5 mg KO
If it is less than H / g, the number of bonding points between the acrylic resin and the urethane resin is decreased, and the performance as a copolymer may not be sufficiently exhibited. If the hydroxyl value based on the aliphatic monomer exceeds 200 mgKOH / g, gelation will proceed due to an increase in crosslink density during synthesis of the isocyanate group-terminated prepolymer, which may make production difficult.

The acrylic polyol used in the present invention preferably has a glass transition temperature (Tg) of -25 to 100 ° C, more preferably 0 to 50 ° C. If the glass transition temperature is lower than -25 ° C, the water resistance and alkali resistance of the coating film may be insufficient. If the glass transition temperature exceeds 100 ° C, the film forming property and crack resistance may be insufficient. The acrylic polyol used in the present invention preferably has a weight average molecular weight of 1,000 to 500,000, and more preferably 8,000 to 100,000. In the present invention, commercially available acrylic polyol can be used. Examples of such a commercially available product include Uedable UV-6010 manufactured by Nippon Shokubai Co., Ltd. In the present invention, the content of the acrylic polyol in the (b) high molecular weight polyol is preferably 5 to 60% by weight based on the total weight of the high molecular weight polyol, and 10 to 4
It is more preferably 0% by weight. When the content of the acrylic polyol is less than 5% by weight based on the total weight of the high molecular weight polyol, the acrylic resin may not sufficiently exhibit advantageous properties such as weather resistance. When the content of the acrylic polyol exceeds 60% by weight based on the total weight of the high molecular weight polyol, the urethane resin may exhibit insufficient mechanical resistance, particularly advantageous performance such as elasticity.

In the present invention, as the high molecular weight polyol (b), other polyols can be contained in addition to the above acrylic polyol. Other polyols are not particularly limited, but polyester polyols,
Polycarbonate polyol, polyether polyol or dimer diol can be preferably used. As the polyester polyol, for example, polyethylene adipate diol, polybutylene adipate diol,
Polyethylene butylene adipate diol, polyhexamethylene isophthalate adipate diol, polyethylene succinate diol, polybutylene succinate diol, polyethylene sebacate diol, polybutylene sebacate diol, poly-ε-caprolactone diol, poly (3-methyl-1, 5-pentylene adipate) diol, a polycondensation product of 1,6-hexanediol and dimer acid and the like can be mentioned. Examples of the polycarbonate polyol include polytetramethylene carbonate diol, polyhexamethylene carbonate diol, poly (1,4-cyclohexane dimethylene carbonate) diol, poly (hexamethylene-1,4-cyclohexane dimethylene) carbonate diol, and the like. be able to. As a polyether polyol,
Examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, random or block copolymers of ethylene oxide and butylene oxide, random or block copolymers of ethylene oxide and butylene oxide, and the like. Furthermore, it is also possible to use a polyether polyester polyol having an ether bond and an ester bond. Dimer diol is a polyol whose main component is a diol obtained by reducing dimer acid. here,
The dimer acid is mainly an unsaturated fatty acid having 18 carbon atoms such as oleic acid, linoleic acid, and linoleic acid, a drying oil fatty acid, a semi-drying oil fatty acid or a lower monoalkyl ester of these fatty acids, if necessary using a catalyst, It is a compound obtained by a Diels-Alder type bimolecular polymerization. Although various types of dimer acids are commercially available, a typical example is a monocarboxylic acid having 18 carbon atoms.
-30% by weight.

In the present invention, the high molecular weight polyol (b) preferably contains at least one polyol selected from the group consisting of polyester polyols, polycarbonate polyols, polyether polyols and dimer diols, and its total weight. Is more preferably 10 to 95% by weight of the total weight of the high molecular weight polyol (b). Further, in the present invention, the content of the dimer diol in the high molecular weight polyol is preferably 1 to 30% by weight based on the total weight of the high molecular weight polyol, and 5-2.
It is more preferably 0% by weight. By including dimer diol in the high molecular weight polyol, the effect of the dimer diol as a hydrophobic component can improve the water resistance of the coating film. When the content of the dimer diol is less than 1% by weight of the total weight of the high molecular weight polyol, the water resistance of the coating film may be insufficiently improved. When the content of the dimer diol exceeds 30% by weight of the total weight of the high molecular weight polyol, the physical properties derived from the urethane resin may be deteriorated. In the present invention, a rosin-containing polyol can be used as the other polyol component. The rosin-containing polyol is a reaction product composed of one molecule of diepoxy compound and two molecules of resin acid contained in rosins. There is no particular limitation on the rosin used, for example, gum rosin, wood rosin, natural rosin such as tall oil rosin, purified rosin, disproportionated rosin, purified disproportionated rosin, processed rosin such as hydrogenated rosin, and the like. A mixture etc. can be mentioned. Examples of diepoxy compounds include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, and tripropylene glycol diglycidyl ether. , Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, aliphatic diglycidyl ethers such as 1,6-hexanediol diglycidyl ether, 2,2-bis (4-hydroxyphenyl) propane diglycidyl ether, 3, Aromatic diglycines such as 3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl diglycidyl ether Ethers, 2,2-bis
Alicyclic diglycidyl ethers such as (4-hydroxycyclohexyl) propane diglycidyl ether, 3,4
Examples thereof include cyclic oxiranes such as -epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and vinylcyclohexanedioxide.

In the present invention, the compound (c) having an anionic hydrophilic group and at least two active hydrogens is not particularly limited, but the anionic hydrophilic group is a carboxyl group,
A compound in which active hydrogen is hydrogen of a hydroxyl group can be preferably used. Examples of such compounds include 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid. As such a carboxyl group-containing diol, a polyester polyol having a pendant carboxyl group obtained from a diol component having a carboxyl group and a dicarboxylic acid such as an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid or an alicyclic dicarboxylic acid is used. It can also be used. When synthesizing such a diol having a carboxyl group,
If necessary, a diol having no carboxyl group can be used in combination. These (c) anionic hydrophilic groups and 2
The compounds having one or more active hydrogens can be used alone or in combination of two or more. In the present invention, the content of the carboxyl group derived from the component (c) in the acrylic-urethane copolymer is preferably 0.3 to 2.5% by weight based on the total weight of the copolymer, and the content of the carboxyl group is 0.3 to 2.5% by weight. More preferably, it is 5 to 1.5% by weight. When the content of the carboxyl group is less than 0.3% by weight of the total weight of the copolymer, it may be difficult to emulsify the acrylic-urethane copolymer, or the emulsion stability may be insufficient. When the content of the carboxyl group exceeds 2.5% by weight based on the total weight of the copolymer, the water resistance of the coating film may decrease.

