JP2002284838A - Aqueous dispersion of hydroxyl group-containing acrylic/ urethane copolymer, two-pack aqueous acrylic/urethane composition, and coating material and adhesive containing the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous dispersion of a hydroxyl group-containing acrylic/ urethane copolymer which has excellent adhesion even to a base material having hard adhesion and gives a two-pack aqueous acrylic/urethane copolymer composition having excellent film properties, a two-pack aqueous composition having the aqueous dispersion as the major agent, and a coating material and an adhesive which contain the composition. SOLUTION: The aqueous dispersion of a hydroxyl group-containing acrylic/urethane copolymer is obtained by chain extending a neutralized product of an isocyanate group-terminated prepolymer to be obtained from (a) an organic polyisocyanate compound, (b) a high-molecular weight polyol containing an acrylic polyol copolymerized with an ultraviolet-absorbing monomer, and (c) a compound having an anionic hydrophilic group and two or more active hydrogens with the use of (d) a water soluble polyamine, hydrazine or a derivative thereof in water, and subsequently or simultaneously with the chain-extension, blocking the terminal isocyanate group with (e) a primary or secondary amine having a hydroxyl group. The two-pack aqueous acrylic/urethane composition, the coating material and the adhesive are also described.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer, a two-part aqueous acryl-urethane composition, and an adhesive and a coating agent containing the composition. More specifically, the present invention relates to an aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer which gives a two-part aqueous acryl-urethane composition which forms a film having excellent adhesion, water resistance, weather resistance and bending resistance. A two-part aqueous acrylic-urethane composition obtained by blending a main agent containing the aqueous dispersion and a curing agent comprising an aqueous polyisocyanate compound, and a coating agent and an adhesive containing the composition .

[0002]

2. Description of the Related Art Conventionally, organic solvent-based resins have been mainly used in the fields of various adhesives, coating materials such as paints and printing inks. For reasons such as environmental improvement, it is being replaced by aqueous resins. Furthermore, with the sophistication of quality, diversification of coating base materials, use for new applications, etc., such water-based resins are also required to be highly functional. For example, exterior walls, roofs, buildings, etc. in the construction field In the field of painting, durability performance under more severe conditions is required. As an aqueous resin in such applications, acrylic copolymers are used in a wide range of fields such as building interiors, leather, metals, and wooden floors because they are inexpensive, have excellent weather resistance, light resistance, and toughness. I have. However, it is difficult to achieve both softness and hardness with acrylic resin alone. Due to the inferiority, there arises a problem that the coating film is peeled off when the base material expands and contracts due to a temperature difference of the outside air. In addition, the aqueous urethane resin,
It is mainly used as a coating agent for woodwork products and flooring materials because of its excellent elasticity, abrasion resistance, and bending resistance.However, the resulting coating film has poor water and weather resistance. is there. In order to improve these drawbacks, various aqueous resins that combine the advantageous properties of urethane resin and acrylic resin have been developed by blending, compounding or copolymerizing aqueous acrylic resin and aqueous urethane resin. Has been
Although an aqueous resin having excellent adhesion to various substrates, water resistance, and bending resistance has been obtained, sufficient performance has not been obtained in terms of long-term weather resistance.

[0003]

SUMMARY OF THE INVENTION The present invention has excellent adhesion to poorly adherent substrates such as plastics, urethane elastomers, concrete materials, etc., and has excellent water resistance, weather resistance and bending resistance. Hydroxyl group-containing acryl-urethane copolymer aqueous dispersion giving a two-part aqueous acryl-urethane composition that forms an excellent film; The purpose of the present invention is to provide a two-part aqueous acrylic-urethane composition obtained by the above method, and a coating agent and an adhesive containing the composition.

[0004]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the hydroxyl value obtained by copolymerizing a polyisocyanate compound and an ultraviolet-absorbing monomer has a hydroxyl value of 5 to 200 mg KOH. / G of a high molecular weight polyol containing an acrylic polyol and a neutralized isocyanate group-terminated prepolymer obtained from the reaction of a compound having an anionic hydrophilic group and two or more active hydrogens, A main agent comprising a hydroxyl group-containing aqueous acrylic-urethane copolymer composition in which a terminal isocyanate group obtained by reacting an amine compound having a hydroxyl group is blocked, and a curing agent comprising an aqueous polyisocyanate compound. The two-part aqueous acryl-urethane composition has excellent adhesion to poorly adherent substrates, and is resistant to water and bending. Not only excellent sex, found that forming a film excellent in weather resistance, and have completed the present invention based on this finding. That is, the present invention provides a method of (1) copolymerizing (a) an organic polyisocyanate compound, (b) an ultraviolet absorbing monomer, and a monomer having one ethylenically unsaturated bond and a hydroxyl group. Neutralized isocyanate group-terminated prepolymer obtained from a high molecular weight polyol containing an acrylic polyol having a hydroxyl value of 5 to 200 mgKOH / g and (c) a compound having an anionic hydrophilic group and two or more active hydrogens. To
(d) a water-soluble polyamine, after elongating a chain in water using at least one selected from the group consisting of hydrazine and derivatives thereof, or simultaneously with elongating the chain, (e) a primary amine having a hydroxyl group; And / or a hydroxyl group-containing acryl-urethane copolymer aqueous dispersion obtained by blocking a terminal isocyanate group with a secondary amine, (2) (a) an organic polyisocyanate 2. The aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer according to claim 1, wherein the compound is at least one selected from an aliphatic diisocyanate compound and an alicyclic diisocyanate compound; The hydroxyl group-containing acryl-urethane copolymer aqueous dispersion according to item 1, which is a compound represented by the general formula [1],

Embedded image (Wherein, 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 (4) an acrylic polyol represented by the general formula [2]. 2. The aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer according to claim 1, wherein the ultraviolet light-stable monomer and / or the ultraviolet light-stable monomer represented by the general formula [3] is copolymerized.

Embedded image (Wherein, 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, Y is an oxygen atom or an imino group. ), (5) an acrylic polyol, an ultraviolet absorbing monomer used for copolymerization, an ultraviolet stable monomer represented by the general formula [2], and an ultraviolet stable monomer represented by the general formula [3] The total weight of the body is 1 to 1 of all monomers used for copolymerization.
Item 5. The hydroxyl group-containing acrylic-urethane copolymer aqueous dispersion according to item 1, 3 or 4, which is 30% by weight,
(6) The aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer according to (1), wherein the content of the acrylic polyol is 5 to 60% by weight of the total weight of the high molecular weight polyol (b), (7) (b) The hydroxyl group-containing acrylic-urethane copolymer aqueous dispersion according to claim 1, wherein the high molecular weight polyol contains at least one selected from polyester polyol, polycarbonate polyol, polyether polyol and dimer diol, in addition to acrylic polyol, (8) (c) In a 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 hydroxyl group-containing acryl-urethane copolymer is ,
2. The aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer according to claim 1, which is 0.3 to 2.5% by weight of the total weight of the copolymer, (9) (e) a primary group having a hydroxyl group. 2. The hydroxyl group-containing acrylic-urethane copolymer according to claim 1, wherein the content of hydroxyl groups derived from the amine and the secondary amine is 0.1 to 5% by weight based on the total weight of the hydroxyl group-containing acrylic-urethane copolymer. Aqueous polymer dispersion,
(10) The aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer according to item 1, wherein (e) the primary amine having a hydroxyl group is monoethanolamine and the secondary amine having a hydroxyl group is diethanolamine. (11) (A) a main agent comprising the aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer according to any one of items 1 to 10 and (B) a curing agent comprising an aqueous polyisocyanate compound, Equivalent ratio (OH / N) of hydroxyl group (OH) of isocyanate group (NCO) to isocyanate group of curing agent
CO ratio) is 1: 3 to 2: 1, wherein the two-component aqueous acrylic-urethane composition is
(12) A coating agent containing the two-part aqueous acryl-urethane composition according to item 11, and (13) an adhesive containing the two-part aqueous acryl-urethane composition according to item 11. To provide. Further, as a preferred embodiment of the present invention, (14) an aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer according to item 1, wherein the glass transition temperature (Tg) of the acrylic polyol is from -25 to 100 ° C, (15) (B) The hydroxyl group-containing acrylic resin according to item 7, wherein the total weight of the polyester polyol, polycarbonate polyol, polyether polyol and dimer diol in the high molecular weight polyol is 10 to 95% by weight based on the total weight of the high molecular weight polyol. 8. The hydroxyl group-containing acrylic resin according to claim 7, wherein the content of the dimer diol in the urethane copolymer aqueous dispersion, (16) (b) the high molecular weight polyol is 1 to 30% by weight based on the total weight of the high molecular weight polyol. Urethane copolymer aqueous dispersion, and (17)
(B) The two-component aqueous acrylic-urethane composition according to item 11, wherein the content of the hydrophilic chain in the aqueous polyisocyanate compound is 2 to 50% by weight.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer of the present invention comprises (a) an organic polyisocyanate compound, (b) an ultraviolet absorbing monomer, and one ethylenically unsaturated bond. Has a hydroxyl value of from 5 to 200, obtained by copolymerizing
A neutralized isocyanate group-terminated prepolymer obtained from a high molecular weight polyol containing mg KOH / g of acrylic polyol and (c) a compound having an anionic hydrophilic group and two or more active hydrogens, (E) a primary amine and / or a secondary amine having a hydroxyl group after chain extension in water using at least one selected from the group consisting of polyamines, hydrazines and derivatives thereof, or simultaneously with the chain extension. It is a hydroxyl group-containing acrylic-urethane copolymer aqueous dispersion obtained by blocking a terminal isocyanate group with an amine. There is no particular limitation on the (a) organic polyisocyanate compound used in the present invention, for example,
Aliphatic diisocyanate compounds such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate; tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, Aromatic diisocyanates such as xylylene diisocyanate can be exemplified. These organic polyisocyanate compounds,
One type may be used alone, or two or more types may be used in combination. Among these, aliphatic diisocyanate compounds and alicyclic diisocyanate compounds can be suitably used because the film obtained from the two-pack type aqueous acrylic-urethane composition is excellent in non-yellowing, and is preferably used as isophorone diisocyanate or dicyclohexylmethane diisocyanate. , Norbornane diisocyanate and hexamethylene diisocyanate can be particularly preferably used.

