TW201329160A - Water-based polyurethane resin dispersion and use thereof - Google Patents

Abstract

The present invention provides a water-based polyurethane resin dispersion which can provide a coating film having an excellent adhesion-free before curing by irradiating an active energy ray, and can provide a coating film having a high condensation with various plastics after curing by irradiating an active energy ray at the same time. The present invention provides a water-based polyurethane resin dispersion, a light-curable composition containing said water-based polyurethane resin dispersion and a photopolymerization initiator, and a coating composition or a coating agent composition containing said water-based polyurethane resin dispersion, said water-based polyurethane resin dispersion including at least a polyurethane resin (A) with a polymerism unsaturated bond and a polyurethane resin (B) without a polymerism unsaturated bond dispersed in an aqueous medium; wherein said polyurethane resin (B) is obtained by having at least a polyhydric alcohol (Ba), a polyhydric alcohol containing acidic group (Bb), a polyisocyanate ester (Bc) and a chain elongation agent (Bd) react with one another, and the content rate of alicyclic structure of said polyurethane resin (B) is 16 to 70 weight %.

Description

Aqueous polyurethane resin dispersion and use thereof

The present invention relates to an aqueous amine ester resin dispersion which can be cured by irradiation with an active energy ray such as ultraviolet rays, and uses thereof.

The polycarbonate polyol is a compound which is used as a raw material of a polyurethane resin, and can be produced by reacting with an isocyanate compound, and can be used for a rigid foam, a soft foam, a paint, an adhesive, a synthetic leather, an ink adhesive ( Ink binder) and other polyurethane resin. In addition, a coating film obtained by coating an aqueous polyurethane resin dispersion containing a polycarbonate polyol as a raw material is known, and is excellent in light resistance, heat resistance, hydrolysis resistance, and oil resistance (see Patent Document 1).

Among them, a coating film obtained by coating an aqueous amine ester resin dispersion of an aliphatic polycarbonate polyol is known, because it improves the adhesion to the substrate and antiblocking property, so It is used as a primer (refer to Patent Document 2).

On the other hand, the radically polymerizable compound is generally excellent in curability because it is a method other than heating, and is generally considered to be particularly advantageous from the viewpoint of productivity and energy saving. Free radical polymerization The active energy ray-curable resin composition of the compound is used as an active ingredient of various coatings and adhesives such as a metal coating material, a protective coating material for various plastic films, a woodworking paint, and a printing ink according to such characteristics. . For example, it has been reported that an energy ray-curable aqueous resin composition is obtained by dispersing a (meth) acrylate compound in an aqueous polyurethane resin dispersion (see Patent Document 3). This method is characterized in that a coating film having high hardness after ultraviolet curing can be obtained.

Prior technical literature Patent literature

[Patent Document 1] Japanese Patent Laid-Open No. Hei 10-120757

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-281544

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2008-248014

However, in the aqueous polyurethane resin dispersion using a polycarbonate polyol as a raw material, when only an aliphatic polycarbonate polyol is used as the polycarbonate polyol, the aqueous polyurethane resin dispersion may be coated. The problem of insufficient adhesion and hardness of the coating film. For example, in the field of paints and coating agents for synthetic resin molded bodies such as interior materials for automobiles, mobile phone cases, home appliance housings, personal computer cases, decorative films, optical films, flooring, etc., pencils are required. The hardness is "H" or more, but the aqueous polyurethane resin dispersion using only the aliphatic polycarbonate polyol has a problem that the hardness is insufficient.

On the other hand, for the energy ray-curable water-based resin composition, There is a disadvantage that the coating film before hardening by irradiation with an active energy ray is inferior in tack-free. If it is not sticky, when it is used as a coating agent, contamination of a coating film such as dust adhesion is likely to occur. Further, when a component such as a film composed of a plurality of layers is used, there is a possibility that it is difficult to laminate the coating film. Further, the coating film after ultraviolet curing of the composition has a problem that the adhesion to various plastic substrates such as PMMA resin and ABS resin is insufficient.

An object of the present invention is to provide an aqueous polyurethane resin dispersion which is an active energy ray (for example, ultraviolet ray)-curable aqueous polyurethane resin dispersion which exhibits excellent non-stickiness by curing the active energy ray before curing. The coating film which has been cured by irradiation with an active energy ray is excellent in adhesion to various plastics.

The inventors of the present invention conducted various studies in order to overcome the problems of the prior art described above, and as a result, it was found that a polyurethane resin (A) having a polymerizable unsaturated bond was dispersed by using an aqueous medium, and specifically, it was not polymerizable. The aqueous polyurethane resin dispersion of the bond of the polyurethane resin (B) can solve the problem. According to the present invention, it is possible to obtain a coating film which is excellent in non-stickiness before curing by irradiation with an active energy ray, and at the same time, it is possible to obtain a coating film which is cured by irradiation with an active energy ray and has high adhesion to various plastics.

The present invention relates to an aqueous polyurethane resin dispersion in which at least a polyurethane resin (A) having a polymerizable unsaturated bond and a polyurethane resin (B) having no polymerizable unsaturated bond are dispersed in an aqueous medium. Wherein the aforementioned polyurethane resin (B) is at least a polyol (Ba), containing an acid The polyol (Bb), the polyisocyanate (Bc), and the chain extender (Bd) are reacted, and the urethane structure content of the polyurethane resin (B) is 16 to 70% by weight.