In the present invention, the above-mentioned component (a), (b)
Using the component and the component (c), first, an isocyanate group-terminated prepolymer having an isocyanate group at the terminal is synthesized. The isocyanate group-terminated prepolymer is synthesized by, for example, a conventionally known one-shot method (one-step method) or a multi-step isocyanate polyaddition reaction method at a reaction temperature of 40 to 1
It can be performed under the condition of 50 ° C. At this time, if necessary, a reaction catalyst such as dibutyltin dilaurate, stannas octanoate, dibutyltin-2-ethylhexanoate, triethylamine, triethylenediamine, N-methylmorpholine can be added. These reaction catalysts can be used alone, or
It is also possible to use two or more types in combination. In addition, an organic solvent that does not react with an isocyanate group can be added in the reaction stage or after the reaction is completed.
Examples of such an organic solvent include acetone, methyl ethyl ketone, toluene, tetrahydrofuran, dioxane, dimethylformamide, N-methylpyrrolidone, and the like. In the present invention, when synthesizing the isocyanate group-terminated prepolymer, (e) a chain extender for prepolymer can be used, if necessary. The chain extender for prepolymer is not particularly limited, and examples thereof include ethylene glycol, 1,4-butanediol, 1,
Low molecular weight polyhydric alcohols such as 6-hexanediol, trimethylolpropane, pentaerythritol, and sorbitol, ethylenediamine, propylenediamine, hexamethylenediamine, di (aminocyclohexyl) methane, piperazine, 2-methylpiperazine, isophoronediamine, diethylenetriamine, triethyldiamine. Examples thereof include low molecular weight polyamines such as ethylene tetramine. These chain extenders for prepolymers may be used alone or in combination of two or more. In the present invention, the neutralized product of the isocyanate group-terminated prepolymer means, before or after the synthesis of the isocyanate group-terminated prepolymer, trimethylamine, triethylamine, tri-n-propylamine, tributylamine, N-methyldiethanolamine, N,
By using amines such as N-dimethylmonoethanolamine, N, N-diethylmonoethanolamine and triethanolamine, potassium hydroxide, sodium hydroxide, ammonia and the like, the anionic hydrophilic group in the component (c) is neutralized. It is obtained by harmonizing. In the present invention, the neutralized product of the isocyanate group-terminated prepolymer and the resulting acrylic-urethane copolymer can be stably emulsified and dispersed in water without adding an emulsifier.

In the present invention, the neutralized product of the isocyanate group-terminated prepolymer is polymerized by chain extension in water using at least one selected from (d) water-soluble polyamine, hydrazine and derivatives thereof. . Examples of the water-soluble polyamine used as the component (d) include ethylenediamine, propylenediamine, hexamethylenediamine, diaminocyclohexylmethane, piperazine, 2-
Methylpiperazine, isophoronediamine, diethylenetriamine, triethylenetetramine and the like can be mentioned. Examples of the water-soluble amine derivative used as the component (d) include amidoamines derived from diprimary amines and monocarboxylic acids, and monoketimines of diprimary amines. Examples of the hydrazine derivative used as the component (d) include compounds having at least two hydrazino groups in the molecule. Among these, dihydrazides of dicarboxylic acids having 2 to 10 carbon atoms and aliphatic water-soluble dihydrazine having 2 to 4 carbon atoms can be preferably used. 2 to 1 carbon atoms
Examples of the dicarboxylic acid dihydrazide of 0 include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, itadonic acid dihydrazide. You can Examples of the aliphatic water-soluble dihydrazine having 2 to 4 carbon atoms include 1,1′-ethylenedihydrazine, 1,1′-trimethylenedihydrazine, and 1,1′-butylene dihydrazine. it can. In the present invention, when the isocyanate group-terminated prepolymer is prepared using an organic solvent, it is preferable to remove the organic solvent by, for example, vacuum distillation after blocking the terminal isocyanate group. When removing the organic solvent, a surfactant such as a higher fatty acid, a resin acid, an acidic fatty alcohol, a sulfuric acid ester, a higher alkyl sulfonate, an alkylallyl sulfonate, a sulfonated castor oil, or an anionic surface of a sulfosuccinic acid ester is used. The emulsifiability can be maintained by using an activator, a nonionic surfactant such as a reaction product of ethylene oxide and a long-chain aliphatic alcohol or a phenol, and the like in combination.

The coating agent and adhesive of the present invention are coating agents and adhesives containing the acrylic-urethane copolymer water dispersion of the present invention. In the coating agent and adhesive of the present invention,
The concentration of the acrylic-urethane copolymer can be appropriately selected according to the purpose. In the coating agent and adhesive of the present invention, various surfactants such as fluorine-based or acetylene glycol-based as a leveling agent, and n-methylpyrrolidone, propylene glycol monomethyl ether acetate, ethylene as a solvent, if necessary. Glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether and the like can be contained. The acrylic-urethane copolymer aqueous dispersion of the present invention itself has durability, light resistance, weather resistance, and excellent resin physical properties with respect to water resistance, but an aqueous oxazoline-based crosslinking agent, an aqueous polycarbodiimide-based crosslinking agent, A water-based epoxy resin-based cross-linking agent or other cross-linking agent having reactivity with a carboxyl group or a water-dispersible polyisocyanate-based cross-linking agent may be used in combination to further improve the water resistance of the coating agent and the adhesive. it can. The water dispersion of the acrylic-urethane copolymer of the present invention is used as various coating agents such as adhesives, paints, printing inks, and the like, in various plastic groups such as acrylic resin, ABS resin, polycarbonate resin, polyurethane resin, epoxy resin and the like. Materials, difficult-to-adhere plastic base materials such as polyolefin resins and polyester resins, elastomers such as urethane elastomers, concrete base materials, glass base materials, metals such as stainless steel, wood, paper, leather, and various bases such as fibers It can be widely used for materials, and shows excellent adhesion, especially as a top coat agent for urethane-based waterproofing materials for buildings, and important characteristics such as smoothness of coated surface, water resistance, and weather resistance. , Which satisfies the bending resistance at low temperatures. The acrylic-urethane copolymer aqueous dispersion of the present invention is a completely uniform copolymer in which the acrylic-urethane copolymer is uniformly incorporated into the polyurethane resin, and the acrylic resin portion absorbs ultraviolet rays. UV-absorbing ability and UV-ray due to the synergistic effect of the UV-absorbing aromatic monomer and the UV-stabilizing monomer because of the structure containing the aromatic aromatic monomer and optionally the UV-stabilizing monomer. It is considered that the stability is sufficiently exhibited and the weather resistance is excellent.

