JP6123465B2 - Aqueous polyurethane resin dispersion and use thereof - Google Patents

Description

  The present invention relates to an aqueous polyurethane resin dispersion curable with active energy rays such as ultraviolet rays and the use thereof.

  Polycarbonate polyol is a useful compound that can be used as a raw material for polyurethane resins, and can react with isocyanate compounds to produce polyurethane resins used in rigid foams, flexible foams, paints, adhesives, synthetic leather, ink binders, and the like. . Moreover, it is known that the coating film obtained by apply | coating the aqueous polyurethane resin dispersion which used polycarbonate polyol as the raw material is excellent in light resistance, heat resistance, hydrolysis resistance, and oil resistance (refer patent document 1). .

  Among them, a coating film obtained by applying an aqueous urethane resin dispersion using an aliphatic polycarbonate polyol is known to be used as an undercoat agent because of improved adhesion to a substrate and blocking resistance. (See Patent Document 2).

  On the other hand, since radically polymerizable compounds are excellent in curability even in methods other than heating, they are generally recognized as having features from the viewpoint of productivity and energy saving. In view of these characteristics, the active energy ray-curable resin composition having a radical polymerizable compound is an active ingredient for various coatings and adhesives such as metal paints, various plastic film overcoat agents, woodwork paints, and printing inks. Has been adopted as. For example, an energy ray curable aqueous resin composition in which a (meth) acrylate compound is dispersed in an aqueous polyurethane resin dispersion has been reported (see Patent Document 3). This method is characterized in that a coating film having high hardness is obtained after UV curing.

JP-A-10-120757 JP 2005-281544 A JP 2008-248014 A

  In an aqueous polyurethane resin dispersion using polycarbonate polyol as a raw material, if only an aliphatic polycarbonate polyol is used as the polycarbonate polyol, the adhesion and hardness of the coating film obtained by applying the aqueous polyurethane resin dispersion is not sufficient. was there. For example, in the field of coatings and coating agents for synthetic resin moldings such as flooring materials such as automobile interior materials, mobile phone cases, home appliance cases, personal computer cases, decorative films, optical films, flooring, A pencil hardness of “H” or higher and excellent adhesion are required, but there is a problem that an aqueous polyurethane resin dispersion using only an aliphatic polycarbonate polyol is not sufficient.

  On the other hand, the energy ray curable aqueous resin composition also has a problem that adhesion to a plastic substrate such as polymethyl methacrylate (PMMA) is low.

  The present invention relates to an active energy ray (for example, ultraviolet ray) curable aqueous resin dispersion composition, wherein the coating film after curing by irradiation with active energy rays has excellent adhesion and high hardness. An object is to obtain a body composition.

  As a result of various studies to overcome the problems of the prior art, the present inventors have at least a polyurethane resin (A) having a polymerizable unsaturated bond and a compound having a polymerizable unsaturated bond ( A ′) and a carbodiimide compound (B) and / or an oxazoline compound (C) are dispersed in an aqueous medium, and the polyurethane resin (A) having a polymerizable unsaturated bond is an aqueous resin dispersion composition. At least the reaction of at least the polyol (a), the carboxyl group-containing polyol (b), the polyisocyanate compound (c), the compound (d) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups. In the aqueous resin dispersion composition, the compound (d) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups, and the polymerizable unsaturated bond Compounds having a (A ') by using a specific amount, and can be solved problems. In the present specification, the compound having a urethane bond and a polymerizable unsaturated bond is not a compound (A ′) having a polymerizable unsaturated bond but a polyurethane resin (A) having a polymerizable unsaturated bond.

The present invention (1) includes at least a polyurethane resin (A) having a polymerizable unsaturated bond, a compound (A ′) having a polymerizable unsaturated bond, a carbodiimide compound (B) and / or an oxazoline compound (C). Is an aqueous resin dispersion composition in which a polyurethane resin (A) having a polymerizable unsaturated bond comprises a polyol (a), a carboxyl group-containing polyol (b), and a polyisocyanate. It is obtained by reacting at least a compound (c) with a compound (d) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups,
A polyurethane resin in which the total amount of the compound (d) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups and the compound (A ′) having a polymerizable unsaturated bond has a polymerizable unsaturated bond The aqueous resin dispersion composition is characterized by being 65 to 75% by weight based on 100% by weight of the total of (A) and the compound (A ′) having a polymerizable unsaturated bond.
In the present invention (2), at least a polyurethane resin (A) having a polymerizable unsaturated bond, a compound (A ′) having a polymerizable unsaturated bond, and a carbodiimide compound (B) are dispersed in an aqueous medium. The aqueous resin dispersion composition of the present invention (1), which is an aqueous resin dispersion composition.
This invention (3) relates to the aqueous resin dispersion composition of this invention (1) or (2) whose carbodiimide equivalent of a carbodiimide compound (B) is 1,000 or less.
The present invention (4) relates to the aqueous resin dispersion composition according to any one of the present inventions (1) to (3), wherein the polyol (a) is a polycarbonate polyol.
The present invention (5) includes the present invention (1) to (4), wherein the compound (d) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups is a compound having a (meth) acryloyl group. To any one of the aqueous resin dispersion compositions.
In the present invention (6), the compound (d) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups is mixed with a polymerizable unsaturated bond as a mixture with a (meth) acrylate which is inert to an isocyanato group. It is related with the aqueous resin dispersion composition in any one of this invention (1)-(5) attached | subjected to reaction for obtaining the polyurethane resin (A) which has this.
The present invention (7) is a compound in which the compound (d) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups has three or more polymerizable unsaturated bonds and one or more hydroxyl groups. The aqueous resin dispersion composition according to any one of the present inventions (1) to (6).
In the present invention (8), the compound (d) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups is a mixture of pentaerythritol tetra (meth) acrylate and pentaerythritol tri (meth) acrylate, It is related with the aqueous resin dispersion composition of this invention (7) attached | subjected to reaction for obtaining a polyurethane resin (A).
The present invention (9) is a compound in which the compound (d) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups has five or more polymerizable unsaturated bonds and one or more hydroxyl groups. , It relates to the aqueous resin dispersion composition of the present invention (7).
In the present invention (10), the compound (d) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups is converted into a polymerizable unsaturated bond as a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate. It is related with the aqueous resin dispersion composition of this invention (9) attached | subjected to reaction for obtaining the polyurethane resin (A) which has this.
In the present invention (11), a total of 100 parts by weight of the polyurethane resin (A) having a polymerizable unsaturated bond, the compound (A ′) having a polymerizable unsaturated bond, the carbodiimide compound (B) and the oxazoline compound (C) is used. On the other hand, it is related with the aqueous resin dispersion composition in any one of this invention (1)-(10) whose total amount of a carbodiimide compound (B) and an oxazoline compound (C) is 3-30 weight part.
In the present invention (12), a total of 100 parts by weight of the polyurethane resin (A) having a polymerizable unsaturated bond, the compound (A ′) having a polymerizable unsaturated bond, the carbodiimide compound (B) and the oxazoline compound (C) is used. On the other hand, it is related with the aqueous resin dispersion composition in any one of this invention (1)-(11) whose total amount of a carbodiimide compound (B) and an oxazoline compound (C) is 5-10 weight part.
This invention (13) relates to the photocurable composition containing the aqueous resin dispersion composition in any one of this invention (1)-(12), and a photoinitiator.
This invention (14) relates to the coating composition containing the aqueous resin dispersion composition in any one of this invention (1)-(12).
This invention (15) relates to the coating agent composition containing the aqueous resin dispersion composition in any one of this invention (1)-(12).

  ADVANTAGE OF THE INVENTION According to this invention, the water-based polyurethane resin dispersion with which the coating film after hardening by active energy ray irradiation is excellent in adhesiveness is provided. Moreover, according to this invention, the aqueous resin dispersion composition in which the coating film after hardening by active energy ray irradiation has high hardness is provided. The aqueous resin dispersion composition of the present invention is useful as a raw material for paints, coating agents, and paint compositions.

  The aqueous resin dispersion composition of the present invention comprises at least a polyurethane resin (A) having a polymerizable unsaturated bond, a compound (A ′) having a polymerizable unsaturated bond, a carbodiimide compound (B) and / or an oxazoline. The compound (C) is dispersed in an aqueous medium. Specifically, the aqueous resin dispersion composition of the present invention comprises at least a polyurethane resin (A) having a polymerizable unsaturated bond, a compound (A ′) having a polymerizable unsaturated bond, and a carbodiimide compound (B ) In an aqueous medium; at least a polyurethane resin (A) having a polymerizable unsaturated bond, a compound (A ′) having a polymerizable unsaturated bond, and an oxazoline compound (C). What is dispersed in an aqueous medium; and a polyurethane resin (A) having a polymerizable unsaturated bond, a compound (A ′) having a polymerizable unsaturated bond, a carbodiimide compound (B), and an oxazoline compound (C ) Are dispersed in an aqueous medium.

<Polyurethane resin (A) having a polymerizable unsaturated bond>
Polyurethane resin (A) having a polymerizable unsaturated bond (hereinafter sometimes referred to as polyurethane resin (A)) is polyol (a), carboxyl group-containing polyol (b), polyisocyanate (c), 1 It can be obtained by reacting at least one compound (d) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups.