The present invention relates to the aqueous polyurethane resin dispersion according to the first aspect of the invention, wherein the polyol (Ba)-based polycarbonate polyol.

The invention is directed to the aqueous polyurethane resin dispersion according to the invention 2, wherein the polyol (Ba) is a polycarbonate polyol having an alicyclic structure content of 20 to 65% by weight.

The present invention relates to an aqueous polyurethane resin dispersion according to any one of the items 1 to 3 of the present invention, which is characterized in that the aqueous polyurethane resin dispersion of the polyurethane resin (A) is dispersed in an aqueous medium, and The aqueous medium is obtained by dispersing the above polyurethane resin (the aqueous polyurethane resin dispersion of B).

The present invention relates to an aqueous polyurethane resin dispersion according to the present invention, wherein the aqueous polyurethane resin dispersion in which the polyurethane resin (A) is dispersed in the aqueous medium and the aqueous polyurethane resin (B) dispersed in the aqueous medium are water-based. The weight ratio of the polyurethane resin dispersion is from 80:20 to 30:70.

The aqueous polyurethane resin dispersion according to any one of the present invention, wherein the polyurethane resin (B) has an alicyclic structure content of 29 to 60% by weight.

The aqueous polyurethane resin dispersion according to any one of the present invention, wherein the polyurethane resin (A) is at least a polyol (Aa) and an acid group-containing polyol. (Ab), polyisocyanate (Ac), and one or more polymerizable unsaturated bonds and one or more hydroxy groups The compound of the base (Ad) is obtained by reaction.

The present invention relates to an aqueous polyurethane resin dispersion according to the seventh aspect of the invention, wherein the polyurethane resin (A) is supplied as an aqueous polyurethane which is dispersed in an aqueous medium and has a polyurethane resin (A) and has One or more compounds having a polymerizable unsaturated bond (Ae).

The present invention relates to an aqueous polyurethane resin dispersion according to the invention of claim 7 or 8, wherein the compound (Ad) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups has three or more polymerizations. A compound having an unsaturated bond and one or more hydroxyl groups.

According to a tenth aspect of the invention, the aqueous polyurethane resin dispersion of the present invention, wherein the compound (Ad) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups has five or more polymerizable properties A compound having a saturated bond and one or more hydroxyl groups.

The aqueous polyurethane resin dispersion according to any one of the present invention, wherein the one or more polymerizable unsaturated bonds and one or more hydroxyl groups (Ad) It is supplied as a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate.

The aqueous polyurethane resin dispersion according to any one of the items 7 to 11, wherein the polyurethane resin (A) has one or more polymerizable unsaturated bonds and 1 The weight ratio of the compound of more than one hydroxyl group (Ad) is 55 to 75% by weight.

The present invention relates to the aqueous polyurethane resin dispersion according to any one of the items 7 to 12, wherein the aforementioned polyol (Aa) is polycondensed. Carbonate polyol.

The present invention relates to a photocurable composition comprising the aqueous polyurethane resin dispersion according to any one of the items 1 to 13 of the present invention, and a photopolymerization initiator.

The present invention relates to a coating composition comprising the aqueous polyurethane resin dispersion according to any one of the items 1 to 13 of the present invention.

The present invention is directed to a coating composition comprising the aqueous polyurethane resin dispersion according to any one of the items 1 to 13 of the present invention.

According to the present invention, it is possible to provide an aqueous polyurethane resin dispersion which is excellent in non-stickiness before being cured by irradiation with an active energy ray. Moreover, according to the present invention, it is possible to provide an aqueous polyurethane resin dispersion which has high hardness by a coating film which is cured by irradiation with an active energy ray. The aqueous polyurethane resin dispersion system of the present invention can be used as a raw material for coatings, coating agents, and coating compositions.

The present invention relates to an aqueous polyurethane resin dispersion which is at least dispersed in an aqueous medium: a polyurethane resin (A) having a polymerizable unsaturated bond (hereinafter also referred to as (A)) and having no polymerizable unsaturated bond An aqueous polyurethane resin dispersion of the polyurethane resin (B) (hereinafter also referred to as (B)); wherein the polyurethane resin (B) having no polymerizable unsaturated bond is at least a polyol (Ba) and an acidic group Polyol (Bb), polyisocyanate (Bc) The alicyclic structure content of the polyurethane resin (B) which is obtained by the reaction of the chain extender (Bd) and which does not have a polymerizable unsaturated bond is 16 to 70% by weight.

<Polyurethane resin (A) having a polymerizable unsaturated bond>

The polyurethane resin (A) having a polymerizable unsaturated bond which can be used in the present invention is not particularly limited, and at least a polyol (Aa), an acid group-containing polyol (Ab), a polyisocyanate (Ac), and The polyurethane resin obtained by reacting one or more polymerizable unsaturated bonds with one or more hydroxyl group-containing compounds (Ad) may preferably be in the form of an aqueous polyurethane dispersion dispersed in an aqueous medium.