[0018]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The viscosities of the acrylic polyols obtained in Synthetic Examples and Comparative Synthetic Examples were measured using a Gardner one-foam viscometer. The weight average molecular weight of acrylic polyol is the high-speed GPC system [Tosoh Corporation, H
LC-8120GPC], and was measured by gel permeation chromatography and converted into a polystyrene standard sample. In the Synthetic Examples, Comparative Synthetic Examples, Examples, and Comparative Examples, 5.0 g of the non-volatile matter was placed in a Petri dish and dried at 105 ° C. in a dryer [Tabay Espec
It was determined as the heating residue after standing for 3 hours in Perfect Oven PV-210]. Further, in Examples and Comparative Examples, the coating film physical properties were evaluated by the following methods. (1) Preparation of coating film As an adherend, a stretched polypropylene film (OPP) and a polycarbonate (P
C) board, oak board, concrete board, stainless steel plate, glass board, urethane waterproof sheet [Daiflex Co., Ltd., S
P-100] was used to apply a coating agent to a film thickness of 100 μm, and the mixture was allowed to stand at 25 ° C. for 1 week, and then the obtained coating film was tested. (2) Appearance of coating film Cracks appearing in the coating film on the glass plate were visually evaluated. ◯: No crack is observed. Δ: A slight crack is observed. X: Clear cracks are recognized. (3) Adhesion Regarding the obtained coating film, JIS K 5400 8.5.2.
In accordance with (1990), use a cutter knife to make 100 squares in the coating with a clearance of 1 mm, and attach cellophane adhesive tape [Nichiban Co., Ltd.] to the squares at an angle of 60 degrees. The appearance of the coating film when peeled off rapidly was observed and evaluated according to the following criteria. A: 95% or more of the coating film remains on the adherend side. ◯: 80% or more and less than 95% of the coating film remains on the adherend side. Δ: 50% or more and less than 80% of the coating film remains on the adherend side. X: Less than 50% of the coating film remains on the adherend side. (4) Apply the coating film prepared on the water-resistant concrete board to 40 ° C water.
After immersion for 8 hours, the whitening state of the coating film was visually evaluated. ◯: No whitening is observed. Δ: Slightly whitened. X: Remarkable whitening occurs. (5) The coating film produced on the weather-resistant concrete plate was irradiated with a sunshine weatherometer for 5,000 hours to evaluate the change in the appearance of the coating film. ◯: No whitening is observed. Δ: Slightly whitened. X: Remarkable whitening occurs. (6) The coating film formed on the flex-resistant urethane waterproof sheet was bent 180 degrees, and cracks and peeling were visually observed. ◯: No cracking or peeling is observed. B: Slight cracking and peeling are observed. X: Cracks and peeling are clearly seen.