<< Polyol (a) >>
Examples of the polyol (a) include polycarbonate polyol, polyester polyol, polyether polyol and the like, and high molecular weight polyol and low molecular weight polyol can be used. It is preferable to use a high molecular weight diol or a low molecular weight diol because of the ease of producing an aqueous polyurethane resin dispersion containing the polyurethane resin (A).

  The high molecular weight polyol is not particularly limited, but the number average molecular weight is preferably 400 to 8,000. If the number average molecular weight is in this range, an appropriate viscosity and good handleability can be easily obtained. It is easy to ensure the performance as a soft segment, and when a coating film is formed using the aqueous resin dispersion composition of the present invention, it is easy to suppress the occurrence of cracks, and the reactivity with polyisocyanate (c) Is sufficient, and the polyurethane resin (A) can be produced efficiently. The polyol (a) preferably has a number average molecular weight of 400 to 4,000.

  In this specification, the number average molecular weight is the number average molecular weight calculated based on the hydroxyl value measured according to JIS K 1577. Specifically, the hydroxyl value is measured, and is calculated by (56.1 × 1,000 × valence) / hydroxyl value [mgKOH / g] by the terminal group determination method. In the above formula, the valence is the number of hydroxyl groups in one molecule.

  Examples of the high molecular weight polyol include polycarbonate polyol, polyester polyol, and polyether polyol. From the viewpoint of light resistance, weather resistance, heat resistance, hydrolysis resistance, and oil resistance of the coating film obtained from the aqueous resin dispersion composition of the present invention, polycarbonate polyol is preferable, and polycarbonate diol is more preferable.

  Among the polycarbonate polyols, the polyol component is preferably an aliphatic polyol and / or an alicyclic polyol, the polyurethane resin (A) has a low viscosity, is easy to handle, and has good dispersibility in an aqueous medium. From the viewpoint, the polyol component is more preferably an aliphatic polyol having no alicyclic structure, and particularly preferably an aliphatic diol having no alicyclic structure.

  The polycarbonate polyol is obtained by reacting one or more polyol monomers with a carbonate ester or phosgene. A polycarbonate polyol obtained by reacting one or more polyol monomers with a carbonate ester is preferred because it is easy to produce and has no by-product formation of terminal chlorinated products.

  The polyol monomer is not particularly limited, and examples thereof include an aliphatic polyol monomer, a polyol monomer having an alicyclic structure, an aromatic polyol monomer, a polyester polyol monomer, and a polyether polyol monomer.

  The aliphatic polyol monomer is not particularly limited, and examples thereof include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1 Linear aliphatic diols such as 1,8-octanediol and 1,9-nonanediol; 2-methyl-1,3-propanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5 -Branched aliphatic diols such as pentanediol and 2-methyl-1,9-nonanediol; and trifunctional or higher functional polyhydric alcohols such as trimethylolpropane and pentaerythritol.

  The polyol monomer having an alicyclic structure is not particularly limited, and examples thereof include 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1, Alicyclic ring in the main chain such as 4-cycloheptanediol, 2,5-bis (hydroxymethyl) -1,4-dioxane, 2,7-norbornanediol, tetrahydrofuran dimethanol, 1,4-bis (hydroxyethoxy) cyclohexane Examples thereof include diols having a formula structure.

  The aromatic polyol monomer is not particularly limited. For example, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 4,4′-naphthalenediethanol, 3,4 '-Naphthalene diethanol and the like.

  Although it does not restrict | limit especially as a polyester polyol monomer, For example, dicarboxylic acid, such as polyester polyol of hydroxycarboxylic acid and diol, such as polyester polyol of 6-hydroxycaproic acid and hexanediol, polyester polyol of adipic acid and hexanediol And polyester polyol of diol.

  The polyether polyol monomer is not particularly limited, and examples thereof include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

  The carbonate is not particularly limited, and examples thereof include aliphatic carbonates such as dimethyl carbonate and diethyl carbonate, aromatic carbonates such as diphenyl carbonate, and cyclic carbonates such as ethylene carbonate. In addition, phosgene or the like capable of producing a polycarbonate polyol can be used. Among these, aliphatic carbonates are preferable and dimethyl carbonate is particularly preferable because of easy production of polycarbonate polyol.

  As a method for producing a polycarbonate polyol from a polyol monomer and a carbonate ester, for example, a carbonate ester and a polyol having an excess number of moles relative to the number of moles of the carbonate ester are added to a reactor, and the temperature is 160 to 200 ° C. Examples include a method of reacting at a pressure of about 50 mmHg for 5 to 6 hours and further reacting at 200 to 220 ° C. for several hours at a pressure of several mmHg or less. In the above reaction, it is preferable to carry out the reaction while extracting by-produced alcohol out of the system. At that time, if the carbonate ester escapes from the system by azeotroping with the by-produced alcohol, an excessive amount of carbonate ester may be added. In the above reaction, a catalyst such as titanium tetrabutoxide may be used.

  Polyester diol is not particularly limited, but 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, polycondensate of 1,6-hexanediol and dimer acid, and the like.

  The polyether diol is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide and propylene oxide, and a random copolymer or block copolymer of ethylene oxide and butylene oxide. Further, a polyether polyester polyol having an ether bond and an ester bond may be used.

  The low molecular weight polyol is not particularly limited, and examples thereof include those having a number average molecular weight of 60 or more and less than 400. For example, ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol Aliphatic diol having 2 to 9 carbon atoms such as diethylene glycol, triethylene glycol and tetraethylene glycol; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-bis (Hydroxyethyl) cyclohexane, 2,7-norbornanediol, tetrahydrofuran Methanol, 2,5-bis can be mentioned diols having an alicyclic structure having 6 to 12 carbon atoms such as (hydroxymethyl) -1,4-dioxane. Furthermore, low molecular weight polyhydric alcohols such as trimethylolpropane, pentaerythritol, and sorbitol may be used as the low molecular weight polyol.

  A polyol (a) may be used independently and may use multiple types together.

<< carboxyl group-containing polyol (b) >>
The carboxyl group-containing polyol (b) contains two or more hydroxyl groups and one or more carboxyl groups in one molecule. As the carboxyl group-containing polyol (b), one containing a compound having two hydroxyl groups and one carboxyl group in one molecule is preferable. A carboxyl group-containing polyol (b) may be used independently and may use multiple types together. The carboxyl group-containing polyol (b) may be used in combination with other acidic group-containing polyols. Examples of acidic groups in other acidic group-containing polyols include sulfonic acid groups, phosphoric acid groups, and phenolic hydroxyl groups.

  Specific examples of the carboxyl group-containing polyol (b) include dimethylol alkanoic acids such as 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid, N, N-bishydroxyethylglycine, N, N-bishydroxyethylalanine, 3,4-dihydroxybutanesulfonic acid, 3,6-dihydroxy-2-toluenesulfonic acid and the like can be mentioned. Among these, from the viewpoint of easy availability, dimethylol alkanoic acid having 4 to 12 carbon atoms containing two methylol groups is preferable, and 2,2-dimethylolpropionic acid is more preferable among dimethylolalkanoic acids.

  In the present invention, the total number of hydroxyl equivalents of the polyol (a) and the carboxyl group-containing polyol (b) is preferably 120 to 600. If the number of hydroxyl equivalents is within this range, the aqueous resin dispersion composition containing the polyurethane resin (A) can be easily produced, and a coating film excellent in hardness can be easily obtained. From the viewpoint of the storage stability of the resulting aqueous resin dispersion composition and the hardness of the coating film obtained by coating, the number of hydroxyl equivalents is preferably 130 to 600, more preferably 150 to 500, and particularly preferably 170 to 400. It is.

The number of hydroxyl equivalents can be calculated by the following formulas (1) and (2).
Number of hydroxyl equivalents of each polyol = molecular weight of each polyol / number of hydroxyl groups of each polyol (1)
Total number of hydroxyl equivalents of polyol = M / total number of moles of polyol (2)
In the case of the polyurethane resin (A), in the formula (2), M is [[number of hydroxyl equivalents of polyol (a) × number of moles of polyol (a)] + [number of hydroxyl equivalents of carboxyl group-containing polyol (b) × The number of moles of the carboxyl group-containing polyol (b)]].

<< Polyisocyanate (c) >>
Although it does not restrict | limit especially as polyisocyanate (c), For example, aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate etc. are mentioned.

  Specific examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, 4,4′-. Diphenylmethane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4 Examples include '-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4', 4 ''-triphenylmethane triisocyanate, m-isocyanatophenylsulfonyl isocyanate, p-isocyanatophenylsulfonyl isocyanate, and the like.

  Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate. Lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexano Eate.

  Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2 -Isocyanatoethyl) -4-dichlorohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate and the like.

  The number of isocyanate groups per molecule of the polyisocyanate is usually two, but a polyisocyanate having three or more isocyanate groups such as triphenylmethane triisocyanate is also used as long as the polyurethane resin in the present invention does not gel. be able to.

  Among the polyisocyanates, alicyclic polyisocyanates having an alicyclic structure are preferable from the viewpoint of increasing the hardness after curing with active energy rays (for example, ultraviolet rays), and isophorone diisocyanate is preferable because the reaction can be easily controlled. (IPDI), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI) is particularly preferred.