<Polyol (Aa)>

The polyol (Aa) (hereinafter also referred to as (Aa)) which can be used in the present invention may, for example, be a high molecular weight polyol (for example, a polycarbonate polyol, a polyester polyol, a polyether polyol, etc.) and a low molecular weight. Polyol. In terms of ease of production of the polyurethane resin (A), it is preferred to use a high molecular weight diol and a low molecular weight diol. Further, a polyol containing two or more hydroxyl groups and one or more acidic groups in one molecule is contained in an acid group-containing polyol (Ab).

The high molecular weight diol is not particularly limited, and the number average molecular weight is preferably from 400 to 8,000. When the number average molecular weight is in this range, appropriate viscosity and good handleability can be easily obtained. Moreover, it is easy to ensure the performance as a soft segment, and when a coating film is formed using the aqueous polyurethane resin dispersion containing the obtained polyurethane resin, it is easy to suppress the occurrence of cracks, and the polyisocyanate (Ac) The reactivity is sufficient, and the polyurethane resin (A) can be efficiently produced. The number average molecular weight of the polyol (Aa) is preferably from 400 to 4,000.

In the present specification, the number average molecular weight is calculated based on the hydroxyl value measured in accordance with JIS K 1557. Specifically, the hydroxyl value was measured and calculated by the terminal group quantitative method based on (56.1 × 1000 × valence) / hydroxyl value [mgKOH / g]. In the above formula, the valence is the number of hydroxyl groups in one molecule.

Examples of the high molecular weight diol include a polycarbonate diol, a polyester diol, and a polyether diol. The polycarbonate is obtained from the aqueous polyurethane resin dispersion containing the polyurethane resin and the coating film obtained by using the aqueous polyurethane resin dispersion in terms of light resistance, heat resistance, hydrolysis resistance, and oil resistance. A diol is preferred.

Further, among the polycarbonate diols, the diol component is preferably an aliphatic diol and/or an alicyclic diol, and the diol component is preferably an aliphatic diol. That is, a polycarbonate diol having no alicyclic structure is preferred.

The polycarbonate polyol can be obtained by reacting one or more kinds of polyol monomers with a carbonate or phosgene. It is preferable to use a polycarbonate polyol obtained by reacting one or more kinds of polyol monomers with a carbonate in terms of ease of production and point of non-produced terminal chloride.

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

The aliphatic polyol monomer is not particularly limited, and examples thereof include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-. a linear aliphatic diol such as hexanediol, 1,7-heptanediol, 1,8-octanediol or 1,9-nonanediol; 2-methyl-1,3-propanediol, 2-methyl Branched chain aliphatic 2 such as keto-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,9-nonanediol Alcohol; a trifunctional or higher polyhydric alcohol such as 1,1,1-trimethylolpropane or neopentyl alcohol.

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

The aromatic polyol monomer is not particularly limited, and examples thereof include 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, and 4,4'-naphthalene dimethanol. 3,4'-naphthalene dimethanol and the like.

The polyester polyol monomer is not particularly limited, and examples thereof include polyester polyols of hydroxycarboxylic acids and diols such as polyester polyols of 6-hydroxycaproic acid and hexanediol, and adipic acid and hexane. A polyester polyol such as a dicarboxylic acid such as an alcohol polyester polyol or a diol.

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

The carbonate is not particularly limited, and examples thereof include an aliphatic carbonate such as dimethyl carbonate or diethyl carbonate, an aromatic carbonate such as diphenyl carbonate, and a cyclic carbonate such as ethyl carbonate. Further, phosgene or the like which can produce a polycarbonate polyol can also be used. Among them, in terms of the ease of producing the above polycarbonate polyol, an aliphatic carbonate is preferred, and dimethyl carbonate is particularly preferred.

As a method of producing a polycarbonate polyol from a polyol monomer and a carbonate, for example, a carbonate is added to the reactor, and relative to the carbonic acid The molar number of the ester is a polyol having an excess molar number, and is reacted at a temperature of 160 to 200 ° C and a pressure of about 50 mmHg for 5 to 6 hours, and further reacted at 200 to 220 ° C under a pressure of several mmHg or less. The method of hours. On the other hand, it is preferred to carry out the reaction while the alcohol produced by the above reaction is taken out of the system. At this time, when the mixture is taken out of the system by azeotropy with the alcohol produced by the carbonate, the balance of the carbonate may be added. Further, a catalyst such as titanium tetrabutoxide may be used in the above reaction.

The polyester diol is not particularly limited, and examples thereof include polyethylene adipate diol, polybutylene adipate butyl diol, and poly(adipic acid) butyl butyl acrylate. Alcohol, polyhexamethylene isocyanate adipate diol, poly(ethyl succinate), butyl butyl succinate, polyethyl phthalate, polysebacic acid Polymerization of butyl ester diol, poly-ε-caprolactone diol, poly(3-methyl-1,5-amyl) adipate, 1,6-hexanediol and dimer acid Condensate, etc.