The (b) high molecular weight polyol used in the present invention has a hydroxyl value obtained by copolymerizing an ultraviolet absorbing monomer and a monomer having one ethylenically unsaturated bond and a hydroxyl group. Contains 5-200 mg KOH / g acrylic polyol. UV absorbing monomer is 3
It is a monomer having an ultraviolet absorbing ability in the wavelength range of 00 to 400 nm, and is, for example, cyano such as 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate or ethyl-2-cyano-3,3-diphenyl acrylate. An acrylate-based UV-absorbing monomer and a benzotriazole-based UV-absorbing monomer can be exemplified. Among these, the ultraviolet absorbing monomer is preferably a compound represented by the general formula [1].

Embedded image In the general formula [1], R ¹ is a hydrogen atom or a group having 1 to 1 carbon atoms.
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, a cyano group or a nitro group having 1 to 4 carbon atoms. The alkyl group having 1 to 8 carbon atoms represented by R ¹ is
It may have a linear or branched, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, amyl group, octyl group and the like Can be mentioned. The alkylene group having 1 to 6 carbon atoms represented by R ² may be linear or branched, and examples thereof include a methylene group, an ethylene group, a propylene group, a trimethylene group, a butylene group, and a hexamethylene group. And the like. 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, for example, methyl, ethyl, propyl, isopropyl, butyl, sec- Examples thereof include a 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.

The compound represented by the general formula [1] includes
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. One of these ultraviolet absorbing monomers can be used alone, or 2
A combination of more than one species can also be used. Examples of the monomer having one ethylenically unsaturated bond and a hydroxyl group used in the present invention include, for example, 2-hydroxyethyl
(Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate,
(Meth) acrylates having a hydroxyl group such as 5,6-dihydroxyhexyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate, and mono (meth) acrylate of polyester diol obtained from phthalic acid and propylene glycol. be able to. Here, (meth) acrylate means acrylate and methacrylate. These monomers are
One type may be used alone, or two or more types may be used in combination.

[0008] The acrylic polyol used in the present invention is further obtained by copolymerizing a UV-stable monomer represented by the general formula [2] and / or a UV-stable monomer represented by the general formula [3]. Is preferred.

Embedded image 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 Or 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, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group,
Examples thereof include a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, and an octadecyl group.

The UV-stable monomer represented by the general formula [2] includes, for example, 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-croto Noylamino-2,2,
6,6-tetramethylpiperidine and the like can be mentioned. One of these UV-stable monomers can be used alone, or two or more can be used in combination. 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. One of these UV-stable monomers can be used alone, or two or more can be used in combination. In addition, (meth) acryloyl means acryloyl and methacryloyl. When producing an acrylic polyol, a UV-absorbing monomer, a UV-stable monomer represented by the general formula [2] and / or a UV-stable monomer represented by the following general formula [3] Is further copolymerized, whereby the coating film obtained from the two-part aqueous acrylic-urethane composition has improved ultraviolet stability and excellent weather resistance.

In the present invention, when the acrylic polyol is produced, a monomer copolymerizable with the above monomer can be further copolymerized. As copolymerizable monomers, 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-n-butoxyethyl (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, tert-
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) acryloyloxy Ethyl 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, α-
Examples include methylstyrene, vinyltoluene, (meth) acrylonitrile, vinyl acetate, vinylpyridine, vinylpyrrolidone, methylcrotonate, and maleic anhydride. One of these copolymerizable monomers can be used alone, or two or more can be used in combination. Note that (meth) acrylate means acrylate and methacrylate, (meth) acrylic acid means acrylic acid and methacrylic acid, (meth) acryloyl means acryloyl and methacryloyl, and (meth) acrylonitrile is acrylonitrile and methacrylonitrile. Means nitrile.

In the acrylic polyol used in the present invention, the ratio of each of the above monomers is not particularly limited, but the ultraviolet absorbing monomer used for copolymerization and the ultraviolet stable monomer represented by the general formula [2] are used. The total weight of the monomer and the UV-stable monomer represented by the general formula [3] is one of the total monomers used for the copolymerization.
It is preferably from 30 to 30% by weight, more preferably from 2 to 20% by weight, even more preferably from 3 to 15% by weight. If the total weight of the UV-absorbing monomer and the UV-stable monomer is less than 1% by weight of the total monomer, the weather resistance of the film obtained from the two-part aqueous acryl-urethane composition may be insufficient. Could be. The total weight of the UV absorbing monomer and the UV stable monomer is 30% by weight of the total monomer
When the ratio exceeds the above, performances such as gloss, solvent resistance and chemical resistance may be reduced. In the present invention, the method for producing the acrylic polyol is not particularly limited, and a conventionally known polymerization method,
For example, it can be produced by a bulk polymerization method or a solution polymerization method. Acrylic polyol, the above monomer,
It can also be obtained by polymerization using other polyol components such as polyester polyol, polycarbonate polyol and polyether polyol as a solvent. The acrylic polyol used in the present invention has a hydroxyl value of 5 to 200 mgKOH / g, more preferably 3 to 200 mgKOH / g.
0-70 mgKOH / g. Hydroxyl value is 5mgKOH /
When it is less than g, the bonding point between the acrylic resin and the urethane resin decreases, and the performance as a copolymer may not be sufficiently exhibited. When the hydroxyl value exceeds 200 mgKOH / g, during the synthesis of the isocyanate group-terminated prepolymer,
Gelation may progress due to an increase in the crosslink density, and production may be 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 film may be insufficient. If the glass transition temperature exceeds 100 ° C., the film-forming properties 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 polyols can be used. Examples of such a commercially available product include Udouble 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 30% by weight.
More preferably, it is% 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 properties such as weather resistance. When the content of the acrylic polyol exceeds 60% by weight of the total weight of the high-molecular-weight polyol, there is a possibility that the urethane resin may exhibit insufficient mechanical resistance, particularly insufficient advantageous properties such as elasticity.

In the present invention, other polyols can be contained as the high molecular weight polyol (b) in addition to the above acrylic polyol. Other polyols are not particularly limited, but polyester polyols, polycarbonate polyols, polyether polyols or dimer diols can be suitably 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, polycondensates of 1,6-hexanediol and dimer acid, and the like. Examples of the polycarbonate polyol include polytetramethylene carbonate diol, polyhexamethylene carbonate diol, poly (1,4-cyclohexane dimethylene carbonate) diol, and poly (hexamethylene-1,4-cyclohexane dimethylene) carbonate diol. be able to. Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, a random or block copolymer of ethylene oxide and propylene oxide, and a random or block copolymer of ethylene oxide and butylene oxide. . Further, a polyether polyester polyol having an ether bond and an ester bond can be used.

The dimer diol is a polyol containing a diol obtained by reducing dimer acid as a main component.
Here, the dimer acid mainly catalyzes an unsaturated fatty acid having 18 carbon atoms such as oleic acid, linoleic acid and linoleic acid, a drying oil fatty acid, a semi-dry oil fatty acid or a lower monoalkyl ester of these fatty acids, if necessary. Is a compound obtained by Diels-Alder type bimolecular polymerization using Various types of dimer acids are commercially available. Typical examples are 0 to 5% by weight of a monocarboxylic acid having 18 carbon atoms and 70 to 9% of a dimer acid having 36 carbon atoms.
Some contain 8% by weight and 0 to 30% by weight of a tricarboxylic acid having 54 carbon atoms. In the present invention, the high molecular weight polyol (b) preferably contains one or more polyols selected from the group consisting of polyester polyols, polycarbonate polyols, polyether polyols and dimer diols, and the total weight thereof is (b) It is preferably from 10 to 95% by weight of the total weight of the high molecular weight polyol. Furthermore, in the present invention, the content of the dimer diol in the high molecular weight polyol is preferably 1 to 30% by weight, more preferably 5 to 15% by weight, based on the total weight of the high molecular weight polyol. The content of dimer diol is 1 of the total weight of the high molecular weight polyol.
When the content is not less than% by weight, the water resistance of the film is improved by the hydrophobic component. 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 reduced.