Synthesis Example 1 (Acrylic Polyol Solution A) In a four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, a gas introduction tube and a reflux condenser tube, xylene 2 was used as a solvent.
Charge 5.0 parts by weight and 25.0 parts by weight of butyl acetate, 1
The temperature was raised to 00 ° C. On the other hand, 2- [2'-hydroxy- which is an ultraviolet absorbing aromatic monomer represented by the general formula [1].
5 '-(methacryloyloxyethyl) phenyl] -2H
-Benzotriazole 1.0 part by weight, cyclohexyl methacrylate 28.5 parts by weight, hydroxyethyl methacrylate 20.0 parts by weight, methacrylic acid 0.5 part by weight and 2,2'-azobisisobutyronitrile 0 as a polymerization initiator. Pour the mixture of 0.5 parts by weight into a dropping funnel,
The mixture was added dropwise at 100 ° C. over 2 hours with stirring under a nitrogen gas stream, and the mixture was stirred for 4 hours while maintaining the temperature at 100 ° C. for copolymerization to obtain an acrylic polyol solution. The viscosity of this acrylic polyol solution is Z + (viscosity standard liquid symbol), the nonvolatile content is 49.8% by weight, the hydroxyl value based on hydroxyethyl methacrylate of the acrylic polyol in the solution is 172 mgKOH / g, and the weight average The molecular weight was 15,000. This acrylic polyol solution is referred to as acrylic polyol solution A. Synthesis Example 2 (Acrylic Polyol Solution B) Xylene 2 was used as a solvent in the same reactor as in Synthesis Example 1.
Charge 0.0 parts by weight and 20.0 parts by weight of butyl acetate, 1
The temperature was raised to 00 ° C. On the other hand, 2- [2'-hydroxy- which is an ultraviolet absorbing aromatic monomer represented by the general formula [1].
5 '-(methacryloyloxyethyl) phenyl] -2H
-Benzotriazole 12.0 parts by weight, cyclohexyl methacrylate 18.0 parts by weight, hydroxyethyl methacrylate 8.0 parts by weight, methacrylic acid 0.5 parts by weight, n
-Add 1.5 parts by weight of butyl acrylate and 0.5 parts by weight of 2,2'-azobisisobutyronitrile as a polymerization initiator into a dropping funnel and stir at 100 ° C under a nitrogen gas stream while stirring. Over 2 hours, add 1 drop
While maintaining at 00 ° C., the mixture was stirred for 4 hours for copolymerization to obtain an acrylic polyol solution. The viscosity of this acrylic polyol solution is Z + (viscosity standard liquid symbol), the nonvolatile content is 49.8% by weight, the hydroxyl value based on hydroxyethyl methacrylate of the acrylic polyol in the solution is 86 mgKOH / g, and the weight average is Molecular weight is 15,000
It was 0. This acrylic polyol solution is referred to as acrylic polyol solution B. Synthesis Example 3 (Acrylic polyol solution C) Xylene 2 was used as a solvent in the same reactor as in Synthesis Example 1.
Charge 5.0 parts by weight and 25.0 parts by weight of butyl acetate, 1
The temperature was raised to 00 ° C. On the other hand, 2- [2'-hydroxy- which is an ultraviolet absorbing aromatic monomer represented by the general formula [1].
5 '-(methacryloyloxyethyl) phenyl] -2H
-Benzotriazole 5.0 parts by weight, cyclohexyl methacrylate 34.5 parts by weight, hydroxyethyl methacrylate 8.0 parts by weight, methacrylic acid 0.5 part by weight, and a UV-stabilized monomer represented by the general formula [2]. 4-methacryloyloxy-2,2,6,6, -tetramethylpiperidine (2.0 parts by weight) and 2,2'-azobisisobutyronitrile (0.5 part by weight) as a polymerization initiator are mixed. Put the liquid in a dropping funnel and stir under nitrogen gas flow for 10
The solution was added dropwise at 0 ° C. over 2 hours, and was stirred for 4 hours while maintaining the temperature at 100 ° C. for copolymerization to obtain an acrylic polyol solution. The viscosity of this acrylic polyol solution is Z +
(Viscosity standard liquid symbol), non-volatile content is 50.1% by weight
And the hydroxyl number based on hydroxyethylmethacrylate of acrylic polyol in the solution is 68 mg KOH
/ G, and the weight average molecular weight was 14,000.
This acrylic polyol solution is referred to as acrylic polyol solution C. Synthetic Example 4 (Acrylic Polyol Solution D) Xylene 2 was used as a solvent in the same reactor as in Synthetic Example 1.
Charge 5.0 parts by weight and 25.0 parts by weight of butyl acetate, 1
The temperature was raised to 00 ° C. On the other hand, 2- [2'-hydroxy- which is an ultraviolet absorbing aromatic monomer represented by the general formula [1].
5 '-(methacryloyloxyethyl) phenyl] -2H
-7.0 parts by weight of benzotriazole, 23.0 parts by weight of cyclohexyl methacrylate, 15.0 parts by weight of hydroxyethyl methacrylate, 4-methacryloyloxy-2, which is an ultraviolet stable monomer represented by the general formula [2].
A mixture of 5.0 parts by weight of 2,6,6, -tetramethylpiperidine and 0.5 parts by weight of 2,2'-azobisisobutyronitrile as a polymerization initiator was placed in a dropping funnel, and a nitrogen gas stream was introduced. The mixture was added dropwise with stirring at 100 ° C. for 2 hours under stirring, and the mixture was stirred for 4 hours while maintaining the temperature at 100 ° C. for copolymerization to obtain an acrylic polyol solution. The viscosity of this acrylic polyol solution is Z + (viscosity standard liquid symbol), the non-volatile content is 50.1% by weight, the hydroxyl value based on hydroxyethyl methacrylate of the acrylic polyol in the solution is 128 mgKOH / g, and the weight average The molecular weight was 14,000. This acrylic polyol solution is referred to as acrylic polyol solution D. Comparative Synthesis Example 1 (Acrylic Polyol Solution E) In a reactor similar to Synthesis Example 1, toluene 2 was used as a solvent.
5.0 parts by weight and 25.0 parts by weight of butyl acetate were charged and heated to 100 ° C. under a nitrogen stream. On the other hand, 20.0 parts by weight of methyl methacrylate and 10.
A mixed solution of 0 parts by weight, 15.0 parts by weight of butyl acrylate, 5.0 parts by weight of hydroxyethyl methacrylate and 0.5 parts by weight of 2,2'-azobisisobutyronitrile as a polymerization initiator was placed in a dropping funnel. Then, the mixture was added dropwise at 100 ° C. over 2 hours with stirring under a nitrogen gas stream, and the mixture was stirred for 4 hours while maintaining the temperature at 100 ° C. for copolymerization.
An acrylic polyol solution was obtained. The viscosity of this acrylic polyol solution is Z + (viscosity standard liquid symbol), the nonvolatile content is 49.9% by weight, the hydroxyl value based on hydroxyethyl methacrylate of the acrylic polyol in the solution is 42 mgKOH / g, and the weight average The molecular weight is 15,
It was 000. This acrylic polyol solution is referred to as acrylic polyol solution E.

Example 1 (Acrylic-Urethane Copolymer Aqueous Dispersion A) 4 equipped with a stirrer, reflux condenser, thermometer and gas inlet tube
In a two-necked flask, 13.0 parts by weight of the acrylic polyol solution A obtained in Synthesis Example 1, 80.0 parts by weight of polyhexamethylene carbonate diol [number average molecular weight 1,000], 0.9 part by weight of 1,4-butanediol. Parts, 6.7 parts by weight of 2,2-dimethylolpropionic acid, 0.001 parts by weight of dibutyltin dilaurate and 60.0 parts of methyl ethyl ketone.
After adding 5 parts by weight of dicyclohexylmethane diisocyanate and mixing them uniformly, the mixture was reacted at 80 ° C. for 2 hours under a nitrogen gas stream to obtain an isocyanate having a free isocyanate group content of 2.0% by weight with respect to the nonvolatile content. A methyl ethyl ketone solution of the group-terminated prepolymer was obtained. This solution was cooled to 30 ° C., 5.0 parts by weight of triethylamine was added to neutralize, then 35.0 parts by weight of water was gradually added to emulsify and disperse, and 15.0 parts by weight of a 20% by weight aqueous solution of ethylenediamine was added. Parts were added and stirred for 2 hours. The solvent was removed under reduced pressure while raising the temperature to 60 ° C. over about 2 hours, and the non-volatile content of 35% by weight of acrylic resin was used.
An aqueous urethane copolymer dispersion was obtained. The content of the carboxyl group derived from 2,2-dimethylolpropionic acid in the acrylic-urethane copolymer in this aqueous dispersion is 1.5% by weight. This water dispersion is referred to as an acrylic-urethane copolymer water dispersion A. Example 2 (Acrylic-Urethane Copolymer Aqueous Dispersion B) In a reactor similar to that of Example 1, 97.6 parts by weight of the acrylic polyol solution B obtained in Synthesis Example 2 and polybutylene adipate diol [number average molecular weight 1 , 700] 102.0
By weight, 2,2-dimethylolbutanoic acid 7.4 parts by weight, dibutyltin dilaurate 0.001 part and methyl ethyl ketone 60.0 parts by weight were charged, and after uniformly mixing, 44.4 parts by weight of isophorone diisocyanate was added, The reaction was carried out at 80 ° C. for 2 hours under a nitrogen gas stream to obtain a methyl ethyl ketone solution of an isocyanate group-terminated prepolymer having a free isocyanate group content of 1.7% by weight based on the nonvolatile content. This solution was cooled to 30 ° C., neutralized by adding 5.0 parts by weight of triethylamine, then gradually added 350.0 parts by weight of water to emulsify and disperse, and then a 5.0% by weight aqueous solution of hydrazine hydrate 5.0%. Part by weight was added and stirred for 2 hours. The solvent was removed under reduced pressure while raising the temperature to 60 ° C. over about 2 hours to obtain an acrylic-urethane copolymer aqueous dispersion having a nonvolatile content of 35% by weight. The content of the carboxyl group derived from 2,2-dimethylolbutanoic acid in the acrylic-urethane copolymer in this aqueous dispersion is 1.0% by weight. This aqueous dispersion is referred to as an acrylic-urethane copolymer aqueous dispersion B. Example 3 (Acrylic-Urethane Copolymer Aqueous Dispersion C) A reactor similar to that used in Example 1 was charged with an acrylic polyol solution [Nippon Shokubai Co., Ltd., Udable UV-6010, about 50% by weight of non-volatile content in the solution]. Glass transition temperature of acrylic polyol 30 ° C., hydroxyl value based on aliphatic monomer having hydroxyl group 27 mg KOH / g] 41.6 parts by weight,
Poly (3-methyl-1,5-pentylene adipate) diol [number average molecular weight 2,000] 80.0 parts by weight, dimer diol [Toagosei Co., Ltd., PESPOL HP-100]
0, number average molecular weight 570] 23.0 parts by weight, 2,2-dimethylolbutanoic acid 7.4 parts by weight, dibutyltin dilaurate 0.001 parts by weight and methyl ethyl ketone 60.0 parts by weight were charged and mixed uniformly. , 52.4 parts by weight of dicyclohexylmethane diisocyanate were added and reacted at 80 ° C. for 2 hours under a nitrogen gas stream to obtain a methyl ethyl ketone solution of an isocyanate group-terminated prepolymer having a free isocyanate group content of 2.0% by weight with respect to a nonvolatile content. . This solution was cooled to 30 ° C., 5.0 parts by weight of triethylamine was added for neutralization, and then 350.0 parts by weight of water was gradually added to emulsify and disperse. To this emulsified dispersion, 1.6 parts by weight of a 60.0% by weight aqueous solution of hydrazine hydrate and 5.5 parts by weight of diethylenetriamine were added and stirred for 2 hours.
The solvent was removed under reduced pressure while raising the temperature to 60 ° C. over about 2 hours to obtain an acrylic-urethane copolymer aqueous dispersion having a nonvolatile content of 35% by weight. The content of the carboxyl group derived from 2,2-dimethylolbutanoic acid in the acrylic-urethane copolymer in this aqueous dispersion is 1.2% by weight. This aqueous dispersion was used as an acrylic-urethane copolymer aqueous dispersion C.
And