  Polyisocyanate may be used independently and may use multiple types together.

<< Compound (d) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups >>
Examples of the polymerizable unsaturated bond in the compound (d) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups (hereinafter also referred to as the compound (d)) include ethylenically unsaturated bonds. Examples of the compound (d) include compounds having one or more (meth) acryloyl groups and one or more hydroxyl groups. In the present specification, “(meth) acryloyl compound”, “(meth) acrylate compound”, and “(meth) acrylate” are all concepts including a compound having an acryloyl group and a compound having a methacryloyl group, You may have either an acryloyl group, a methacryloyl group, or both.

  Examples of the compound (d) include a hydroxyl group-containing (meth) acrylate. For example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerin di (meth) ) Acrylate, diglycerin tri (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, sorbitol penta (meth) acrylate, adduct of glycidyl (meth) acrylate and (meth) acrylic acid, Glycerol mono (meth) acrylate, diglycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, sorbitol mono (meth) acrylate diglycerin di (meth) acrylate, pentaerythritol Ritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, sorbitol di (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra ( Reaction product of (meth) acrylate, 2 molecules of (meth) acrylic acid and 1 molecule of 1,6-hexanediol diglycidyl (for example, “DA-212” manufactured by Nagase Chemtech), 2 molecules of epoxy (meth) Reaction product of acrylic acid and 1 molecule of neopentyl glycol diglycidyl, reaction product of 2 molecules of (meth) acrylic acid and 1 molecule of bisphenol A diglycidyl (for example, “DA-250” manufactured by Nagase Chemtech) 2-molecule (meth) ac Reaction product of phosphoric acid and diglycidyl of propylene oxide adduct of bisphenol A, reaction product of two molecules of (meth) acrylic acid and one molecule of diglycidyl phthalate (for example, “DA-721 manufactured by Nagase Chemtech Co., Ltd.) )) Reaction product of two molecules of (meth) acrylic acid and one molecule of polyethylene glycol diglycidyl (for example, “DM-811”, “DM-832”, “DM-851” manufactured by Nagase Chemtech) Examples include a reaction product of (meth) acrylic acid and polyol diglycidyl such as a reaction product of two molecules of (meth) acrylic acid and one molecule of polypropylene glycol diglycidyl.

  Among the compounds (d), the number of (meth) acryloyl groups in one molecule is preferably 3 or more, preferably 5 or more from the viewpoint that the hardness after curing by irradiation with active energy rays is increased. More preferred. As such (meth) acrylate, diglycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, Examples include dipentaerythritol penta (meth) acrylate, sorbitol tri (meth) acrylate, and sorbitol tetra (meth) acrylate.

  Among the hydroxyl group-containing (meth) acrylates having 3 or more (meth) acryloyl groups in one molecule, (meth) acrylate compounds having a primary hydroxyl group in that the production time of the polyurethane resin (A) is shortened. Is more preferable. Examples of such (meth) acrylates include pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate. From the viewpoint of the hardness of the coating film and the production time, dipentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate are particularly preferable.

  A compound (d) may be individual and may use multiple types together.

  The compound (d) can be subjected to a reaction for obtaining the polyurethane resin (A) as a mixture with (meth) acrylate inert to the isocyanato group. The (meth) acrylate inert to the unreacted isocyanato group can constitute the compound (A ′) having a polymerizable unsaturated bond.

  As the mixture, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate can be used. Pentaerythritol tetraacrylate corresponds to a (meth) acrylate that is inert to the isocyanato group. In this case, the hydroxyl value is preferably 100 to 280 mgKOH / g. If the hydroxyl value is within this range, it is possible to easily avoid the problem that the production of the polyurethane resin (A) takes time and the resin is colored. The hydroxyl value is preferably 120 to 250 mgKOH / g from the viewpoint of suppressing an increase in viscosity during production of the polyurethane resin (A) and avoiding gelation. A more preferred hydroxyl value is 140 to 220 mgKOH / g. Examples of the mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate having a hydroxyl value of 100 to 280 mgKOH / g include Aronix M305 and M306 manufactured by Toagosei Co., Ltd.

  Moreover, as a mixture, about dipentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate, commercially available dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa ( A mixture of (meth) acrylate, a mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, and the like can also be used. Dipentaerythritol hexa (meth) acrylate corresponds to (meth) acrylate that is inert to the isocyanato group.

  A mixture of dipentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, or a mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate The hydroxyl value is preferably 80 mgKOH / g or more. If the hydroxyl value is within this range, it is possible to easily avoid the problem that the production of the polyurethane resin (A) takes time and the resin is colored. The hydroxyl value is preferably 80 to 130 mgKOH / g from the viewpoint of suppressing an increase in viscosity during production of the polyurethane resin (A) and avoiding gelation. A more preferred hydroxyl value is 85 to 120 mgKOH / g. Examples of the mixture of dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate having a hydroxyl value of 80 mgKOH / g or more include Aronix M403 manufactured by Toagosei Co., Ltd.

  The hydroxyl value of the above mixture is measured by the method described in JIS K0070.

  The amount of the compound (d) is preferably 25 to 70% by weight in 100% by weight of the polyurethane resin (A). Within this range, the reaction time of the compound (d) and the isocyanato group can be within an appropriate time, and the hardness of the coating film after curing with active energy rays (for example, ultraviolet rays) can be within an appropriate range. The storage stability of the aqueous polyurethane resin dispersion containing the obtained polyurethane resin can be kept good. The compound (d) is more preferably 30 to 70% by weight.

  Compound (d) is a mixture of (meth) acrylates inert to isocyanato groups (specifically, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth)) As a mixture of acrylates, a mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, etc.) It is preferable that it is 50 to 90 weight% with respect to the weight of the polyurethane resin (A) which has an ionic unsaturated bond, More preferably, it is 60 to 80 weight%.

<Polyurethane resin (A) having a polymerizable unsaturated bond>
The polyurethane resin (A) having a polymerizable unsaturated bond in the present invention comprises at least a polyol (a), a carboxyl group-containing polyol (b), a polyisocyanate (c), and one or more polymerizable unsaturated bonds. And a polyurethane resin obtained by reacting a compound (d) having one or more hydroxyl groups. The polymerizable unsaturated bond in the polyurethane resin (A) can be derived from the compound (d). When the compound (d) has a (meth) acryloyl group, the polyurethane resin (A) is (meth) It can have an acryloyl group.

  The ratio of the number of moles of isocyanate groups of the polyisocyanate (c) to the number of moles of all hydroxyl groups of the polyol (a), the carboxyl group-containing polyol (b), and the compound (d) is 0.3 to 0.95. preferable.

  If it is this range, it is easy to avoid the problem that reaction time becomes long when the number of moles of hydroxyl groups is too small, while the unreacted polyol (a) and carboxyl group-containing The problem that the polyol (b) and the compound (d) remain in a large amount and the storage stability is lowered can be easily avoided. The ratio of the number of moles of isocyanato groups of the polyisocyanate (d) to the number of moles of all hydroxyl groups is preferably 0.4 to 0.9, particularly preferably 0.5 to 0.85.

  The reaction of the polyol (a), the carboxyl group-containing polyol (b), the polyisocyanate (c) and the compound (d) may be carried out by reacting (a), (b) and (d) with (c) in any order. It is also possible to mix a plurality of types and react with (c). Compound (d) may be subjected to the reaction as a mixture with (meth) acrylate inert to the isocyanato group.

  When reacting the polyol (a), the carboxyl group-containing polyol (b), the compound (d) and the polyisocyanate (c), a catalyst can also be used.

  The catalyst is not particularly limited, and examples thereof include salts of metals such as tin (tin) catalysts (trimethyltin laurate, dibutyltin dilaurate, etc.) and lead catalysts (lead octylate, etc.), organic and inorganic acids, and organic metals. Derivatives, amine catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.), diazabicycloundecene catalysts, and the like can be given. Of these, dibutyltin dilaurate and dioctyltin dilaurate are preferable from the viewpoint of reactivity.

  Although the reaction temperature at the time of making it react is not restrict | limited in particular, 40-120 degreeC is preferable. If it is this range, the solubility of a raw material is also good, the viscosity of the obtained urethane resin (A) is appropriate, it can fully stir, a polymerizable unsaturated bond raise | generates a polymerization reaction, gelatinizes, Problems such as side reactions of isocyanato groups are unlikely to occur. The reaction temperature is more preferably 60 to 100 ° C.

  When the compound (d) is reacted with the polyisocyanate (c), it is preferably carried out in the presence of oxygen in order to avoid unnecessary consumption of the polymerizable unsaturated bond of the compound (d).

  In order to avoid unnecessary consumption of the polymerizable unsaturated bond of the compound (d), a polymerization inhibitor may be added to the reaction system.