In the present invention, a rosin-containing polyol can be used as another polyol component. The rosin-containing polyol is a diepoxy compound 1.
It is a reaction product composed of a molecule and two molecules of a rosin. There is no particular limitation on the rosins used, for example, natural rosins such as gum rosin, wood rosin, tall oil rosin, purified rosin, disproportionated rosin, purified disproportionated rosin, and processed rosins such as hydrogenated rosin, and the like. Mixtures and the like can be mentioned. Examples of the diepoxy compound 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;
Aromatic and alicyclic diglycidyl ethers such as 3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyldiglycidyl ether, 2,2-bis (4-hydroxycyclohexyl) propane diglycidyl ether; 3,4
And cycloaliphatic and cyclic oxiranes such as -epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and vinylcyclohexane dioxide.

In the present invention, (c) the compound having an anionic hydrophilic group and two or more active hydrogens is not particularly limited, but the anionic hydrophilic group is a carboxyl group and the active hydrogen is a hydroxyl group hydrogen. Certain compounds can be suitably used. Such compounds include, for example,
2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid and the like can be mentioned. Further, as such a carboxyl group-containing diol, a diol component having a carboxyl group, an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, a polyester polyol having a pendant carboxyl group obtained from a dicarboxylic acid such as an alicyclic dicarboxylic acid. It can also be used. When synthesizing such a carboxyl group-containing diol, a diol having no carboxyl group can be used in combination, if necessary. These (c) compounds having an anionic hydrophilic group and two or more active hydrogens can be used alone or in a combination of two or more. In the present invention, the content of the carboxyl group derived from the component (c) in the hydroxy-containing aqueous acrylic-urethane copolymer is 0.3 to 2.
The content is preferably 5% by weight, more preferably 0.5 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 is difficult to emulsify the hydroxyl-containing acryl-urethane copolymer,
Alternatively, the emulsion stability may be insufficient. When the content of the carboxyl group exceeds 2.5% by weight of the total weight of the copolymer, the water resistance of the film may be reduced.

In the present invention, the above-mentioned component (a) and (b)
First, a urethane prepolymer having an isocyanate group at a terminal (isocyanate group-terminated prepolymer) is synthesized using the component and the component (c). The isocyanate group-terminated prepolymer can be synthesized, for example, by a conventionally known one-shot method (one-stage method) or a multi-stage isocyanate polyaddition reaction method at a reaction temperature of about 40 to 150 ° C. At this time, if necessary, a reaction catalyst such as dibutyltin dilaurate, stannas octanoate, dibutyltin-2-ethylhexanoate, triethylamine, triethylenediamine, N-methylmorpholine and the like can be added. One of these reaction catalysts can be used alone, or two or more can be used in combination. Further, an organic solvent which does not react with the isocyanate group can be added in the reaction stage or after the completion of the reaction. 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, a (f) chain extender can be used as necessary. There is no particular limitation on the chain extender used, for example, ethylene glycol, 1,4-butanediol,
1,6-hexanediol, trimethylolpropane,
Low molecular weight polyhydric alcohols such as pentaerythritol and sorbitol; low molecular weight polyamines such as ethylenediamine, propylenediamine, hexamethylenediamine, di (aminocyclohexyl) methane, piperazine, 2-methylpiperazine, isophoronediamine, diethylenetriamine and triethylenetetramine Can be mentioned. One of these chain extenders can be used alone, or two or more can be used in combination.

In the present invention, the term "neutralized isocyanate group-terminated prepolymer" refers to trimethylamine, triethylamine, tri-n-propylamine, tributylamine, N-methyldiethanolamine before or after the synthesis of the isocyanate group-terminated prepolymer. Amines such as N, N-dimethylmonoethanolamine, N, N-diethylmonoethanolamine, and triethanolamine;
It is obtained by neutralizing the anionic hydrophilic group in the component (c) using potassium hydroxide, sodium hydroxide, ammonia or the like. In the present invention, the neutralized isocyanate-terminated prepolymer is subjected to chain extension in water using at least one member selected from the group consisting of (d) a water-soluble polyamine, hydrazine and a derivative thereof in water, or At the same time as the chain is extended, (e) the terminal isocyanate group is blocked with a primary amine and / or a secondary amine having a hydroxyl group. (e) By blocking the terminal isocyanate group with a primary amine and / or a secondary amine having a hydroxyl group, a hydroxyl group is introduced into a neutralized product of the isocyanate group-terminated prepolymer.
As the water-soluble polyamine used as the component (d), for example, ethylenediamine, propylenediamine, hexamethylenediamine, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine,
Examples thereof include diethylenetriamine and triethylenetetramine. Examples of the water-soluble amine derivative used as the component (d) include an amidoamine derived from a diprimary amine and a monocarboxylic acid, and a diprimary amine monoketimine. Examples of the hydrazine derivative used as the component (d) include compounds having at least two hydrazino groups in the molecule. Among them, dihydrazide of dicarboxylic acid having 2 to 10 carbon atoms, 2 The aliphatic water-soluble dihydrazines of Nos. To 4 can be suitably used. 2 carbon atoms
As the dihydrazide of the dicarboxylic acid of 10, for example,
Examples thereof 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, and itaconic acid dihydrazide. Examples of the aliphatic water-soluble dihydrazine having 2 to 4 carbon atoms include 1,1′-ethylenedihydrazine, 1,1′-trimethylenedihydrazine, and 1,1′-butylenedihydrazine. it can.

In the present invention, the primary amine having a hydroxyl group used as the component (e) for blocking the terminal isocyanate group includes, for example, hydroxylamine, ethanolamine, 3-amino-1-propanol, 2-amine
Examples thereof include amino-2-hydroxymethylpropane-1,3-diol, 2-hydroxyethylethylenediamine, and 2-hydroxyethylpropylenediamine. Examples of the secondary amine having a hydroxyl group include N-methylethanolamine, diethanolamine, N, N′-di-2-hydroxyethylethylenediamine, N, N′-di-2-hydroxypropylethylenediamine, N, N And '-di-2-hydroxypropylpropylenediamine. Among them, monoethanolamine and diethanolamine can be particularly preferably used. One of these primary amines and secondary amines having a hydroxyl group can be used alone, or two or more can be used in combination. In the hydroxyl group-containing acrylic-urethane copolymer of the present invention, the content of the hydroxyl group derived from the component (e) is 0.1% of the total weight of the copolymer.
It is preferably 1 to 5% by weight, and 0.5 to 3% by weight.
Is more preferable. When the content of the hydroxyl group is less than 0.1% by weight of the total weight of the copolymer, the water resistance of the film obtained from the two-part aqueous acrylic-urethane composition is insufficient due to insufficient crosslinking density. Could be. When the content of the hydroxyl group exceeds 5% by weight of the total weight of the copolymer, the liquid stability of the two-pack type aqueous acrylic-urethane composition may be reduced, which may make it difficult to use. In the present invention, when an isocyanate-terminated prepolymer is synthesized using an organic solvent, it is preferable to block the terminal isocyanate group and then remove the organic solvent by, for example, distillation under reduced pressure. The hydroxyl group-containing acrylic-urethane copolymer used in the present invention has a self-emulsifying property and becomes a stable aqueous dispersion by itself, but when removing the organic solvent, a surfactant such as a higher fatty acid, Anionic surfactants such as acids, acidic fatty alcohols, sulfates, higher alkyl sulfonates, alkyl allyl sulfonates, sulfonated castor oil, sulfosuccinates, and the like, reaction products of ethylene oxide with long-chain fatty alcohols or phenols, etc. It is preferable to improve the emulsifiability by using a nonionic surfactant in combination.

The two-part aqueous acryl-urethane composition of the present invention comprises: And a hydroxyl group (OH) of the main agent and an isocyanate group (NC
O) (OH / NCO ratio) in a ratio of 1: 3 to 2: 1. In the present invention, the term "aqueous" means a property capable of stably emulsifying and dispersing in water without using an emulsifier, that is, self-emulsifiability. (B) The aqueous polyisocyanate compound can be obtained by subjecting a raw material polyisocyanate to an addition reaction of a hydrophilic chain having active hydrogen and, if necessary, a lipophilic chain. The aqueous polyisocyanate compound has a good self-emulsifying property in water and a long pot life, and can be suitably used as a curing agent for a two-part aqueous acrylic-urethane composition. In the present invention, the raw material isocyanate used in the production of the aqueous polyisocyanate compound (B) is not particularly limited, and examples thereof include aromatic polyisocyanates such as tolylene diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate; tetramethylene diisocyanate, pentamethylene diisocyanate, Examples thereof include aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate; and alicyclic polyisocyanates such as isophorone diisocyanate and hydrogenated xylylene diisocyanate. Further, a polyisocyanate compound having a biuret structure, an isocyanurate structure, a urethane structure, a uretdione structure, an allophanate structure, a trimer structure, or the like, or an adduct of an aliphatic isocyanate of trimethylolpropane can also be used as the raw material polyisocyanate. .

