JPWO2014106939A1 - Aqueous resin dispersion and use thereof - Google Patents

Abstract

The present invention provides an aqueous resin dispersion that provides a highly transparent coating film and is excellent in storage stability even when mixed with a high molecular weight aqueous polyurethane resin aqueous dispersion. The present invention provides an aqueous solution obtained by dispersing at least a polyurethane resin (A) having a polymerizable unsaturated bond, a compound (B) having a polymerizable unsaturated bond, and a neutralizing agent (C) in an aqueous medium. A polyurethane resin (A) having a polymerizable unsaturated bond, which is a resin dispersion, comprises a polyol (a), an acidic group-containing polyol (b), a polyisocyanate (c), a hydroxyl group-containing (meth) acrylate ( d) is obtained by reacting at least, and the neutralizing agent (C) is represented by the following general formula (1): (wherein R1, R2 and R3 each independently has 1 to 10 carbon atoms. Represents an alkyl group or a hydroxyalkyl group having 1 to 10 carbon atoms, provided that at least one of R1, R2 and R3 is a hydroxyalkyl group having 1 to 10 carbon atoms, and is the total carbon of R1, R2 and R3 number An aqueous resin dispersion characterized in that it is a tertiary amine represented by formula (5) to (20)), and a curable composition, a coating composition and a coating agent composition containing the aqueous resin dispersion. is there.

Description

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

  Polycarbonate polyol is a useful compound as a raw material for polyurethane resin. Polycarbonate polyol can produce a polyurethane resin used for rigid foams, flexible foams, paints, adhesives, synthetic leather, ink binders and the like by reaction with isocyanate compounds. A coating film obtained by applying an aqueous polyurethane resin dispersion using polycarbonate polyol as a raw material is known to have excellent light resistance, weather resistance, heat resistance, hydrolysis resistance, and oil resistance (Patent Documents). 1).

  Among them, a coating film obtained by applying an aqueous urethane resin dispersion using an aliphatic polycarbonate polyol as a raw material can be used as an undercoat agent because adhesion to a substrate and blocking resistance are improved. It is known (see Patent Document 2). However, when only aliphatic polycarbonate polyol is used as a raw material, the hardness and chemical resistance of the coating film obtained from the aqueous polyurethane resin dispersion are, for example, automotive interior materials, mobile phone housings, home appliance housings, There has been a problem that it is not sufficient in the field of paints and coating agents for synthetic resin moldings such as personal computer cases, decorative films, optical films, flooring materials such as flooring.

  The use of urethane (meth) acrylate for the purpose of increasing coating film hardness and chemical resistance has also been studied. For example, an aqueous active energy ray-curable resin composition comprising (meth) acrylated polyurethane (patent document) 3), and an aqueous active energy ray-curable composition containing a (meth) acrylated polyurethane and an ethylenically unsaturated compound (see Patent Document 4). Such an aqueous active energy ray-curable composition gives a hard coating film excellent in chemical resistance, and is, for example, an automobile interior material, a mobile phone housing, a home appliance housing, a personal computer housing, a decorative film. It can be used as a raw material for paints, coating agents, primers and adhesives for synthetic resin moldings such as flooring materials such as optical films and flooring.

  Moreover, as a method for improving the durability of the aqueous active energy ray-curable composition, an aqueous active energy ray-curable composition containing a combination of a low molecular weight ethylenically unsaturated polyurethane and a high molecular weight ethylenically unsaturated polyurethane (patent) Document 5) has been proposed.

JP-A-10-120757 JP 2005-281544 A JP 2010-202869 A Special table 2009-533504 gazette International Publication No. 2009/147092

In the paint / coating agent field, it is known to mix a paint / coating agent composition with a high molecular weight polyurethane in order to improve the coating film performance. However, it has been found that when an aqueous active energy ray-curable composition as disclosed in Patent Documents 3 and 4 is mixed with a high molecular weight polyurethane dispersion, the coating film becomes cloudy. Especially, it turned out that this problem tends to arise in the aqueous | water-based active energy ray-curable composition with large content of a (meth) acrylate compound.
This problem is not observed in the aqueous polyurethane resin dispersion used in a normal aqueous thermosetting composition that does not contain a compound having a polymerizable unsaturated bond, and an active energy ray containing a compound having a polymerizable unsaturated bond. It was specific to the curable aqueous resin dispersion and its composition.

  An object of the present invention is to provide an aqueous resin dispersion which gives a highly transparent coating film and is excellent in storage stability even when mixed with a high molecular weight aqueous polyurethane resin dispersion.

  As a result of various investigations to overcome the above problems, the present inventors have found that a polyurethane resin (A) having a polymerizable unsaturated bond has a polyol (a), an acidic group-containing polyol (b), and , Obtained by reacting at least the polyisocyanate (c) and the hydroxyl group-containing (meth) acrylate (d), the polyurethane resin (A) and a compound (B) having a polymerizable unsaturated bond In the aqueous resin dispersion in which the neutralizing agent (C) is combined, the knowledge that the problem can be solved by using a specific tertiary amine as the neutralizing agent (C) is obtained. Invented.

（式中、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に、炭素数１〜１０のアルキル基又は炭素数１〜１０のヒドロキシアルキル基を表し、ただし、Ｒ^１、Ｒ^２及びＲ^３のうちの少なくとも１つは炭素数１〜１０のヒドロキシアルキル基であり、Ｒ^１、Ｒ^２及びＲ^３の合計の炭素数は５〜２０である。）
で表される第３級アミンである、水性樹脂分散体に関する。
本発明（２）は、中和剤（Ｃ）が、ジエチルエタノールアミン、エチルジエタノールアミン、メチルジエタノールアミン、及びトリエタノールアミンからなる群から選ばれる１種以上である本発明（１）に記載の水性樹脂分散体に関する。
本発明（３）は、中和剤（Ｃ）が、トリエタノールアミンである、本発明（１）又は（２）に記載の水性樹脂分散体に関する。
本発明（４）は、ポリウレタン樹脂（Ａ）中の酸性基のモル数に対する中和剤（Ｃ）のモル数の割合が、０．６５〜０．９５である、本発明（１）〜（３）のいずれか１つに記載の水性樹脂分散体に関する。
本発明（５）は、重合性不飽和結合を有する化合物（Ｂ）が、ポリエチレングリコール構造を含有しない（メタ）アクリレートである、本発明（１）〜（４）のいずれか１つに記載の水性樹脂分散体に関する。
本発明（６）は、重合性不飽和結合を有する化合物（Ｂ）が、ジペンタエリスリトールヘキサ（メタ）アクリレートとジペンタエリスリトールペンタ（メタ）アクリレートとの混合物、ペンタエリスリトールテトラ（メタ）アクリレート、及びジトリメチロールプロパンテトラ（メタ）アクリレートからなる群から選ばれる１種以上である、本発明（１）〜（５）のいずれか１つに記載の水性樹脂分散体。
本発明（７）は、ポリオール（ａ）が、ポリカーボネートジオールである、本発明（１）〜（６）のいずれか１つに記載の水性樹脂分散体に関する。
本発明（８）は、水酸基含有（メタ）アクリレート（ｄ）と重合性不飽和結合を有する化合物（Ｂ）との合計量が、水性樹脂分散体中の樹脂固形分全体の６５〜７５重量％である、本発明（１）〜（７）のいずれか１つに記載の水性樹脂分散体に関する。
本発明（９）は、重合性不飽和結合を有するポリウレタン樹脂（Ａ）が、水酸基含有（メタ）アクリレート（ｄ）を、イソシアナト基に不活性な（メタ）アクリレートとの混合物として、ポリウレタン樹脂（Ａ）を得るための反応に使用して得られるものである、本発明（１）〜（８）のいずれか１つに記載の水性樹脂分散体に関する。
本発明（１０）は、前記水酸基含有（メタ）アクリレート（ｄ）とイソシアナト基に不活性な（メタ）アクリレートとの混合物が、水酸基価が８０〜１２０ｍｇＫＯＨ／ｇ以上のジペンタエリスリトールペンタ（メタ）アクリレートとジペンタエリスリトールヘキサ（メタ）アクリレートとの混合物である、本発明（１）〜（９）のいずれか１つに記載の水性樹脂分散体に関する。
本発明（１１）は、さらに、重合性不飽和結合を有しない水性ポリウレタン樹脂（Ｄ）を含有する、本発明（１）〜（１０）のいずれか１つに記載の水性樹脂分散体に関する。
本発明（１２）は、重合性不飽和結合を有しない水性ポリウレタン樹脂（Ｄ）の重量平均分子量が４０，０００〜１，０００，０００である、本発明（１１）に記載の水性樹脂分散体に関する。
本発明（１３）は、本発明（１）〜（１２）のいずれか１つに記載の水性樹脂分散体と重合開始剤とを含有する、硬化性組成物に関する。
本発明（１４）は、本発明（１）〜（１２）のいずれか１つに記載の水性樹脂分散体を含有する塗料組成物に関する。
本発明（１５）は、本発明（１）〜（１２）のいずれか１つに記載の水性樹脂分散体を含有するコーティング剤組成物に関する。In the present invention (1), at least a polyurethane resin (A) having a polymerizable unsaturated bond, a compound (B) having a polymerizable unsaturated bond, and a neutralizing agent (C) are dispersed in an aqueous medium. An aqueous resin dispersion comprising:
The polyurethane resin (A) having a polymerizable unsaturated bond reacts at least the polyol (a), the acidic group-containing polyol (b), the polyisocyanate (c), and the hydroxyl group-containing (meth) acrylate (d). It is obtained by
The neutralizing agent (C) is represented by the following general formula (1):

