JP2015078274A - Aqueous resin dispersion composition and their use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous resin dispersion composition providing coated film having high adhesion property to various plastic such as PMMA and PET.SOLUTION: There is provided an aqueous resin dispersion composition by dispersing at least a polyurethane resin (A), a compound having a polymerizable unsaturated bond (B) and colloidal silica (C) in an aqueous solvent where the colloidal silica (C) is 15 to 40 wt.% based on the total weight of (A), (B) and (C), and there are also provided a curable composition, a coating composition and a coating agent composition containing the aqueous resin dispersion. The concentration of the polymerizable unsaturated bond is preferably 2.7 to 6.0 mmol/g. The particle size of the colloidal silica is preferably 18 to 50 nm.

Description

  TECHNICAL FIELD The present invention relates to an aqueous resin dispersion composition that can be cured by active energy rays such as ultraviolet rays or heat, and use thereof.

  Polycarbonate polyol is a useful compound that can be used as a raw material for polyurethane resins, and can react with isocyanate compounds to produce polyurethane resins used in rigid foams, flexible foams, paints, adhesives, synthetic leather, ink binders, and the like. . 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 is known to be used as an undercoat agent because of improved adhesion to a substrate and blocking resistance. (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.

  For the purpose of increasing the coating film hardness and chemical resistance, the use of urethane (meth) acrylate has also been studied, for example, an aqueous radiation resin composition comprising a (meth) acrylated polyurethane (see Patent Document 3), And the aqueous radiation-curable composition (refer patent document 4) containing a (meth) acrylated polyurethane and an ethylenically unsaturated compound is proposed. Such an aqueous radiation curable composition gives a hard coating film excellent in chemical resistance. For example, automotive interior materials, mobile phone housings, home appliance housings, personal computer housings, decorative films, optical films, etc. 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 films and flooring.

  Further, as a method for further improving the chemical resistance of the aqueous radiation curable composition, a composition comprising colloidal silica and an aqueous radiation irradiation curable composition has been proposed (see Patent Document 5). Such an aqueous radiation curable composition is excellent in chemical resistance, and can be used for a painted metal material or the like.

JP-A-10-120757 JP 2005-281544 A JP 2010-202869 A Special table 2009-533504 gazette Japanese Patent No. 4246061

However, when an aqueous radiation curable composition as disclosed in Patent Documents 3 and 4 is used, adhesion to a plastic substrate, particularly adhesion to polymethyl methacrylate (PMMA) or polyethylene terephthalate (PET). There was a drawback that was not enough.
Even when the method of adding colloidal silica described in Patent Document 5 is applied, the adhesion to PMMA and PET may be low.

  The present invention provides a water-based resin dispersion composition having a high adhesion to a plastic substrate, in particular, a high adhesion to PMMA and PET, and a coating film having a high hardness, and having excellent storage stability for at least one week. The issue is to provide goods.

  As a result of various studies to overcome the problems of the prior art, the present inventors have found that at least the polyurethane resin (A) (hereinafter also referred to as “(A)”) and polymerizable unsaturated. An aqueous resin dispersion obtained by dispersing a compound (B) having a bond (hereinafter also referred to as “(B)”) and colloidal silica (C) (hereinafter also referred to as “(C)”) in an aqueous medium. An aqueous resin dispersion composition characterized in that the colloidal silica (C) is 15 to 40% by weight in the total weight of (A), (B), and (C). The knowledge that the problem can be solved by the use has been obtained, and the present invention has been achieved.

The present invention (1) is an aqueous resin dispersion composition comprising at least a polyurethane resin (A), a compound (B) having a polymerizable unsaturated bond, and colloidal silica (C) dispersed in an aqueous medium. The content of the colloidal silica (C) is 15 to 40% by weight based on the total weight of (A), (B) and (C), and the aqueous resin dispersion composition is characterized in that About.
In the present invention (2), the concentration of the polymerizable unsaturated bond in the total weight of the polyurethane resin (A), the compound (B) having a polymerizable unsaturated bond and the colloidal silica (C) is 2.7 to 6. It is 0 mmol / g, It is related with the aqueous resin dispersion composition as described in this invention (1) characterized by the above-mentioned.
The present invention (3) relates to the aqueous resin dispersion composition according to the present invention (1) or (2), wherein the colloidal silica (C) has a particle size of 18 to 50 nm.
In the present invention (4), the polyurethane resin (A) is at least a polyol (Aa) having no acidic group, an acidic group-containing polyol (Ab), a polyisocyanate (Ac), and a hydroxyl group-containing (meth) acrylate. It is related with the aqueous resin dispersion composition as described in any one of said this invention (1)-(3) obtained by making (Ad) react.
In the invention (5), the hydroxyl group-containing (meth) acrylate (Ad) is a polyurethane as a mixture of dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate having a hydroxyl value of 80 to 120 mgKOH / g. It is related with the aqueous resin dispersion composition as described in the said this invention (4) attached | subjected to reaction for obtaining resin (A).
The present invention (6) relates to a curable composition containing the aqueous resin dispersion composition according to any one of the present inventions (1) to (5) and a polymerization initiator.
The present invention (7) relates to a coating composition containing the aqueous resin dispersion composition according to any one of the present inventions (1) to (5).
The present invention (8) relates to a coating agent composition containing the aqueous resin dispersion composition according to any one of the present inventions (1) to (5).
The present invention (9) relates to a laminate in which a layer obtained by applying and drying the coating composition according to the present invention (7) is laminated on at least one surface of a synthetic resin layer.
The present invention (10) relates to a laminate in which a layer obtained by applying and drying the coating composition according to the present invention (8) is laminated on at least one surface of a synthetic resin layer.
The present invention (11) relates to the laminate according to the present invention (9) or (10), wherein the synthetic resin layer is a polymethyl methacrylate resin layer or a polyethylene terephthalate resin layer.

  According to the present invention, an aqueous resin dispersion having a high adhesion to a plastic substrate, in particular, a high adhesion to PMMA and PET, and a coating with high hardness and excellent storage stability for at least one week. A body composition can be provided.

The present invention is an aqueous resin dispersion composition in which at least a polyurethane resin (A), a compound (B) having a polymerizable unsaturated bond, and colloidal silica (C) are dispersed in an aqueous medium.
The polyurethane resin (A) is obtained by reacting at least a polyol (Aa) having no acidic group, an acidic group-containing polyol (Ab), and a polyisocyanate (Ac). A polymerizable unsaturated bond-containing compound (Ad) having a hydroxyl group may be reacted, and further a chain extender (D) may be reacted.
A polyurethane resin obtained by reacting a polymerizable unsaturated bond-containing compound (Ad) having a hydroxyl group is preferable from the viewpoint of increasing the hardness of the resulting coating film. Moreover, since the tack-free property of the coating film before ultraviolet curing increases, a polyurethane resin reacted with the chain extender (D) is preferable.
A polyurethane resin obtained by reacting a polymerizable unsaturated bond-containing compound (Ad) having a hydroxyl group with a chain extender (D), or a polyurethane resin and a chain obtained by reacting a polymerizable unsaturated bond-containing compound (Ad) having a hydroxyl group. More preferably, a polyurethane resin reacted with the extender (D) is used in combination.