Example 4 (Acrylic-Urethane Copolymer Aqueous Dispersion D) The same reactor as in Example 1 was charged with an acrylic polyol solution [Nippon Shokubai Co., Ltd., Udable UV-6010, nonvolatile content: about 50% by weight, The glass transition temperature of the acrylic polyol in the solution is 30 ° C., the hydroxyl value based on the aliphatic monomer having a hydroxyl group is 27 mgKOH / g] 41.6 parts by weight,
Poly-ε-caprolactone diol [number average molecular weight 2,
000] 80.0 parts by weight, dimer diol [Toagosei
PESPOL HP-1000, number average molecular weight 57
0] 23.0 parts by weight, a solution obtained by adding 5.0 parts by weight of triethylamine to 7.4 parts by weight of 2,2-dimethylolbutanoic acid in 30.0 parts by weight of methyl ethyl ketone in advance, dibutyltin dilaurate. 001 parts by weight and 30.0 parts by weight of methyl ethyl ketone were charged and uniformly mixed, and then dicyclohexylmethane diisocyanate 52.4
Add parts by weight and react at 80 ° C. for 2 hours under a nitrogen gas stream to obtain a free isocyanate group content of 2.
A methyl ethyl ketone solution of a neutralized product of an isocyanate group-terminated prepolymer of 0% by weight was obtained. This solution was cooled to 30 ° C., and 35.0 parts by weight of water was gradually added to emulsify and disperse. To this emulsified dispersion, 5.0 parts by weight of a 60% by weight aqueous solution of hydrazine hydrate was added and stirred for 2 hours. The solvent was removed while heating to 60 ° C. under reduced pressure for about 2 hours to obtain an acrylic-urethane copolymer aqueous dispersion having a nonvolatile content of 35% by weight. The content of the carboxyl group derived from 2,2-dimethylolbutanoic acid in the acrylic-urethane copolymer in this aqueous dispersion is 1.2% by weight.
This water dispersion is referred to as an acrylic-urethane copolymer water dispersion D. Example 5 (Acrylic-Urethane Copolymer Aqueous Dispersion E) In the same reactor as in Example 1, 52.0 parts by weight of an acrylic polyol solution C and polytetramethylene glycol [number average molecular weight 2,000] 120.0 parts by weight were used. Parts, polyethylene glycol [number average molecular weight 600] 30.0 parts by weight, 2,
2.7 parts by weight of 2-dimethylolpropionic acid, 0.001 part by weight of dibutyltin dilaurate and 60.0 parts by weight of methyl ethyl ketone were charged and uniformly mixed, and then 33.6 parts by weight of hexamethylene diisocyanate was added to obtain 8 parts.
The reaction was carried out at 0 ° C. for 2 hours to obtain a methyl ethyl ketone solution of an isocyanate group-terminated prepolymer having a free isocyanate group content of 1.7% by weight with respect to the nonvolatile content. This solution was cooled to 30 ° C., 5.0 parts by weight of triethylamine was added for neutralization, and then 350.0 parts by weight of water was gradually added to emulsify and disperse. To this emulsified dispersion, 4.5 parts by weight of a 60% by weight aqueous solution of hydrazine hydrate was added and stirred for 2 hours. The solvent was removed while heating to 60 ° C. under reduced pressure for about 2 hours to obtain an acrylic-urethane copolymer aqueous dispersion having a nonvolatile content of 35% by weight. The content of carboxyl group derived from 2,2-dimethylolpropionic acid in the acrylic-urethane copolymer in this aqueous dispersion was 0.4.
% By weight. This water dispersion is referred to as an acrylic-urethane copolymer water dispersion E. Example 6 (Acrylic-Urethane Copolymer Aqueous Dispersion F) In a reactor similar to that of Example 1, 17.4 parts by weight of acrylic polyol solution D, poly (3-methyl-1,5-pentylene adipate) diol [ Number average molecular weight 2,000] 8
0.0 parts by weight, polyethylene glycol [number average molecular weight 600] 24.0 parts by weight, 2,2-dimethylolpropionic acid 6.7 parts by weight, dibutyltin dilaurate 0.001 parts by weight and methyl ethyl ketone 60.0 parts by weight. Preparation,
After uniformly mixing, 52.4 parts by weight of dicyclohexylmethane diisocyanate was added, and the mixture was mixed with 80% nitrogen gas stream.
The reaction was carried out at 0 ° C. for 2 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 2.1% by weight with respect to the nonvolatile content. This solution was cooled to 30 ° C., 5.0 parts by weight of triethylamine was added for neutralization, and then 350.0 parts by weight of water was gradually added to emulsify and disperse. To this emulsified dispersion, 5.0 parts by weight of a 60% by weight aqueous solution of hydrazine hydrate was added and stirred for 2 hours. The solvent was removed while heating to 60 ° C. under reduced pressure for about 2 hours to obtain an acrylic-urethane copolymer aqueous dispersion having a nonvolatile content of 35% by weight. Acrylic in this water dispersion
The content of carboxyl group derived from 2,2-dimethylolpropionic acid in the urethane copolymer is 1.3% by weight.
This water dispersion was used as an acrylic-urethane copolymer water dispersion F
And