^(Wherein, R 1, ^{R 2} and ^{R 3} each independently represent an alkyl group or hydroxyalkyl group having 1 to 10 carbon atoms having 1 to 10 carbon atoms, provided ^that the R 1, ^{R 2} and ^{R 3} (At least one of them is a hydroxyalkyl group having 1 to 10 carbon atoms, and the total carbon number of R ¹ , R ² and R ³ is 5 to 20).
It is related with the aqueous resin dispersion which is the tertiary amine represented by these.
The present invention (2) is the aqueous resin according to the present invention (1), wherein the neutralizing agent (C) is at least one selected from the group consisting of diethylethanolamine, ethyldiethanolamine, methyldiethanolamine, and triethanolamine. Concerning the dispersion.
The present invention (3) relates to the aqueous resin dispersion according to the present invention (1) or (2), wherein the neutralizing agent (C) is triethanolamine.
In the present invention (4), the ratio of the number of moles of the neutralizing agent (C) to the number of moles of acidic groups in the polyurethane resin (A) is 0.65 to 0.95. The aqueous resin dispersion according to any one of 3).
This invention (5) is as described in any one of this invention (1)-(4) whose compound (B) which has a polymerizable unsaturated bond is (meth) acrylate which does not contain a polyethyleneglycol structure. The present invention relates to an aqueous resin dispersion.
In the present invention (6), the compound (B) having a polymerizable unsaturated bond is a mixture of dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and The aqueous resin dispersion according to any one of the present inventions (1) to (5), which is at least one selected from the group consisting of ditrimethylolpropane tetra (meth) acrylate.
This invention (7) relates to the aqueous resin dispersion as described in any one of this invention (1)-(6) whose polyol (a) is polycarbonate diol.
In the present invention (8), the total amount of the hydroxyl group-containing (meth) acrylate (d) and the compound (B) having a polymerizable unsaturated bond is 65 to 75% by weight based on the entire resin solid content in the aqueous resin dispersion. It is related with the aqueous resin dispersion as described in any one of this invention (1)-(7) which is.
In the present invention (9), the polyurethane resin (A) having a polymerizable unsaturated bond comprises a polyurethane resin (A) containing a hydroxyl group-containing (meth) acrylate (d) as a mixture with (meth) acrylate that is inert to an isocyanato group. The aqueous resin dispersion according to any one of the present inventions (1) to (8), which is obtained by using the reaction for obtaining A).
In the present invention (10), the mixture of the hydroxyl group-containing (meth) acrylate (d) and the (meth) acrylate inert to the isocyanate group is a dipentaerythritol penta (meth) having a hydroxyl value of 80 to 120 mgKOH / g or more. It is related with the aqueous resin dispersion as described in any one of this invention (1)-(9) which is a mixture of an acrylate and dipentaerythritol hexa (meth) acrylate.
The present invention (11) further relates to the aqueous resin dispersion according to any one of the present inventions (1) to (10), further comprising an aqueous polyurethane resin (D) having no polymerizable unsaturated bond.
The aqueous resin dispersion according to the invention (11), wherein the weight average molecular weight of the aqueous polyurethane resin (D) having no polymerizable unsaturated bond is 40,000 to 1,000,000. About.
This invention (13) relates to the curable composition containing the aqueous resin dispersion and polymerization initiator as described in any one of this invention (1)-(12).
This invention (14) relates to the coating composition containing the aqueous resin dispersion as described in any one of this invention (1)-(12).
This invention (15) is related with the coating agent composition containing the aqueous resin dispersion as described in any one of this invention (1)-(12).

  According to the present invention, even when mixed with a high molecular weight polyurethane, an aqueous resin dispersion that provides a highly transparent coating film and is excellent in storage stability is provided.

The present invention provides an aqueous solution obtained by dispersing at least a polyurethane resin (A) having a polymerizable unsaturated bond, a compound (B) having a polymerizable unsaturated bond, and a neutralizing agent (C) in an aqueous medium. It relates to a resin dispersion.
<Polyurethane resin (A) having a polymerizable unsaturated bond>
The polyurethane resin (A) having a polymerizable unsaturated bond of the present invention (hereinafter sometimes simply referred to as “polyurethane resin (A)”) includes a polyol (a), an acidic group-containing polyol (b), It is obtained by reacting at least the isocyanate (c) and the hydroxyl group-containing (meth) acrylate (d).

<< Polyol (a) >>
As the polyol (a), for example, a high molecular weight polyol or a low molecular weight polyol can be used, a high molecular weight polyol is preferably used, and a high molecular weight polyol having a number average molecular weight of 400 to 8000 is more preferably used. It is more preferable to use a high molecular weight polyol having an average molecular weight of 400 to 4000, and a polycarbonate polyol having a number average molecular weight of 400 to 4000 is particularly preferable. It is preferable to use a high molecular weight diol or a low molecular weight diol because of the ease of production of the aqueous resin dispersion.

  The high molecular weight diol is not particularly limited, but preferably has a number average molecular weight of 400 to 8000. If the number average molecular weight is in this range, an appropriate viscosity and good handleability can be easily obtained. It is easy to secure the performance as a soft segment in the polyurethane resin, and when a coating film is formed using the aqueous resin dispersion containing the obtained polyurethane resin, it is easy to suppress the occurrence of cracks. Furthermore, the reactivity with the polyisocyanate (c) is sufficient, and the polyurethane resin (A) can be produced efficiently. The number average molecular weight of the high molecular weight diol is more preferably 400 to 4000.

In the present specification, the number average molecular weight (Mn) is determined from the hydroxyl value [mgKOH / g] by the following formula.
Mn = (56100 × valence) / hydroxyl value In the above formula, the valence is the number of hydroxyl groups in one molecule, and the hydroxyl value is measured according to the method B of JIS K1557. When the polyol is a diol, the valence is 2.

  Examples of the high molecular weight diol include polycarbonate diol, polyester diol, and polyether diol. From the viewpoint of light resistance, weather resistance, heat resistance, hydrolysis resistance, and oil resistance of the aqueous resin dispersion containing the obtained polyurethane resin and the coating film obtained therefrom, polycarbonate diol is preferred.

  Among polycarbonate diols, polycarbonate diols whose diol components are aliphatic diols and / or alicyclic diols are preferred, and the resulting polyurethane resin has low viscosity, is easy to handle, and has good dispersibility in aqueous media. In view of this, polycarbonate diols in which the diol component is an aliphatic diol having no alicyclic structure, that is, polycarbonate diols in which the diol component is a linear or branched aliphatic diol are more preferable, and the diol component is a linear fat. More preferred is a polycarbonate diol which is a group diol.

The polycarbonate polyol is obtained by reacting one or more polyol monomers with carbonate ester and / 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 polycarbonate polyol referred to in the present invention may contain an ether bond or an ester bond having a number equal to or less than the average number of carbonate bonds in one molecule.

  Examples of the polyol monomer are 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.

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

  Examples of the polyol monomer having an alicyclic structure are not particularly limited. For example, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, In the main chain such as 1,4-cycloheptanediol, 2,5-bis (hydroxymethyl) -1,4-dioxane, 2,7-norbornanediol, tetrahydrofuran dimethanol, 1,4-bis (hydroxyethoxy) cyclohexane Examples thereof include diols having an alicyclic structure.

  Examples of the aromatic polyol monomer are not particularly limited. For example, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 4,4′-naphthalenediethanol, 3 , 4'-naphthalene diethanol and the like.

  Examples of the polyester polyol monomer are not particularly limited. For example, a polyester polyol of a hydroxycarboxylic acid and a diol such as a polyester polyol of 6-hydroxycaproic acid and hexanediol, a polyester polyol of adipic acid and hexanediol, or the like. Examples include polyester polyols of dicarboxylic acid and diol.

  Examples of the polyether polyol monomer are not particularly limited, and examples thereof include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

  As the polyol, a diol having two hydroxyl groups per molecule is preferable. Among the diols, linear or branched aliphatic diols are preferable. Specifically, 1,6-hexanediol, or 1,6-hexanediol and 1,3-propanediol, 1,4-butanediol A combination with a diol selected from 1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, and 1,9-nonanediol is more preferable.

  Examples of the carbonate ester are not particularly limited, and examples thereof include aliphatic carbonate esters such as dimethyl carbonate and diethyl carbonate, aromatic carbonate esters such as diphenyl carbonate, and cyclic carbonate esters such as ethylene carbonate. In addition, phosgene or the like capable of producing a polycarbonate polyol can be used. Of these, aliphatic carbonates are preferred and dimethyl carbonate is more preferred because of the ease of production of polycarbonate polyols.

  The method for producing the polycarbonate polyol from the polyol and the carbonate compound is not particularly limited. For example, the carbonate compound and the polyol are added to the reactor, and the reaction is performed at a temperature of 160 to 200 ° C. at normal pressure for 15 to 25 hours. Then, a method of reacting at 200 to 220 ° C. for 10 to 20 hours at a pressure of about 30 mmHg can be mentioned. 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 compound escapes from the system by azeotroping with the by-produced alcohol, an excess amount of the carbonate compound may be added. In the above reaction, a catalyst such as titanium tetrabutoxide may be used.

  Examples of the polyester diol include, but are not limited to, polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyhexamethylene isophthalate adipate diol, polyethylene succinate diol, polybutylene succinate diol, polyethylene seba Examples thereof include keto diol, polybutylene sebacate diol, poly-ε-caprolactone diol, poly (3-methyl-1,5-pentylene adipate) diol, polycondensate of 1,6-hexanediol and dimer acid. .

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

  Although it does not restrict | limit especially as low molecular weight diol, For example, a number average molecular weight is 60 or more and less than 400 thing is mentioned. 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 Examples thereof include diols having an alicyclic structure having 6 to 12 carbon atoms such as methanol and 2,5-bis (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.

<< Acid group-containing polyol (b) >>
The acidic group-containing polyol (b) contains two or more hydroxyl groups and one or more acidic groups in one molecule. Examples of the acidic group include a carboxy group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. The acidic group-containing polyol (b) preferably contains a compound having two hydroxyl groups and one carboxy group in one molecule. An acidic group containing polyol (b) may be used independently and may use multiple types together.

  Specific examples of the acidic 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. Among dimethylolalkanoic acids, 2,2-dimethylolpropionic acid and / or 2,2 -More preferred is dimethylolbutanoic acid.

  In the present invention, the total number of hydroxyl equivalents of the polyol (a) and the acidic group-containing polyol (b) is preferably 120 to 600. When the number of hydroxyl equivalents is within this range, the aqueous resin dispersion containing the obtained polyurethane resin can be easily produced, and a coating film excellent in hardness can be easily obtained. From the viewpoint of the storage stability of the obtained aqueous resin dispersion 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 even more preferably 170 to 400. .