<Polyurethane resin (A)>
<< Polyol (Aa) not having an acidic group >>
As the polyol (Aa) having no acidic group (hereinafter also referred to as “(Aa)”), for example, a high molecular weight polyol or a low molecular weight polyol can be used. From the viewpoint of ease of production of the aqueous resin dispersion composition, it is preferable to use a high molecular weight diol or a low molecular weight diol.
The acidic group is a carboxy group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group or the like, and does not include a hydroxyl group bonded to an aliphatic hydrocarbon or an alicyclic hydrocarbon.

  Although the said high molecular weight polyol does not have a restriction | limiting in particular, It is preferable that a number average molecular weight is 400-8000. If the number average molecular weight is in this range, an appropriate viscosity and good handleability can be easily obtained. It is easy to ensure the performance as a soft segment, and when a coating film is formed using the aqueous resin dispersion composition containing the obtained polyurethane resin, it is easy to suppress the occurrence of cracks, and further polyisocyanate (Ac) And the polyurethane resin (A) can be produced efficiently. The polyol (Aa) having no acidic group is more preferably a high molecular weight polyol having a number average molecular weight of 400 to 4000, and particularly preferably a high molecular weight diol having a number average molecular weight of 800 to 4000.

  In the present specification, the number average molecular weight is a number average molecular weight calculated based on a hydroxyl value measured in accordance with JIS K 1577. Specifically, the hydroxyl value is measured, and is calculated as (56.1 × 1000 × valence) / hydroxyl value [mgKOH / g] by a terminal group quantification method. In the above formula, the valence is the number of hydroxyl groups in one molecule.

  Examples of the high molecular weight polyol include polycarbonate 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 composition containing the obtained polyurethane resin and the coating film obtained therefrom, polycarbonate diol is preferred.

  Among the polycarbonate diols, the diol component is preferably an aliphatic diol and / or an alicyclic diol, and the diol component is an aliphatic diol from the viewpoint of good water dispersibility of the polyurethane resin (A). More preferred.

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

  Although the said polyol monomer used as the raw material of the said polycarbonate polyol is not restrict | limited in particular, For example, an aliphatic polyol monomer, a polyol monomer which has an alicyclic structure, an aromatic polyol monomer, a polyester polyol monomer, a polyether polyol monomer etc. are mentioned.

  The aliphatic polyol monomer is not particularly limited. For example, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 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, Examples include branched aliphatic diols such as 5-pentanediol and 2-methyl-1,9-nonanediol; trifunctional or more polyhydric alcohols such as trimethylolpropane and pentaerythritol.

  The polyol monomer having an alicyclic structure is not particularly limited, and examples thereof include 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, , 4-cycloheptanediol, 2,5-bis (hydroxymethyl) -1,4-dioxane, 2,7-norbornanediol, tetrahydrofuran dimethanol, 1,4-bis (hydroxyethoxy) cyclohexane, etc. Examples thereof include diols having a cyclic structure.

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

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

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

  The carbonate ester is 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. Among these, aliphatic carbonates are preferable and dimethyl carbonate is particularly preferable because of easy manufacture of polycarbonate polyols.

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

  The polyester diol as the high molecular weight polyol is not particularly limited. For example, polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyhexamethylene isophthalate adipate diol, polyethylene succinate diol, polybutylene succinate diol. Polyethylene sebacate diol, polybutylene sebacate diol, poly-ε-caprolactone diol, poly (3-methyl-1,5-pentylene adipate) diol, polycondensate of 1,6-hexanediol and dimer acid, etc. Is mentioned.

  The polyether diol as the high molecular weight polyol is not particularly limited. For example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide and propylene oxide, ethylene oxide and butylene oxide random copolymer, block copolymer, etc. Is mentioned. Further, a polyether polyester polyol having an ether bond and an ester bond may be used.

  The low molecular weight polyol is not particularly limited, and examples thereof include those having a number average molecular weight of 60 or more and less than 400. For example, ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol Aliphatic diol having 2 to 9 carbon atoms such as diethylene glycol, triethylene glycol and tetraethylene glycol; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-bis (Hydroxyethyl) cyclohexane, 2,7-norbornanediol, tetrahydrofuran 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.

  The polyol (Aa) which does not have an acidic group may be used independently and may use multiple types together.

<< Acid group-containing polyol (Ab) >>
The acidic group-containing polyol (Ab) (hereinafter also referred to as “(Ab)”) 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 (Ab) preferably contains a compound having two hydroxyl groups and one carboxy group in one molecule. An acidic group containing polyol (Ab) may be used independently and may use multiple types together.

  Specific examples of the acidic group-containing polyol (Ab) include 2,2-dimethylolpropionic acid, dimethylolalkanoic acid such as 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 them, from the viewpoint of easy availability, dimethylol alkanoic acid having 4 to 12 carbon atoms containing two methylol groups is preferable, and 2,2-dimethylolpropionic acid is more preferable among dimethylolalkanoic acids.

  In the present invention, the total number of hydroxyl equivalents of the polyol (Aa) having no acidic group and the acidic group-containing polyol (Ab) is preferably 120 to 600. If the number of hydroxyl equivalents is within this range, the aqueous resin dispersion composition 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 resulting aqueous resin dispersion composition and the hardness of the coating film obtained by coating, the number of hydroxyl equivalents is preferably 130 to 600, more preferably 150 to 500, and particularly preferably 170 to 400. It is.

The number of hydroxyl equivalents can be calculated by the following formulas (1) and (2).
Number of hydroxyl equivalents of each polyol = molecular weight of each polyol / number of hydroxyl groups of each polyol (1)
Total number of hydroxyl equivalents of polyol = M / total number of moles of polyol (2)
In the case of the polyurethane resin (A), in the formula (2), M is [[number of hydroxyl equivalents of polyol (Aa) having no acidic group × number of moles of polyol (Aa) having no acidic group] + [ The number of hydroxyl group equivalents of the acidic group-containing polyol (Ab) × the number of moles of the acidic group-containing polyol (Ab)]].

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

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

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

  Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2 -Isocyanatoethyl) -4-dichlorohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane (hydrogenated XDI), etc. Can be mentioned.

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

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

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

<< Hydroxyl group-containing (meth) acrylate (Ad) >>
In some cases, a hydroxyl group-containing (meth) acrylate (Ad) (hereinafter also referred to as “(Ad)”) can be used as a raw material for the polyurethane resin (A). The hydroxyl group-containing (meth) acrylate may be a (meth) acrylate having a primary hydroxyl group or a secondary hydroxyl group-containing (meth) acrylate. In view of shortening the production time of the polyurethane resin (A), a (meth) acrylate having a primary hydroxyl group is preferred.
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. In addition, “(meth) acryloyl compound”, “(meth) acrylate”, and “(meth) acrylate” in the present specification are concepts including a compound having an acryloyl group and a compound having a methacryloyl group. And may have both an acryloyl group and a methacryloyl group.