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

The low molecular weight diol is not particularly limited, and examples thereof include 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 - an aliphatic diol having 2 to 9 carbon atoms such as methyl-1,8-octanediol, diethylene glycol, triethylene glycol or tetraethylene glycol; 1,4-cyclohexanedimethanol; 3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-bis(hydroxyethyl)cyclohexane, 2,7-norbornanediol, tetrahydrofuran dimethanol, 2,5-double (hydroxymethyl)-1,4-di A diol or the like having an alicyclic structure of 6 to 12 carbon atoms or the like. Further, as the low molecular weight polyol, a low molecular weight polyol such as trimethylolpropane, neopentyl alcohol or sorbitol may be used.

The polyol (Aa) may be used singly or in combination of plural kinds.

<Acid group-containing polyol (Ab)>

The acid group-containing polyol (Ab) which can be used in the present invention is not particularly limited as long as it contains two or more hydroxyl groups in one molecule and one or more acidic groups. Examples of the acidic group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. In particular, the acid group-containing polyol (Ab) is preferably one containing a compound having two hydroxyl groups and one carboxyl group in one molecule. The acid group-containing polyol (Ab) may be used singly or in combination of plural kinds.

Specific examples of the acid group-containing polyol (Ab) include 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid, and the like is dimethylol alkanoic acid. Alkanol alkanoic acid; N,N-dihydroxyethylglycine, N,N-bishydroxyethylalanine, 3,4-dihydroxybutanesulfonic acid, 3,6-dihydroxy-2-toluene An acid, an acid group-containing polyether polyol, an acid group-containing polyester polyol, and the like. Among them, in view of the easiness of obtaining, a dimethylol alkanoic acid having a carbon number of 4 to 12 containing two methylol groups is preferred, and among the dimethylol alkanoic acids, 2,2- Dimethylolpropionic acid is preferred.

<Hydroxyl equivalent of a polyol-containing component>

In the present invention, the polyol (Aa) and the acid group-containing polyol (Ab) The total number of hydroxyl equivalents is preferably from 120 to 600. When the number of hydroxyl group equivalents is within this range, it is easy to produce an aqueous polyurethane resin dispersion containing the polyurethane resin (A), and it is easy to obtain a coating film excellent in hardness. From the viewpoint of the storage stability of the obtained aqueous polyurethane resin dispersion and the hardness of the coating film obtained by coating, it is preferably from 130 to 600, preferably from 150 to 500, particularly preferably from 170 to 400.

The hydroxyl equivalent system can be calculated according to the following formulas (1) and (2).

The number of hydroxyl equivalents of the polyol = the molecular weight of each polyol / the number of hydroxyl groups of the polyol. . . (1)

The total number of hydroxyl equivalents of the polyol = M / the total number of moles of polyol. . . (2)

In the case of the polyurethane resin (A), the M system of the formula (2) represents [[number of hydroxyl groups of the polyol (Aa) × number of moles of the polyol (Aa)] + [acid group-containing polyol (Ab) The number of hydroxyl equivalents × the number of moles of the acid group-containing polyol (Ab)]].

<polyisocyanate (Ac)>

The polyisocyanate (Ac) which can be used in the present invention is not particularly limited, and examples thereof include an aromatic polyisocyanate, an aliphatic polyisocyanate, and an alicyclic polyisocyanate.

Specific examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, and 2,4-tolylenediisocyanate (TDI). , 2,6-methylphenylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl , 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5 - Streptyl diisocyanate, 4,4',4"-triphenylmethane triisocyanate, meta-isocyanylphenylsulfonyl isocyanate, p-isocyanatophenylsulfonyl isocyanate, and the like.

Specific examples of the aliphatic polyisocyanate include ethylidene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11- Undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, quaternary acid diisocyanate, 2,6-diisocyanatomethyl hexanoate, bis(2-isocyanate) Bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl)carbonate, 2-isocyanatoethyl-2,6-diisocyanate Acid hexanoate and the like.

Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexyl diisocyanate, and methylcyclohexyl group. Diisocyanate (hydrogenated TDI), bis(2-isocyanatoethyl)-4-dicyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-lower Decane diisocyanate and the like.

The polyisocyanate usually has two isocyanato groups per molecule, but it is also possible to use a polyisocyanate group such as triphenylmethane triisocyanate in the range in which the polyurethane resin of the present invention is not gelled. Isocyanate.

Among the polyisocyanates, from the viewpoint of increasing the hardness after ultraviolet curing, it is preferable to use an alicyclic polyisocyanate having an alicyclic structure, and it is easy to control the reaction, and isophorone diisocyanate (IPDI) is used. 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI) is particularly preferred.

The polyisocyanate may be used singly or in combination of plural kinds.

<The combination of one or more polymerizable unsaturated bonds and one or more hydroxyl groups Object (Ad)>

The polymerizable unsaturated bond in the compound (Ad) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups (hereinafter also referred to as an unsaturated compound (Ad)) is, for example, a A bond contained in an unsaturated group which is polymerized by a radical generated by a photopolymerization initiator or the like. Such an unsaturated group may be a well-known one, and a group containing an ethylenically unsaturated bond may be mentioned, and a point which is easy to obtain and high in reactivity is preferable, and a (meth) acrylonitrile group is preferable. In the present specification, (meth)acrylonitrile group means propylene fluorenyl or/and methacryl fluorenyl group, and (meth) acrylate means acrylate or/and methacrylate, (methyl) Acrylic means acrylic or/and methacrylic acid. The unsaturated compound (Ad) has one or more polymerizable unsaturated bonds in the molecule. The unsaturated compound (Ad) is preferably a compound having three or more polymerizable unsaturated bonds and one or more hydroxyl groups, and preferably a compound having five or more polymerizable unsaturated bonds and one or more hydroxyl groups. .