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)
When calculating the number of hydroxyl equivalents of the polyol (a) of the polyurethane resin (A) and the acidic group-containing polyol (b), in the above formula (2), M is [[polyol (a calculated in formula (1) (a ) Number of hydroxyl group equivalents × number of moles of polyol (a)] + [number of hydroxyl group equivalents of acidic group-containing polyol (b) calculated by formula (1) × number of moles of acidic 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 aromatic polyisocyanates 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 4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m-isocyanatophenylsulfonyl isocyanate, p-isocyanatophenylsulfonyl isocyanate, and the like. It is done.

  Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexaisocyanate. Methylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanate Examples include hexanoate.

  Specific examples of alicyclic polyisocyanates 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 polyisocyanate is preferably a diisocyanate having two isocyanato groups per molecule, but has three or more isocyanato groups such as triphenylmethane triisocyanate as long as the polyurethane resin in the present invention does not gel. Polyisocyanates can also be used.

  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) and / or 4,4′-dicyclohexylmethane diisocyanate (H12-MDI) are particularly preferred.

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

<< hydroxyl group-containing (meth) acrylate (d) >>
In the present invention, as the hydroxyl group-containing (meth) acrylate (d), a primary hydroxyl group-containing (meth) acrylate compound and a secondary hydroxyl group-containing (meth) acrylate compound can be used. The “primary hydroxyl group” in the present specification means a hydroxyl group in which an oxygen atom of the hydroxyl group is bonded to a methylene group. The “secondary hydroxyl group” in the present specification means a hydroxyl group in which an oxygen atom of the hydroxyl group is bonded to a methine group. In addition, “(meth) acryloyl compound”, “(meth) acrylate compound”, and “(meth) acrylate” in the present specification are all concepts including a compound having an acryloyl group and a compound having a methacryloyl group. Yes, used interchangeably and may have both acryloyl and methacryloyl groups. A primary hydroxyl group-containing (meth) acrylate compound is preferred because the production time of the polyurethane resin (A) having a polymerizable unsaturated bond is shortened.

  Examples of primary hydroxyl group-containing (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerin mono (meth) acrylate, 3-hydroxy Propane-1,2-diyl di (meth) acrylate, diglycerin tri (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, sorbitol penta (meth) acrylate, glycerin mono (meth) acrylate , Diglycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, sorbitol mono (meth) acrylate diglycerin di (meth) acrylate, pentaerythritol di (meth) Chryrate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, sorbitol di (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, etc. Is mentioned.

  Examples of the secondary hydroxyl group-containing (meth) acrylate include adducts of glycidyl (meth) acrylate and (meth) acrylic acid, glycerin mono (meth) acrylate, 2-hydroxypropane-1,3-diyldi (meth) acrylate, Diglycerin mono (meth) acrylate, sorbitol mono (meth) acrylate diglycerin di (meth) acrylate, sorbitol di (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, 2 molecules of (meth) acrylic Reaction product of acid and 1 molecule of 1,6-hexanediol diglycidyl (eg, “DA-212” manufactured by Nagase Chemtech) 2 molecules of epoxy (meth) acrylic acid and 1 molecule of neopentyl glycol diglycidyl Product of reaction with 2 molecules Reaction product of (meth) acrylic acid and one molecule of bisphenol A diglycidyl (for example, “DA-250” manufactured by Nagase Chemtech), diglycidyl compound of propylene oxide adduct of two molecules (meth) acrylic acid and bisphenol A, Reaction product of 2 molecules of (meth) acrylic acid and 1 molecule of diglycidyl phthalate (for example, “DA-721” manufactured by Nagase Chemtech) 2 molecules of (meth) acrylic acid and 1 molecule Reaction product of polyethylene glycol diglycidyl (eg, “DM-811”, “DM-832”, “DM-851” manufactured by Nagase Chemtech) with 2 molecules of (meth) acrylic acid and 1 molecule of polypropylene glycol Examples include reaction products of (meth) acrylic acid and polyol diglycidyl, such as reaction products of diglycidyl. .

  Among these, a hydroxyl group-containing (meth) acrylate in which the number of (meth) acryloyl groups in one molecule is 3 or more is preferable from the viewpoint of increasing the hardness after curing with active energy rays (for example, ultraviolet rays). Examples of the hydroxyl group-containing (meth) acrylate (d) having 3 or more (meth) acryloyl groups in one molecule include diglycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, sorbitol penta (meth) ) Acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, and the like.

  Among the hydroxyl group-containing (meth) acrylates (d) having 3 or more (meth) acryloyl groups in one molecule, the hydroxyl group is primary hydroxyl group in that the production time of the polyurethane resin (A) can be shortened. A (meth) acrylate compound containing only benzene is more preferred. Examples of such hydroxyl group-containing (meth) acrylate (d) include pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate. Is mentioned. From the viewpoint of the hardness of the coating film and the production time, dipentaerythritol tetra (meth) acrylate and / or dipentaerythritol penta (meth) acrylate is particularly preferable as the hydroxyl group-containing (meth) acrylate compound.

  The hydroxyl group-containing (meth) acrylate (d) may be used alone or in combination.

  A commercially available product may be used as it is as the hydroxyl group-containing (meth) acrylate (d).

  The hydroxyl group-containing (meth) acrylate (d) can be used in the reaction for obtaining the polyurethane resin (A) as a mixture with (meth) acrylate that is inert to the isocyanato group. The (meth) acrylate inert to the isocyanato group used as a mixture with the hydroxyl group-containing (meth) acrylate (d) can be a compound (B) having a polymerizable unsaturated bond in the aqueous resin dispersion. The (meth) acrylate inert to the isocyanato group refers to a (meth) acrylate having no group capable of reacting with an isocyanato group such as a hydroxyl group, an amino group or a carboxylic acid in the molecule.

  Examples of the mixture of the hydroxyl group-containing (meth) acrylate (d) and the (meth) acrylate inert to the isocyanato group include dipentaerythritol tetra (meth) acrylate and / or dipenta as the hydroxyl group-containing (meth) acrylate (d). A mixture of erythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate as (meth) acrylate inert to the isocyanato group may be mentioned. As such a mixture, commercially available dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol Examples thereof include a mixture with hexa (meth) acrylate. Dipentaerythritol hexa (meth) acrylate corresponds to (meth) acrylate that is inert to the isocyanato group.

  A mixture of dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, or dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate The hydroxyl value of the mixture 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. From the viewpoint of suppressing an increase in viscosity during the production of the polyurethane resin (A) and avoiding gelation, the hydroxyl value of the mixture is preferably 80 to 130 mgKOH / g, more preferably 80 to 120 mgKOH / g, and 85 to 120 mgKOH / g. g is more preferable. 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.

  Moreover, the mixture of a pentaerythritol triacrylate and a pentaerythritol tetraacrylate can also be used as a mixture of hydroxyl-containing (meth) acrylate (d) and (meth) acrylate inactive to an isocyanato group. In this case, the hydroxyl value of the mixture 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. From the viewpoint of suppressing an increase in viscosity during the production of the polyurethane resin (A) and avoiding gelation, the hydroxyl value of the mixture is preferably 120 to 250 mgKOH / g, more preferably 140 to 220 mgKOH / g. . Examples of the mixture of pentaerythritol triacrylate having a hydroxyl value of 100 to 280 mg KOH / g and pentaerythritol tetraacrylate include Aronix M305 and M306 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 hydroxyl group-containing (meth) acrylate (d) is preferably 25 to 70% by weight in the weight of the polyurethane resin (A) having a polymerizable unsaturated bond. Within this range, the reaction time of the hydroxyl group-containing (meth) acrylate (d) and the isocyanato group is set within an appropriate time, and the hardness of the coating film after curing with active energy rays (for example, ultraviolet rays) is set within an appropriate range. And the storage stability of the aqueous resin dispersion containing the obtained polyurethane resin can be kept good. The amount of the hydroxyl group-containing (meth) acrylate (d) is more preferably 30 to 70% by weight in the weight of the polyurethane resin (A).

  Hydroxyl-containing (meth) acrylate (d) and a mixture of (meth) acrylate that is inert to the isocyanato group (specifically, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipenta As a mixture of erythritol hexa (meth) acrylate, a mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, etc. In this case, the addition amount of the mixture is preferably 50 to 80% by weight, more preferably 60 to 80% by weight, based on the weight of the polyurethane resin (A) having a polymerizable unsaturated bond.

  The ratio of the number of moles of isocyanate groups of polyisocyanate (c) to the number of moles of all hydroxyl groups of polyol (a), acidic group-containing polyol (b), and hydroxyl group-containing (meth) acrylate (d) is 0.1. ~ 0.9 is preferred.

  If it is this range, while it is easy to avoid the problem that reaction time becomes long when there are too few moles of a hydroxyl group, an unreacted polyol (a) and acidic group containing by too many moles of a hydroxyl group The problem that the polyol (b) and the hydroxyl group-containing (meth) acrylate (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 (c) to the number of moles of all hydroxyl groups is preferably 0.15 to 0.8, more preferably 0.2 to 0.7.

  The reaction of the polyol (a), the acidic group-containing polyol (b), the polyisocyanate (c), and the hydroxyl group-containing (meth) acrylate (d) is the order of (a), (b), (d), (c) Or may be reacted with (c) by mixing a plurality of types (a), (b), and (d). The hydroxyl group-containing (meth) acrylate (d) may be subjected to a reaction for obtaining the polyurethane resin (A) as a mixture with (meth) acrylate that is inert to the isocyanato group.

  When reacting the polyol (a), the acidic group-containing polyol (b), the hydroxyl group-containing (meth) acrylate (d) and the polyisocyanate (c), a catalyst may be used.

  Examples of the catalyst are not particularly limited. For example, salts of metals such as tin (tin) catalysts (trimethyltin laurate, dibutyltin dilaurate, etc.) and lead catalysts (lead octylate, etc.), organic and inorganic acids, In addition, organic metal 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 polyurethane resin (A) is appropriate, and it can fully stir. In addition, it is difficult for the (meth) acryloyl group to undergo a polymerization reaction to cause gelation or the isocyanato group to cause a side reaction. The reaction temperature is more preferably 60 to 100 ° C.

  When the hydroxyl group-containing (meth) acrylate (d) is reacted with the polyisocyanate (c), oxygen is present to avoid unnecessary consumption of the (meth) acryloyl group of the hydroxyl group-containing (meth) acrylate (d). Preferably it is carried out below.