  Among the hydroxyl group-containing (meth) acrylates (Ad), those that are primary hydroxyl group-containing (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl. (Meth) acrylate, glycerin 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) acrylate 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.

  Among the hydroxyl group-containing (meth) acrylates (Ad), those that are secondary hydroxyl group-containing (meth) acrylates include adducts of glycidyl (meth) acrylate and (meth) acrylic acid, glycerin mono (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 (meta Reaction product of acrylic acid and 1 molecule of bisphenol A diglycidyl (eg, “DA-250” manufactured by Nagase ChemteX Corp.) Reaction of 2 molecules of (meth) acrylic acid and diglycidyl compound of propylene oxide adduct of bisphenol A Product: Reaction product of 2 molecules of (meth) acrylic acid and 1 molecule of diglycidyl phthalate (eg “DA-721” manufactured by Nagase Chemtech) 2 molecules of (meth) acrylic acid and 1 molecule of polyethylene Reaction product with glycol diglycidyl (eg, “DM-811”, “DM-832”, “DM-851” manufactured by Nagase Chemtech) 2 molecules (meth) acrylic acid and 1 molecule polypropylene glycol diglycidyl Reaction products of (meth) acrylic acid and polyol diglycidyl such as reaction products of

  Among them, those having 3 or more (meth) acryloyl groups in one molecule are preferable from the viewpoint of increasing the hardness after curing with active energy rays (for example, ultraviolet rays). As such (meth) acrylate, diglycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, Examples include dipentaerythritol penta (meth) acrylate, sorbitol tri (meth) acrylate, and sorbitol tetra (meth) acrylate.

  The number of (meth) acryloyl groups in one molecule has only primary hydroxyl groups in that the production time of the polyurethane resin (A) can be shortened among the hydroxyl group-containing (meth) acrylates having 3 or more hydroxyl groups ( More preferred is (meth) acrylate. Examples of such (meth) acrylates include pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate. From the viewpoint of the hardness of the coating film and the production time, dipentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate are particularly preferable.

  The hydroxyl group-containing (meth) acrylate (Ad) may be used alone or in combination of two or more.

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

  The hydroxyl group-containing (meth) acrylate (Ad) can be subjected to a reaction for obtaining the polyurethane resin (A) as a mixture with (meth) acrylate that is inert to the isocyanato group. The (meth) acrylate that is inert to the unreacted isocyanato group constitutes the compound (B) having a polymerizable unsaturated bond.

  As the mixture, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, commercially available dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) Examples thereof include a mixture with acrylate, a mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, and the like. 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. The hydroxyl value is preferably 80 to 130 mgKOH / g from the viewpoint of suppressing an increase in viscosity during production of the polyurethane resin (A) and avoiding gelation. More preferably, the hydroxyl value is 85 to 120 mg KOH / g. Examples of the mixture of dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate having a hydroxyl value of 80 mgKOH / g or more include Aronix M403 manufactured by Toagosei Co., Ltd.

  Moreover, the mixture of a pentaerythritol triacrylate and a pentaerythritol tetraacrylate can also be used as a mixture. 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. A more preferred hydroxyl value is 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 (Ad) is preferably 25 to 70% by weight in the weight of the polyurethane resin (A). Within this range, the reaction time of the hydroxyl group-containing (meth) acrylate (Ad) and the isocyanato group should be within an appropriate time, and the coating film hardness after curing with active energy rays (for example, ultraviolet rays) should be within an appropriate range. And the storage stability of the aqueous resin dispersion composition containing the obtained polyurethane resin can be kept good. The hydroxyl group-containing (meth) acrylate (Ad) is more preferably 30 to 70% by weight.

  Hydroxyl group-containing (meth) acrylate (Ad) is mixed with isocyanato group-inactive (meth) acrylate (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 0.3 to 4.0 times the weight of the polyurethane resin (A) from the viewpoint of the hardness of the obtained coating film and the stability of the aqueous resin dispersion composition, and more Preferably, 1.0 to 2.5 It is.

  When the hydroxyl group-containing (meth) acrylate (Ad) is used, the polyol (Aa) having no acidic group, the acidic group-containing polyol (Ab), and the number of moles of all hydroxyl groups of the hydroxyl group-containing (meth) acrylate (Ad) The ratio of the number of isocyanato groups in the polyisocyanate (Ac) is preferably 0.1 to 0.9.

  Within this range, it is easy to avoid the problem that the reaction time is prolonged due to the too few moles of hydroxyl groups, while the polyol having no unreacted acidic group (Aa) due to too many moles of hydroxyl groups. ), Acidic group-containing polyol (Ab), and hydroxyl group-containing (meth) acrylate (Ad) remain in large amounts, and the problem of reduced storage stability can be easily avoided. The ratio of the number of moles of isocyanato groups of the polyisocyanate (Ac) to the number of moles of all hydroxyl groups is preferably 0.15 to 0.8, particularly preferably 0.2 to 0.7.

  The reaction of polyol (Aa) having no acidic group, acidic group-containing polyol (Ab), polyisocyanate (Ac) and hydroxyl group-containing (meth) acrylate (Ad) is obtained by (Aa), (Ab), (Ad). They may be reacted with (Ac) in any order, and a plurality of types may be mixed and reacted with (Ac). The hydroxyl group-containing (meth) acrylate (Ad) may be subjected to the reaction as a mixture with (meth) acrylate that is inert to the isocyanato group.

  When reacting the polyol (Aa) having no acidic group, the acidic group-containing polyol (Ab), the hydroxyl group-containing (meth) acrylate (Ad) and the polyisocyanate (Ac), a catalyst may be used.

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

  Although the reaction temperature at the time of making it react is not restrict | limited in particular, 40-120 degreeC is preferable. If it is this range, the solubility of the raw material is good, the viscosity of the obtained urethane resin (A) is appropriate and can be sufficiently stirred, the (meth) acryloyl group causes a polymerization reaction, gelled, Problems such as the isocyanato group causing side reactions are less likely to occur. The reaction temperature is more preferably 60 to 100 ° C.

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

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

  As the polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, benzoquinone, 2-tert-butylhydroquinone, p-tert-butylcatechol, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, 2, Quinone polymerization inhibitors such as 5-bis (1,1-dimethylbutyl) hydroquinone; 2,6-bis (1,1-dimethylethyl) -4-methylphenol, 2,6-di-tert-butylphenol, 2 , 4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, etc. Alkylphenol polymerization inhibitors; aromatic amine polymerization inhibitors such as phenothiazine; alkylated diph Nilamine, N, N′-diphenyl-p-phenylenediamine, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1 , 4-dihydroxy-2,2,6,6-tetramethylpiperidine, 1-hydroxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine, di-p-fluorophenylamine, 2,2 Amine polymerization inhibitors such as 1,6,6-tetramethylpiperidine-1-oxyl (TEMPO); 2,2-diphenylpicrylhydrazyl (DPPH), tri-p-nitrophenylmethyl, N- (3N-oxyanilino) Quaternary anions such as -1,3-dimethylbutylidene) -aniline oxide, benzyltrimethylammonium chloride, etc. Nitric chloride; diethylhydroxylamine, cyclic amide, nitrile compound, substituted urea, benzothiazole, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 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 with respect to a total of 100 parts by weight of the polyol (Aa) having no acidic group, the acidic group-containing polyol (Ab), the hydroxyl group-containing (meth) acrylate (Ad) and the polyisocyanate (Ac). 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight.