In the present invention, the compound for adding a hydrophilic chain to the starting polyisocyanate is not particularly limited.
A hydrophilic compound having up to 50 ethylene oxide repeating units and a hydroxyl group at one end can be suitably used. Examples of such a hydrophilic compound include polyethylene glycol monoalkyl ether, and a monoalkyl ether of a random or block copolymer of ethylene oxide and propylene oxide. If the number of ethylene oxide repeating units is less than 5, the self-emulsifiability of the aqueous polyisocyanate compound may be insufficient. If the number of ethylene oxide repeating units exceeds 50, the aqueous polyisocyanate compound may have high crystallinity and solidify. In the present invention, the content of the hydrophilic chain in the aqueous polyisocyanate compound (B) is preferably 2 to 50% by weight. When the content of the hydrophilic chain is less than 2% by weight, the effect of lowering the interfacial tension is not sufficient, and the self-emulsifiability of the aqueous polyisocyanate compound may be insufficient. When the content of the hydrophilic chain exceeds 50% by weight, the reactivity between the isocyanate group of the aqueous polyisocyanate compound and water may be too high. The method for producing the aqueous polyisocyanate compound (B) used in the present invention is not particularly limited, but it can be easily produced by reacting an isocyanate group of a raw material polyisocyanate with a terminal hydroxyl group of a hydrophilic compound. In the present invention, as the aqueous polyisocyanate compound (B), for example, a modified adduct of hexamethylene diisocyanate [Asahi Chemical Industry
Commercial products such as Co., Ltd., Duranate WB40-80D], isocyanurate-modified hexamethylene diisocyanate [Sumitomo Bayer Urethane Co., Ltd., Bayhidur 3100], [Nippon Polyurethane Industry Co., Ltd., Aquanate 100, Aquanate 200] Can also be used. In the two-part aqueous acrylic-urethane composition of the present invention,
If the equivalent ratio (OH / NCO ratio) of (A) the hydroxyl group (OH) of the main ingredient and (B) the isocyanate group (NCO) of the curing agent is less than 1: 3, the excess isocyanate group reacts with water. Carbon dioxide gas is generated, which may impair the appearance of the coating film. When the OH / NCO ratio exceeds 2: 1, the strength of the coating film decreases due to insufficient crosslinking density, and the water resistance may decrease due to exposure of hydroxyl groups.

The two-part aqueous acryl-urethane composition of the present invention may optionally contain various surfactants such as fluorine-based or acetylene glycol-based surfactants as leveling agents.
As a solvent, N-methylpyrrolidone, propylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, or the like can be added. The two-part aqueous acryl-urethane composition of the present invention itself forms a film excellent in durability, light resistance, weather resistance, and water resistance, but an aqueous oxazoline-based crosslinking agent, an aqueous polycarbodiimide-based crosslinking agent, By using a crosslinking agent having reactivity with a carboxyl group, such as an aqueous epoxy resin-based crosslinking agent, in combination with a curing agent, it is possible to impart more excellent water resistance. The two-part aqueous acrylic-urethane composition of the present invention can be used as various coating agents such as adhesives, paints, printing inks, etc. as various plastic bases such as acrylic resin, ABS resin, polycarbonate resin, polyurethane resin and epoxy resin. It can be used for hard-to-adhesive plastic substrates such as polyolefin resins and polyester resins, urethane elastomers, concrete substrates, glass substrates, stainless steel, etc., especially for urethane waterproofing materials for buildings. As a topcoat agent, it exhibits excellent adhesion and satisfies the demands for the smoothness of the coated surface, water resistance, weather resistance, bending resistance at low temperatures, etc., which are important properties for such a composition. It is considered that the two-pack type aqueous acrylic-urethane composition of the present invention exerts these effects for the following reasons. That is, (A) the hydroxyl group-containing acryl-urethane copolymer in the main component is a completely uniform copolymer in which a polyurethane resin and an acrylic resin are uniformly incorporated, and the acrylic resin portion is an ultraviolet absorbing unit. UV-absorbing monomer and UV-stable monomer due to the synergistic effect of UV-absorbing monomer and UV-stable monomer And
Excellent weather resistance. In addition, by using the aqueous polyisocyanate compound (B) as a curing agent, a highly crosslinked structure that cannot be obtained with a one-pack type aqueous resin is formed.

[0023]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. In addition, the viscosity of the acrylic polyol obtained in the synthesis example and the comparative synthesis example was measured using a Gardner foam viscometer. The weight average molecular weight of the acrylic polyol was determined by gel permeation chromatography using HLC-8120GPC [Tosoh Corporation]
And polystyrene conversion. In Examples and Comparative Examples, the properties of the coating film were evaluated by the following methods. (1) Preparation of coating film As an adherend, stretched polypropylene film (OPP) whose surface has been subjected to corona discharge treatment, ABS plate, oak plate, concrete plate, stainless steel plate, glass plate, urethane waterproof sheet [Daiflex Co., Ltd.] , SP-100]
After applying the coating agent so that the film thickness becomes 200 μm,
After leaving at 25 ° C. for one week, the obtained coating film is tested. (2) Appearance of coating film Cracks appearing on a coating film on a glass plate are visually evaluated. ；: No crack was observed. Δ: Slight cracking is observed. X: Cracks are clearly observed. (3) Adhesion JIS K 5400 8.5.2.
According to, using a cutter knife, the gap 1
100 square grids of mm were made, and cellophane adhesive tape [Nichiban Co., Ltd.] was attached to these squares, and an angle of 6
The appearance of the coating film when rapidly peeled at 0 ° is 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 remain on the adherend side. Δ: 50% or more and less than 80% of the coating film remain on the adherend side. ×: Less than 50% of the coating film remains on the adherend side. (4) Warm water resistance After the coating film prepared on the urethane waterproof sheet is immersed in water at 50 ° C. for 24 hours, JIS K 5400 8.5.
According to 2, using a cutter knife, 100 cross-cut grids with a gap of 1 mm were made on the coating film, and a cellophane adhesive tape [Nichiban Co., Ltd.] was attached to these grids, and quickly at an angle of 60 degrees. The appearance of the coating film when peeled is 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 remain on the adherend side. Δ: 50% or more and less than 80% of the coating film remain on the adherend side. ×: Less than 50% of the coating film remains on the adherend side. (5) Weather resistance The coating film prepared on the urethane waterproof sheet is irradiated for 1,000 hours with a sunshine weatherometer, and the gloss retention of the coating film is measured and evaluated according to the following criteria. A: Gloss retention of 95% or more. ；: Gloss retention of 80% or more and less than 95%. Δ: Gloss retention of 60% or more and less than 80%. X: Gloss retention less than 60%. (6) Bending resistance The coating film prepared on the urethane waterproof sheet is bent at 180 ° C., and cracks and peeling of the coating film are visually observed. ；: No cracking or peeling was observed at all. Δ: Cracking and peeling are slightly observed. C: Cracks and peeling are clearly observed.