  In order to avoid unnecessary consumption of the (meth) acryloyl group of the hydroxyl group-containing (meth) acrylate (d), a polymerization inhibitor can be added to the reaction system.

  Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, benzoquinone, 2-tert-butylhydroquinone, p-tert-butylcatechol, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, Quinone polymerization inhibitors such as 2,5-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 Alkylphenol polymerization inhibitors such as phenothiazine and other aromatic amine polymerization inhibitors; alkylation Phenylamine, 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, Amine polymerization inhibitors such as 2,6,6-tetramethylpiperidine-1-oxyl (TEMPO); 2,2-diphenylpicrylhydrazyl (DPPH), tri-p-nitrophenylmethyl, N- (3N- Quaternary such as oxyanilino-1,3-dimethylbutylidene) -aniline oxide, benzyltrimethylammonium chloride 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, the consumption due to polymerization of the (meth) acryloyl group can be further reduced.

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

  The reaction with the polyol (a), the acidic group-containing polyol (b), the hydroxyl group-containing (meth) acrylate (d) and the polyisocyanate (c) may be performed without a solvent or in the presence of an organic solvent. Also good. Examples of the organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N-ethylpyrrolidone, ethyl acetate and the like. Among these, acetone, methyl ethyl ketone, and ethyl acetate are preferable because the polyurethane resin (A) 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 produced using the obtained aqueous resin dispersion containing a polyurethane resin.

  The amount of the organic solvent is preferably 0 to 2.0 on a weight basis with respect to the total amount of the polyol (a), the acidic group-containing polyol (b), the hydroxyl group-containing (meth) acrylate (d) and the polyisocyanate (c). Times, more preferably 0.05 to 0.7 times. If it is this range, the process of removing an organic solvent does not take time, and the dispersibility to the water of the obtained polyurethane resin is also favorable. Moreover, the problem that an organic solvent remains in the coating film produced using the aqueous resin dispersion and the physical properties of the coating film deteriorate can be avoided.

<Compound (B) having polymerizable unsaturated bond>
The aqueous resin dispersion of the present invention contains a compound (B) having a polymerizable unsaturated bond. The compound (B) having a polymerizable unsaturated bond is a compound other than the polyurethane resin (A) having a polymerizable unsaturated bond. The compound (B) 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.

  Examples of monomers (meth) acrylate compounds include mono (meth) acrylate, di (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, hexa (meth) acrylate, etc. Poly (meth) acrylate is mentioned.

  Examples of mono (meth) acrylates include, for example, acryloylmorpholine, 2-ethylhexyl (meth) acrylate, styrene, methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate , Dicyclopentenyl (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, methoxypolyethylene glycol mono (meth) acrylate, octoxypolyethyleneglycol-polypropyleneglycol mono (meth) acrylate, lauroxypolyethyleneglycol Examples include mono (meth) acrylate, stearoxypolyethylene glycol mono (meth) acrylate, nonylphenoxypolyethylene glycol mono (meth) acrylate, and nonylphenoxypolypropylene glycol polyethylene glycol mono (meth) acrylate.

  Examples of di (meth) acrylates include, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 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) Pyreneglycol-tetramethyleneglycol) di (meth) acrylate, methoxypolyethyleneglycol di (meth) acrylate, octoxypolyethyleneglycol-polypropyleneglycoldi (meth) acrylate, lauroxypolyethyleneglycoldi (meth) acrylate, stearoxypolyethyleneglycoldi Reaction of (meth) acrylate, nonylphenoxypolyethylene glycol di (meth) acrylate, nonylphenoxypolypropylene glycol polyethylene glycol di (meth) acrylate, 2 molecules of (meth) acrylic acid and 1 molecule of 1,6-hexanediol diglycidyl Product (for example, “DA-212” manufactured by Nagase Chemtech) 2 molecules of epoxy (meth) acrylic acid and 1 molecule of neopentylglyco Reaction product with 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 Co.), 2 molecules of (meth) acrylic acid and A reaction product of a propylene oxide adduct of bisphenol A with a diglycidyl compound, a reaction product of two molecules of (meth) acrylic acid and one molecule of diglycidyl phthalate (for example, “DA-721” manufactured by Nagase Chemtech) 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) (Meth) acrylic acid and polyol jig such as a reaction product of (meth) acrylic acid and one molecule of polypropylene glycol diglycidyl Reaction products with ricidyl, adducts of glycidyl (meth) acrylate and (meth) acrylic acid and the like can be mentioned.

  Examples of tri (meth) acrylates include, for example, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) Alkylene oxide modified trimethylolpropane tri (meth) acrylate (BASF Laromer (registered trademark) PO33F) such as acrylate, ethylene oxide (6 mol) modified trimethylolpropane tri (meth) acrylate (Laromer (registered trademark) LR8863 manufactured by BASF) ) And the like.

  Examples of tetra (meth) acrylate include, for example, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethylene oxide (4 mol) modified pentaerythritol tetra (meth) acrylate (Daicel Ornex, Ebecryl 40). And the like, and the like.

  Examples of penta (meth) acrylate include dipentaerythritol penta (meth) acrylate and the like.

  Examples of hexa (meth) acrylate include dipentaerythritol hexa (meth) acrylate and the like.

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

  Among these radically polymerizable compounds, (meth) acrylates that are not modified with ethylene oxide, that is, do not contain a polyethylene glycol structure, are preferred from the viewpoint of the transparency of the resulting coating film. More preferred are pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and mixtures thereof.

  Among these radically polymerizable compounds, from the point of adhesion of the resulting coating to the substrate, a mixture of dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate Ditrimethylolpropane tetra (meth) acrylate is preferred. More preferred is ditrimethylolpropane tetra (meth) acrylate.

  These compounds (B) having a polymerizable unsaturated bond may be used alone or in combination.

  When a mixture of a hydroxyl group-containing (meth) acrylate (d) and an isocyanato group-inactive (meth) acrylate is subjected to the reaction in order to obtain the polyurethane resin (A), it is inactive to the isocyanato group contained in the reaction system. The (meth) acrylate can be a compound (B) having a polymerizable unsaturated bond in the aqueous resin dispersion.

  The total amount of the hydroxyl group-containing (meth) acrylate (d) of the polyurethane resin (A) having a polymerizable unsaturated bond and the compound (B) having a polymerizable unsaturated bond is based on the total resin solid content of the aqueous resin dispersion. It is preferable that it is 60 to 85 weight%. When it is less than 60% by weight, the hardness of the coating film prepared using the aqueous resin dispersion may be reduced, and when it is more than 85% by weight, the storage stability of the aqueous resin dispersion may be reduced. The total amount of the hydroxyl group-containing (meth) acrylate (d) of the polyurethane resin (A) and the compound (B) having a polymerizable unsaturated bond is more preferably 60 to 80% by weight, still more preferably 65 ~ 75 wt%.

  When the total amount of the hydroxyl group-containing (meth) acrylate (d) and the compound (B) having a polymerizable unsaturated bond is 100% by weight, the amount of the compound (B) having a polymerizable unsaturated bond is: It is preferably 30 to 50% by weight.

(Aqueous medium)
In the aqueous resin dispersion of the present invention, the polyurethane resin (A), the compound (B) having a polymerizable unsaturated bond, and the neutralizing agent (C) 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.

(Aqueous resin dispersion)
In the present invention, the acid value of the aqueous resin dispersion 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 (mgKOH / g)] = [mmol number of acidic groups of acidic group-containing polyol (b)] × 56.1 / [Compound having polyurethane unsaturated resin (A) and polymerizable unsaturated bond Total weight of (B)] ... (3)
The acid value of the aqueous resin dispersion is more preferably 12 to 70 mgKOH / g, 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 acidic group-containing polyol (b) is 1 to 15 parts by weight. It is preferable to prepare the polyurethane resin (A) in such an amount.

If the ratio of a polyol (a) is the said range, the dispersibility to the aqueous medium of a polyurethane resin (A) will be favorable, and favorable film forming property can be obtained also about an aqueous resin dispersion. When the ratio of the acidic 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, still more preferably 5 to 30 parts by weight. The ratio of the acidic group-containing polyol (b) is more preferably 2 to 10 parts by weight, still more preferably 3 to 7 parts by weight.

（式中、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に、炭素数１〜１０のアルキル基又は炭素数１〜１０のヒドロキシアルキル基を表し、ただし、Ｒ^１、Ｒ^２及びＲ^３のうちの少なくとも１つは炭素数１〜１０のヒドロキシアルキル基であり、Ｒ^１、Ｒ^２及びＲ^３の合計の炭素数は５〜２０である。）
一般式（１）において、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に、炭素数１〜６のアルキル基又は炭素数１〜６のヒドロキシアルキル基であることが好ましい。Ｒ^１、Ｒ^２及びＲ^３の炭素数が大きくなりすぎると、ポリウレタン樹脂（Ａ）の分散性が低下し、水性樹脂分散体が得られなかったり、得られた水性樹脂分散体の安定性が低下し、水性樹脂が沈降したりする場合がある。
また、一般式（１）において、Ｒ^１、Ｒ^２及びＲ^３の合計の炭素数は、５〜１５であることが好ましい。Ｒ^１、Ｒ^２及びＲ^３の合計の炭素数が大きくなりすぎると、ポリウレタン樹脂（Ａ）の分散性が低下し、水性樹脂分散体が得られなかったり、得られた水性樹脂分散体の安定性が低下し、水性樹脂が沈降したりする場合がある。
前記一般式（１）の第３級アミンの例としては、例えば、トリエタノールアミン、Ｎ−メチルジエタノールアミン、Ｎ−エチルジエタノールアミン、ジエチルエタノールアミン、が挙げられる。ここで、ポリウレタン樹脂（Ａ）の酸性基とは、カルボキシル基、スルホン酸基、リン酸基、フェノール性水酸基等をいう。
これらの中和剤（Ｃ）は、1種類を単独で用いてもよいし、複数種を併用してもよい。また、本発明の効果を阻害しない範囲で、一般式（１）で表される第３級アミン以外のアミンを併用することもできる。
しかし、水性樹脂分散体を用いて得られた塗膜のヘイズが低くなる点から、中和剤として一般式（１）で表される第３級アミンのみを用いることが好ましい。<Neutralizing agent (C)>
The aqueous resin dispersion of the present invention contains a neutralizing agent (C). A neutralizer (C) neutralizes the acidic group of a polyurethane resin (A). The neutralizing agent (C) is not particularly limited as long as it is a tertiary amine represented by the following general formula (1).