  As the polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, benzoquinone, 2-tert-butylhydroquinone, p-tert-butylcatechol, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, 2, Quinone polymerization inhibitors such as 5-bis (1,1-dimethylbutyl) hydroquinone; 2,6-bis (1,1-dimethylethyl) -4-methylphenol, 2,6-di-tert-butylphenol, 2 , 4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, etc. Alkylphenol polymerization inhibitors; aromatic amine polymerization inhibitors such as phenothiazine; alkylated diph Nilamine, N, N′-diphenyl-p-phenylenediamine, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1 , 4-Dihydroxy-2,2,6,6-tetramethylpiperidine, 1-hydroxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine, di-p-fluorophenylamine, 2,2, Amine polymerization inhibitors such as 6,6-tetramethylpiperidine-1-oxyl (TEMPO); 2,2-diphenylpicrylhydrazyl (DPPH), tri-p-nitrophenylmethyl, N- (3N-oxyanilino) -1,3-dimethylbutylidene) -aniline oxide, benzyltrimethylammonium chloride, etc. Ammonium chloride; diethylhydroxylamine, cyclic amide, nitrile compound, substituted urea, benzothiazole, bis- (1,2,2,6,6 pentamethyl-4-pipedinyl) sepacate, lactic acid, oxalic acid, citric acid, tartaric acid, benzoic acid Organic acids such as acids; organic phosphines, phosphites and the like. These may be single and may use multiple types together. In particular, by using a quinone polymerization inhibitor and an alkylphenol polymerization inhibitor in combination, it is possible to reduce the consumption of the polymerizable unsaturated bond due to polymerization.

  The amount of the polymerization inhibitor is 0.001 to 1 part by weight based on 100 parts by weight of the total of the polyol (a), the carboxyl group-containing polyol (b), the compound (d) and the polyisocyanate (c). Preferably 0.01 to 0.5 parts by weight.

  The reaction with the polyol (a), the carboxyl group-containing polyol (b), the compound (d) and the polyisocyanate (c) may be carried out without a solvent or in the presence of an organic solvent. Examples of the organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N-ethylpyrrolidone, and ethyl acetate. Among these, acetone, methyl ethyl ketone, and ethyl acetate are preferable because the polyurethane prepolymer can be removed by heating under reduced pressure after being dispersed in water. Further, N-methylpyrrolidone and N-ethylpyrrolidone are preferable because they function as a film-forming aid when a coating film is prepared using the aqueous resin dispersion composition containing the obtained polyurethane resin.

  The amount of the organic solvent is preferably 0 to 2.0 times by weight based on the total amount of the polyol (a), the carboxyl group-containing polyol (b), the compound (d) and the polyisocyanate (c). Preferably it is 0.01 to 0.7 times. If it is this range, the dispersibility to water of the obtained polyurethane resin is also good, and it takes time to remove the organic solvent, or in the coating film produced using the aqueous resin dispersion composition. The problem that the organic solvent remains and the physical properties of the coating film deteriorate can be avoided.

<Compound having a polymerizable unsaturated bond (A ′)>
The aqueous resin dispersion composition of the present invention contains a compound (A ′) having a polymerizable unsaturated bond. Here, the compound (A ′) having a polymerizable unsaturated bond does not include the polyurethane resin (A) having a polymerizable unsaturated bond.

  The compound (A ′) having a polymerizable unsaturated bond is preferably a radical polymerizable compound. The radical polymerizable compound is not particularly limited as long as it is polymerized in the presence of a photo radical generator or in the presence of a thermal radical generator, but a (meth) acrylate compound is preferable.

  Examples of the radical polymerizable compound include monomers (meth) acrylate compounds, polyurethane (meth) acrylate compounds, polyester (meth) acrylate compounds, polyalkylene (meth) acrylate compounds, and the like.

  Monomer (meth) acrylate compounds include mono (meth) acrylate, di (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, hexa (meth) acrylate and the like ( And (meth) acrylate.

  Examples of the mono (meth) acrylate include acryloylmorpholine, 2-ethylhexyl (meth) acrylate, styrene, methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, di Cyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, N-vinyl-2-pyrrolidone, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono ( (Meth) acrylate, polyethylene glycol-polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) ) Mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate, methoxypolyethyleneglycol mono (meth) acrylate, octoxypolyethyleneglycol-polypropyleneglycolmono (meth) acrylate, lauroxypolyethyleneglycolmono ( And (meth) acrylate, stearoxy polyethylene glycol mono (meth) acrylate, nonylphenoxy polyethylene glycol mono (meth) acrylate, nonylphenoxy polypropylene glycol polyethylene glycol mono (meth) acrylate, and the like.

  Examples of the di (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate. 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) Acrylate, polyethylene glycol-polypropylene glycol di (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene Glycol-tetramethylene glycol) di (meth) acrylate, methoxypolyethyleneglycol di (meth) acrylate, octoxypolyethyleneglycol-polypropyleneglycoldi (meth) acrylate, lauroxypolyethyleneglycoldi (meth) acrylate, stearoxypolyethyleneglycoldi (Meth) acrylate, nonylphenoxypolyethylene glycol di (meth) acrylate, nonylphenoxypolypropylene glycol polyethylene glycol di (meth) acrylate and the like.

  Examples of the tri (meth) acrylate include trimethylolpropane triacrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and ethylene oxide. Examples include (6 mol) modified trimethylolpropane triacrylate (Laromer (registered trademark) LR8863 manufactured by BASF) and alkylene oxide modified trimethylolpropane triacrylate (Laromer (registered trademark) PO33F manufactured by BASF).

  Examples of the tetra (meth) acrylate include pentaerythritol tetra (meth) acrylate, ethylene oxide (4 mol) modified pentaerythritol tetra (meth) acrylate (Daicel Cytec, Ebecryl 40) and other alkylene oxide modified pentaerythritol tetra ( And (meth) acrylate.

  Examples of penta (meth) acrylate include dipentaerythritol penta (meth) acrylate.

  Examples of hexa (meth) acrylate include dipentaerythritol hexa (meth) acrylate.

  A well-known thing can be used as a (meth) acrylate compound of polymers. Examples of the (meth) acrylate compounds of the polymers include poly (meth) acrylates such as di (meth) acrylate, tri (meth) acrylate, and tetra (meth) acrylate in addition to mono (meth) acrylate.

  Among these radical polymerizable compounds, poly (meth) acrylates such as tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate are preferable from the viewpoint of the hardness of the resulting coating film. .

  In order to obtain the polyurethane resin (A), when the compound (d) and (meth) acrylate that is inert to the isocyanato group are subjected to the reaction as a mixture, the compound (d) that is inert to the isocyanato group (meta ) Acrylate can constitute the compound (A ′) having a polymerizable unsaturated bond.

  In addition, after obtaining the polyurethane resin (A), a mixture of the compound (d) and (meth) acrylate that is inert to the isocyanato group may be added. In this case, the mixture has a polymerizable unsaturated bond. A compound (A ') may be comprised.

  As the mixture, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, commercially available dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) ) A mixture of acrylates, a mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, or the like can be used. Dipentaerythritol hexa (meth) acrylate corresponds to (meth) acrylate that is inert to the isocyanato group.

  Examples of the mixture of dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate include Aronix M403, M400, M402, M404, M406, and M405 manufactured by Toagosei Co., Ltd.

  Moreover, the mixture of a pentaerythritol triacrylate and a pentaerythritol tetraacrylate can also be used as a mixture. Pentaerythritol tetraacrylate corresponds to a (meth) acrylate that is inert to the isocyanato group. Examples of the mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate include Aronix M305, M306, M451, and M450 manufactured by Toagosei Co., Ltd.

  In the present invention, one or more polymerizable unsaturated bonds and one or more hydroxyl groups are added from the viewpoint that the hardness of the obtained coating film is appropriate and the adhesiveness with a plastic substrate such as PMMA resin is good. The total amount of the compound (d) having and the compound (A ′) having a polymerizable unsaturated bond is a polyurethane resin (A) having a polymerizable unsaturated bond and the compound (A ′) having a polymerizable unsaturated bond It is 65 to 75% by weight with respect to the total of 100% by weight. If it is less than 65% by weight, the hardness and adhesion of the coating film obtained using the aqueous resin dispersion composition may be reduced, and if it exceeds 75% by weight, the dispersibility of the aqueous resin dispersion during production, and The stability of the aqueous resin dispersion during storage may be reduced. More preferably, the total amount of the compound (d) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups and the compound (A ′) having a polymerizable unsaturated bond is 66 to 72% by weight. It is.

  When the total amount of the compound (d) and the compound (A ′) having a polymerizable unsaturated bond is 100% by weight, the compound (A ′) having a polymerizable unsaturated bond is 45 to 65% by weight. It is preferable that If it is this range, what has high hardness of the coating film produced using the aqueous resin dispersion composition will be obtained easily, and also the storage stability of the aqueous resin dispersion composition is also good.

  In the aqueous resin dispersion composition of the present invention, the polyurethane resin (A) and the compound (A ′) having a polymerizable unsaturated bond are dispersed in an aqueous medium. Examples of the aqueous medium include water and a mixed medium of water and a hydrophilic organic solvent.

  Examples of water include clean water, ion exchange water, distilled water, and ultrapure water. Among them, it is preferable to use ion-exchanged water in consideration of the availability and the fact that the particles become unstable due to the influence of salt.

  Examples of hydrophilic organic solvents include lower monohydric alcohols such as methanol, ethanol and propanol; polyhydric alcohols such as ethylene glycol and glycerin; N-methylmorpholine, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone and the like. Examples include aprotic hydrophilic organic solvents. The amount of the hydrophilic organic solvent in the aqueous medium is preferably 0 to 20% by weight.