The unsaturated compound (Ad) is preferably a compound having one or more hydroxyl groups and one or more (meth) acrylonitrile groups in terms of ease of handling.

The unsaturated compound (Ad) may, for example, be a hydroxyl group-containing (meth) acrylate, and specific examples thereof include 2-hydroxyethyl (meth)acrylate and 3-hydroxypropyl (meth)acrylate. 4-hydroxybutyl (meth)acrylate, glyceryl di(meth)acrylate, diglyceryl tris(meth)acrylate, trimethylolpropane di(meth)acrylate, neopentyl alcohol three (a) Acrylate, sorbitol penta(meth)acrylate, glycidyl (meth)acrylate and (meth)acrylic acid Adduct, glycerol mono(meth)acrylate, diglyceryl mono(meth)acrylate, pentaerythritol mono(meth)acrylate, sorbitol mono(meth)acrylate, di(a) Dialkyl acrylate, neopentyl alcohol 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, 2 molecules of (meth)acrylic acid Reaction product of 1 molecule of 1,6-hexanediol diepoxypropyl group (for example, "DA-212" manufactured by NAGASE CHEMTEX Co., Ltd.), 2 molecules of epoxy (meth)acrylic acid and 1 molecule of neopentyl glycol Reaction product of a di-glycidyl group, a reaction product of two molecules of (meth)acrylic acid and one molecule of bisphenol A diglycidyl group (for example, "DA-250" manufactured by NAGASE CHEMTEX Co., Ltd.), two molecules Reaction product of (meth)acrylic acid with a diepoxypropyl group of propylene oxide adduct of bisphenol A, reaction of two molecules of (meth)acrylic acid with one molecule of decanoic acid decyloxypropyl group (for example, "DA-721" manufactured by NAGASE CHEMTEX Co., Ltd.), a reaction product of two molecules of (meth)acrylic acid and one molecule of polyethylene glycol digoxypropyl group (for example, "DM-811" manufactured by NAGASE CHEMTEX Co., Ltd., "DM-832", "DM-851"), a reaction product of two molecules of (meth)acrylic acid and one molecule of polypropylene glycol diepoxypropyl group, etc. (meth)acrylic acid and polyol diepoxypropyl group Reaction product, etc.

From the viewpoint of increasing the hardness after hardening by irradiation with an active energy ray (for example, ultraviolet ray), among the hydroxyl group-containing (meth) acrylates, the number of (meth) acryl fluorenyl groups in one molecule is used. It is better for 3 or more people. Examples of such (meth) acrylate include di(tri)(meth)acrylate and new Pentaerythritol tri(meth)acrylate, sorbitol penta (meth) acrylate, dipentaerythritol tri(meth) acrylate, dipentaerythritol tetra(meth) acrylate, two new Pentaerythritol penta (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, and the like.

In the point that the production time of the amine ester (meth) acrylate resin (A) is shortened, the number of (meth) acryl fluorenyl groups in one molecule is three or more hydroxyl group-containing (meth) acrylates. Among them, a (meth) acrylate compound having a hydroxyl group of a first order is preferred. Examples of such a (meth) acrylate include pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, and dipentaerythritol tetra(meth)acrylate. Dipentaerythritol penta (meth) acrylate. From the viewpoint of the hardness of the coating film and the production time, it is particularly preferable to use dipentaerythritol tetra(meth)acrylate or dipentaerythritol penta(meth)acrylate.

Dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, commercially available dipentaerythritol tetra(meth)acrylate, dipentaerythritol a mixture of (meth) acrylate and dipentaerythritol hexa (meth) acrylate; a mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, etc. Way to supply. Further, the pentaerythritol triacrylate can be supplied as a mixture of commercially available pentaerythritol triacrylate and pentaerythritol tetraacrylate.

When it is a mixture of dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate; or dipentaerythritol When a mixture of penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate is used, the hydroxyl value of the mixture is preferably from 80 to 130 mg KOH/g. When the hydroxyl value is in this range, it can be easily avoided in the production of poly The amine ester resin (A) takes time and resin coloring problems, and maintains the viscosity in an appropriate range at the time of production and prevents gelation. The hydroxyl value is preferably from 85 to 120 mgKOH/g.

a mixture of dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa(meth) acrylate; or dipentaerythritol hexa The hydroxyl value of a mixture of methyl acrylate and dipentaerythritol penta (meth) acrylate was measured by the method described in JIS K 0070.

The unsaturated compound (Ad) can be supplied as it is by using a commercial item. A mixture of dipentaerythritol hexa(meth) acrylate and dipentaerythritol penta (meth) acrylate having a hydroxyl value of 80 mg KOH/g or more is, for example, ARONIX M403 manufactured by Toagosei Co., Ltd., and the like.