^(Wherein, R 1, ^{R 2} and ^{R 3} each independently represent an alkyl group or hydroxyalkyl group having 1 to 10 carbon atoms having 1 to 10 carbon atoms, provided ^that the R 1, ^{R 2} and ^{R 3} (At least one of them is a hydroxyalkyl group having 1 to 10 carbon atoms, and the total carbon number of R ¹ , R ² and R ³ is 5 to 20).
In the general formula ^{(1), R 1, R} 2 and ^{R 3} each independently is preferably a hydroxyalkyl group having 1 to 6 alkyl carbon atoms or 1 to 6 carbon atoms. When the carbon number of R ¹ , R ² and R ³ becomes too large, the dispersibility of the polyurethane resin (A) is lowered, and an aqueous resin dispersion cannot be obtained, or the stability of the obtained aqueous resin dispersion is low. In some cases, the aqueous resin settles down.
In the general formula ^{(1), R 1, R} 2 and the total number of carbon atoms of ^{R 3} is preferably 5 to 15. When the total carbon number of R ¹ , R ² and R ³ becomes too large, the dispersibility of the polyurethane resin (A) is lowered, and an aqueous resin dispersion cannot be obtained, or the stability of the obtained aqueous resin dispersion is decreased. In some cases, the water-based resin may settle out.
Examples of the tertiary amine of the general formula (1) include triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, and diethylethanolamine. Here, the acidic group of the polyurethane resin (A) refers to a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, and the like.
These neutralizing agents (C) may be used alone or in combination of two or more. In addition, an amine other than the tertiary amine represented by the general formula (1) can be used in combination as long as the effect of the present invention is not impaired.
However, it is preferable to use only the tertiary amine represented by the general formula (1) as the neutralizing agent from the viewpoint that the haze of the coating film obtained using the aqueous resin dispersion is lowered.

  Among these neutralizing agents (C), the transparency of the coating film obtained from the composition obtained by mixing the aqueous resin dispersion of the present invention with a high molecular weight aqueous urethane resin dispersion different from the polyurethane resin (A). From this point, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, and diethylethanolamine are preferable.

Among these neutralizing agents (C), the aqueous resin dispersion of the present invention is mixed with a high molecular weight aqueous urethane resin dispersion different from the polyurethane resin (A) and stored at 40 ° C. From the viewpoint of the transparency of the coating film obtained from the dispersion, triethanolamine is preferred.
That is, by using triethanolamine as the neutralizing agent (C), the aqueous resin dispersion can be stored at room temperature for a long time.

The ratio of the number of moles of the neutralizing agent (C) to the number of moles of acidic groups of the polyurethane resin (A) in the aqueous resin aqueous dispersion is 0.5 to 1.7. Within this range, the degree of neutralization is low, storage stability is reduced, or the aqueous resin dispersion of the present invention is mixed with an aqueous urethane resin aqueous dispersion having a high molecular weight different from that of the polyurethane resin (A). It can be avoided that the transparency of the coating film obtained from the aqueous resin dispersion after storage at 40 ° C. is lowered. The ratio of the number of moles of the neutralizing agent (C) to the number of moles of acidic groups of the polyurethane resin (A) is more preferably 0.65 to 1.05, and still more preferably 0.65 to 0.95. It is.
The number of moles of acidic groups in the polyurethane resin (A) is basically the number of moles of acidic group-containing polyol (b) used for the synthesis of the polyurethane resin (A). Further, the number of moles of the neutralizing agent (C) is the number of moles of the neutralizing agent added to the aqueous resin dispersion.

  When the compound (B) having a polymerizable unsaturated bond has an acidic group, the acidic group of (B) is also calculated as an acidic group of the polyurethane resin (A).

<Aqueous resin dispersion>
In the aqueous resin dispersion of the present invention, the solid content is preferably 1 to 70% by weight, and more preferably 5 to 50% by weight of the entire aqueous resin dispersion.
In the present invention, the solid content of the aqueous resin dispersion is a component that remains as a coating film after the aqueous resin dispersion is applied to a substrate, dried, and crosslinked by light irradiation or / and heating. Aqueous media and neutralizing agents are not included in the solid content.
Moreover, the aqueous resin dispersion of the present invention may be a curable composition without adding a polymerization initiator described later.

<Method for producing aqueous resin dispersion>
Next, the manufacturing method of an aqueous resin dispersion is demonstrated.
The method for producing an aqueous resin dispersion of the present invention comprises at least reacting a polyol (a), an acidic group-containing polyol (b), a polyisocyanate (c), and a hydroxyl group-containing (meth) acrylate (d). A step (α) of obtaining a polyurethane resin (A);
A step (β) of mixing the polyurethane resin (A) and the neutralizing agent (C) to neutralize acidic groups of the polyurethane resin (A);
A step (γ) of dispersing the polyurethane resin (A) and the compound (B) having a polymerizable unsaturated bond 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 process ((alpha)) which obtains a polyurethane resin (A) can be performed at 0-120 degreeC in order to avoid the unnecessary superposition | polymerization of a polymerizable unsaturated bond. Preferably it is 0-100 degreeC.

  As long as the acidic group of the polyurethane resin (A) can be neutralized in the step (β) of neutralizing the acidic group of the polyurethane resin (A), its method and operation order are not particularly limited. For example, a method of adding a neutralizing agent (C) to the reaction product of step (α), a method of mixing (A) and (B), an aqueous medium and a neutralizing agent (C) at a time, a neutralizing agent A method of mixing (C) with an aqueous medium or (B) in advance and mixing these with (A) can be mentioned.

  In the step (γ) of dispersing the polyurethane resin (A) and the compound (B) having a polymerizable unsaturated bond in the aqueous medium, as long as (A) and (B) can be dispersed in the aqueous medium. The method and the operation order are not particularly limited. For example, a method of mixing (B) with (A) and dispersing in an aqueous medium, a method of mixing (A) with (B) and dispersing in an aqueous medium, or (A) in an aqueous medium. A method of mixing and dispersing (B) after dispersion, a method of mixing and dispersing (A) after dispersing (B) in an aqueous medium, and (A) and (B) in an aqueous medium, respectively. The method of mixing after making it disperse | distribute, the method of mixing (B) and dispersing it in an aqueous medium at the time of (A) manufacture, etc. are mentioned.

  In the step (α) of obtaining the polyurethane resin (A), the hydroxyl group-containing (meth) acrylate (d) is subjected to a reaction for obtaining the polyurethane resin (A) as a mixture with the (meth) acrylate inert to the isocyanato group. The (meth) acrylate inert to the isocyanato group is contained in the reaction product of the step (α) together with the polyurethane resin (A), and is subjected to the step (β) and the step (γ) to obtain a final aqueous solution. In the resin dispersion, the compound (B) having a polymerizable unsaturated bond is constituted. In this case, the neutralizing agent (C) can be added to the reaction product of the step (α) and can be dispersed in the aqueous dispersion medium together with the compound (B) having a further polymerizable unsaturated bond. Before adding the compound (B) 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. In addition, a hydrophilic organic solvent or water is added to the polyurethane resin (A) or the compound (B) having a polymerizable unsaturated bond in advance before mixing for viscosity adjustment, workability improvement, and dispersibility improvement. It can also be left.

  The step (γ) of mixing the polyurethane resin (A) and the compound (B) 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 when mixing the polyurethane resin (A) and the compound (B) having a polymerizable unsaturated bond 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 to 90 ° C, more preferably 0 to 80 ° C, and particularly preferably 50 to 70 ° C.

  In the production method of the present invention, the step (β) of neutralizing the acidic group of the polyurethane resin (A) and the polyurethane resin (A) and the compound (B) having a polymerizable unsaturated bond are dispersed in an aqueous medium. Either step (γ) may be performed first, or may be performed simultaneously. In this case, (A) and (B), the aqueous medium and the neutralizing agent (C) may be mixed at once, or the neutralizing agent (C) is previously mixed with the aqueous medium and (B). These may be mixed with (A).

  The proportion of the polyurethane resin (A) in the aqueous resin dispersion is preferably 5 to 60% by weight, more preferably 15 to 50% by weight, and still more preferably 25 to 40% by weight. Moreover, it is preferable that the number average molecular weights of a polyurethane resin (A) are 1,000-1,000,000.

  If necessary, the aqueous resin dispersion of the present invention includes 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, and the like. These additives can also be added. An additive may be individual and may use multiple types together. The aqueous resin dispersion 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.

  The aqueous resin dispersion of the present invention can be mixed with a vinyl chloride resin emulsion in order to increase the bulk. The vinyl chloride resin emulsion is obtained by a known method such as an emulsion polymerization method, a phase inversion emulsification method, an emulsion dispersion method, etc. Among them, a vinyl chloride resin emulsion obtained by an emulsion polymerization method is preferable. This is because a high molecular weight, low acid value vinyl chloride resin can be emulsified with a high solid content by using an emulsification dispersion method. Specific examples of the vinyl chloride resin emulsion include Nibsin Chemical Co., Ltd., Viniblanc 271, Vinibrand 278, Vinibrand 603, Vinibrand 690, Vinibrand 900, Vinibrand 902, Vinibrand 985, and UCAR AW-875 manufactured by Dow Chemical. The vinyl chloride resin emulsion is preferably contained in the aqueous resin dispersion in an amount of 0.1 to 40% by weight, more preferably 3.0 to 30% by weight.