In the present invention, the acid value of the aqueous resin dispersion composition is preferably 10 to 80 mgKOH / g. If it is this range, it will be easy to ensure the dispersibility to an aqueous medium and the water resistance of a coating film. Specifically, the acid value can be derived from the following formula (3).
[Acid Value of Aqueous Resin Dispersion Composition] = [Mole Number of Carboxyl Group of Carboxyl Group-Containing Polyol (b)] × 56.11 / [Polyurethane Resin (A) and Compound (A ′) ) Total weight] ... (3)
The acid value is more preferably 12 to 70 mgKOH / g, and still more preferably 14 to 60 mgKOH / g.

  In the present invention, when the solid content of the polyurethane resin aqueous dispersion is 100 parts by weight, the proportion of the polyol (a) is 2 to 50 parts by weight, and the proportion of the carboxyl group-containing polyol (b) is 1 to 15 parts by weight. It is preferable to prepare the polyurethane resin (A) in such an amount.

When the ratio of the polyol (a) is in the above range, the polyurethane resin (A) has good dispersibility in an aqueous medium, and a good film-forming property can be obtained for the aqueous resin dispersion composition. When the ratio of the group-containing polyol (b) is within the above range, the water resistance of the coating film is good and the dispersibility of the polyurethane resin (A) in the aqueous medium can be good.
The proportion of the polyol (a) is more preferably 3 to 40 parts by weight, particularly preferably 5 to 30 parts by weight, and the proportion of the carboxyl group-containing polyol (b) is more preferably 2 to 10 parts by weight, particularly preferably. Is 3 to 7 parts by weight.

<Method for producing dispersion of polyurethane resin (A) and compound (A ') having polymerizable unsaturated bond>
The dispersion of the polyurethane resin (A) and the compound (A ′) having a polymerizable unsaturated bond includes a polyol (a), a carboxyl group-containing polyol (b), a polyisocyanate (c), and a compound (d). (Α) to obtain a polyurethane resin (A) by reacting at least
A step (β) of neutralizing the carboxyl group of the polyurethane resin (A);
A step (γ) of dispersing the polyurethane resin (A) and a compound having a polymerizable unsaturated bond (A ′) in an aqueous medium;
Can be included.

  The step (α) for obtaining the polyurethane resin (A) is preferably performed in the presence of oxygen in order to avoid unnecessary consumption of the polymerizable unsaturated bond. Moreover, it is desirable to add a polymerization inhibitor into the reaction system as necessary.

  The temperature of the step (α) for obtaining the polyurethane resin (A) can be carried out at 0 to 120 ° C. in order to avoid unnecessary consumption of the polymerizable unsaturated bond. Preferably it is 0-100 degreeC.

  Examples of the acidic group neutralizing agent that can be used in the step (β) of neutralizing the carboxyl group of the polyurethane resin (A) include trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, and N-phenyl. Organic amines such as diethanolamine, dimethylethanolamine, diethylethanolamine, N-methylmorpholine and pyridine; inorganic alkalis such as sodium hydroxide and potassium hydroxide, ammonia and the like. Among these, organic amines can be preferably used, more preferably tertiary amines can be used, and most preferably triethylamine can be used.

  The amount of the acidic group neutralizing agent used is preferably such that the molar number is 0.8 to 1.5 with respect to the carboxyl group of the polyurethane resin (A). If it is this range, it can avoid easily that the dispersibility to the water of a polyurethane resin (A) falls or the storage stability of an aqueous resin dispersion composition falls, and aqueous resin dispersion | distribution. The situation where the odor of the body composition becomes strong can be easily avoided.

  In the step (γ) of dispersing the polyurethane resin (A) and the compound (A ′) having a polymerizable unsaturated bond in the aqueous medium, (A) and (A ′) can be dispersed in the aqueous medium. If there are any, the method and operation order thereof are not particularly limited. For example, a method of mixing (A ') with (A') and dispersing it in an aqueous medium, a method of mixing (A ') with (A) and dispersing in an aqueous medium, or (A) with an aqueous medium. A method of mixing and dispersing (A ′) after dispersing in, a method of mixing and dispersing (A) after dispersing (A ′) in an aqueous medium, and (A) and (A ′) Examples thereof include a method of mixing after each dispersion in an aqueous medium, a method of mixing (A ′) at the time of production (A) and dispersing in an aqueous medium, and the like.

  In the production of the polyurethane resin (A), when the compound (d) is subjected to a reaction as a mixture with an (meth) acrylate that is inert to the isocyanato group, the (meth) acrylate that is inert to the isocyanato group is converted into a polyurethane resin (A ) And a compound (A ′) which is contained in the reaction product of the step (α), is subjected to the steps (β) and (γ), and has a polymerizable unsaturated bond in the final aqueous polyurethane resin dispersion. ). In this case, an acidic group neutralizing agent can be added to the reaction product of step (α) and dispersed in an aqueous dispersion medium together with a compound (A ′) having a further polymerizable unsaturated bond. Before adding the compound (A ′) having a further polymerizable unsaturated bond, an aqueous medium may optionally be added.

  For the mixing, stirring, and dispersion, a known stirring device such as a homomixer or a homogenizer can be used. The polyurethane resin (A) and the compound (A ′) having a polymerizable unsaturated bond are preliminarily mixed with the hydrophilic organic solvent or water before mixing in order to adjust viscosity, improve workability, and improve dispersibility. It can also be added.

  The step (γ) of mixing the polyurethane resin (A) and the compound (A ′) having a polymerizable unsaturated bond is preferably performed in the presence of oxygen in order to avoid unnecessary consumption of the polymerizable unsaturated bond. Moreover, you may add a polymerization inhibitor as needed. The temperature at which the polyurethane resin (A) and the compound (A ′) having a polymerizable unsaturated bond are mixed is preferably 0 to 100 ° C. in order to avoid unnecessary consumption of the polymerizable unsaturated bond. More preferably, it is carried out at 0-90 ° C, more preferably at 0-80 ° C, particularly preferably at 50-70 ° C.

  The step (β) of neutralizing the carboxyl group of the polyurethane resin (A) and the step (γ) of dispersing the polyurethane resin (A) and the compound (A ′) having a polymerizable unsaturated bond in an aqueous medium. Either can be done first or at the same time. In this case, the polyurethane resin (A), the compound (A ′) having a polymerizable unsaturated bond, the aqueous medium and the acidic group neutralizing agent may be mixed at once, or the acidic group neutralizing agent may be mixed in advance with the aqueous medium. Or a compound (A ′) having a polymerizable unsaturated bond, and (A) may be mixed therewith.

  The proportion of the polyurethane resin in the aqueous resin dispersion composition is preferably 5 to 60% by weight, more preferably 15 to 50% by weight, and further preferably 25 to 40% by weight. The number average molecular weight is preferably 1,000 to 1,000,000.

<Carbodiimide compound (B)>
The carbodiimide compound (B) is not particularly limited as long as it has a carbodiimide structure (—N═C═N—) in the molecule, but is a compound having two or more carbodiimide structures in the molecule (polycarbodiimide compound). Is preferred.

  The polycarbodiimide compound is generally obtained by subjecting diisocyanate to a decarboxylation condensation reaction in the presence of a carbodiimidization catalyst. Examples of the diisocyanate include aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates exemplified as polyisocyanate (c).

  The carbodiimide compound (B) is preferably a water-soluble polycarbodiimide compound, and can be used in the form of an aqueous solution or a water-soluble emulsion. As commercial products, as the aqueous solution, trade names “Carbodilite V-02”, “Carbodilite V-02-L2”, “Carbodilite V-04”, “Carbodilite V-06” manufactured by Nisshinbo Chemical Co., Ltd. and the like can be mentioned. Examples of water-soluble emulsions include trade names “Carbodilite E-01” and “Carbodilite E-02” manufactured by Nisshinbo.

  The carbodiimide equivalent of the carbodiimide compound (B) is preferably 1,000 or less from the viewpoint that the hardness of the obtained coating film is appropriate and the adhesiveness with a plastic substrate such as PMMA resin is also good. In this specification, carbodiimide equivalent means the number represented by (molecular weight of carbodiimide compound) / (number of carbodiimide structures in one molecule of carbodiimide compound). More preferably, a carbodiimide equivalent is 800 or less, More preferably, it is 650-200, More preferably, it is 400-200.

  The carbodiimide compound can be used alone or in combination of two or more.

<Oxazoline compound (C)>
The oxazoline compound (C) is not particularly limited as long as it is a compound having an oxazoline structure in the molecule, but a compound having two or more oxazoline structures in the molecule (polyoxazoline compound) is preferable. Examples of the polyoxazoline compound include a compound having two or more low molecular weight oxazoline structures, or a polymer having two or more oxazoline structures. The oxazoline structure is a structure obtained by removing any one hydrogen from oxazoline.