Comparative Example 1 (Polyurethane Resin Aqueous Dispersion) Poly (3-methyl-1,5) was placed in the same reactor as in Example 1.
-Pentylene adipate) diol [number average molecular weight 2,0
00] 100.0 parts by weight, dimer diol [Toagosei
PESPOL HP-1000, number average molecular weight 57
0] 23.0 parts by weight 2,2-dimethylolbutanoic acid 7.
After charging 4 parts by weight, 0.001 part by weight of dibutyltin dilaurate and 60.0 parts by weight of methyl ethyl ketone and mixing them uniformly, 52.4 parts by weight of dicyclohexylmethane diisocyanate was added, and the mixture was heated at 80 ° C. under a nitrogen gas stream at 2 ° C. for 2 hours.
The reaction was carried out for a time to obtain a methyl ethyl ketone solution of an isocyanate group-terminated prepolymer having a free isocyanate group content of 2.1% by weight with respect to the nonvolatile content. This solution at 30 ℃
After cooling to 5.0 and neutralizing by adding 5.0 parts by weight of triethylamine, 350.0 parts by weight of water was gradually added to emulsify and disperse. This emulsion dispersion contains 60.0% of hydrazine hydrate.
4.9 parts by weight of a wt% aqueous solution was added and stirred for 2 hours. While heating to 60 ° C under reduced pressure for about 2 hours,
The solvent was removed to obtain a polyurethane resin aqueous dispersion having a nonvolatile content of 35% by weight. The content of carboxy group derived from 2,2-dimethylolbutanoic acid in the polyurethane resin in this water dispersion is 1.2% by weight. Comparative Example 2 (Acrylic-Urethane Copolymer Aqueous Dispersion G) In a reactor similar to that of Example 1, 52.0 parts by weight of acrylic polyol solution E, poly (3-methyl-pentylene adipate) diol [number average molecular weight 2 , 000] 80.0 parts by weight, dimer diol [Toagosei Co., Ltd., PESPOL HP
-1000, number average molecular weight 570] 23.0 parts by weight, 2,
2-Dimethylolpropionic acid (6.7 parts by weight), dibutyltin dilaurate (0.001 part by weight) and methyl ethyl ketone (60.0 parts by weight) were charged and mixed uniformly, and then isophorone diisocyanate (44.4 parts by weight) was added under a nitrogen gas stream. The resulting mixture was reacted at 80 ° C. for 2 hours to obtain a methyl ethyl ketone solution of an isocyanate group-terminated prepolymer having a free isocyanate group content of 1.9% by weight with respect to the nonvolatile content. This solution was cooled to 30 ° C., 5.0 parts by weight of triethylamine was added for neutralization, and then 350.0 parts by weight of water was gradually added to emulsify and disperse. To this emulsified dispersion was added 4.9 parts by weight of a 60.0% by weight aqueous hydrazine hydrate solution, and the mixture was stirred for 2 hours. The solvent was removed under reduced pressure while raising the temperature to 60 ° C over about 2 hours, and the nonvolatile content was 35% by weight.
Acrylic-urethane copolymer water dispersion of was obtained. 2,2 in the acrylic-urethane copolymer in this water dispersion
The carboxy group content derived from dimethylolpropionic acid is 1.2% by weight. This aqueous dispersion is referred to as an acrylic-urethane copolymer aqueous dispersion G. Comparative Example 3 (Acrylic-Urethane Copolymer Aqueous Dispersion H) An acrylic polyol solution [Dainippon Ink and Chemicals, Inc., Acridic A-81 was added to the same reactor as in Example 1.
1, non-volatile content about 50% by weight, glass transition temperature of acrylic polyol in solution 58 ° C., hydroxyl value based on monomer having hydroxyl group 17 mg KOH / g] 66.0 parts by weight, poly-ε-caprolactone diol [average Molecular weight 2,000] 80.0 parts by weight, polyethylene glycol [average molecular weight 1,000] 10.0 parts by weight, 2,2-dimethylolpropionic acid 6.7 parts by weight, 1,4-butanediol 2.7 parts by weight Parts, dibutyltin dilaurate 0.001 parts by weight and methyl ethyl ketone 60.0 parts by weight,
After homogeneously mixing, 52.4 parts by weight of dicyclohexylmethane diisocyanate was added, and the mixture was reacted at 80 ° C. for 2 hours under a nitrogen stream to give an isocyanate group-terminated prepolymer having a free isocyanate group content of 1.9% by weight based on the nonvolatile content. To obtain a solution of methyl ethyl ketone. 30 this solution
After cooling to ℃ and neutralizing by adding 5.0 parts by weight of triethylamine, 350.0 parts by weight of water is gradually added to emulsify and disperse, and 18.0 parts by weight of a 20% by weight aqueous solution of ethylenediamine is added thereto. Stir for 2 hours. After the reaction, the solvent was removed while heating to 60 ° C. under reduced pressure for about 2 hours to obtain an acrylic-urethane copolymer aqueous dispersion having a nonvolatile content of 35% by weight. The content of the carboxyl group derived from 2,2-dimethylolpropionic acid in the acrylic-urethane copolymer in this composition was 1.2% by weight. This water dispersion is referred to as an acrylic-urethane copolymer water dispersion H.