Synthesis Example 1 (Acrylic Polyol A) A flask equipped with a thermometer, a stirrer, a dropping funnel, a gas inlet tube and a reflux condenser was charged with 25 parts by weight of xylene and 25 parts by weight of butyl acetate as a solvent, and heated at 100 ° C. The temperature rose. On the other hand, 1 part by weight of 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 28.5 parts by weight of cyclohexyl methacrylate, and 20 parts by weight of hydroxyethyl methacrylate are used as ultraviolet absorbing monomers. A mixture of 0.5 parts by weight of methacrylic acid and 0.5 parts by weight of 2,2'-azobisisobutyronitrile as a polymerization initiator was put into a dropping funnel and stirred at 100 ° C. under a nitrogen gas stream. , And the mixture was stirred for 4 hours while keeping the temperature at 100 ° C to copolymerize, thereby obtaining an acrylic polyol. The viscosity of this acrylic polyol is Z + (viscosity standard liquid symbol), the nonvolatile content is 49.8% by weight, the weight average molecular weight is 15,000, and the hydroxyl value is 86 mgKOH / g.
Met. This acrylic polyol is referred to as acrylic polyol A. Synthesis Example 2 (acrylic polyol B) Xylene 20 was used as a solvent in the same reactor as in Synthesis Example 1.
Parts by weight and 20 parts by weight of butyl acetate were charged, and the temperature was raised to 100 ° C. On the other hand, 2- as an ultraviolet absorbing monomer
[2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole 12 parts by weight, cyclohexyl methacrylate 18 parts by weight, hydroxyethyl methacrylate 8 parts by weight, methacrylic acid 0.1 part by weight.
A mixture of 5 parts by weight, 1.5 parts by weight of n-butyl acrylate, and 0.5 parts by weight of 2,2′-azobisisobutyronitrile as a polymerization initiator was put into a dropping funnel and placed under a stream of nitrogen gas. The mixture was added dropwise at 100 ° C. over 2 hours with stirring, and further stirred for 4 hours while maintaining the temperature at 100 ° C. to copolymerize, thereby obtaining an acrylic polyol. The viscosity of the acrylic polyol is Z + (viscosity standard liquid symbol), the nonvolatile content is 49.8% by weight, and the weight average molecular weight is 15.0.
00 and the hydroxyl number was 43 mg KOH / g. This acrylic polyol is converted to acrylic polyol B
And Synthesis Example 3 (acrylic polyol C) Xylene 25 was used as a solvent in the same reactor as in Synthesis Example 1.
Parts by weight and 25 parts by weight of butyl acetate were charged, and the temperature was raised to 100 ° C. On the other hand, 2- [2 ′
-Hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole 5 parts by weight, cyclohexyl methacrylate 34.5 parts by weight, hydroxyethyl methacrylate 8 parts by weight, methacrylic acid 0.5 parts by weight, general formula [2] 2 parts by weight of 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine as an ultraviolet-stable monomer represented by the formula and 2,2'-azobisisobutyronitrile 0.5 as a polymerization initiator The mixture obtained by mixing parts by weight was placed in a dropping funnel. This mixture was added dropwise at 100 ° C. over 2 hours while stirring under a nitrogen gas stream, and further stirred for 4 hours while maintaining the temperature at 100 ° C. to carry out copolymerization to obtain an acrylic polyol. The viscosity of this acrylic polyol is Z + (viscosity standard liquid symbol), and the nonvolatile content is 50.
The weight average molecular weight was 14,000, and the hydroxyl value was 34 mgKOH / g. This acrylic polyol is referred to as acrylic polyol C. Synthesis Example 4 (acrylic polyol D) In a reaction apparatus similar to that of Synthesis Example 1, xylene 25 was used as a solvent.
Parts by weight and 25 parts by weight of butyl acetate were charged, and the temperature was raised to 100 ° C. On the other hand, 2- [2 ′
-Hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole 7 parts by weight, cyclohexyl methacrylate 23 parts by weight, hydroxyethyl methacrylate 15 parts by weight, an ultraviolet-stable monomer represented by the general formula [2] 4-methacryloyloxy-
A mixed liquid obtained by mixing 5 parts by weight of 2,2,6,6-tetramethylpiperidine and 0.5 part by weight of 2,2′-azobisisobutyronitrile as a polymerization initiator was put into a dropping funnel. Thereafter, the mixed solution was dropped at 100 ° C. over 2 hours while stirring under a nitrogen gas stream, and further stirred for 4 hours while maintaining the temperature at 100 ° C. to copolymerize, thereby obtaining an acrylic polyol. The viscosity of this acrylic polyol is Z +
(Viscosity standard liquid symbol), nonvolatile content is 50.1% by weight
The weight average molecular weight was 14,000, and the hydroxyl value was 64 mgKOH / g. This acrylic polyol is referred to as acrylic polyol D. Comparative Synthesis Example 1 (acrylic polyol E) Toluene 2 was used as a solvent in the same reaction apparatus as in Synthesis Example 1.
5 parts by weight and 25 parts by weight of butyl acetate were charged and heated to 100 ° C. under a nitrogen stream. After that, 1
While maintaining the temperature at 00 ° C., 20 parts by weight of methyl methacrylate, 10 parts by weight of stearyl methacrylate, 15 parts by weight of butyl acrylate, 5 parts by weight of 2-hydroxyethyl methacrylate and 2,2′-azobisisobutyronitrile 0 as a polymerization initiator. A mixed solution obtained by mixing 0.5 parts by weight was put into a dropping funnel. Thereafter, the mixture was dropped at 100 ° C. over 2 hours while stirring under a nitrogen gas stream, and further stirred for 4 hours while maintaining the temperature at 100 ° C. to copolymerize the mixture.
An acrylic polyol was obtained. The viscosity of this acrylic polyol is Z + (viscosity standard liquid symbol), and the nonvolatile content is 4
It was 9.9% by weight, the weight average molecular weight was 15,000, and the hydroxyl value was 21 mgKOH / g. This acrylic polyol is referred to as acrylic polyol E.

Synthesis Example 5 (Acryl containing hydroxyl group)
Urethane copolymer aqueous dispersion A) Acrylic polyol A1 obtained in Synthesis Example 1 was placed in a flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube.
3 parts by weight, 80 parts by weight of polyhexamethylene carbonate diol [number average molecular weight 1,000], 0.9 part by weight of 1,4-butanediol, 6.7 parts by weight of 2,2-dimethylolpropionic acid, dibutyltin dilaurate After 0.001 part by weight and 60 parts by weight of methyl ethyl ketone were charged and uniformly mixed, 52.4 parts by weight of dicyclohexylmethane diisocyanate was added, and the mixture was reacted at 80 ° C. for 2 hours. % Of a urethane prepolymer in methyl ethyl ketone was obtained. The solution was cooled to 30 ° C., neutralized by adding 5 parts by weight of triethylamine, and then gradually added with 350 parts by weight of water to emulsify and disperse.
A 6% by weight aqueous solution was added and stirred for 0.5 hours, and then 6.3 parts by weight of diethanolamine was added and stirred for 2 hours. The solvent was removed while heating to 60 ° C. over about 2 hours under reduced pressure to obtain an aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer having a nonvolatile content of about 35% by weight.
The hydroxyl group-containing acryl-urethane copolymer in this aqueous dispersion had a carboxyl group content derived from 2,2-dimethylolpropionic acid of 1.5% by weight and a hydroxyl group content of 1.3% by weight. This aqueous dispersion was converted to a hydroxyl group-containing acrylic-urethane copolymer aqueous dispersion A.
And Synthesis Example 6 (Hydroxyl Group-Containing Acrylic-Urethane Copolymer Aqueous Dispersion B) In the same reactor as in Synthesis Example 5, 97.6 parts by weight of the acrylic polyol B obtained in Synthesis Example 2, polybutylene adipate diol [number average [Molecular weight 1,700] 102 parts by weight, 7.4 parts by weight of 2,2-dimethylolbutanoic acid, 0.001 part by weight of dibutyltin dilaurate and 60 parts by weight of methyl ethyl ketone are charged and uniformly mixed, and then 44.4 parts of isophorone diisocyanate is mixed. The reaction was carried out at 80 ° C. for 2 hours to obtain a urethane prepolymer solution containing 1.7% by weight of a free isocyanate group based on nonvolatile components in methyl ethyl ketone. The solution was cooled to 30 ° C. and neutralized by adding 5 parts by weight of triethylamine.
350 parts by weight of water is gradually added to emulsify and disperse,
12.6 parts by weight of diethanolamine was added and stirred for 2 hours. The solvent was removed while heating to 60 ° C. over about 2 hours under reduced pressure to obtain an aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer having a nonvolatile content of about 35% by weight. The hydroxyl group-containing acrylic-urethane copolymer in this aqueous dispersion had a carboxyl group content derived from 2,2-dimethylolbutanoic acid of 1.0% by weight and a hydroxyl group content of 1.9% by weight. This aqueous dispersion is referred to as a hydroxyl group-containing acrylic-urethane copolymer aqueous dispersion B. Synthesis Example 7 (Hydroxyl Group-Containing Acrylic-Urethane Copolymer Aqueous Dispersion C) In the same reactor as in Synthesis Example 5, an acrylic polyol [Nippon Shokubai Co., Ltd., Udouble UV-6010, a nonvolatile content of about 50% by weight, glass Transition temperature 30 ° C., hydroxyl value 27 mg KOH / g] 41.6 parts by weight, poly (3-methyl-1,
5-pentane adipate) diol [number average molecular weight 2,0
00] 80.0 parts by weight, dimer diol [Toa Gosei
Co., Ltd., Pespol HP-1000, number average molecular weight 57
0] 23.0 parts by weight, 7.4 parts by weight of 2,2-dimethylolpropionic acid, 0.001 parts by weight of dibutyltin dilaurate and 60 parts by weight of methyl ethyl ketone are charged and uniformly mixed, and then, dicyclohexylmethane diisocyanate 52.4 is added. The reaction was carried out at 80 ° C. for 2 hours, and the free isocyanate group content relative to the nonvolatile content was 2.0% by weight.
To obtain a solution of the urethane prepolymer in methyl ethyl ketone. The solution was cooled to 30 ° C., neutralized by adding 5.0 parts by weight of triethylamine, and then gradually emulsified and dispersed by adding 350 parts by weight of water. To this emulsified dispersion, 1.6 parts by weight of a 60% by weight aqueous solution of hydrazine hydrate was added to form an aqueous dispersion.
The mixture was stirred for 5 hours, then 8.4 parts by weight of diethanolamine was added, and the mixture was stirred for 2 hours. The solvent was removed while heating to 60 ° C. over about 2 hours under reduced pressure.
By weight, an aqueous dispersion of hydroxyl group-containing acrylic-urethane copolymer was obtained. The hydroxyl group-containing acryl-urethane copolymer aqueous dispersion in this aqueous dispersion had a carboxyl group content derived from 2,2-dimethylolpropionic acid of 1.
2% by weight and a hydroxyl group content of 1.4% by weight. This aqueous dispersion is treated with a hydroxyl group-containing acrylic-
The urethane copolymer aqueous dispersion C was used. Synthesis Example 8 (Hydroxyl Group-Containing Acrylic-Urethane Copolymer Aqueous Dispersion D) In the same reaction apparatus as in Synthesis Example 5, an acrylic polyol [Nippon Shokubai Co., Ltd., Udouble UV-6010, about 50% by weight of nonvolatile components, glass Transition temperature 30 ° C., hydroxyl value 27 mg KOH / g] 41.6 parts by weight, poly-ε-caprolactone diol [number average molecular weight 2,000] 80.0 parts by weight, dimer diol [Toa Gosei Co., Ltd., Pespol HP]
-1000, number average molecular weight 570] 23.0 parts by weight, 7.4 parts by weight of 2,2-dimethylolbutanoic acid in 30 parts by weight of methyl ethyl ketone and 5.
A solution neutralized by adding 0 parts by weight, 0.001 parts by weight of dibutyltin dilaurate and 30 parts by weight of methyl ethyl ketone were charged and mixed uniformly, and 52.4 parts by weight of dicyclohexylmethane diisocyanate was added.
The reaction was carried out for a period of time to obtain a solution of a urethane prepolymer in methyl ethyl ketone having a free isocyanate group content of 2.0% by weight based on the nonvolatile content. Cool the solution to 30 ° C.
350 parts by weight of water was gradually added and emulsified and dispersed. A 1.6% by weight aqueous solution of hydrazine hydrate (1.6%) was added to this emulsified dispersion.
Then, 8.4 parts by weight of diethanolamine was added and the mixture was stirred for 2 hours. The solvent was removed while heating to 60 ° C. over about 2 hours under reduced pressure to obtain an aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer having a nonvolatile content of about 35% by weight. The hydroxyl group-containing acryl-urethane copolymer in the aqueous dispersion had a carboxyl group content derived from 2,2-dimethylolbutanoic acid of 1.2% by weight and a hydroxyl group content of 1.4% by weight. This aqueous dispersion is designated as a hydroxyl group-containing acrylic-urethane copolymer aqueous dispersion D. Synthesis Example 9 (Hydroxyl Group-Containing Acrylic-Urethane Copolymer Aqueous Dispersion E) In the same reactor as in Synthesis Example 5, 52.0 parts by weight of the acrylic polyol C obtained in Synthesis Example 3, polytetramethylene glycol [number average] Molecular weight 2,000] 120.0 parts by weight, polyethylene glycol [number average molecular weight 600] 3
0.0 parts by weight, 2.7 2,2-dimethylolpropionic acid
Parts by weight, 0.001 part by weight of dibutyltin dilaurate and 60 parts by weight of methyl ethyl ketone, and after uniformly mixing, 33.6 parts by weight of hexamethylene diisocyanate was added, and the mixture was reacted at 80 ° C. for 2 hours. A urethane prepolymer solution having a content of 1.7% by weight in methyl ethyl ketone was obtained. The solution was cooled to 30 ° C., neutralized by adding 5.0 parts by weight of triethylamine, and then gradually emulsified and dispersed by adding 350 parts by weight of water. To this emulsified dispersion, add 60 parts of hydrazine hydrate.
1.6 parts by weight of a 1% by weight aqueous solution was added, and the mixture was stirred for 0.5 hour.
Then, 8.4 parts by weight of diethanolamine was added to add 2 parts by weight.
Stirred for hours. The solvent was removed while heating to 60 ° C. over about 2 hours under reduced pressure to obtain an aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer having a nonvolatile content of about 35% by weight. The hydroxyl group-containing acrylic-urethane copolymer in this aqueous dispersion had a carboxyl group content derived from 2,2-dimethylolpropionic acid of 0.4% by weight and a hydroxyl group content of 1.2% by weight. . This aqueous dispersion is referred to as a hydroxyl group-containing acrylic-urethane copolymer aqueous dispersion E. Synthesis Example 10 (Hydroxyl Group-Containing Acrylic-Urethane Copolymer Aqueous Dispersion F) In the same reactor as in Synthesis Example 5, 17.4 parts by weight of the acrylic polyol D obtained in Synthesis Example 4, poly (3-methyl-
1,5-pentane adipate) diol [number average molecular weight 2,000] 88.0 parts by weight, polyethylene glycol [number average molecular weight 600] 24.0 parts by weight, 2,2-dimethylolpropionic acid 6.7 parts by weight, After 0.001 part by weight of dibutyltin dilaurate and 60 parts by weight of methyl ethyl ketone were mixed and uniformly mixed, 52.4 parts by weight of dicyclohexylmethane diisocyanate was added, and the mixture was reacted at 80 ° C. for 2 hours. A .1% by weight urethane prepolymer solution in methyl ethyl ketone was obtained. The solution was cooled to 30 ° C., neutralized by adding 5.0 parts by weight of triethylamine, and then emulsified and dispersed by gradually adding 355.0 parts by weight of water. 1.6 parts by weight of a 60% by weight aqueous hydrazine aqueous solution was added to this emulsified dispersion and stirred for 0.5 hours, and then 4.9 parts by weight of monoethanolamine was added and stirred for 2 hours. The solvent was removed while heating to 60 ° C. over about 2 hours under reduced pressure to obtain an aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer having a nonvolatile content of about 35% by weight. The hydroxyl group-containing acrylic-urethane copolymer in this aqueous dispersion had a carboxyl group content derived from 2,2-dimethylolpropionic acid of 1.3% by weight and a hydroxyl group content of 0.8% by weight. This aqueous dispersion is referred to as a hydroxyl group-containing acrylic-urethane copolymer aqueous dispersion F.