  Examples of the compound having two or more low molecular weight oxazoline structures include 2,2′-bis- (2-oxazoline), 2,2′-methylene-bis- (2-oxazoline), and 2,2′-ethylene. -Bis- (2-oxazoline), 2,2'-trimethylene-bis- (2-oxazoline), 2,2'-tetramethylene-bis- (2-oxazoline), 2,2'-hexamethylene-bis- (2-oxazoline), 2,2′-octamethylene-bis- (2-oxazoline), 2,2′-ethylene-bis- (4,4′-dimethyl-2-oxazoline), 2,2′-p -Phenylene-bis- (2-oxazoline), 2,2'-m-phenylene-bis- (2-oxazoline), 2,2'-m-phenylene-bis- (4,4'-dimethyl-2-oxazoline) ) - (2-oxazolinyl sulfonyl cyclohexane) sulfide, bis - (2-oxazolinyl sulfonyl norbornane) sulfide, and the like.

  Examples of the polymer having two or more oxazoline structures include a polymer obtained by homopolymerizing an oxazoline group-containing ethylenically unsaturated monomer using a known polymerization method, or an oxazoline group-containing ethylenically unsaturated monomer and the like. And those obtained by copolymerization with a vinyl monomer.

  Although the oxazoline group-containing ethylenically unsaturated monomer is not particularly limited, specifically, for example, 2-isopropenyl-2-oxazoline, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl 2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-5 And ethyl-2-oxazoline. The oxazoline group-containing ethylenically unsaturated monomer can be used alone or in combination of two or more.

  The other vinyl monomer is not particularly limited as long as it is a monomer copolymerizable with an oxazoline group-containing ethylenically unsaturated monomer. For example, a hydroxyl group-containing polymerizable unsaturated monomer described later; an olefin monomer described later; an olefin described later Other monomers that can be copolymerized with the system monomer may be mentioned. Other vinyl monomers can be copolymerized with an oxazoline group-containing ethylenically unsaturated monomer alone or in combination of two or more.

  The oxazoline compound can be used in the form of an aqueous solution or a water-soluble emulsion. Commercially available products include, for example, trade names “Epocross WS500” manufactured by Nippon Shokubai Co., Ltd. as aqueous solutions, and trade names “Epocross K2010E” and “Epocross K2020E” manufactured by Nippon Shokubai Co., Ltd. as water-soluble emulsions. , “Epocross K2030E” and the like.

  The oxazoline equivalent of the oxazoline compound (C) is preferably 1,000 or less from the viewpoint that the hardness of the obtained coating film is appropriate and the adhesiveness with a plastic substrate such as PMMA resin is good. In the present specification, the oxazoline equivalent means a number represented by (molecular weight of oxazoline compound) / (number of oxazoline structures in one molecule of oxazoline compound). More preferably, a carbodiimide equivalent is 800 or less, More preferably, it is 650-200, More preferably, it is 600-400.

  The oxazoline compounds can be used alone or in combination of two or more.

  In the aqueous resin dispersion composition of the present invention, the polyurethane resin (A), the compound (A ′) having a polymerizable unsaturated bond, the carbodiimide compound (B) and / or the oxazoline compound (C) are contained in an aqueous medium. Is distributed.

  The method for preparing the aqueous resin dispersion composition is not particularly limited. For example, the aqueous polyurethane resin dispersion containing a polyurethane resin (A) and a compound (A ′) having a polymerizable unsaturated bond, and a carbodiimide compound (B And / or an oxazoline compound (C) in an aqueous solution, a water-soluble emulsion, or an aqueous dispersion (hereinafter also referred to as “aqueous solution”). An aqueous solution of the carbodiimide compound (B) and / or the oxazoline compound (C) may be added to the aqueous polyurethane resin dispersion containing the polyurethane resin (A) and the compound (A ′) having a polymerizable unsaturated bond. An aqueous polyurethane resin dispersion containing the polyurethane resin (A) and the compound (A ′) having a polymerizable unsaturated bond may be added to an aqueous solution of the carbodiimide compound (B) and / or the oxazoline compound (C). . The compound (A ′) having a polymerizable unsaturated bond is added after mixing the aqueous dispersion of the polyurethane resin (A) with the aqueous solution of the carbodiimide compound (B) and / or the oxazoline compound (C). Also good.

  In the present invention, the polyurethane resin (A), the compound having a polymerizable unsaturated bond (A ′), and a carbodiimide compound (from the viewpoint of securing good hardness and obtaining a good adhesion of the cured coating film. The total amount of the carbodiimide compound (B) and the oxazoline compound (C) is preferably 3 to 30 parts by weight with respect to 100 parts by weight of the total of B) and the oxazoline compound (C). More preferably, the total amount of the carbodiimide compound (B) and the oxazoline compound (C) is 4 to 20 parts by weight, and more preferably 5 to 10 parts by weight. When the carbodiimide compound (B) or the oxazoline compound (C) is used alone, the total amount of the carbodiimide compound (B) and the oxazoline compound (C) is the carbodiimide compound (B) or oxazoline compound ( C).

  In the aqueous resin dispersion composition of the present invention, if necessary, a thickener, a photosensitizer, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a plasticizer, a surface conditioner, an anti-settling agent Additives such as an agent can also be added. An additive may be individual and may use multiple types together. The aqueous resin dispersion composition of the present invention preferably contains substantially no protective colloid, emulsifier, or surfactant from the viewpoint of the hardness and chemical resistance of the resulting coating film.

<Photocurable composition>
The present invention also relates to a photocurable composition comprising the aqueous resin dispersion composition and a photopolymerization initiator. As the photopolymerization initiator, known ones can be used. For example, a photocleavable initiator that can be easily cleaved into two radicals by irradiation with ultraviolet rays, or a hydrogen abstraction initiator is used. Can do. These may be used in combination. Examples of these compounds include acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, benzophenone, 2-chlorobenzophenone, p, p′-bisdiethylaminobenzophenone, benzoin ethyl ether, benzoin n-propyl ether, Benzoin isopropyl ether, benzoin isobutyl ether, benzoin n-butyl ether, benzoin dimethyl ketal, thioxanthone, p-isopropyl-α-hydroxyisobutylphenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl -1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-hydroxy-2-methyl-1-phenylpro Down-1-one, 2,4,6, - trimethyl benzophenone, 4-methylbenzophenone, 2,2-dimethoxy-1,2-diphenyl-ethanone, and the like. Preferably, hydroxycyclohexyl phenyl ketone is used.

  When the photopolymerization initiator is added, it is preferably added after the step (γ) of dispersing the polyurethane resin (A) and the compound (A ′) having a polymerizable unsaturated bond in an aqueous medium. The amount of the photopolymerization initiator is preferably 0.5 to 5% by weight based on 100% by weight in total of the polyurethane resin (A) and the compound (A ′) having a polymerizable unsaturated bond.

  An aqueous polyurethane resin dispersion in which a polyurethane resin (A) and a compound (A ′) having a polymerizable unsaturated bond are dispersed in an aqueous medium, a carbodiimide compound (B) and / or an oxazoline compound (C), and photopolymerization The order of mixing the initiator is not particularly limited, but a method of adding a photopolymerization initiator to a mixture of an aqueous polyurethane resin dispersion and a carbodiimide compound (B) and / or an oxazoline compound (C), an aqueous polyurethane resin Method of adding carbodiimide compound (B) and / or oxazoline compound (C) after adding photopolymerization initiator to dispersion, adding photopolymerization initiator to carbodiimide compound (B) and / or oxazoline compound (C) Then, there is a method of adding an aqueous polyurethane resin dispersion.

<Coating composition and coating agent composition>
The present invention also relates to a coating composition and a coating agent composition containing the aqueous resin dispersion composition.
In addition to the aqueous polyurethane resin dispersion, other resins can be added to the coating composition and the coating composition of the present invention. Examples of other resins include polyester resins, acrylic resins, polyether resins, polycarbonate resins, polyurethane resins, epoxy resins, alkyd resins, and polyolefin resins. These may be single and may use multiple types together. The other resin preferably has one or more hydrophilic groups. Examples of the hydrophilic group include a hydroxyl group, a carboxy group, a sulfonic acid group, and a polyethylene glycol group.

  The other resin is preferably at least one selected from the group consisting of a polyester resin, an acrylic resin, and a polyolefin resin.

The polyester resin can be usually produced by an esterification reaction or an ester exchange reaction between an acid component and an alcohol component. As an acid component, the compound normally used as an acid component at the time of manufacture of a polyester resin can be used. As an acid component, an aliphatic polybasic acid, an alicyclic polybasic acid, an aromatic polybasic acid, etc. can be used, for example.
The hydroxyl value of the polyester resin is preferably about 10 to 300 mgKOH / g, more preferably about 50 to 250 mgKOH / g, and still more preferably about 80 to 180 mgKOH / g. The acid value of the polyester resin is preferably about 1 to 200 mgKOH / g, more preferably about 15 to 100 mgKOH / g, and still more preferably about 25 to 60 mgKOH / g.
The weight average molecular weight of the polyester resin is preferably 500 to 500,000, more preferably 1,000 to 300,000, and still more preferably 1,500 to 200,000.

As the acrylic resin, a hydroxyl group-containing acrylic resin is preferable. Hydroxyl group-containing acrylic resin is a hydroxyl group-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer, for example, in a solution polymerization method in an organic solvent, in water It can manufacture by making it copolymerize by known methods, such as an emulsion polymerization method.
The hydroxyl group-containing polymerizable unsaturated monomer is a compound having one or more hydroxyl groups and one or more polymerizable unsaturated bonds in one molecule. For example, (meth) acrylic acid such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like and 2 to 8 carbon atoms. Monoesterified products of dihydric alcohols with these compounds; ε-caprolactone modified products of these monoesterified products; N-hydroxymethyl (meth) acrylamide; allyl alcohol; (meth) acrylates having a polyoxyethylene chain whose molecular ends are hydroxyl groups Etc.