Example 7 (Evaluation of coating film physical properties of acrylic-urethane copolymer aqueous dispersion A) Acrylic-urethane copolymer aqueous dispersion A obtained in Example 1 was used as a coating agent to form a coating film. Was produced. No crack was observed in the coating film. In the adhesion test, the coating film made on the polycarbonate plate, oak plate, stainless steel plate, glass plate, concrete plate, urethane waterproof sheet all remained on the adherend side, but the coating film made on the stretched polypropylene film 10 squares were peeled off. In the water resistance test, slight whitening was observed. No whitening was observed in the weather resistance test. No cracking or peeling was observed in the flex resistance test. Example 8 (Aqueous acrylic-urethane copolymer aqueous dispersion A)
Evaluation of coating film physical properties of 100 parts by weight of the acrylic-urethane copolymer water dispersion A obtained in Example 1 and a polycarbodiimide resin aqueous emulsion [Nisshinbo Co., Ltd., Carbodilite E-01, nonvolatile content 40% by weight] ] The coating agent was prepared by mixing 5.0 parts by weight until uniform. A coating film was produced using this coating agent. No crack was observed in the coating film. In the adhesion test, the coating film made on the polycarbonate plate, oak plate, stainless steel plate, glass plate, concrete plate, urethane waterproof sheet all remained on the adherend side, but the coating film made on the stretched polypropylene film Eight squares were peeled off. No whitening was observed in the water resistance test. No whitening was observed in the weather resistance test. No cracking or peeling was observed in the flex resistance test. Example 9 (Evaluation of coating film physical properties of acrylic-urethane copolymer aqueous dispersion B) A coating film was prepared using the acrylic-urethane copolymer aqueous dispersion B obtained in Example 2 as a coating agent. . No crack was observed in the coating film. In the adhesion test, the coating film made on the polycarbonate plate, oak plate, stainless steel plate, glass plate, concrete plate, urethane waterproof sheet all remained on the adherend side, but the coating film made on the stretched polypropylene film Seven squares have come off. In the water resistance test, slight whitening was observed. No whitening was observed in the weather resistance test. No cracking or peeling was observed in the flex resistance test. Example 10 (Evaluation of coating film physical properties of acrylic-urethane copolymer aqueous dispersion C) A coating film was prepared using the acrylic-urethane copolymer aqueous dispersion C obtained in Example 3 as a coating agent. . No crack was observed in the coating film. In the adhesion test, all the coating films prepared on the stretched polypropylene film, the polycarbonate plate, the oak plate, the stainless steel plate, the glass plate, the concrete plate and the urethane waterproof sheet remained on the adherend side.
No whitening was observed in the water resistance test. No whitening was observed in the weather resistance test. No cracking or peeling was observed in the flex resistance test. Example 11 (Evaluation of coating film physical properties of acrylic-urethane copolymer aqueous dispersion D) A coating film was prepared using the acrylic-urethane copolymer aqueous dispersion D obtained in Example 4 as a coating agent. . No crack was observed in the coating film. In the adhesion test, all the coating films prepared on the stretched polypropylene film, the polycarbonate plate, the oak plate, the stainless steel plate, the glass plate, the concrete plate and the urethane waterproof sheet remained on the adherend side.
No whitening was observed in the water resistance test. No whitening was observed in the weather resistance test. No cracking or peeling was observed in the flex resistance test. Example 12 (Evaluation of coating film physical properties of acrylic-urethane copolymer aqueous dispersion E) A coating film was prepared by using the acrylic-urethane copolymer aqueous dispersion E obtained in Example 5 as a coating agent. No crack was observed in the coating film. In the adhesion test, the coating film made on the polycarbonate plate, oak plate, stainless steel plate, glass plate, concrete plate, urethane waterproof sheet all remained on the adherend side, but the coating film made on the stretched polypropylene film Eight squares were peeled off. In the water resistance test, slight whitening was observed. No whitening was observed in the weather resistance test. No cracking or peeling was observed in the flex resistance test. Example 13 (Evaluation of coating film physical properties of acrylic-urethane copolymer aqueous dispersion F) Acrylic-urethane resin aqueous dispersion F obtained in Example 6
Was used as a coating agent to prepare a coating film. In the adhesion test, polycarbonate plate, oak plate, stainless steel plate,
All the coating films prepared on the glass plate, concrete plate and urethane waterproof sheet remained on the adherend side, but 6 squares of the coating film prepared on the stretched polypropylene film were peeled off. In the water resistance test, slight whitening was observed.
No whitening was observed in the weather resistance test. No cracking or peeling was observed in the flex resistance test.

Comparative Example 4 (Evaluation of coating film physical properties of polyurethane resin water dispersion) A coating film was prepared using the polyurethane resin water dispersion obtained in Comparative Example 1 as a coating agent. No crack was observed in the coating film. In the adhesion test, a polycarbonate plate,
Oak plate, stainless steel plate, glass plate, concrete plate,
All the coating films formed on the urethane waterproof sheet remained on the adherend side, but 12 squares of the coating film formed on the stretched polypropylene film were peeled off. In a water resistance test,
A slight bleaching was observed. In the weather resistance test, remarkable whitening occurred. No cracking or peeling was observed in the flex resistance test. Comparative Example 5 (Evaluation of coating film physical properties of acrylic-urethane copolymer water dispersion G) A coating film was prepared using the acrylic-urethane copolymer water dispersion G obtained in Comparative Example 2 as a coating agent. . No crack was observed in the coating film. In the adhesion test, all the coating films prepared on the stretched polypropylene film, the polycarbonate plate, the oak plate, the stainless steel plate, the glass plate, the concrete plate and the urethane waterproof sheet remained on the adherend side.
No whitening was observed in the water resistance test. In the weather resistance test, remarkable whitening occurred. No cracking or peeling was observed in the flex resistance test. Comparative Example 6 (Evaluation of coating film physical properties of acrylic-urethane copolymer water dispersion H) A coating film was prepared using the acrylic-urethane copolymer water dispersion H obtained in Comparative Example 3 as a coating agent. did. On the coating
No crack was observed. In the adhesion test, the coating film made on the polycarbonate plate, oak plate, stainless steel plate, glass plate, concrete plate, urethane waterproof sheet all remained on the adherend side, but the coating film made on the stretched polypropylene film 11 squares were peeled off. In the water resistance test, slight whitening was observed. In the weather resistance test, remarkable whitening occurred. No cracking or peeling was observed in the flex resistance test. Example 7-
The results of No. 13 and Comparative Examples 4 to 6 are shown in Table 1.