Comparative Synthetic Example 2 (Hydroxyl Group-Containing Polyurethane Resin Aqueous Dispersion) In the same reactor as in Synthetic Example 5, poly (3-methyl-1,5
-Pentylene) adipate diol [number average molecular weight 2,0
00] 100.0 parts by weight, dimer diol [Toa Gosei
Co., Ltd., Pespol HP-1000, number average molecular weight 57
0] 23.0 parts by weight, 2,2-dimethylolbutanoic acid 7.
4 parts by weight, 0.001 part by weight of dibutyltin dilaurate and 60 parts by weight of methyl ethyl ketone were charged and uniformly mixed, and then mixed with dicyclohexylmethane diisocyanate 5
2.4 parts by weight were added and reacted at 80 ° C. for 2 hours to obtain a solution of a urethane prepolymer in methyl ethyl ketone having a free isocyanate group content of 2.1% by weight based on the nonvolatile components. The solution was cooled to 30 ° C., neutralized by adding 5.0 parts by weight of triethylamine, and then gradually emulsified and dispersed by adding 350 parts by weight of water. To this emulsified dispersion, 1.6 parts by weight of a 60% by weight aqueous solution of hydrazine hydrate was added to form an aqueous dispersion.
The mixture was stirred for 5 hours, then 8.4 parts by weight of diethanolamine was added, and the mixture was stirred for 2 hours. The solvent was removed while heating to 60 ° C. over about 2 hours under reduced pressure.
By weight, an aqueous dispersion of hydroxyl group-containing polyurethane resin was obtained. The carboxyl group content derived from 2,2-dimethylolbutanoic acid in the hydroxyl group-containing polyurethane resin in this aqueous dispersion was 1.2% by weight, and the hydroxyl group content was 1.4% by weight. Comparative Synthetic Example 3 (Hydroxyl Group-Containing Acrylic-Urethane Copolymer Aqueous Dispersion G)
2.0 parts by weight, 80.0 parts by weight of poly (3-methyl-1,5-pentane adipate) diol [number average molecular weight 2,000], dimer diol [Toa Gosei Co., Ltd., Pespol H]
P-1000, number average molecular weight 570] 23.0 parts by weight,
6.7 parts by weight of 2,2-dimethylolpropionic acid, 0.001 part by weight of dibutyltin dilaurate and 60 parts by weight of methyl ethyl ketone were charged and uniformly mixed, and then 44.4 parts by weight of isophorone diisocyanate was added. The reaction was carried out for a period of time to obtain a urethane prepolymer solution in methyl ethyl ketone having a free isocyanate group content of 1.9% by weight based on the nonvolatile content. The solution was cooled to 30 ° C., neutralized by adding 5.0 parts by weight of tosoethylamine, and then gradually added with 350 parts by weight of water to emulsify and disperse. A 60% by weight aqueous solution of hydrazine hydrate was added to this emulsified dispersion.
6 parts by weight were added and stirred for 0.5 hours, and then 8.4 parts by weight of diethanolamine was added and stirred for 2 hours.
The solvent was removed while heating to 60 ° C. over about 2 hours under reduced pressure to obtain an aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer having a nonvolatile content of about 35% by weight. The carboxyl group content derived from 2,2-dimethylolpropionic acid in the hydroxyl group-containing acryl-urethane copolymer in this aqueous dispersion was 1.2% by weight, and the hydroxyl group content was 1.5% by weight. . This aqueous dispersion is referred to as a hydroxyl group-containing acrylic-urethane copolymer aqueous dispersion G. Comparative Synthesis Example 4 (Hydroxyl Group-Containing Acrylic-Urethane Copolymer Aqueous Dispersion H) An acrylic polyol [Dainippon Ink Chemical Industry Co., Ltd., Acridic A-811,
Non-volatile content: about 50% by weight, glass transition temperature: 58 ° C., hydroxyl value: 17 mgKOH / g] 66.0 parts by weight, poly-ε-caprolactone diol [average molecular weight: 2,000] 80 parts by weight, polyethylene glycol [average molecular weight: 1,000]
0] 10 parts by weight, 2,2-dimethylolpropionic acid 6.
7 parts by weight, 2.7 parts by weight of 1,4-butanediol, 0.001 part by weight of dibutyltin dilaurate and 60 parts by weight of methyl ethyl ketone were charged and uniformly mixed, and 52.4 parts by weight of dicyclohexylmethane diisocyanate was added. The reaction was carried out at a temperature of 2 ° C. for 2 hours to obtain a urethane prepolymer solution containing 1.9% by weight of a free isocyanate group based on nonvolatile components in methyl ethyl ketone. Add this solution to 30
After cooling to 5.0 ° C. and neutralizing by adding 5.0 parts by weight of triethylamine, 350 parts by weight of water was gradually added to emulsify and disperse the mixture. Then, 6.0 parts by weight of a 20% by weight aqueous solution of ethylenediamine was added to obtain 0% by weight. The mixture was stirred for 1.5 hours, and 8.4 parts by weight of diethanolamine was added, followed by stirring for 2 hours. The solvent was removed while heating to 60 ° C. over about 2 hours under reduced pressure to obtain an aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer having a nonvolatile content of about 35% by weight. The carboxyl group content derived from 2,2-dimethylolpropionic acid in the hydroxyl group-containing acryl-urethane copolymer in this aqueous dispersion was 1.2% by weight, and the hydroxyl group content was 1.4% by weight. . Comparative Synthesis Example 5 (Aqueous Emulsion of Acrylic Resin) Temperature Controller, Squeeze Stirrer, Reflux Cooling Tube, Supply Container,
Water 265 was placed in a reaction vessel equipped with a thermometer and a nitrogen inlet tube.
5 parts by weight of a 35% by weight aqueous solution of an anionic emulsifier (a sodium salt of a sulfuric acid half ester of an adduct of 20 moles of ethylene oxide of p-nonylphenol) and a nonionic emulsifier (ethylene oxide 25% of p-nonylphenol)
20 weight parts of a 20% by weight aqueous solution of
The inside of the reaction vessel was replaced with nitrogen gas. Water 20
2.5 parts by weight of a 35% by weight aqueous solution of the above anionic emulsifier, 16 parts by weight of methyl methacrylate, n-
A monomer mixture containing 14 parts by weight of butyl acrylate, 8 parts by weight of styrene and 2 parts by weight of 2-hydroxyethyl acrylate was added, heated to 90 ° C., and 0.25 parts by weight of potassium persulfate was added to 8.5 parts by weight of water. A dissolved aqueous initiator solution was added. Then, 180 parts by weight of water, 22.5 parts by weight of a 35% by weight aqueous solution of the above anionic emulsifier, 144 parts by weight of methyl methacrylate, 12 parts of n-butyl acrylate
A monomer mixture containing 6 parts by weight, 72 parts by weight of styrene, and 18 parts by weight of 2-hydroxyethyl acrylate;
An aqueous initiator solution in which 2.25 parts by weight of potassium persulfate was dissolved in 4.5 parts by weight was supplied to the reaction vessel maintained at 90 ° C. over 3.5 hours, and further maintained at 90 ° C. for 2 hours after the supply. Polymerization was performed to obtain an aqueous emulsion of an acrylic resin. The glass transition temperature of this acrylic resin was 22 ° C. The hydroxyl group content in the acrylic resin in this aqueous emulsion is 0.7% by weight.