The unsaturated compound (Ad) may be used singly or in combination of plural kinds.

In the polyurethane resin (A) having a polymerizable unsaturated bond, the unsaturated compound (Ad) is preferably used in an amount of 50 to 80% by weight. In this range, the reaction time of the unsaturated compound (Ad) and the isocyanate group of the polyisocyanate (Ac) can be set to an appropriate range, and the obtained aqueous polyurethane resin dispersion can ensure good storage. The stability of the coating film which is cured by irradiation with an active energy ray (for example, ultraviolet ray) is in a good range. The amount used is preferably from 55 to 75% by weight, more preferably from 60 to 70% by weight.

<Polyurethane resin (A)>

The polyurethane resin (A) of the present invention is at least a polyol The polyurethane resin obtained by reacting (Aa), an acid group-containing polyol (Ab), a polyisocyanate (Ac), and an unsaturated compound (Ad) is preferred.

When the polyurethane resin (A) is obtained, the isocyanate of the polyisocyanate (Ac) is relative to the molar number of the total hydroxyl groups of the polyol (Aa), the acid group-containing polyol (Ab), and the unsaturated compound (Ad). The molar ratio of the acid groups is preferably from 0.3 to 0.95. In this range, the problem that the reaction time becomes long due to too few moles of the hydroxyl group can be easily avoided, and the unreacted polyol (Aa), the acid group-containing polyol (Ab), and the like are easily avoided. The saturated compound (Ad) remains in a large amount, resulting in a problem of a decrease in storage stability. The number of moles of the isocyanato group of the polyisocyanate (Ac) is preferably from 0.4 to 0.9, particularly preferably from 0.5 to 0.85, relative to the molar number of the total hydroxyl groups of the polyol component.

When the polyurethane resin (A) is obtained, the reaction of the polyol (Aa), the acid group-containing polyol (Ab), the polyisocyanate (Ac), and the unsaturated compound (Ad) can be carried out by (Aa), (Ab). (Ad) may be reacted with (Ac) in a different order, and a plurality of kinds may be mixed and reacted with (Ac).

When the polyol (Aa), the acid group-containing polyol (Ab), the polyisocyanate (Ac), and the unsaturated compound (Ad) are reacted, a catalyst can also be used.

The catalyst system is not particularly limited, and examples thereof include metals such as tin (Sn)-based catalysts (trimethyltin laurate, dibutyltin dilaurate, etc.), lead-based catalysts (such as lead octoate), and organic and inorganic acids. Salts, and organometallic derivatives, amine-based catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.), diazabicycloundecene-based catalysts, and the like. Among them, from the viewpoint of reactivity, dibutyltin dilaurate and dioctyltin dilaurate are preferred.

As a polyol (Aa), an acid group-containing polyol (Ab), polyisocyanate The reaction temperature at the time of the reaction between the acid ester (Ac) and the unsaturated compound (Ad) is not particularly limited, and is preferably 40 to 120 °C. In this range, the dissolution of the raw material is sufficient, and the viscosity of the obtained aqueous dispersion is appropriate and easy to stir, and the polymerization of the polymerizable unsaturated bond in the unsaturated compound (Ad) can be easily prevented from being gelled. The isocyanate group in the polyisocyanate (Ac) has a side reaction or the like. The reaction temperature is preferably from 60 to 100 °C.

When the unsaturated compound (Ad) is reacted with the polyisocyanate (Ac), in order to avoid unnecessary consumption of the polymerizable unsaturated bond of the unsaturated compound (Ad), it is preferred to carry out the reaction in the presence of oxygen.

In the present invention, in the step of obtaining the polyurethane resin (A), in order to avoid unnecessary consumption of the polymerizable unsaturated bond of the unsaturated compound (Ad), a polymerization inhibitor may be added to the reaction system.

Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, benzoquinone, 2-tert-butylhydroquinone, p-tert-butylcatechol, and 2,5-bis (1,1,3). , 3-tetramethylbutyl)hydroquinone, 2,5-bis(1,1-dimethylbutyl)hydroquinone and other lanthanide polymerization inhibitors; 2,6-bis(1,1-dimethyl Ethyl)-4-methylphenol, 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, Alkylphenol-based polymerization inhibitors such as 2,6-di-t-butyl-4-methylphenol and 2,4,6-tri-tert-butylphenol; Aromatic amine-based polymerization inhibitor; alkylated diphenylamine, N,N'-diphenyl-p-phenylenediamine, thiophene 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-benzylideneoxy-2,2,6,6-tetramethylpiperidine, 1,4-dihydroxy-2, 2,6,6-tetramethylpiperidine, 1-hydroxy-4-benzylideneoxy-2,2,6,6-tetramethylpiperidine, di-p-fluoroaniline, 2,2,6, Amine polymerization inhibitor such as 6-tetramethylpiperidin-1-oxyl (TEMPO); 2,2-diphenyl-picrylhydrazyl (DPPH), tri-p-nitro Grade 4 ammonium chloride such as phenylmethyl, N-(3-N-oxyanilino-1,3-dimethylbutylene)-aniline or benzyltrimethylammonium chloride; Hydroxylamine, cyclic guanamine, nitrile compound, substituted urea, benzothiazole, bis-(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, lactic acid, oxalic acid Organic acids such as citric acid, tartaric acid and benzoic acid; organic phosphines and phosphites. These systems may be used alone or in combination. In particular, by using a lanthanide polymerization inhibitor and an alkylphenol-based polymerization inhibitor in combination, the consumption due to polymerization of a polymerizable unsaturated bond can be reduced.