  The vinyl chloride resin emulsion may be one obtained by polymerizing vinyl chloride alone, or may be one obtained by copolymerizing vinyl chloride-vinyl acetate or vinyl chloride and an acrylic monomer. As acrylic monomers, alkyl acrylate esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isononyl acrylate, lauryl acrylate, stearyl acrylate, etc. Body, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and methacrylic acid alkyl ester monomers such as stearyl methacrylate can be used alone or in combination of two or more. In addition, aromatic vinyl monomers such as styrene, α-methylstyrene, vinyl toluene, and ethyl vinyl benzene, saturated fatty acid vinyl monomers such as vinyl propionate and vinyl versatate, acrylonitrile, methacrylonitrile, etc. Vinyl cyanide monomers, olefin monomers such as propylene and butadiene, monoalkyl esters of ethylene dicarboxylic acids such as monobutylmaleic acid, and ethylene carboxylates such as ammonium salts or alkali metal salts thereof , Acid amides of ethylene carboxylic acids such as acrylamide, methacrylamide and diacetone acrylamide, ethylene carboxylic acids such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxy methacrylate Hydroxyalkyl esters, dimethylaminoethyl methacrylate, esters of an alcohol having an ethylenic carboxylic acid and an amino group such as diethylaminoethyl methacrylate, etc. may be used alone or in combination of two or more.

  The larger the molecular weight of the vinyl chloride resin, the better the coating film resistance and the coating film stretchability.

  The average particle size of the particles in the vinyl chloride resin emulsion is preferably 30 to 500 nm, and more preferably 50 to 400 nm. When the average particle size is 500 nm or more, the viscosity of the emulsion itself may increase.

  The acid value of the vinyl chloride resin is preferably 1 to 100 mgKOH / g, more preferably 1 to 50 mgKOH / g, and still more preferably 1 to 10 mgKOH / g. If the acid value is 1 mgKOH / g or more, it can be emulsified and is stable over time, and if it is 100 mgKOH / g or less, the rub resistance, water resistance, and chemical resistance of the coating film are improved.

  When the aqueous resin dispersion of the present invention contains a vinyl chloride resin emulsion, discoloration of the vinyl chloride resin emulsion can be suppressed by adding an unsaturated group-containing vegetable oil. Unsaturated group-containing vegetable oil is a vegetable oil containing unsaturated fatty acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, erucic acid as constituent fatty acids, specifically linseed oil, safflower oil, Examples include sunflower oil, soybean oil, corn oil, peanut oil, cottonseed oil, sesame oil, rapeseed oil, olive oil, palm oil, palm kernel oil, coconut oil, and castor oil.

  The blending amount of the unsaturated group-containing vegetable oil is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the solid content of the vinyl chloride resin emulsion. When the amount is 1 part by weight or more, the discoloration suppressing effect is remarkably exhibited, and when the amount is 10 parts by weight or less, the influence on other physical properties such as flame retardancy can be suppressed.

<Curable composition>
The aqueous resin dispersion of the present invention and a polymerization initiator can be mixed to obtain a curable composition. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator. These may use only 1 type and can also use multiple types together. A chain transfer agent can also be added.

<Photopolymerization initiator>
A photopolymerization initiator may be added to the aqueous resin dispersion of the present invention to form a photocurable composition. As the photopolymerization initiator, known ones can be used. For example, a photocleavage type initiator that can be easily cleaved to form two radicals by irradiation with ultraviolet rays, or a hydrogen abstraction type initiator is used. be able to. These may be used in combination. Examples of these photopolymerization initiators include, for example, 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 Phenylketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-hydroxy-2-methyl-1 Phenylpropan-1-one, 2,4,6, - trimethyl benzophenone, 4-methylbenzophenone, 2,2-dimethoxy-1,2-diphenyl-ethanone, and the like. These may use only 1 type and can also use multiple types together. 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 (B) 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 the total solid content of the aqueous resin dispersion (including the compound (B) having a polymerizable unsaturated bond).

<Thermal polymerization initiator>
A thermopolymerization initiator can be added to the aqueous resin dispersion of the present invention to obtain a thermosetting composition. As the thermal polymerization initiator, known ones such as organic peroxides can be used. Examples of these thermal polymerization initiators include, for example, azo compounds; diacyl peroxide compounds; peroxy ester compounds; hydroperoxide compounds; dialkyl peroxide compounds; ketone peroxide compounds; Compound, alkyl peroxy ester compound, peroxy carbonate compound and the like. Examples of these compounds include azonitrile compounds [2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methyl). Butyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile)], azoamide compound {2,2′-azobis {2-methyl-N- [1,1-bis ( Hydroxymethyl) -2-hydroxyethyl] propionamide} and the like}, azoamidine compounds {2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazoline-2- Yl) propane] dihydrochloride, etc.}, azoalkane compounds [2,2′-azobis (2,4,4-trimethylpentane), 4,4′-azobis (4-cyanopentanoic acid), etc. , Azo compounds such as 2,2′-azobis (2-methylpropionamide oxime); dialkanoyl peroxide (such as lauroyl peroxide), dialoyl peroxide (benzoyl peroxide, benzoyl toluyl peroxide, toluyl peroxide) Diacyl peroxide compounds; hydroperoxide compounds; dialkyl peroxide compounds such as di-t-butyl peroxide and dicumyl peroxide; ketone peroxide compounds; Ketal compounds; alkyl peroxy ester compounds such as t-butyl peracetate, t-butyl peroxy octoate and t-butyl peroxybenzoate; peroxy carbonate compounds . These may use only 1 type and can also use multiple types together.

  When the thermal polymerization initiator is added, it is preferably added after the step (γ) of dispersing the polyurethane resin (A) and the compound (B) having a polymerizable unsaturated bond in an aqueous medium. The amount of the thermal polymerization initiator is preferably 0.05 to 5% by weight based on the total solid content of the aqueous resin dispersion (including the compound (B) having a polymerizable unsaturated bond).

<Aqueous polyurethane resin (D) having no polymerizable unsaturated bond>
An aqueous polyurethane resin (D) having no polymerizable unsaturated bond can be added to the aqueous resin dispersion of the present invention. The aqueous polyurethane resin is a polyurethane resin that can be dispersed in an aqueous medium. The aqueous medium means not only pure water but also a mixed solvent of water and an organic solvent compatible with water.
The aqueous polyurethane resin (D) having no polymerizable unsaturated bond may be mixed with the aqueous resin dispersion of the present invention in the state of an aqueous polyurethane resin dispersion.
In addition, the weight average molecular weight of the water-based polyurethane resin (D) having no polymerizable unsaturated bond is good in tack-free property of the coating film before being cured with active energy rays obtained by applying the water-based resin dispersion. Therefore, it is preferably 40,000 to 1,000,0000.
As the aqueous polyurethane resin (D) having no polymerizable unsaturated bond, a commercially available product may be used, or in the method for producing the polyurethane resin (A), a hydroxyl group-containing (meth) acrylate (d) may be used. It can also be obtained by producing a polyurethane resin without addition.

<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.
In addition to the aqueous resin dispersion, other resins may 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 at least one hydroxyl group and one polymerizable unsaturated bond 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 isocyanate 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 isocyanate group of the aforementioned polyisocyanate. Examples of the blocking agent include phenols such as phenol and cresol, and fats such as methanol and ethanol. Alcohols, active methylenes such as dimethyl malonate and acetylacetone, mercaptans such as butyl mercaptan and dodecyl mercaptan, acid amides such as acetanilide and acetic acid amide, lactams such as ε-caprolactam and δ-valerolactam, succinic acid Blocking agents such as acid imides such as imide and maleic imide, oximes such as acetoaldoxime, acetone oxime and methyl ethyl ketoxime, and amines such as diphenylaniline, aniline and ethyleneimine .

  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.

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 resin dispersion and the various additives described above, adding an aqueous medium, and adjusting the viscosity according to the coating method. .

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.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited to these.

[Synthesis Example 1]
In a 1000 ml glass round bottom flask equipped with a rectifying column, a stirrer, a thermometer, and a nitrogen introduction tube, 372.0 g (4.13 mol) of dimethyl carbonate, 195.6 g (1.66 mol) of 1,6-hexanediol, The ester exchange reaction was conducted while charging 186.8 g (1.79 mol) of 1,5-pentanediol and 0.05 g of titanium tetrabutoxide and distilling off the mixture of methanol and dimethyl carbonate in a nitrogen stream under normal pressure and stirring. It went for 10 hours. During this time, the reaction temperature was gradually raised from 95 ° C. to 200 ° C., and the composition of the distillate was adjusted to be the azeotropic composition of methanol and dimethyl carbonate or in the vicinity thereof.
Thereafter, the pressure was gradually reduced to 30 mmHg, and a transesterification reaction was further performed at 180 ° C. for 10 hours while distilling off a mixture of methanol and dimethyl carbonate with stirring. After completion of the reaction (after completion of distillation of methanol and dimethyl carbonate), the reaction solution was cooled to room temperature to obtain 439.20 g of polycarbonate diol.
The number average molecular weight (Mn) of the obtained polycarbonate diol is 991, the acid value is 0.05 mgKOH / g, the weight average molecular weight (Mw) is 2900, and the dispersity (Mw / Mn) is 2.2. Met.

[Example 1]
In a reactor equipped with a stirrer and a heater, the polycarbonate diol (PCD, 41.0 g) obtained in Synthesis Example 1, 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. Furthermore, a mixture (DPHA, hydroxyl value 95 mgKOH / g, 181 g) of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate 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, 12.0 g was extracted and ethylene oxide-modified pentaerythritol tetraacrylate (EO-modified PETA, tetraacrylate derived from alcohol obtained by adding 4 mol of ethylene oxide to 1 mol of pentaerythritol; , 2.58 g) and diethylethanolamine (0.56 g, pKa = 11.5) were added and mixed, and then water (27.9 g) was added and stirred vigorously to obtain an aqueous resin dispersion. Obtained.

[Example 2]
In a reactor equipped with a stirrer and a heater, the polycarbonate diol (PCD, 41.0 g) obtained in Synthesis Example 1, 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. Furthermore, a mixture (DPHA, hydroxyl value 95 mgKOH / g, 181 g) of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate 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, 12.0 g was extracted and ethylene oxide-modified pentaerythritol tetraacrylate (EO-modified PETA, tetraacrylate derived from alcohol obtained by adding 4 mol of ethylene oxide to 1 mol of pentaerythritol; 2.58 g) and ethyldiethanolamine (0.63 g, pKa = 10.9) were added and mixed, and then water (27.8 g) was added and stirred vigorously to obtain an aqueous resin dispersion. It was.