Example 1 An aqueous polyisocyanate compound [Sumitomo Bayer Urethane] was prepared by using 100 parts by weight of the hydroxyl group-containing acrylic-urethane copolymer aqueous dispersion A obtained in Synthesis Example 5 as a main component.
Co., Ltd., Baihijur 3100, NCO content 17.2
9.8 parts by weight] as a curing agent, and stirred until uniform to prepare a two-part aqueous acrylic-urethane composition. The equivalent ratio (OH / NCO ratio) of the hydroxyl group in the main agent to the isocyanate group in the curing agent is 2: 3. A coating film was prepared using this two-part aqueous acryl-urethane composition as a coating agent, and the physical properties were evaluated. The appearance of the coating film was good without any cracks. In the adhesion test, all the coating films formed on the ABS plate, oak plate, concrete plate, stainless steel plate, glass plate, urethane waterproof sheet remained on the adherend side, but the grid of the coating film formed on OPP 7 Individual peeled off. In the warm water resistance test, all the coating films remained on the adherend side. In the weather resistance test, the gloss retention was 88%. In the bending resistance test, no cracking or peeling was observed. Example 2 An aqueous polyisocyanate compound [Sumitomo Bayer Urethane] was prepared by using 100 parts by weight of the hydroxyl group-containing acrylic-urethane copolymer aqueous dispersion B obtained in Synthesis Example 6 as a main component.
Co., Ltd., Baihijur 3100, NCO content 17.2
% By weight] as a curing agent and stirred until uniform to prepare a two-part aqueous acryl-urethane composition. The equivalent ratio (OH / NCO ratio) of the hydroxyl group in the main agent to the isocyanate group in the curing agent is 2: 3. A coating film was prepared using this two-part aqueous acryl-urethane composition as a coating agent, and the physical properties were evaluated. The appearance of the coating film was good without cracking. In the adhesion test, the coatings on the ABS plate, oak plate, concrete plate, stainless steel plate, glass plate and urethane waterproof sheet all remained on the adherend side, but the 6 coatings on the OPP peeled off. Was. In the warm water resistance test, all the coating films remained on the adherend side. In the weather resistance test, the gloss retention was 95%. In the bending resistance test, no cracking or peeling was observed. Example 3 An aqueous polyisocyanate compound [Sumitomo Bayer Urethane] containing 100 parts by weight of the hydroxyl group-containing acrylic-urethane copolymer aqueous dispersion C obtained in Synthesis Example 7 as a main component
Co., Ltd., Baihijur 3100, NCO content 17.2
1% by weight] as a curing agent and stirred until uniform to prepare a two-part aqueous acryl-urethane composition. The equivalent ratio (OH / NCO ratio) of the hydroxyl group in the main agent to the isocyanate group in the curing agent is 2: 3. A coating film was prepared using this two-part aqueous acryl-urethane composition as a coating agent, and the physical properties were evaluated. The appearance of the coating film was good without cracking. In the adhesion test, all the coating films remained on the adherend material side. In the warm water resistance test, all the coating films remained on the adherend side. In the weather resistance test, the gloss retention was 90%. In the bending resistance test, no cracking or peeling was observed. Example 4 An aqueous polyisocyanate compound [Sumitomo Bayer Urethane] containing 100 parts by weight of the hydroxyl group-containing acrylic-urethane copolymer aqueous dispersion D obtained in Synthesis Example 8 as a main component
Co., Ltd., Baihijur 3100, NCO content 17.2
1% by weight] as a curing agent, and stirred until uniform to prepare a two-part aqueous acryl-urethane composition. The equivalent ratio (OH / NCO ratio) of the hydroxyl group in the main agent to the isocyanate group in the curing agent is 2: 3.
It is. A coating film was prepared using this two-part aqueous acryl-urethane composition as a coating agent, and the physical properties were evaluated. The appearance of the coating film was good without cracking. In the adhesion test, all the coating films remained on the adherend side. In the warm water resistance test, all the coating films remained on the adherend side. In the weather resistance test, the gloss retention was 91%. In the bending resistance test, no cracking or peeling was observed. Example 5 An aqueous polyisocyanate compound [Sumitomo Bayer Urethane] was prepared by using 100 parts by weight of the hydroxyl group-containing acrylic-urethane copolymer aqueous dispersion E obtained in Synthesis Example 9 as a main component.
Co., Ltd., Baihijur 3100, NCO content 17.2
% By weight] as a curing agent, and stirred until uniform to prepare a two-part aqueous acrylic-urethane composition. The equivalent ratio (OH / NCO ratio) of the hydroxyl group in the main agent to the isocyanate group in the curing agent is 2: 3. A coating film was prepared using this two-part aqueous acryl-urethane composition as a coating agent, and the physical properties were evaluated. The appearance of the coating is
Cracks were not observed and were good. In the adhesion test,
ABS, oak, concrete, stainless steel,
All coating films on the glass plate and urethane waterproof sheet remained on the adherend side, but seven squares of the coating film on OPP were peeled off. In the warm water resistance test, all the coating films remained on the adherend side. In the weather resistance test, the gloss retention was 95%. In the bending resistance test, no cracking or peeling was observed. Example 6 An aqueous polyisocyanate compound [Sumitomo Bayer Urethane Co., Ltd., Bihidur 3100, NCO content 17.2% by weight] was used, as a main component, with 100 parts by weight of the hydroxyl group-containing acrylic-urethane copolymer F obtained in Synthesis Example 10 as a main component. 6.
0 parts by weight were blended as a curing agent, and the mixture was stirred until it became uniform to prepare a two-part aqueous acrylic-urethane composition. The equivalent ratio (OH / NCO ratio) of the hydroxyl group in the main agent to the isocyanate group in the curing agent is 2: 3. A coating film was prepared using this two-part aqueous acryl-urethane composition as a coating agent, and the physical properties were evaluated. The appearance of the coating film was good without cracking. In the adhesion test, the coatings on the ABS plate, oak plate, concrete plate, stainless steel plate, glass plate and urethane waterproof sheet all remained on the adherend side, but the 6 coatings on the OPP peeled off. Was. In the warm water resistance test, all the coating films remained on the adherend side. In the weather resistance test, the gloss retention was 88%. In the bending resistance test, no cracking or peeling was observed.