The hydroxyl group-containing acrylic resin preferably has an anionic functional group. For the hydroxyl group-containing acrylic resin having an anionic functional group, for example, a polymerizable unsaturated monomer having an anionic functional group such as a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group is used as one kind of the polymerizable unsaturated monomer. It can be manufactured by using.
The hydroxyl value of the hydroxyl group-containing acrylic resin is preferably about 1 to 200 mgKOH / g, more preferably about 2 to 100 mgKOH / g, and more preferably 3 to 60 mgKOH from the viewpoints of storage stability of the composition and water resistance of the resulting coating film. / G is more preferable.
When the hydroxyl group-containing acrylic resin has an acid group such as a carboxyl group, the acid value of the hydroxyl group-containing acrylic resin is preferably about 1 to 200 mgKOH / g from the viewpoint of water resistance of the resulting coating film, About 150 mgKOH / g is more preferable, and about 5 to 100 mgKOH / g is still more preferable.
The weight average molecular weight of the hydroxyl group-containing acrylic resin is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, and still more preferably in the range of 3,000 to 50,000. is there.

  Examples of the polyether resin include polymers or copolymers having an ether bond, and examples include aromatics such as polyoxyethylene-based polyether, polyoxypropylene-based polyether, polyoxybutylene-based polyether, bisphenol A or bisphenol F. And polyethers derived from group polyhydroxy compounds.

  Examples of the polycarbonate resin include a polymer produced from a bisphenol compound, such as bisphenol A / polycarbonate.

  Examples of the polyurethane resin include resins having a urethane bond obtained by reacting various polyol components such as acrylic, polyester, polyether, and polycarbonate with polyisocyanate.

  Examples of the epoxy resin include a resin obtained by a reaction between a bisphenol compound and epichlorohydrin. Examples of bisphenol include bisphenol A and bisphenol F.

  Alkyd resins include polybasic acids such as phthalic acid, terephthalic acid and succinic acid and polyhydric alcohols, as well as fats and oils and fatty acids (soybean oil, linseed oil, coconut oil, stearic acid, etc.) and natural resins (rosin, succinic acid). Alkyd resin obtained by reacting a modifier such as

As the polyolefin resin, a polyolefin resin obtained by polymerizing or copolymerizing an olefin monomer with another monomer in accordance with a normal polymerization method is dispersed in water using an emulsifier, or the olefin monomer is appropriately replaced with another monomer. And a resin obtained by emulsion polymerization. In some cases, a so-called chlorinated polyolefin-modified resin in which the polyolefin resin is chlorinated may be used.
Examples of the olefin monomer include ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene, 1-hexene, Examples include α-olefins such as decene and 1-dodecene; conjugated dienes such as butadiene, ethylidene norbornene, dicyclopentadiene, 1,5-hexadiene, styrenes, and the like. These monomers are used alone. It may also be used in combination.
Examples of other monomers copolymerizable with olefinic monomers include vinyl acetate, vinyl alcohol, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, and the like. May be used alone or in combination.

  The coating composition and the coating composition of the present invention may contain a curing agent, whereby the coating film or multilayer coating film obtained by using the coating composition or the coating composition, the water resistance of the coating film Etc. can be improved.

  As the curing agent, for example, amino resin, polyisocyanate, blocked polyisocyanate, melamine resin, carbodiimide and the like can be used. A hardening | curing agent may be individual and may use multiple types together.

  Examples of the amino resin include a partial or completely methylolated amino resin obtained by a reaction between an amino component and an aldehyde component. Examples of the amino component include melamine, urea, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine, dicyandiamide and the like. Examples of the aldehyde component include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and the like.

  Examples of the polyisocyanate include compounds having two or more isocyanato groups in one molecule, such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.

  Examples of the blocked polyisocyanate include those obtained by adding a blocking agent to the polyisocyanate group of the aforementioned polyisocyanate. Examples of the blocking agent include phenols such as phenol and cresol, methanol, ethanol, and the like. Aliphatic alcohols, active methylenes such as dimethyl malonate and acetylacetone, mercaptans such as butyl mercaptan and dodecyl mercaptan, acid amides such as acetanilide and acetate amide, lactams such as ε-caprolactam and δ-valerolactam, Blocking agents such as acid imides such as succinimide and maleic imide, oximes such as acetoaldoxime, acetone oxime and methyl ethyl ketoxime, and amines such as diphenylaniline, aniline and ethyleneimine It is.

  Examples of the melamine resin include methylol melamines such as dimethylol melamine and trimethylol melamine; alkyl etherified products or condensates of these methylol melamines; condensates of alkyl etherified products of methylol melamine, and the like.

Coloring pigments, extender pigments, and glitter pigments can be added to the coating composition and coating agent composition of the present invention.
Examples of the color pigment include titanium oxide, zinc white, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindoline pigment, selenium pigment, and perylene pigment. These may be single and may use multiple types together. In particular, it is preferable to use titanium oxide and / or carbon black as the color pigment.
Examples of extender pigments include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, and alumina white. These may be single and may use multiple types together. In particular, barium sulfate and / or talc are preferably used as extender pigments, and barium sulfate is more preferably used.
As the bright pigment, for example, aluminum, copper, zinc, brass, nickel, aluminum oxide, mica, aluminum oxide coated with titanium oxide or iron oxide, mica coated with titanium oxide or iron oxide, or the like may be used. it can.

  The coating composition and coating composition of the present invention include a thickener, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a plasticizer, a surface conditioner, an anti-settling agent, etc., if necessary. Usual paint additives can be contained. These may be single and may use multiple types together.

  Although the manufacturing method in particular of the coating composition and coating agent composition of this invention is not restrict | limited, A well-known manufacturing method can be used. In general, the coating composition and the coating composition are produced by mixing the aqueous polyurethane resin dispersion and the various additives described above, adding an aqueous medium, and adjusting the viscosity according to the coating method. The

Examples of the coating material of the coating composition or the coating material of the coating agent composition include metals, plastics, inorganic materials, and wood.
The coating composition and the coating agent composition of the present invention have high adhesion to plastic, and particularly high adhesion to poly (meth) acrylic resin and ABS resin. For this reason, as the material to be coated and the material to be coated, poly (meth) acrylate resin and / or ABS resin are preferable.

  Examples of the coating method of the coating composition or the coating method of the coating agent composition include bell coating, spray coating, roll coating, shower coating, and dip coating.

  The coating composition and the coating composition of the present invention are cured by irradiating active energy rays after coating or coating, evaporating at least a part of the aqueous medium under heating or non-heating. Is preferred. As the active energy ray, ultraviolet rays are preferable.

  As the ultraviolet light source, a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a tungsten lamp, or the like can be used. The irradiation time can be appropriately changed depending on conditions such as the type of the compound having a polymerizable unsaturated bond, the type of the photopolymerization initiator, the coating thickness, and the ultraviolet ray source. From the viewpoint of workability, it is preferable to irradiate for 1 to 60 seconds. Further, for the purpose of completing the curing reaction, heat treatment can also be performed after irradiation with ultraviolet rays.

The irradiation amount of ultraviolet rays used when the composition of the present invention is cured is preferably 300 to 3,000 mJ / cm ² from the viewpoint of fast curability and workability.

  An electron beam or the like can also be used as the active energy ray. In the case of curing with an electron beam, a photopolymerization initiator may not be added, and an electron beam accelerator having an energy of 100 to 500 eV is preferably used.

  Although the thickness of the coating film after hardening is not restrict | limited, The thickness of 1-100 micrometers is preferable. More preferably, it is preferable to form a coating film having a thickness of 3 to 50 μm.

  Next, the present invention will be described in more detail with reference to examples and comparative examples.