  The reaction with the polyol (Aa) having no acidic group, the acidic group-containing polyol (Ab), the polyisocyanate (Ac) and the hydroxyl group-containing (meth) acrylate (Ad) may be carried out without a solvent, or an organic solvent. May be performed in the presence of Examples of the organic solvent include acetone, ethyl methyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N-ethylpyrrolidone, and ethyl acetate. Among these, acetone, ethyl methyl ketone, and ethyl acetate are preferable because the polyurethane resin (A) can be removed by heating and decompression after being dispersed in water. Further, N-methylpyrrolidone and N-ethylpyrrolidone are preferable because they function as a film-forming aid when a coating film is prepared using the aqueous resin dispersion composition containing the obtained polyurethane resin.

  The amount of the organic solvent is preferably based on weight based on the total amount of polyol (Aa) having no acidic group, acidic group-containing polyol (Ab), hydroxyl group-containing (meth) acrylate (Ad) and polyisocyanate (Ac). Is 0 to 2.0 times, more preferably 0.05 to 0.7 times. If it is this range, the process which removes an organic solvent takes time, the dispersibility to the water of the obtained polyurethane resin is also favorable, and in the coating film produced using the aqueous resin dispersion composition, The problem that the organic solvent remains and the physical properties of the coating film deteriorate can be avoided.

<Chain extender (D)>
In some cases, a compound having reactivity with an isocyanato group can be used as the chain extender (D) (hereinafter also referred to as “D”). For example, ethylenediamine, 1,4-tetramethylenediamine, 2-methyl-1,5-pentanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-hexamethylenediamine, 3-aminomethyl -Amines such as 3,5,5-trimethylcyclohexylamine, 1,3-bis (aminomethyl) cyclohexane, xylylenediamine, piperazine, adipoylhydrazide, hydrazine, 2,5-dimethylpiperazine, diethylenetriamine, triethylenetetramine Compounds, diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, polyalkylene glycols typified by polyethylene glycol, water, etc., among which primary diamine compounds are preferred. And the like. These may be used alone or in combination of two or more.

  When the chain extender (D) is used, the amount of (D) can be appropriately selected. When an aqueous polyurethane resin dispersion is produced by the second production method described below, the isocyanate group in the chain extender other than water and a group having reactivity with the isocyanate group in the polyurethane prepolymer are in a molar ratio. It can be used in an amount of 2: 1 or less. The molar ratio is more preferably 1: 1 to 0.8: 1.

  Moreover, in this invention, a terminal terminator can be used as needed. Specific examples of the terminal stopper include monoamines such as n-butylamine, di-n-butylamine and diethanolamine; monohydric alcohols such as ethanol, isopropanol and butanol. These terminal stoppers may be used alone or Two or more kinds are mixed and used. Moreover, you may use with the chain extender mentioned above.

<Compound (B) having polymerizable unsaturated bond>
The aqueous resin dispersion composition of the present invention contains a compound (B) 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 (meth) acrylate is preferable.

  Examples of the radical polymerizable compound include (meth) acrylate monomers and (meth) acrylate polymers.

  Examples of the (meth) acrylate of the monomers include poly (meth) acrylate such as mono (meth) acrylate, di (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate. And (meth) acrylate.

  Examples of the mono (meth) acrylate include acryloylmorpholine, 2-ethylhexyl (meth) acrylate, styrene, methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, 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 the di (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di (meth). Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, polyethylene glycol-polypropylene glycol di (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene) 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 the tri (meth) acrylate include trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate. , Alkylene oxide-modified trimethylolpropane tri (meth) acrylate (BASF, Laromer (registered trademark) PO33F) such as ethylene oxide (6 mol) modified trimethylolpropane tri (meth) acrylate (BASF, Laromer (registered trademark) LR8863) Etc.

  Examples of the tetra (meth) acrylate include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and ethylene oxide (4 mol) -modified pentaerythritol tetra (meth) acrylate (Daicel Cytec, Ebecryl 40). An alkylene oxide-modified pentaerythritol tetra (meth) acrylate such as

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

  As said hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate etc. are mentioned, for example.

As the (meth) acrylate of the polymers, known ones can be used.
Examples of the (meth) acrylates of the polymers include poly (meth) acrylates such as polyurethane (meth) acrylate, polyester (meth) acrylate compounds, and polyalkylene (meth) acrylate compounds.

  Among these radically polymerizable compounds, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( Meth) acrylates and mixtures thereof are preferred.

  These radically polymerizable compounds may use only 1 type and may use multiple types.

  In order to obtain a polyurethane resin (A), when subjected to the reaction as a mixture of a hydroxyl group-containing (meth) acrylate (Ad) and a (meth) acrylate having no group capable of reacting with an isocyanato group, the isocyanate contained in the reaction system The (meth) acrylate having no group capable of reacting with the group can constitute the compound (B) having a polymerizable unsaturated bond.

The concentration of the polymerizable unsaturated bond of the hydroxyl group-containing (meth) acrylate (Ad) component and the compound (B) having a polymerizable unsaturated bond in the polyurethane resin (A) is (A), (B), (C ) To a total weight of 2.7 to 6.0 mmol / g. When the concentration of the polymerizable unsaturated bond relative to the total weight of (A), (B), and (C) is 2.7 mmol / g or more, the coating film produced using the aqueous resin dispersion composition Hardness can be increased. Moreover, the storage stability of the aqueous resin dispersion composition can be improved by setting the concentration of the polymerizable unsaturated bond to 6.0 mmol / g or less. The total amount of the compound (B) having a polymerizable unsaturated bond relative to the total weight of (A), (B), and (C) is more preferably 3.0 to 5.5 mmol / g, still more preferably. Is 3.3-5.0 mmol / g.
The concentration of the polymerizable unsaturated bond can be calculated by the following formula.

[Equation 1]
Concentration of polymerizable unsaturated bond [mmol / g] = (mmol of compound having polymerizable unsaturated bond [mmol]) × (number of polymerizable unsaturated bonds in one molecule) / ((A), ( B), (C) total weight [g])

In the formula for calculating the concentration of the polymerizable unsaturated bond, the number of millimoles of the compound having a polymerizable unsaturated bond can be calculated from the charged amount of the raw material, and can also be measured by ¹ H-NMR.
In addition, when there are multiple types of compounds having polymerizable unsaturated bonds, the "polymerizable unsaturated bond concentration" of each compound having polymerizable unsaturated bonds is calculated and added to obtain a total polymerizable property. The concentration of unsaturated bonds can be calculated.