Comparative Example 1 An aqueous polyisocyanate compound (Sumitomo Bayer Urethane Co., Ltd., Bihidur 3100, NCO content 17.2) was used as a main component, with 100 parts by weight of the hydroxyl group-containing polyurethane resin aqueous dispersion obtained in Comparative Synthesis Example 2 as a main component. Wt%] 10.
5 parts by weight were blended as a curing agent, and the mixture was stirred until the mixture became uniform to prepare a two-part aqueous urethane composition. The equivalent ratio (OH / NCO ratio) of the hydroxyl group in the main agent to the isocyanate group in the curing agent is 2: 3. A coating film was prepared using this two-pack type aqueous urethane composition as a coating agent, and the physical properties were evaluated. The appearance of the coating film was good without cracking.
In the adhesion test, all the coating films remained on the adherend side.
In the warm water resistance test, all the coating films remained on the adherend side. In the weather resistance test, the gloss retention was 40%. In the bending resistance test, no cracking or peeling was observed. Comparative Example 2 Hydroxyl group-containing acryl obtained in Comparative Synthesis Example 3
The main component is 100 parts by weight of the urethane copolymer aqueous dispersion G,
Aqueous polyisocyanate compound [Sumitomo Bayer Urethane
Co., Ltd., Baihijur 3100, NCO content 17.2
% By weight] of 11.3 parts by weight as a curing agent, and stirred until uniform to prepare a two-part aqueous acryl-urethane composition. The equivalent ratio (OH / NCO ratio) of the hydroxyl group in the main agent to the isocyanate group in the curing agent is 2: 3.
It is. A coating film was prepared using this two-part aqueous acryl-urethane composition as a coating agent, and the physical properties were evaluated. The appearance of the coating film was good without cracking. In the adhesion test, all the coating films remained on the adherend side. In the warm water resistance test, all the coating films remained on the adherend side. In the weather resistance test, the gloss retention was 45%. In the bending resistance test, no cracking or peeling was observed. Comparative Example 3 Hydroxyl group-containing acryl obtained in Comparative Synthesis Example 4
Urethane copolymer water dispersion H100 parts by weight as a main component,
Aqueous polyisocyanate compound [Sumitomo Bayer Urethane
Co., Ltd., Baihijur 3100, NCO content 17.2
1% by weight] as a curing agent, and stirred until uniform to prepare a two-part aqueous acrylic-urethane composition. The equivalent ratio (OH / NCO ratio) of the hydroxyl group in the main agent to the isocyanate group in the curing agent is 2: 3.
It is. A coating film was prepared using this two-part aqueous acryl-urethane composition as a coating agent, and the physical properties were evaluated. The appearance of the coating film was good without cracking. In the adhesion test, the coatings on the ABS plate, oak plate, concrete plate, stainless steel plate, glass plate and urethane waterproof sheet all remained on the adherend side, but the 6 coatings on the OPP peeled off. Was. In the warm water resistance test, all the coating films remained on the adherend side. In the weather resistance test, the gloss retention was 40%. In the bending resistance test, no cracking or peeling was observed. Comparative Example 4 An aqueous polyisocyanate compound [Sumitomo Bayer Urethane Co., Ltd .;
6.3 parts by weight of NCO content, 17.2% by weight] was added as a curing agent, and the mixture was stirred until it became uniform to prepare a two-part aqueous acrylic composition. The equivalent ratio (OH / NC) of the hydroxyl group in the main agent and the isocyanate group in the curing agent
O ratio) is 2: 3. A coating film was prepared using this two-part aqueous acrylic composition as a coating agent, and the physical properties were evaluated. The appearance of the coating film was slightly cracked. In the adhesion test, the coatings on the oak plate, concrete plate, stainless steel plate, and glass plate all remained on the adherend side, but the coating on the OPP peeled off 90 squares and the coating on the ABS plate In the test, 87 squares were peeled off, and 40 coats of the coating film on the urethane waterproof sheet were peeled off. In the warm water resistance test, all the coating films were peeled off. 75% gloss retention in weathering test
Met. In the bending resistance test, both cracking and peeling were clearly observed. Table 1 shows the results of Examples 1 to 6 and Comparative Examples 1 to 4.

[0029]

[Table 1]

[0030]

[Table 2]

As can be seen from Table 1, the coating films of Examples 1 to 6 in which the two-part aqueous acrylic-urethane composition of the present invention was formed as a coating agent had good appearance and various coatings. It has good adhesion to the dressing material and is not only excellent in bending resistance but also excellent in weather resistance. On the other hand, the coating agents of Comparative Examples 1 to 3 using the acrylic polyol containing no UV-absorbing monomer have good appearance and adhesion of the coating film, but poor weather resistance. In addition, the coating film produced using the two-part aqueous acrylic composition of Comparative Example 4 had cracks in the appearance of the coating film, and had insufficient weather resistance,
Warm water resistance and bending resistance are poor.

[0032]

According to the present invention, the two-part aqueous acrylic-urethane composition and the coating film obtained from the coating agent of the present invention are formed of OPP and ABS.
Required as a coating agent, such as adhesion to various substrates such as hard-to-adhere plastic substrates such as boards, wood, concrete boards, stainless steel boards, and urethane sheets, warm water resistance, weather resistance, and bending resistance. It has excellent performance and can be widely developed as an aqueous coating agent.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 175/04 C09D 175/04 C09J 175/04 C09J 175/04 F term (Reference) 4J002 CK02W CK03X CK04X CK05X DE026 GH00 HA07 4J034 BA08 CA03 CA04 CA05 CA13 CA14 CA15 CA22 CB03 CB04 CB07 CB08 CC03 CC26 CC34 CC45 CC52 CC61 CC62 CC65 CC67 CE03 DA01 DB03 DB07 DC02 DC20 DC23 DC35 DC37 DC39 DC42 DF01 DF02 DF12 DF12 DG22 DG22 DF22 DG22 DG22 DG22 DG22 DG22 DG22 DG22 DG22 DG22 DG22 DG22 DP18 EA14 FA01 FA04 FB04 FC03 FD01 FD05 HA01 HA02 HA07 HB07 HB08 HC03 HC12 HC13 HC17 HC22 HC35 HC46 HC52 HC53 HC61 HC64 HC67 HC71 HC73 HD02 HD07 JA42 KB02 KC17 KD02 KD12 QA02 QA03 QB03 QC05 RA07 RA08 4DG01 DG1 DG1 DG1 DG281 DG291 GA03 GA06 GA08 MA08 MA10 NA03 NA04 NA12 4J040 EF051 EF061 EF111 EF121 EF131 EF181 GA05 GA17 JA13 LA06 LA07

Claims (13)

[Claims] (1) (a) an organic polyisocyanate compound,
(B) UV absorbing monomer and ethylenically unsaturated bond 1
High molecular weight polyol containing an acrylic polyol having a hydroxyl value of 5 to 200 mgKOH / g obtained by copolymerizing a monomer having a hydroxyl group and a monomer having a hydroxyl group and (c) an anionic hydrophilic group and two or more active hydrogens And (d) at least one compound selected from the group consisting of water-soluble polyamines, hydrazines and derivatives thereof.
(E) a primary amine having a hydroxyl group and / or after chain extension in water using a seed or simultaneously with the chain extension.
Or an aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer, which is obtained by blocking a terminal isocyanate group with a secondary amine. 2. The method according to claim 1, wherein (a) the organic polyisocyanate compound is
The at least one member selected from an aliphatic diisocyanate compound and an alicyclic diisocyanate compound.
An aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer according to the above. 3. The aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer according to claim 1, wherein the ultraviolet absorbing monomer is a compound represented by the general formula [1]. Embedded image (Wherein, 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.) 4. 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
An aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer according to the above. Embedded image (Wherein, 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, Y is an oxygen atom or an imino group. ) 5. An acrylic polyol, a UV-absorbing monomer used for copolymerization, a UV-stable monomer represented by the general formula [2] and a UV-stable monomer represented by the general formula [3] The total weight of the body is 1 to 3 of all monomers used for copolymerization.
5. The aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer according to claim 1, wherein the amount is 0% by weight. 6. The aqueous dispersion of a hydroxyl group-containing acrylic-urethane copolymer 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). 7. The hydroxyl group-containing acrylic resin according to claim 1, wherein (b) the high molecular weight polyol contains at least one selected from a polyester polyol, a polycarbonate polyol, a polyether polyol and a dimer diol, in addition to the acrylic polyol. Water dispersion of urethane copolymer. 8. The compound (c) having an anionic hydrophilic group and two or more active hydrogens, wherein the anionic hydrophilic group is a carboxyl group and the hydroxyl group-containing acryl-urethane copolymer contains the carboxyl group. Quantity
2. The aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer according to claim 1, wherein the amount is 0.3 to 2.5% by weight based on the total weight of the copolymer. 9. The content of the hydroxyl group derived from the primary amine and the secondary amine having (e) a hydroxyl group is 0.1 to 5% by weight of the total weight of the hydroxyl group-containing acryl-urethane copolymer. % Of the hydroxyl group-containing acryl-urethane copolymer aqueous dispersion according to claim 1. 10. The hydroxyl group-containing acryl-urethane copolymer water according to claim 1, wherein (e) the primary amine having a hydroxyl group is monoethanolamine, and the secondary amine having a hydroxyl group is diethanolamine. Dispersion. 11. A main agent comprising (A) an aqueous dispersion of a hydroxyl group-containing acryl-urethane copolymer according to any one of claims 1 to 10 and (B) a curing agent comprising an aqueous polyisocyanate compound. Equivalent ratio (OH) between hydroxyl group (OH) and isocyanate group (NCO) of the curing agent
/ NCO ratio) in a ratio of 1: 3 to 2: 1. 12. The two-part aqueous acryl according to claim 11,
A coating agent containing a urethane composition. 13. The two-part aqueous acryl according to claim 11,
An adhesive containing a urethane composition.