[Example 3]
In a reactor equipped with a stirrer and a heater, the polycarbonate diol (PCD, 41.0 g) obtained in Synthesis Example 1, 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. Furthermore, a mixture (DPHA, hydroxyl value 95 mgKOH / g, 181 g) of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate 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, 12.0 g was extracted and ethylene oxide-modified pentaerythritol tetraacrylate (EO-modified PETA, tetraacrylate derived from alcohol obtained by adding 4 mol of ethylene oxide to 1 mol of pentaerythritol; 2.59 g) and methyldiethanolamine (0.57 g, pKa = 10.8) were added and mixed, and then water (27.9 g) was added and stirred vigorously to obtain an aqueous resin dispersion. It was.

[Example 4]
In a reactor equipped with a stirrer and a heater, the polycarbonate diol (PCD, 41.0 g) obtained in Synthesis Example 1, 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. Furthermore, a mixture (DPHA, hydroxyl value 95 mgKOH / g, 181 g) of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate 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, 12.0 g was extracted and ethylene oxide-modified pentaerythritol tetraacrylate (EO-modified PETA, tetraacrylate derived from alcohol obtained by adding 4 mol of ethylene oxide to 1 mol of pentaerythritol; 2.60 g) and triethanolamine (0.71 g, pKa = 7.8) were added and mixed, and then water (27.8 g) was added and stirred vigorously to obtain an aqueous resin dispersion. Obtained.

[Example 5]
In a reactor equipped with a stirrer and a heater, the polycarbonate diol (PCD, 41.0 g) obtained in Synthesis Example 1, 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. Furthermore, a mixture (DPHA, hydroxyl value 95 mgKOH / g, 181 g) of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate 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, 12.0 g was extracted and trimethylolpropane triacrylate (TMPTA, 1.3 g), tripropylene glycol diacrylate (TPGDA, 1.3 g), and diethylethanolamine (0.56 g, pKa = 11). .5) was added and mixed. The reaction mixture was cooled to 45 ° C. and water (28.0 g) was slowly added with stirring to obtain an aqueous resin dispersion.

[Example 6]
In a reactor equipped with a stirrer and a heater, the polycarbonate diol (PCD, 41.0 g) obtained in Synthesis Example 1, 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. Furthermore, a mixture (DPHA, hydroxyl value 95 mgKOH / g, 181 g) of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate 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, 12.0 g was extracted and trimethylolpropane triacrylate (TMPTA, 1.3 g), tripropylene glycol diacrylate (TPGDA, 1.3 g), and methyldiethanolamine (0.57 g, pKa = 10. 8) was added and mixed. Water (27.9 g) was added to the reaction mixture to obtain an aqueous resin dispersion.

[Example 7]
In a reactor equipped with a stirrer and a heater, the polycarbonate diol (PCD, 41.0 g) obtained in Synthesis Example 1, 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. Furthermore, a mixture (DPHA, hydroxyl value 95 mgKOH / g, 181 g) of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate 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, 15.3 g was extracted and trimethylolpropane triacrylate (TMPTA, 1.7 g), tripropylene glycol diacrylate (TPGDA, 1.7 g), and triethanolamine (0.90 g, pKa = 7). .8) was added and mixed. Water (34.1 g) was added to the reaction mixture to obtain an aqueous resin dispersion.

[Example 8]
In a reactor equipped with a stirrer and a heater, the polycarbonate diol (PCD, 41.0 g) obtained in Synthesis Example 1, 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. Furthermore, a mixture (DPHA, hydroxyl value 95 mgKOH / g, 181 g) of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate 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, 12.1 g was extracted and trimethylolpropane triacrylate (TMPTA, 1.3 g), tripropylene glycol diacrylate (TPGDA, 1.3 g), and triethanolamine (0.85 g, pKa = 7). .8) was added and mixed. The reaction mixture was cooled to 45 ° C. and water (26.9 g) was slowly added with stirring to obtain an aqueous resin dispersion.

[Example 9]
In a reactor equipped with a stirrer and a heater, the polycarbonate diol (PCD, 41.0 g) obtained in Synthesis Example 1, 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. Furthermore, a mixture (DPHA, hydroxyl value 95 mgKOH / g, 181 g) of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate 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, 12.3 g was extracted, trimethylolpropane triacrylate (TMPTA, 1.32 g), tripropylene glycol diacrylate (TPGDA, 1.32 g), and triethanolamine (0.63 g, pKa = 7). .8) was added and mixed. The reaction mixture was cooled to 45 ° C. and water (27.4 g) was slowly added with stirring to obtain an aqueous resin dispersion.

[Example 10]
In a reactor equipped with a stirrer and a heater, the polycarbonate diol (PCD, 41.0 g) obtained in Synthesis Example 1, 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. Furthermore, a mixture (DPHA, hydroxyl value 95 mgKOH / g, 181 g) of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate 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, 12.1 g was extracted and trimethylolpropane triacrylate (TMPTA, 1.3 g), tripropylene glycol diacrylate (TPGDA, 1.3 g), and triethanolamine (0.57 g, pKa = 7). .8) was added and mixed. The reaction mixture was cooled to 45 ° C., and water (27.8 g) was slowly added with stirring to obtain an aqueous resin dispersion.

[Example 11]
In a reactor equipped with a stirrer and a heater, the polycarbonate diol (PCD, 41.0 g) obtained in Synthesis Example 1, 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. Furthermore, a mixture (DPHA, hydroxyl value 95 mgKOH / g, 181 g) of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate 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, 12.2 g was extracted and trimethylolpropane triacrylate (TMPTA, 1.3 g), tripropylene glycol diacrylate (TPGDA, 1.3 g), and triethanolamine (0.52 g, pKa = 7). .8) was added and mixed. The reaction mixture was cooled to 45 ° C., and water (28.5 g) was slowly added with stirring to obtain an aqueous resin dispersion.

[Example 12]
In a reactor equipped with a stirrer and a heater, the polycarbonate diol (PCD, 41.0 g) obtained in Synthesis Example 1, 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. Furthermore, a mixture (DPHA, hydroxyl value 95 mgKOH / g, 181 g) of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate 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, 12.0 g was extracted, trimethylolpropane triacrylate (TMPTA, 1.3 g), tripropylene glycol diacrylate (TPGDA, 1.3 g), and triethanolamine (0.46 g, pKa = 7). .8) was added and mixed. The reaction mixture was cooled to 45 ° C. and water (28.2 g) was slowly added with stirring to obtain an aqueous resin dispersion.

[Example 13]
In a reactor equipped with a stirrer and a heater, the polycarbonate diol (PCD, 41.0 g) obtained in Synthesis Example 1, 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. Furthermore, a mixture (DPHA, hydroxyl value 95 mgKOH / g, 181 g) of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate 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, 12.1 g was extracted and trimethylolpropane triacrylate (TMPTA, 1.3 g), tripropylene glycol diacrylate (TPGDA, 1.3 g), and triethanolamine (0.40 g, pKa = 7). .8) was added and mixed. The reaction mixture was cooled to 45 ° C., and water (28.6 g) was slowly added with stirring to obtain an aqueous resin dispersion.

[Example 14]
In a reactor equipped with a stirrer and a heater, the polycarbonate diol (PCD, 41.0 g) obtained in Synthesis Example 1, 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. Furthermore, a mixture (DPHA, hydroxyl value 95 mgKOH / g, 181 g) of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate 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, 12.1 g was extracted and trimethylolpropane triacrylate (TMPTA, 1.3 g), tripropylene glycol diacrylate (TPGDA, 1.3 g), and triethanolamine (0.35 g, pKa = 7). .8) was added and mixed. The reaction mixture was cooled to 45 ° C., and water (28.5 g) was slowly added with stirring to obtain an aqueous resin dispersion.

[Example 15]
In a reactor equipped with a stirrer and a heater, the polycarbonate diol (PCD, 41.0 g) obtained in Synthesis Example 1, 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. Furthermore, a mixture (DPHA, hydroxyl value 95 mgKOH / g, 181 g) of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate 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, 12.1 g was extracted and a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (DPHA, hydroxyl value 95 mgKOH / g, 2.6 g) and triethanolamine (0.57 g, pKa = 7.8) was added and mixed. The reaction mixture was cooled to 45 ° C., and water (27.8 g) was slowly added with stirring to obtain an aqueous resin dispersion.

[Example 16]
In a reactor equipped with a stirrer and a heater, the polycarbonate diol (PCD, 41.0 g) obtained in Synthesis Example 1, 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. Furthermore, a mixture (DPHA, hydroxyl value 95 mgKOH / g, 181 g) of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate 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. 12.0 g was extracted from the reaction mixture, and a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (DPHA, hydroxyl value 42 mgKOH / g, 2.6 g) and triethanolamine (0.57 g, pKa = 7.8) was added and mixed. The reaction mixture was cooled to 45 ° C., and water (27.7 g) was slowly added with stirring to obtain an aqueous resin dispersion.

[Example 17]
In a reactor equipped with a stirrer and a heater, the polycarbonate diol (PCD, 41.0 g) obtained in Synthesis Example 1, 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. Furthermore, a mixture (DPHA, hydroxyl value 95 mgKOH / g, 181 g) of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate 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. 12.1 g was extracted from the reaction mixture, and pentaerythritol tetraacrylate (PETA, 2.6 g) and triethanolamine (0.57 g, pKa = 7.8) were added and mixed. The reaction mixture was cooled to 45 ° C., and water (27.8 g) was slowly added with stirring to obtain an aqueous resin dispersion.

[Example 18]
In a reactor equipped with a stirrer and a heater, the polycarbonate diol (PCD, 41.0 g) obtained in Synthesis Example 1, 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. Furthermore, a mixture (DPHA, hydroxyl value 95 mgKOH / g, 181 g) of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate 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. 12.1 g was extracted from the reaction mixture, and ditrimethylolpropane tetraacrylate (DTMPTA, 2.6 g) and triethanolamine (0.57 g, pKa = 7.8) were added and mixed. The reaction mixture was cooled to 45 ° C., and water (27.8 g) was slowly added with stirring to obtain an aqueous resin dispersion.