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

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

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

In the present invention, the acid value of the aqueous resin dispersion 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 Composition] = [Number of Mole of Acidic Group in Acidic Group-Containing Polyol (Ab)] × 56.11 / [Total Polyurethane Resin (A) and Compound (B) Having Polymerizable Unsaturation Bond Weight] ... (3)
The acid value is more preferably 12 to 70 mgKOH / g, and still more preferably 14 to 60 mgKOH / g.

  In the present invention, when the solid content of the polyurethane resin aqueous dispersion is 100 parts by weight, the proportion of the polyol (Aa) having no acidic group is 2 to 50 parts by weight, and the proportion of the acidic group-containing polyol (Ab) It is preferable to prepare the polyurethane resin (A) so as to be 1 to 15 parts by weight.

If the ratio of the polyol (Aa) which does not have an acidic group 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. Moreover, if the ratio of acidic group containing polyol (Ab) is the said range, the water resistance of a coating film will be favorable and the dispersibility to the aqueous medium of a polyurethane resin (A) can also be made favorable.
When the solid content of the polyurethane resin aqueous dispersion is 100 parts by weight, the proportion of the polyol (Aa) having no acidic group is more preferably 3 to 40 parts by weight, and particularly preferably 5 to 30 parts by weight. The ratio of the acidic group-containing polyol (Ab) is more preferably 2 to 10 parts by weight, particularly preferably 3 to 7 parts by weight.

<Neutralizing agent>
The neutralizing agent for neutralizing the acidic group of the polyurethane resin (A) includes trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, dimethylethanolamine, diethylethanolamine. Organic amines such as N-methylmorpholine and pyridine; inorganic alkalis such as sodium hydroxide and potassium hydroxide; ammonia and the like. Among these, organic amines are preferable, tertiary amines are more preferable, and triethylamine is most preferable. These may be used alone or in combination of two or more.

<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. Therefore, the aqueous medium and the neutralizing agent 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>
The manufacturing method in particular of an aqueous polyurethane resin dispersion (A) is not restrict | limited, For example, the following manufacturing methods are mentioned.
The first production method is a method of obtaining an aqueous polyurethane resin dispersion by mixing all the raw materials, reacting them, and dispersing them in an aqueous medium.
The second production method involves reacting a polyol compound (Aa), an acidic group-containing polyol compound (Ab), and a polyisocyanate (Ac), and optionally a hydroxyl group-containing (meth) acrylate (Ad), to form a polyurethane prepolymer. This is a method for producing an aqueous polyurethane resin dispersion by producing and neutralizing acidic groups of the polyurethane prepolymer, then dispersing in an aqueous medium, and optionally reacting with a chain extender (D). As a manufacturing method of the aqueous polyurethane resin dispersion of the present invention, the second manufacturing method is preferable from the viewpoint of dispersibility.
The compound (B) having a polymerizable unsaturated bond may be dispersed in an aqueous medium after being mixed with the polyurethane prepolymer, or may be separately dispersed in an aqueous medium simultaneously with the polyurethane prepolymer, The compound (B) having a polymerizable unsaturated bond may be added in advance in an aqueous medium, and then the polyurethane prepolymer may be added and dispersed in the aqueous medium.

Specifically, the aqueous polyurethane resin dispersion of the present invention can be obtained by a method including the following steps.
Polyurethane prepolymer or polyurethane resin by reacting polyol (Aa) having no acidic group, acidic group-containing polyol compound (Ab), and polyisocyanate (Ac), and optionally hydroxyl group-containing (meth) acrylate (Ad) Obtaining step (1);
Step (2) of neutralizing acid groups in the polyurethane prepolymer or polyurethane resin with an acidic group neutralizing agent;
A step (3) of dispersing the neutralized polyurethane prepolymer or polyurethane resin and the compound (B) having a polymerizable unsaturated bond in an aqueous medium; and a chain extender in the polyurethane prepolymer dispersed in the aqueous medium Step (4).

  When the chain extender (D) is used, what is obtained in the step (1) is a polyurethane prepolymer, the polyurethane prepolymer is neutralized in the step (2), and neutralized in the step (3). The finished polyurethane prepolymer is dispersed in an aqueous medium, and the step (4) is performed. When step (4) is performed, steps (3) and (4) may be performed simultaneously. Further, after dispersing the polyurethane prepolymer in a solvent other than water, it is further mixed with water, and then the solvent is distilled off to obtain a desired aqueous polyurethane resin dispersion. In this case, water also functions as a chain extender.

  When the chain extender (D) is not used, what is obtained in the step (1) is a polyurethane resin, the polyurethane resin is neutralized in the step (2), and neutralized in the step (3). The polyurethane resin was dispersed in an aqueous medium, and the step (4) was not performed.

  The step (1) 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 reaction temperature in the step (1) can be carried out at 0 to 120 ° C. in order to avoid unnecessary polymerization of polymerizable unsaturated bonds. Preferably it is 0-100 degreeC.

  In the step (3), as long as the polyurethane prepolymer, the polyurethane resin (A), and the compound (B) having a polymerizable unsaturated bond can be dispersed in an aqueous medium, the method and operation order thereof are particularly limited. Not. For example, a method in which (B) is mixed with a polyurethane prepolymer or polyurethane resin (A) and dispersed in an aqueous medium, or a polyurethane prepolymer or polyurethane resin (A) is mixed in (B) and dispersed in an aqueous medium. A method in which (B) is mixed and dispersed after the polyurethane prepolymer or polyurethane resin (A) is dispersed in an aqueous medium, or a polyurethane prepolymer or polyurethane resin after (B) is dispersed in an aqueous medium. A method of mixing and dispersing (A), a method of mixing polyurethane prepolymers and polyurethane resins (A) and (B) after being dispersed in an aqueous medium, and production of polyurethane prepolymers and polyurethane resins (A) A method in which (B) is sometimes mixed and dispersed in an aqueous medium is exemplified.

  In the step (1), when the hydroxyl group-containing (meth) acrylate (Ad) is subjected to a reaction as a mixture with an (meth) acrylate that is inert to an isocyanato group, the (meth) acrylate that is inert to the isocyanato group is a polyurethane. Along with the prepolymer and the polyurethane resin (A), it is contained in the reaction product of the step (1), is subjected to the step (2) and the step (3), and is polymerizable in the final aqueous resin dispersion. The compound (B) having an unsaturated bond is constituted. In this case, an acidic group neutralizing agent is added to the reaction product of the step (1), and is dispersed in the aqueous dispersion medium together with the compound (B) having a further polymerizable unsaturated bond in the step (3). Can do. When the compound (B) having a further polymerizable unsaturated bond is added, the compound (B) having a further polymerizable unsaturated bond may be diluted with an aqueous medium.

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

  The step (3) is preferably performed in the presence of oxygen in order to avoid unnecessary consumption of the polymerizable unsaturated bond. Moreover, you may add a polymerization inhibitor as needed. The temperature at which the polyurethane prepolymer or polyurethane resin (A) and the compound (B) having a polymerizable unsaturated bond are mixed is 0 to 100 ° C. in order to avoid unnecessary consumption of the polymerizable unsaturated bond. It is preferably carried out at 0 to 90 ° C, more preferably at 0 to 80 ° C, particularly preferably at 50 to 70 ° C.