[Production Example 1]
In a reactor equipped with a stirrer and a heater, ETERNACOLL (registered trademark) PH100 (manufactured by Ube Industries; number average molecular weight 1054; hydroxyl value 106 mgKOH / g; polyol component 1,5-pentanediol: 1,6-hexanediol Polycarbonate diol (41.0 g) obtained by reacting a 1: 1 molar ratio polyol mixture with carbonate ester, 2,2-dimethylolpropionic acid (DMPA, 14.4 g), and isophorone diisocyanate (IPDI). , 56.7 g) in N-ethylpyrrolidone (45.9 g) in the presence of dibutyltin dilaurate (0.2 g) under nitrogen atmosphere at 80-90 ° C. for 3 hours. 2,6-Di-tert-butyl-4-methylphenol (0.4 g) and 4-methoxyphenol (0.4 g) were added and the atmosphere was air. Further, a mixture of dipentaerystol hexaacrylate and dipentaerythritol pentaacrylate (DPHA (dipentaerythritol pentaacrylate 50-60 mol%), hydroxyl value 95 mgKOH / g, 181 g) was added and heated at 90 ° C. for 7 hours. . The NCO group content at the end of the urethanization reaction was 0.23% by weight. From the reaction mixture, 57.9 g was extracted and cooled to 70 ° C., and a mixture of dipentaerystol hexaacrylate and dipentaerythritol pentaacrylate (DPHA (dipentaerythritol pentaacrylate 20 to 30 mol%), hydroxyl value 41 mgKOH / g, 12.9 g) and triethylamine (2.8 g) were added and mixed. The reaction mixture was cooled to 45 ° C., and water (136 g) was slowly added with stirring to obtain an aqueous polyurethane resin dispersion (UV-PUD1). The total amount of the compound (d) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups and the compound (A ′) having a polymerizable unsaturated bond is a polyurethane resin having a polymerizable unsaturated bond. It was 69 weight% with respect to a total of 100 weight% of (A) and the compound (A ') which has a polymerizable unsaturated bond.
[Production Example 2]
In a reactor equipped with a stirrer and a heater, ETERNACOLL (registered trademark) PH100 (manufactured by Ube Industries; number average molecular weight 1054; hydroxyl value 106 mgKOH / g; polyol component is 1,5-pentanediol: 1,6-hexanediol = Polycarbonate diol (41.0 g) obtained by reacting a 1: 1 molar ratio polyol mixture with carbonate ester, 2,2-dimethylolpropionic acid (DMPA, 14.4 g), and isophorone diisocyanate (IPDI). , 56.7 g) in N-ethylpyrrolidone (45.9 g) in the presence of dibutyltin dilaurate (0.2 g) under nitrogen atmosphere at 80-90 ° C. for 3 hours. 2,6-Di-tert-butyl-4-methylphenol (0.4 g) and 4-methoxyphenol (0.4 g) were added and the atmosphere was air. Further, a mixture of dipentaerystol hexaacrylate and dipentaerythritol pentaacrylate (DPHA (dipentaerythritol pentaacrylate 50-60 mol%), hydroxyl value 95 mgKOH / g, 181 g) was added and heated at 90 ° C. for 7 hours. . The NCO group content at the end of the urethanization reaction was 0.23% by weight. 60.4 g was extracted from the reaction mixture, cooled to 70 ° C., and triethylamine (2.9 g) was added and mixed. The reaction mixture was cooled to 45 ° C. and water (111 g) was slowly added while stirring to obtain an aqueous polyurethane resin dispersion (UV-PUD2). The total amount of the compound (d) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups and the compound (A ′) having a polymerizable unsaturated bond is a polyurethane resin having a polymerizable unsaturated bond. It was 62 weight% with respect to 100 weight% of the total of (A) and the compound (A ') which has a polymerizable unsaturated bond.

Carbodiimide 1: Carbodilite manufactured by Nisshinbo Chemical Co., Ltd., resin solid content 40% by weight, carbodiimide equivalent 600
Carbodiimide 2: Carbodilite manufactured by Nisshinbo Chemical Co., Ltd., resin solid content 40% by weight, carbodiimide equivalent 385
Oxazoline: Nippon Shokubai Epocross K-2030E, resin solid content 40% by weight, oxazoline equivalent 550

[Sample preparation for pencil hardness and adhesion evaluation]
Each aqueous polyurethane resin dispersion of Production Example 1 or Production Example 2 and the carbodiimide 1, carbodiimide 2, or oxazoline were mixed so as to have a weight ratio in the table to obtain an aqueous resin dispersion composition ( Examples 1 to 6, Comparative Examples 1 and 2). A polymerization initiator (IRGACURE500, manufactured by Ciba Specialty Chemicals) was added at 3% by weight / solid, and stirred well to obtain a coating agent. This was uniformly applied onto a PMMA resin (polymethyl methacrylate resin) so that the film thickness after drying was about 20 μm. Subsequently, the coating film (before ultraviolet irradiation) was obtained by drying at 60 degreeC for 30 minutes. The obtained coating film was passed under a high-pressure mercury lamp (once irradiation, ultraviolet irradiation amount of 1,000 mJ / cm ² ) to obtain an ultraviolet curable coating film. The obtained polyurethane resin coating film was subjected to pencil hardness measurement and adhesion test evaluation.

(Evaluation of hardness)
It evaluated by measuring the pencil hardness of a polyurethane resin coating film.
[Measurement of pencil hardness]
In the polyurethane resin coating film on the PMMA resin (polymethyl methacrylate resin) obtained above, the pencil hardness of the resin coating film was measured by a method based on JIS K 5600-5-4.
2H: The 2H pencil does not scratch at all, and the 3H pencil always scratches.
2-3H: A 3H pencil with or without scratches, and 2H with no scratches.
3-4H: With 4H pencil, scratches are not attached or not, and at 3H, no scratches are made.

(Evaluation of adhesion)
The polyurethane resin coating film of the PMMA resin (polymethyl methacrylate resin) obtained above was evaluated by a cross cut method. That is, 25 squares of 4 mm ² were prepared on a test piece with a cutter, and peelability was examined with a cellophane tape. Measurement was performed three times, and each measurement value is shown in the following table.
X / 25: After the test, the X mass was in close contact with the 25 masses.

＊表中の重量部は、樹脂中の全固形分を１００重量部としたときの各化合物の重量部を表す。なお、ＵＶ−ＰＵＤ１又は２の固形分には、（Ａ）成分及び（Ａ’）成分の両方を含む。

* The weight parts in the table represent the weight parts of each compound when the total solid content in the resin is 100 weight parts. The solid content of UV-PUD 1 or 2 includes both the component (A) and the component (A ′).

  The aqueous polyurethane resin dispersion of the present invention can be widely used as a raw material for paints and coating agents.

Claims (14)

At least a polyurethane resin (A) having a polymerizable unsaturated bond, a compound (A ′) having a polymerizable unsaturated bond, a carbodiimide compound (B) and / or an oxazoline compound (C) are dispersed in an aqueous medium. An aqueous resin dispersion composition comprising:
The polyurethane resin (A) having a polymerizable unsaturated bond is a polyol (a), a carboxyl group-containing polyol (b), a polyisocyanate compound (c), one or more polymerizable unsaturated bonds and one or more. Obtained by reacting at least with the compound (d) having a hydroxyl group of
A polyurethane resin in which the total amount of the compound (d) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups and the compound (A ′) having a polymerizable unsaturated bond has a polymerizable unsaturated bond per 100 wt% of (a) and a polymerizable unsaturated compound having a bond (a '), Ri 65-75 wt% der,
Polyurethane resin (A) in which compound (d) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups has a polymerizable unsaturated bond as a mixture with (meth) acrylate that is inert to an isocyanato group An aqueous resin dispersion composition, which is subjected to a reaction to obtain   An aqueous resin dispersion composition in which at least a polyurethane resin (A) having a polymerizable unsaturated bond, a compound (A ′) having a polymerizable unsaturated bond, and a carbodiimide compound (B) are dispersed in an aqueous medium. The aqueous resin dispersion composition according to claim 1, wherein   The aqueous resin dispersion composition according to claim 1 or 2, wherein a carbodiimide equivalent of the carbodiimide compound (B) is 1,000 or less.   The aqueous resin dispersion composition according to any one of claims 1 to 3, wherein the polyol (a) is a polycarbonate polyol.   The aqueous resin dispersion according to any one of claims 1 to 4, wherein the compound (d) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups is a compound having a (meth) acryloyl group. Body composition. One or more polymerizable unsaturated bond and a compound having one or more hydroxyl groups (d) is a compound having three or more polymerizable unsaturated bonds and one or more hydroxyl groups, of claim 1-5 The aqueous resin dispersion composition according to any one of the above. The compound (d) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups obtains a polyurethane resin (A) as a mixture of pentaerythritol tetra (meth) acrylate and pentaerythritol tri (meth) acrylate. The aqueous resin dispersion composition according to claim 6 , which is subjected to a reaction for the purpose. One or more polymerizable unsaturated bond and a compound having one or more hydroxyl groups (d) is a compound having five or more polymerizable unsaturated bonds and one or more hydroxyl groups, as claimed in claim 6 An aqueous resin dispersion composition. Polyurethane resin (A) in which compound (d) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups has a polymerizable unsaturated bond as a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate The aqueous resin dispersion composition according to claim 8 , which is subjected to a reaction to obtain The carbodiimide compound (B) with respect to a total of 100 parts by weight of the polyurethane resin (A) having a polymerizable unsaturated bond, the compound (A ′) having a polymerizable unsaturated bond, the carbodiimide compound (B) and the oxazoline compound (C). The aqueous resin dispersion composition according to any one of claims 1 to 9 , wherein the total amount of the oxazoline compound (C) is 3 to 30 parts by weight. The carbodiimide compound (B) with respect to a total of 100 parts by weight of the polyurethane resin (A) having a polymerizable unsaturated bond, the compound (A ′) having a polymerizable unsaturated bond, the carbodiimide compound (B) and the oxazoline compound (C). The aqueous resin dispersion composition according to any one of claims 1 to 10 , wherein the total amount of the oxazoline compound (C) is 5 to 10 parts by weight. An aqueous resin dispersion composition according to any one of claims 1 to 11 photocurable composition containing a photopolymerization initiator. Coating composition containing an aqueous resin dispersion composition according to any one of claims 1 to 11. The coating composition containing an aqueous resin dispersion composition according to any one of claims 1 to 11.