The polymerization inhibitor may be added in an amount of 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the polyurethane resin (A).

The reaction of the polyol (Aa), the acid group-containing polyol (Ab), the polyisocyanate (Ac), and the unsaturated compound (Ad) may be carried out in the form of no solvent, or may be carried out by adding an organic solvent. Examples of the organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, and Alkane, dimethylformamide, dimethylhydrazine, N-methylpyrrolidone, N-ethylpyrrolidone, ethyl acetate, and the like. Among them, acetone, methyl ethyl ketone, and ethyl acetate are preferred because they can be removed by heating and depressurizing the polyurethane prepolymer after dispersing it in water. Further, N-methylpyrrolidone and N-ethylpyrrolidone are preferred as a film-forming auxiliary agent for producing a coating film from the obtained aqueous polyurethane resin dispersion. The amount of the organic solvent added is 0 to 2.0 times by weight based on the total amount of the polyol (Aa), the acid group-containing polyol (Ab), the unsaturated compound (Ad), and the polyisocyanate (Ac). Preferably, it is preferably 0.05 to 0.7 times. When it is in this range, the viscosity in the case of obtaining the aqueous dispersion of the polyurethane resin (A) can be in an appropriate range, and good dispersion can be obtained. On the other hand, it is not necessary to spend too much time on removing the organic solvent, and it is possible to easily avoid the deterioration of the physical properties of the coating film because the organic solvent remains in the coating film obtained by using the aqueous polyurethane resin dispersion.

In the present invention, the acid value of the polyurethane resin (A) is preferably from 10 to 80 mgKOH/g. In this range, it is easy to ensure good dispersibility to the aqueous medium and water resistance of the coating film. The aforementioned acid value is preferably from 12 to 70 mgKOH/g, more preferably from 14 to 60 mgKOH/g.

The acid value of the polyurethane resin (A), that is, the average content of the acidic groups in the solid fraction, can be derived from the following formula (3). When a solvent is used in the production of the polyurethane resin (A) and a neutralizing agent is used in order to disperse the polyurethane resin (A) in an aqueous medium, when the solid content is calculated, the solvent and the medium are used. And agent deduction.

[Acid Value of Polyurethane Resin (A)] = [Mole Number of Acid Group of Acid Group-Containing Polyol (Ab)] × 56.11 / [Polyol (Aa), Acid Group-Based Polyol (Ab), No Total weight of saturated compound (Ad) and polyisocyanate (Ac)]. . . (3)

<Compound (Ae) having a polymerizable unsaturated bond>

In the present invention, when the polyurethane resin (A) is used in the form of an aqueous dispersion, the aqueous dispersion may contain a compound (Ae) having a polymerizable unsaturated bond (in the case of an unsaturated compound (Ae)). The unsaturated compound (Ae) is preferably a radically polymerizable compound. The radically polymerizable compound is a coexistence of a thermal radical generating agent in the presence of a photoradical generating agent The polymerization is carried out, that is, it is not particularly limited, and a (meth) acrylate compound is preferred. The unsaturated compound (Ae) does not contain a polyurethane resin (A) having a polymerizable unsaturated bond. Further, although the unsaturated compound (Ad) is substantially consumed in the synthesis of the polyurethane resin (A), for example, after the synthesis of the polyurethane resin (A), a compound exemplified as the unsaturated compound (Ad) may be added. Therefore, the unsaturated compound (Ae) may also be a compound exemplified as the unsaturated compound (Ad). Further, when the unsaturated compound (Ae) is supplied as a mixture of a compound having a polymerizable unsaturated bond having no hydroxyl group, the unsaturated compound (Ae) has no or not included in the synthesis of the polyurethane resin (A). The compound of the polymerizable unsaturated bond of the reflected hydroxyl group may constitute an unsaturated compound (Ae).

Examples of the radically polymerizable compound include a monomeric (meth) acrylate compound, a polyurethane (meth) acrylate compound, a polyester (meth) acrylate compound, and a poly(meth) acrylate. An ester compound or the like.

As the monomeric (meth) acrylate compound, mono (meth) acrylate, di (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate, and penta (A) can be used. Poly(meth) acrylate such as acrylate or hexa(meth) acrylate.

Examples of the mono(meth)acrylate include acryloylmorpholine, 2-ethylhexyl (meth)acrylate, styrene, methyl (meth)acrylate, and tetrahydroanthracene (meth)acrylate. Ester, dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, (meth)acrylic acid Phenoxyethyl ester, isodecyl (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, methoxy polyethylene glycol mono (meth) acrylate, octyloxy polyethylene glycol - polypropylene glycol mono (meth) acrylate, lauric oxygen Polyethylene glycol mono(meth)acrylate, stearyloxy polyethylene glycol mono(meth)acrylate, nonylphenoxy polyethylene glycol mono(meth)acrylate, mercaptobenzene Oxypolypropylene glycol polyethylene glycol mono(meth)acrylate or the like.