  In the production method of the present invention, either the step (2) or the step (3) may be performed first or at the same time. In this case, each component may be mixed at once, or an acidic group neutralizing agent is previously mixed in an aqueous medium or (B), and these are mixed with a polyurethane prepolymer or polyurethane resin (A). Also good.

  The number average molecular weight of the polyurethane resin (A) in the aqueous resin dispersion is preferably 1,000 to 1,000,000.

  Two or more kinds of polyurethane resins (A) in the aqueous resin dispersion can be mixed and used. From the point of coexistence of hardness and tack-free property, from polyol (Aa) having no acidic group, acidic group-containing polyol (Ab), polyisocyanate (Ac), and hydroxyl group-containing (meth) acrylate (Ad) A polyurethane resin (A ′), a polyol (Aa) having no acidic group, an acidic group-containing polyol (Ab), a polyisocyanate (Ac), and a chain extender (D). 2) are preferably used in combination.

<Colloidal silica (C)>
Colloidal silica is a colloid composed of fine particles of inorganic oxide containing silicon having an average particle size of several 300 nm or less. Silicon dioxide (including hydrates thereof) may be included as a main component, and aluminate may be included as a minor component. Examples of the aluminate that may be contained as a minor component include sodium aluminate and potassium aluminate.

  In addition, colloidal silica may contain inorganic salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide, and organic salts such as tetramethylammonium hydroxide. These inorganic salts and organic salts act, for example, as colloid stabilizers.

There is no restriction | limiting in particular as a dispersion medium of colloidal silica, Any of water, an organic solvent, and these mixtures may be sufficient. The organic solvent may be a water-soluble organic solvent or a water-insoluble organic solvent, but is preferably a water-soluble organic solvent. Specifically, methanol, ethanol, isopropyl alcohol, n-propanol etc. can be mentioned.
The dispersion medium is preferably water from the viewpoint of easy mixing with the aqueous resin dispersion.

  There is no restriction | limiting in particular in the manufacturing method of colloidal silica, It can manufacture by the method used normally. For example, it can be produced from aerosil synthesis by thermal decomposition of silicon tetrachloride or water glass. Alternatively, it can also be produced by a liquid phase synthesis method such as hydrolysis of alkoxide.

Although there is no restriction | limiting in particular as an average particle diameter of the particle | grains contained in the colloidal silica in this invention, Preferably it is 15-100 nm, More preferably, it is 18-50 nm, More preferably, it is 20-30 nm.
If the average particle size is less than 15 nm, the pencil hardness, adhesion, and storage stability of the resin water dispersion composition may be lowered. When the average particle size is larger than 100 nm, the storage stability of the resin water dispersion may be lowered, or the transparency of the coating film may be lowered.
In the present invention, the average particle diameter of colloidal silica can be measured by a method such as a light scattering method or a laser diffraction method, which is a general measurement of dispersed particles. In the present invention, however, a TEM (transmission type) is more directly used. In a photograph taken by an electron microscope) photographing method, the particle size of 300 colloidal silica particles was measured, and the average value was taken as the average particle size.
In the present invention, the particle diameter of colloidal silica refers to an image of 30 arbitrary colloidal silica particles in a photograph taken by a TEM (transmission electron microscope) photographing method, and the longest diameter of the image of each particle. It is an average diameter obtained by using the following formula using (φ _L ) and the shortest diameter (φ _S ).
[Equation 1]
Particle size = {(φ _L1 + φ _L2 +... + Φ _L30 ) + (φ _S1 + φ _S2 +... + Φ _S30 )} / (2 × 30)
Note that, in the formula, phi _L1 is a phi _L of first images, phi _L2 is a phi _L of the second image, phi _S1 is a phi _S of first images, phi _S2 are two representing the φ _S of the eye of the image.

  Moreover, the shape of the colloidal silica which can be used is not specifically limited. For example, any of a spherical shape, a long shape, a needle shape, and a bead shape may be used.

  The colloidal silica that can be used in the present invention may be one produced by the above production method or a commercial product. Specific examples of commercially available products include, for example, Ludox AM, Ludox AS, Ludox LS, Ludox TM, Ludox HS and the like (manufactured by EI Du Pont de Nemours &Co); SNOWTEX S, SNOWTEX XS, SNOWTEX 20, Snowtex 30, Snowtex 40, Snowtex N, Snowtex C, Snowtex CM, Snowtex QAS, Snowtex O (above, manufactured by Nissan Chemical Co., Ltd.); Syton C-30, Syton ZOO, etc. (above, Monsanto Co); Nalcoag-1060, Nalcoag-ID 21-64 (above, Nalco Chem Co); methanol sol, IPA sol, MEK sol, and toluene sol, Quattron PL-1, PL-3, PL- 7, PL-20 (manufactured by Fuso Chemical Industries); Cataloid-S, Cataloid-F120, Cataloid SI-350, Cataloid SI-500, Cataloid SI-30, Cataloid S-20L, Cataloid S-20H, Cataloid S-30L , Cataloid S-30H, Cataloid SI-40, OSCAL-1432 (isopropyl alcohol sol), etc. (above, manufactured by JGC Catalysts &Chemicals); Adelite (manufactured by Asahi Denka Co., Ltd.); As beaded colloidal silica, for example, Snowtex ST- UP, SNOWTEX PS-S, SNOWTEX PS-M, SNOWTEX ST-OUP, SNOWTEX PS-SO, SNOWTEX PS-MO (above, manufactured by Nissan Chemical Co., Ltd.) Which can be easily obtained.

  The pH of the commercially available colloidal silica dispersion is often adjusted to be acidic or alkaline. This is because the stable dispersion region of colloidal silica exists on the acidic side or alkaline side. When commercially available colloidal silica is added to the aqueous resin dispersion, the pH of the stable dispersion region of colloidal silica and the aqueous resin dispersion It is necessary to add it in consideration of the pH. From the viewpoint of excellent storage stability of the aqueous resin dispersion to which colloidal silica is added, it is preferable to use a colloidal silica dispersion that is stable in a neutral pH range (pH 6-8). Examples of such colloidal silica dispersion include Snowtex C, Snowtex CM, (manufactured by Nissan Chemical Co., Ltd.); Quartron PL-1, PL-3, PL-7, PL-20 (more, Fuso Chemical). Industrial)).

The content of the colloidal silica (C) in the aqueous resin dispersion composition of the present invention includes the total weight of the polyurethane resin (A), the compound (B) having a polymerizable unsaturated bond, and the colloidal silica (C). On the other hand, it is preferably 15% by weight or more and 40% by weight or less. More preferably, it is 22 wt% or more and 35 wt% or less of the total amount of the composition, and particularly preferably 27 wt% or more and 32 wt% or less.
When the amount of colloidal silica (C) added is 15% by weight or less, the hardness and adhesion may not be sufficient. When the addition amount is 40% by weight or more, the hardness of the coating film, the transparency, and the storage stability of the resin water dispersion may be insufficient or the film may not be formed.