[Comparative Example 1]
In a reactor equipped with a stirrer and a heater, the polycarbonate diol (PCD, 41.0 g) obtained in Synthesis Example 1, 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. Furthermore, a mixture (DPHA, hydroxyl value 95 mgKOH / g, 181 g) of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate 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, 12.0 g was extracted and ethylene oxide-modified pentaerythritol tetraacrylate (EO-modified PETA, tetraacrylate derived from alcohol obtained by adding 4 mol of ethylene oxide to 1 mol of pentaerythritol; 2.59 g) and triethylamine (0.48 g, pKa = 10.9) were added and mixed, and then water (28.0 g) was added and stirred vigorously to obtain an aqueous resin dispersion. .

[Comparative Example 2]
In a reactor equipped with a stirrer and a heater, the polycarbonate diol (PCD, 41.0 g) obtained in Synthesis Example 1, 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. Furthermore, a mixture (DPHA, hydroxyl value 95 mgKOH / g, 181 g) of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate 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, 12.0 g was extracted and ethylene oxide-modified pentaerythritol tetraacrylate (EO-modified PETA, tetraacrylate derived from alcohol obtained by adding 4 mol of ethylene oxide to 1 mol of pentaerythritol; 2.58 g) and dimethylethanolamine (0.42 g, pKa = 9.3) are added and mixed, and then water (28.0 g) is added and stirred vigorously to obtain an aqueous resin dispersion. Obtained.

[Comparative Example 3]
In a reactor equipped with a stirrer and a heater, the polycarbonate diol (PCD, 41.0 g) obtained in Synthesis Example 1, 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. Furthermore, a mixture (DPHA, hydroxyl value 95 mgKOH / g, 181 g) of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate 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, 12.0 g was extracted and ethylene oxide-modified pentaerythritol tetraacrylate (EO-modified PETA, tetraacrylate derived from alcohol obtained by adding 4 mol of ethylene oxide to 1 mol of pentaerythritol; 2.59 g) and N-methylmorpholine (0.48 g, pKa = 7.4) were added and mixed, and then water (28.0 g) was added and stirred vigorously to obtain an aqueous resin dispersion. Got.

[Evaluation of transparency of coating film]
Ube Industries as a high molecular weight aqueous urethane resin aqueous dispersion in the aqueous resin dispersion (aqueous ultraviolet curable urethane dispersion composition) (7.0 g) obtained in Examples 1 to 18 and Comparative Examples 1 to 3 UW-5034E (weight average molecular weight of 100,000 or more, no polymerizable unsaturated bond contained, 3.0 g) was added and stirred well. Further, 3 wt% / solid content of a polymerization initiator (IRGACURE500, manufactured by BASF) was added and stirred well to obtain a coating agent. The obtained coating agent was applied to a polycarbonate resin panel so that the final film thickness was 20 microns. Then, the dried coating film was obtained by heat-drying for 30 minutes at 60 degreeC.
About the sample on the polycarbonate obtained above, haze was measured by the method based on JISK7136. In addition, when only the polycarbonate used for the base material was measured, the haze of the base material was 0.2%. The results are shown in Tables 1-7. In the table, “-” means that haze measurement was impossible.

[Evaluation of film transparency after long-term storage]
Ube Industries as a high molecular weight aqueous urethane resin aqueous dispersion in the aqueous resin dispersion (aqueous ultraviolet curable urethane dispersion composition) (7.0 g) obtained in Examples 1 to 18 and Comparative Examples 1 to 3 UW-5034E (weight average molecular weight of 100,000 or more, no polymerizable unsaturated bond contained, 3.0 g) was added and stirred well. After the obtained aqueous resin composition was stored at 40 ° C. for 1 month, 3 wt% / solid content of a polymerization initiator (IRGACURE500, manufactured by BASF) was added to obtain a coating agent. The resulting coating was applied to a polycarbonate resin panel so that the final film thickness was 20 microns. Then, the dried coating film was obtained by heat-drying for 30 minutes at 60 degreeC.
About the sample on the polycarbonate obtained above, haze was measured by the method based on JISK7136. In addition, when only the polycarbonate used for the base material was measured, the haze of the base material was 0.1%. The results are shown in Tables 1-7. In the table, “-” means that haze measurement was impossible.

(Evaluation of storage stability)
The appearance of each of the aqueous resin dispersions of Examples 1 to 18 and Comparative Examples 1 to 3 was observed immediately after production and 1 week after production to confirm storage stability. The evaluation criteria are as follows. The results are shown in Tables 1-7.
○: Aggregates are not seen.
X: Aggregates are observed.

(Evaluation of adhesion)
High-molecular-weight aqueous urethane resin aqueous dispersion in aqueous resin dispersion (aqueous ultraviolet curable urethane dispersion composition) (7.0 g) obtained in Example 10, Examples 15 to 18 and Comparative Examples 1 to 3 UW-5034E (weight average molecular weight 100,000 or more, 3.0 g) manufactured by Ube Industries was added as a body and stirred well. The obtained aqueous resin composition was stored at 40 ° C. for 1 month, and then 5 wt% / solid content of a polymerization initiator (IRGACURE500, manufactured by BASF) was added to obtain a coating agent. The obtained coating was applied to various resin panels so that the final film thickness was 20 microns. Then, the dried coating film was obtained by heat-drying for 30 minutes at 60 degreeC. A high-pressure mercury lamp was used to irradiate the dried coating film with ultraviolet rays so that the integrated light amount was 1000 mJ / cm ² .
About the sample on resin obtained above, adhesiveness was evaluated by the cross-cut peeling 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. The peel test was repeated 10 times.
○: No peeling was observed even after repeating the test 10 times.
Δ: Peeling was observed in the 2-10th test.
X: Peeling was observed in the first test.

NR ₃ / COOH in Tables 1 to 7 represents the ratio of the number of moles of NR ₃ (neutralizing agent) to the number of moles of COOH (acidic group). As the number of moles of the acidic group, the number of moles of the acidic group-containing polyol used for the synthesis of the polyurethane resin was calculated using the number of moles of the neutralizing agent added to the aqueous resin dispersion as the number of moles of the neutralizing agent.
In Table 7, ABS represents acrylonitrile-butadiene-styrene resin, PMMA represents polymethyl methacrylate resin, PC represents polycarbonate resin, and PET represents polyethylene terephthalate resin.

  Whether using N-methylmorpholine (pKa = 7.4) having a lower pKa than a tertiary amine having a hydroxyl group, or using triethylamine (pKa = 10.9) having a higher pKa, the haze of the coating film As can be seen from the above, the degree of effect is not determined by the pKa of the tertiary amine.

  The aqueous resin dispersion of the present invention can be widely used as a raw material for paints, coating agents, primers, adhesives, and the like. In particular, it can be suitably used as a plastic (film) coating agent and its raw material.

Claims (15)

An aqueous resin dispersion in which at least a polyurethane resin (A) having a polymerizable unsaturated bond, a compound (B) having a polymerizable unsaturated bond, and a neutralizing agent (C) are dispersed in an aqueous medium. There,
The polyurethane resin (A) having a polymerizable unsaturated bond reacts at least the polyol (a), the acidic group-containing polyol (b), the polyisocyanate (c), and the hydroxyl group-containing (meth) acrylate (d). It is obtained by
The neutralizing agent (C) is represented by the following general formula (1):

^(Wherein, R 1, ^{R 2} and ^{R 3} each independently represent an alkyl group or hydroxyalkyl group having 1 to 10 carbon atoms having 1 to 10 carbon atoms, provided ^that the R 1, ^{R 2} and ^{R 3} (At least one of them is a hydroxyalkyl group having 1 to 10 carbon atoms, and the total carbon number of R ¹ , R ² and R ³ is 5 to 20).
A water-based resin dispersion, which is a tertiary amine represented by the formula:   The aqueous resin dispersion according to claim 1, wherein the neutralizing agent (C) is at least one selected from the group consisting of diethylethanolamine, ethyldiethanolamine, methyldiethanolamine, and triethanolamine.   The aqueous resin dispersion according to claim 1 or 2, wherein the neutralizing agent (C) is triethanolamine.   The aqueous ratio according to any one of claims 1 to 3, wherein the ratio of the number of moles of the neutralizing agent (C) to the number of moles of acidic groups in the polyurethane resin (A) is 0.65 to 0.95. Resin dispersion.   The aqueous resin dispersion according to any one of claims 1 to 4, wherein the compound (B) having a polymerizable unsaturated bond is a (meth) acrylate that does not contain a polyethylene glycol structure.   Compound (B) having a polymerizable unsaturated bond is a mixture of dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrimethylolpropane tetra (meth) The aqueous resin dispersion according to any one of claims 1 to 5, which is at least one selected from the group consisting of acrylates.   The aqueous resin dispersion according to any one of claims 1 to 6, wherein the polyol (a) is a polycarbonate diol.   The total amount of the hydroxyl group-containing (meth) acrylate (d) and the compound (B) having a polymerizable unsaturated bond is 65 to 75% by weight of the entire resin solid content of the aqueous resin dispersion. The aqueous resin dispersion according to any one of the above.   Reaction for obtaining a polyurethane resin (A) by using a polyurethane resin (A) having a polymerizable unsaturated bond as a mixture of a hydroxyl group-containing (meth) acrylate (d) with a (meth) acrylate that is inert to an isocyanato group The aqueous resin dispersion according to claim 1, wherein the aqueous resin dispersion is obtained by using the product.   A mixture of the hydroxyl group-containing (meth) acrylate (d) and the (meth) acrylate inert to the isocyanato group is a dipentaerythritol penta (meth) acrylate having a hydroxyl value of 80 to 120 mgKOH / g or more and dipentaerythritol hexa ( The aqueous resin dispersion according to claim 9, which is a mixture with (meth) acrylate.   Furthermore, the aqueous resin dispersion of any one of Claims 1-10 containing the aqueous polyurethane resin (D) which does not have a polymerizable unsaturated bond.   The aqueous resin dispersion according to claim 11, wherein the aqueous polyurethane resin (D) having no polymerizable unsaturated bond has a weight average molecular weight of 40,000 to 1,000,000.   A curable composition comprising the aqueous resin dispersion according to any one of claims 1 to 12 and a polymerization initiator.   The coating composition containing the aqueous resin dispersion of any one of Claims 1-12.   The coating agent composition containing the aqueous resin dispersion of any one of Claims 1-12.