[0025]

[Table 1]

As can be seen from Table 1, the coating films of Examples 7 to 13 prepared by using the acrylic-urethane copolymer aqueous dispersion of the present invention have a good appearance and can be applied to various substrates. On the other hand, it has good adhesion, excellent flex resistance, and very good weather resistance. On the other hand, it was prepared by using the polyurethane resin water dispersion of Comparative Example 1 and the acrylic-urethane copolymer water dispersions of Comparative Examples 2 and 3 using an acrylic polyol containing no ultraviolet absorbing aromatic monomer. The coating films of Comparative Examples 4 to 6 all have good coating appearance and adhesiveness, but are significantly inferior in weather resistance. Example 14 (Evaluation of Adhesive Performance of Acrylic-Urethane Copolymer Aqueous Dispersion C) Using the acrylic-urethane copolymer aqueous dispersion C obtained in Example 3 as an adhesive, according to JIS K 6582, The wood compressive shear bond strength was measured. Thirty test pieces were prepared using a Oak plate having a thickness of 10 mm. After 10 test pieces were conditioned at 23 ° C. and 50% RH for 48 hours, a compression test was performed at a crosshead moving speed of 1.0 mm / min.
The average value of tensile shear bond strength was 2,210 N / cm ² . Ten test pieces were dipped in water at 30 ° C. for 3 hours, then dipped in water at 20 ° C. for 10 minutes, and a compression test was similarly performed in a wet state. The average value of the compressive shear bond strength was 1,920 N / cm ² . Ten test pieces were dipped in water at 60 ° C. for 3 hours, then dipped in water at 20 ° C. for 30 minutes, and a compression test was similarly performed in a wet state. Average value of compressive shear adhesive strength is 1.4
It was 50 N / cm ² .

[0027]

The coating film obtained from the water dispersion of the acrylic-urethane copolymer of the present invention and the coating agent is a stretched polypropylene film, a hard-to-adhesive plastic substrate such as a polycarbonate plate, wood, concrete plate, stainless steel. It excels in adhesion to various base materials such as plates and urethane sheets, as well as water-resistant and flex-resistant properties required for coating agents, and can be widely applied as an aqueous coating agent. The coating film obtained from the acrylic-urethane copolymer water dispersion and the coating agent of the present invention is particularly excellent in terms of weather resistance as compared with the conventionally used water-based resin water dispersion and the water-based coating agent. However, the present invention can be applied to more severe environments, for example, coating fields such as outer walls, roofs and structures in the field of construction.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 175/04 C09D 175/04 C09J 175/04 C09J 175/04 // C09D 133/14 C09D 133/14 C09J 133/14 C09J 133/14 F term (reference) 4J034 BA08 BA09 CA04 CA15 CA22 CA24 CB01 CB03 CB08 CC09 CC22 DA01 DB03 DC02 DC07 DC20 DC23 DC39 DC43 DE04 DP03 DP18 HA01 HA07 HC03 HC16 HC17 HC46 HC52 HC54 HC61 HC64 HC71 HC73 QC05141CJQQRA07 4J0383038 DG271 DG281 GA03 GA09 JB04 JB05 JB07 JB17 KA03 MA08 MA10 NA03 NA04 NA11 NA12 NA14 4J040 DF041 DF051 DM001 EF191 EF291 EF301 GA05 GA17 HC04 HC05 HC06 HC15 BC03 JA65 KAQ LAQQAQQQAQQQAQQQQQAQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQH

Claims (9)

[Claims] 1. A polyisocyanate compound (a), (b)
UV absorbing aromatic monomer and ethylenically unsaturated bond 1
And a high molecular weight polyol containing an acrylic polyol having a hydroxyl value of 5 to 200 mgKOH / g based on the aliphatic monomer obtained by copolymerizing an individual monomer and an aliphatic monomer having a hydroxyl group, and (c) anion A neutralized product of an isocyanate group-terminated prepolymer obtained from a compound having a hydrophilic hydrophilic group and two or more active hydrogens, and (d) at least one selected from the group consisting of water-soluble polyamines, hydrazine and their derivatives. Acrylic, characterized in that it is an aqueous dispersion obtained by chain extension in water.
Urethane copolymer water dispersion. 2. The acrylic-urethane copolymer aqueous dispersion according to claim 1, wherein the ultraviolet absorbing aromatic monomer is a compound represented by the general formula [1]. [Chemical 1] (However, in the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ² is an alkylene group having 1 to 6 carbon atoms, R ³ is a hydrogen atom or a methyl group, and X is It is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a cyano group or a nitro group.) 3. The acrylic polyol is copolymerized with a UV stable monomer represented by the general formula [2] and / or a UV stable monomer represented by the general formula [3]. 1
The acrylic-urethane copolymer aqueous dispersion described. [Chemical 2] (However, in the formula, R ⁴ is a hydrogen atom or a cyano group,
R ⁵ and R ⁶ are each independently a hydrogen atom, a methyl group or an ethyl group, R ⁷ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and Y is an oxygen atom or an imino group. ) 4. In an acrylic polyol, a UV absorbing aromatic monomer used for copolymerization, a UV stable monomer represented by the general formula [2] and a UV stability represented by the general formula [3]. The acrylic-urethane copolymer aqueous dispersion according to claim 1 or 3, wherein the total weight of the monomers is 1 to 30% by weight of all the monomers used for the copolymerization. 5. The acrylic-urethane copolymer aqueous dispersion according to claim 1, wherein the content of the acrylic polyol is 5 to 60% by weight based on the total weight of the high molecular weight polyol (b). 6. The acrylic-urethane copolymer water dispersion according to claim 1, wherein the high molecular weight polyol contains, in addition to the acrylic polyol, at least one selected from polyester polyol, polycarbonate polyol, polyether polyol and dimer diol. object. 7. A compound having (c) an anionic hydrophilic group and two or more active hydrogens, wherein the anionic hydrophilic group is a carboxyl group, and the content of the carboxyl group in the acrylic-urethane copolymer is 0.1% of the total weight of the copolymer.
The acrylic-urethane copolymer aqueous dispersion according to claim 1, which is 3 to 2.5% by weight. 8. A coating agent containing the acrylic-urethane copolymer aqueous dispersion according to claim 1. 9. An adhesive containing the acrylic-urethane copolymer water dispersion according to any one of claims 1 to 7.