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

  The aqueous resin dispersion composition 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>
The aqueous resin dispersion composition of the present invention can be made into a photocurable composition by adding a photopolymerization initiator. 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 compounds include acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, benzophenone, 2-chlorobenzophenone, p, p′-bisdiethylaminobenzophenone, benzoin ethyl ether, benzoin n-propyl ether, Benzoin isopropyl ether, benzoin isobutyl ether, benzoin n-butyl ether, benzoin dimethyl ketal, thioxanthone, p-isopropyl-α-hydroxyisobutylphenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl -1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-hydroxy-2-methyl-1-phenylpro Down-1-one, 2,4,6, - trimethyl benzophenone, 4-methylbenzophenone, 2,2-dimethoxy-1,2-diphenyl-ethanone, and the like. These may use only 1 type and can also use multiple types together. Preferably, 1-hydroxycyclohexyl phenyl ketone is used.

  When adding a photoinitiator, it is preferable to add after the said process (3). The amount of the photopolymerization initiator is 0.1 to 5% by weight with respect to the total solid content of the aqueous resin dispersion composition (including the compound (B) having a polymerizable unsaturated bond and colloidal silica (C)). Is preferred.

<Thermal polymerization initiator>
The aqueous resin dispersion composition of the present invention can be made into a thermosetting composition by adding a thermal polymerization initiator. As the thermal polymerization initiator, known ones such as organic peroxides can be used. Examples of these compounds include azo compounds; diacyl peroxide compounds; peroxy ester compounds; hydroperoxide compounds; dialkyl peroxide compounds; ketone peroxide compounds; peroxy ketal compounds; Examples include oxyester compounds; peroxycarbonate compounds. These may use only 1 type and can also use multiple types together.

  When adding a thermal polymerization initiator, it is preferable to add after the said process (3). The amount of the thermal polymerization initiator is 0.01 to 5% by weight based on the total solid content of the aqueous resin dispersion composition (including the compound (B) having a polymerizable unsaturated bond and colloidal silica (C)). Is preferred.

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

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

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

As the acrylic resin, a hydroxyl group-containing acrylic resin is preferable. Hydroxyl group-containing acrylic resin is a hydroxyl group-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer, for example, in a solution polymerization method in an organic solvent, in water It can manufacture by making it copolymerize by known methods, such as an emulsion polymerization method.
The hydroxyl group-containing polymerizable unsaturated monomer is a compound having 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 compounds having two or more isocyanato groups in one molecule, such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.

  Examples of the blocked polyisocyanate include those obtained by adding a blocking agent to the polyisocyanate group of the aforementioned polyisocyanate. Examples of the blocking agent include phenols such as phenol and cresol, methanol, ethanol and the like. Fatty 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 Blocking agents such as acid imides, acid imides such as maleic imides, oximes such as acetoaldoxime, acetone oxime, methyl ethyl ketoxime, amines such as diphenylaniline, aniline, ethyleneimine The

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

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

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

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

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 in particular, PMMA resin (poly (meth) acrylic resin), ABS resin (acrylonitrile-butylene-styrene resin), PET resin (polyethylene terephthalate resin). High adhesion to For this reason, as the material to be coated and the material to be coated, poly (meth) acrylate resin, ABS resin and PET 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 0.01-100 micrometers is preferable. More preferably, it is preferable to form a coating film having a thickness of 0.1 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, Polycarbonate Diol]
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, A transesterification reaction was carried out while 186.8 g (1.79 mol) of 1,5-pentanediol and 0.05 g of titanium tetrabutoxide were charged and a mixture of methanol and dimethyl carbonate was distilled off in a nitrogen stream under normal pressure and stirring. 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 carried out 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 of the obtained polycarbonate diol was 1054, and the acid value was 0.05 mgKOH / g.

[Synthesis Example 2, UV-PUD-1]
In a reactor equipped with a stirrer and a heater, the polycarbonate diol produced in Synthesis Example 1 (number average molecular weight 1054; hydroxyl value 106 mg KOH / g, 41.0 g) and 2,2-dimethylolpropionic acid (14.4) g) and isophorone diisocyanate (56.7 g) in N-ethylpyrrolidone (45.9 g) in the presence of dibutyltin dilaurate (0.2 g) at 80 to 90 ° C. under nitrogen atmosphere. Heated for hours. 2,6-Di-tert-butyl-4-methylphenol (0.4 g) and 4-methoxyphenol (0.4 g) were added and the atmosphere was air. Further, a mixture of dipentaerystol hexaacrylate and dipentaerythritol pentaacrylate (hydroxyl value 95 mg KOH / g, polymerizable unsaturated bond concentration 9.63 mmol / g, 181 g) was added, and the mixture was at 90 ° C. for 7 hours. Heated. The NCO group content at the end of the urethanization reaction was 0.23% by weight. From the reaction mixture, 57.9 g was extracted, cooled to 70 ° C., and a mixture of dipentaerystol hexaacrylate and dipentaerythritol pentaacrylate (hydroxyl value 41 mg KOH / g, polymerizable unsaturated bond concentration 9.63 mmol). / G, 14.2 g) and triethylamine (2.8 g) were added and mixed. The reaction mixture was cooled to 45 ° C. and water (136 g) was slowly added with stirring to obtain an aqueous resin dispersion. The concentration of the polymerizable unsaturated bond in the solid content of the obtained aqueous resin dispersion was 6.74 mmol / g.

[Synthesis Example 3, UV-PUD-2]
In a reaction vessel equipped with a stirrer and a heater, ETERNACOLL (registered trademark) UM90 (1/1) (manufactured by Ube Industries; number average molecular weight 916; hydroxyl value 122 mgKOH / g; polyol component is 1,4-cyclohexanedimethanol: 1,6-hexanediol = 1: 1 molar ratio of a polyol mixture obtained by reacting with a carbonate ester, 179 g), 2,2-dimethylolpropionic acid (31.8 g), Isophorone diisocyanate (169 g) was heated in N-ethylpyrrolidone (163 g) in the presence of dibutyltin dilaurate (0.3 g) at 80 to 90 ° C. for 3.5 hours. The NCO group content at the end of the urethanization reaction was 5.04% by weight.
The reaction mixture was cooled to 80 ° C., and triethylamine (24.0 g) was added and mixed thereto. A reaction mixture (517 g), a mixture of pentaerythritol triacrylate (PETA) and dipropylene glycol diacrylate (DPGDA) (weight ratio 1: 1, polymerizable unsaturated bond concentration 9.16 mmol / g, 147 g) Mix and add into water (1438 g) under vigorous stirring. Subsequently, 35% by weight of an aqueous 2-methyl-1,5-pentanediamine solution (89.5 g) was added to obtain an aqueous resin dispersion. The concentration of polymerizable unsaturated bonds in the solid content of the obtained aqueous resin dispersion was 2.49 mmol / g.

[Synthesis Example 4, PUD]
In a reaction apparatus equipped with a stirrer and a heater, ETERNCOLLUC UC100 (manufactured by Ube Industries; number average molecular weight 964; hydroxyl value 116 mg KOH / g; polycarbonate diol obtained by reacting 1,4-cyclohexanedimethanol and carbonate, 200 g), 2,2-dimethylolpropionic acid (29.7 g), 1,4-butanediol (1.3 g), and hydrogenated MDI (197 g) in N-ethylpyrrolidone (180 g), The mixture was heated at 80 to 90 ° C. for 6 hours in the presence of dibutyltin dilaurate (0.4 g) under a nitrogen atmosphere. The NCO group content at the end of the urethanization reaction was 4.13% by weight. The reaction mixture was cooled to 80 ° C., and triethylamine (22.2 g) was added and mixed thereto. From the reaction mixture, 488 g was extracted and added into water (767 g) under vigorous stirring. Subsequently, 35% by weight 2-methyl-1,5-pentanediamine aqueous solution (72 g) was added to obtain an aqueous polyurethane resin dispersion. The concentration of the polymerizable unsaturated bond in the solid content of the obtained aqueous polyurethane resin dispersion was 0 mmol / g.

[Example 1]
Snowtex CM (Nissan Chemical, particle size 20-30 nm, solid content 30%, 3.0 g) was added to UV-PUD-1 (solid content 30%, 7.0 g) produced in Synthesis Example 2 with stirring. It was. The concentration of the polymerizable unsaturated bond in the solid content of the obtained aqueous polyurethane resin dispersion composition was 4.7 mmol / g.
Further, 3 wt% / solid content of a polymerization initiator (IRGACURE500, manufactured by BASF) was added and stirred well to obtain a coating agent.

[Examples 2-7, Comparative Examples 1-8]
UV-PUD-1, UV-PUD-2, PUD, and colloidal silica were mixed so that the weight ratio in the solid content was the number shown in the table. Tables 1 and 2 show the concentration of polymerizable unsaturated bonds in the obtained aqueous polyurethane resin dispersion composition.
Further, 3 wt% / solid content of a polymerization initiator (IRGACURE500, manufactured by BASF) was added and stirred well to obtain a coating agent.

(Evaluation of storage stability)
The appearance of each coating agent of Examples 1 to 7 and Comparative Examples 1 to 8 was observed 1 week after production and 3 months after production to confirm the storage stability. The evaluation criteria are as follows.
○: No thickening is observed.
X: Thickening is seen.

[Evaluation of tack-free]
The finger was pressed against the coating film obtained above (before UV irradiation), and the state of the coating film was observed.
The state of the coating film was evaluated in the following three stages.
X: The coating film is attached to the hand, ○: The fingerprint is not attached to the coating film.

[Evaluation of transparency of coating film]
The coating agents obtained in Examples 1 to 7 and Comparative Examples 1 to 8 were applied to a polycarbonate resin panel so that the final film thickness was 10 to 20 μm. 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 the polycarbonate obtained above, it measured by the method based on JISK7136. In addition, when only the polycarbonate resin panel used for the base material was measured, the haze of the coating film was 0.2%.

(Evaluation of hardness)
It evaluated by measuring the pencil hardness of a polyurethane resin coating film.
[Measurement of pencil hardness]
The coating agents obtained in Examples 1 to 7 and Comparative Examples 1 to 8 were applied to a PMMA resin panel so that the final film thickness was 10 to 20 μm. 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 .
In the polyurethane resin coating film on the PMMA resin obtained above, the pencil hardness of the resin coating film was measured by a method based on JIS K 5600-5-4.
Note that “H-2H” indicates an intermediate hardness between “H” and “2H”.

(Evaluation of adhesion)
The coatings obtained in Examples 1 to 7 and Comparative Examples 1 to 8 were applied to various resin panels so that the final film thickness was 10 to 20 μm. 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.
(Number of sheets not peeled) / 25, “25/25” indicates that no peeling occurred.
In addition, the resin of the resin panel used by adhesive evaluation is as follows.
PMMA: Polymethyl methacrylate resin ABS: Acrylonitrile-butylene-styrene resin PET: Polyethylene terephthalate resin

In Table 1 and Table 2, each symbol described as a colloidal silica grade represents the following.
CM: Snowtex CM made by Nissan Chemical, particle size 20-30nm, solid content 30%
PL-7: Fuso Chemical's Quartron PL-7, particle size 75 nm, solid content 23%
C: Nissan Chemical Snowtex C, particle size 10-15 nm, solid content 20%

It turns out that the direction of Examples 1-5 using UV-PUD-1 can obtain a coating film with high pencil hardness compared with Examples 6 and 7 using UV-PUD-2.
In addition, Examples 1 to 4 using colloidal silica having a particle size of 20 nm or more are more excellent in storage stability than Examples 5 to 7 using colloidal silica having a particle size of less than 20 nm. I understand.
Furthermore, it turns out that Example 2 and 3 containing UV-PUD and PUD are excellent in tack-free property compared with Example 1 using only UV-PUD.
Compared to Example 3 using colloidal silica having a particle size of more than 50 nm, Example 2 using colloidal silica having a particle size of 50 nm or less has a small coating film haze and is excellent in transparency.

  The aqueous resin dispersion composition 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 (11)

  An aqueous resin dispersion composition in which at least a polyurethane resin (A), a compound (B) having a polymerizable unsaturated bond, and colloidal silica (C) are dispersed in an aqueous medium, the colloidal silica Content of (C) is 15 to 40 weight% with respect to the total weight of (A), (B), and (C), The aqueous resin dispersion composition characterized by the above-mentioned.   The concentration of the polymerizable unsaturated bond in the total weight of the polyurethane resin (A), the compound (B) having a polymerizable unsaturated bond and the colloidal silica (C) is 2.7 to 6.0 mmol / g. The aqueous resin dispersion composition according to claim 1, wherein   The aqueous resin dispersion composition according to claim 1 or 2, wherein the colloidal silica (C) has a particle size of 18 to 50 nm.   The polyurethane resin (A) reacts at least a polyol (Aa) having no acidic group, an acidic group-containing polyol (Ab), a polyisocyanate (Ac), and a hydroxyl group-containing (meth) acrylate (Ad). The aqueous resin dispersion composition as described in any one of Claims 1-3 obtained by the above.   In order to obtain a polyurethane resin (A) as a mixture of dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate having a hydroxyl value of 80 to 120 mgKOH / g as the hydroxyl group-containing (meth) acrylate (Ad). The aqueous resin dispersion composition according to claim 4, which is subjected to the reaction of   The curable composition containing the aqueous resin dispersion composition as described in any one of Claims 1-5, and a polymerization initiator.   The coating composition containing the aqueous resin dispersion composition as described in any one of Claims 1-5.   The coating agent composition containing the aqueous resin dispersion composition as described in any one of Claims 1-5.   A laminate in which a layer obtained by applying and drying the coating composition according to claim 7 is laminated on at least one surface of a synthetic resin layer.   The laminated body by which the layer which apply | coated and dried the coating agent composition of Claim 8 was laminated | stacked on the at least 1 surface of the synthetic resin layer.   The laminate according to claim 9 or 10, wherein the synthetic resin layer is a polymethyl methacrylate resin layer or a polyethylene terephthalate resin layer.