Examples of the di(meth)acrylate include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and polyethylene glycol. Di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, tricyclic Decane dimethanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene glycol-polypropylene glycol di(meth)acrylate, poly (ethylene glycol-tetramethylene glycol) di(meth)acrylate, poly(propylene glycol-tetramethylene glycol) di(meth)acrylate, methoxypolyethylene glycol di(methyl) Acrylate, octyloxy polyethylene glycol-polypropylene glycol di(meth) acrylate, lauryloxy polyethylene glycol di(meth) acrylate, stearoxy ethoxypoly polyethylene glycol di(methyl) Acrylate, nonylphenoxy polyethylene glycol di(meth)acrylate, nonylphenoxy polypropylene glycol polyethylene glycol di(meth)acrylate, and the like.

Examples of the tri(meth)acrylate include trimethylolpropane triacrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, and propylene oxide-modified trishydroxymethyl group. Propane tri(meth)acrylate, neopentane Ethylene oxide modified trishydroxymethyl ester such as tetraol tri(meth)acrylate or ethylene oxide (6 mol) modified trimethylolpropane triacrylate (Laromer (registered trademark) LR8863 manufactured by BASF Corporation) Propane triacrylate (Laromer (registered trademark) PO33F, manufactured by BASF Corporation).

Examples of the tetra (meth) acrylate include pentaerythritol tetra (meth) acrylate and ethylene oxide (4 mol) modified pentaerythritol tetra (meth) acrylate (DAICEL- CYTEC, Ebecryl 40) and other alkylene oxide modified pentaerythritol tetra (meth) acrylate.

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

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

Further, as the polymer-based (meth) acrylate compound, those skilled in the art can be used. Examples of the (meth) acrylate compound of the polymer include di(meth)acrylate, tri(meth)acrylate, tetra(meth)acrylate, etc., in addition to the mono(meth)acrylate. Poly(meth) acrylate.

Among these radically polymerizable compounds, tris (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa are used as the hardness of the obtained coating film. The so-called poly(meth) acrylate of methyl acrylate is preferred.

The unsaturated compound (Ae) may be used singly or in combination of plural kinds.

When the polyurethane resin (A) is obtained as an aqueous dispersion, the total amount of the solid dispersion (including the unsaturated compound (Ae)) of the aqueous dispersion is set to 100. The polyol (Aa) is preferably 2 to 50 parts by weight, and the acid group-containing polyol (Ab) is preferably 1 to 15 parts by weight. When the polyol (Aa) is in the above range, the dispersibility of the polyurethane resin (A) in water is good, and the aqueous polyurethane resin dispersion containing the polyurethane resin (A) can easily obtain excellent film forming properties. The polyol (Aa) is preferably 2 to 50 parts by weight, preferably 3 to 40 parts by weight, particularly preferably 5 to 30 parts by weight. As long as the acid group-containing polyol (Ab) is in the above range, the water resistance of the coating film obtained from the aqueous polyurethane resin dispersion is good, and the dispersibility of the polyurethane resin (A) in the aqueous medium is good. The acid group-containing polyol (Ab) is preferably 1 to 15 parts by weight, preferably 2 to 10 parts by weight, particularly preferably 3 to 7 parts by weight.

The total amount of the unsaturated compound (Ad) and the unsaturated compound (Ae) of the polyurethane resin (A) having a polymerizable unsaturated bond in the total amount of the polyurethane resin (A) (including the unsaturated compound (Ae)), It is preferably 50 to 85% by weight. When it is in this range, the hardness of the obtained coating film is appropriate, and the adhesiveness with the PMMA resin is also good, and the reaction time of an isocyanate group and an unsaturated compound (Ad) can be avoided, and it can make it. The resulting aqueous polyurethane resin dispersion has suitable storage stability. It is preferably 60 to 80% by weight, more preferably 65 to 75% by weight.

In the present invention, the polyurethane resin (A) may be used in a form of being dispersed in an aqueous medium. Examples of the aqueous medium include water, a mixed medium of water and a hydrophilic organic solvent, and the like.

Examples of the water include fresh water, ion-exchanged water, distilled water, and ultrapure water. Among them, ion exchange water is preferred in view of the ease of acquisition and the influence of salt on the particles to become unstable.

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

<Method for Producing Polyurethane Resin (A)>

Next, a method of producing the polyurethane resin (A) will be described.

When the polyurethane resin (A) is used in the form of an aqueous dispersion, the aqueous dispersion can be obtained by a production method comprising the steps of at least a polyol (Aa), an acid group-containing polyol (Ab), and a polyisocyanate. (Ac), an unsaturated compound (Ad) to obtain a step (Aα) of the polyurethane resin (A); a step of neutralizing the acidic group of the polyurethane resin (A) (Aβ); and dispersing the polyurethane resin (A) in the water system The step in the medium (Aγ).

Further, by dispersing the polyurethane resin (A) and the unsaturated compound (Ae) in an aqueous medium, the polyurethane resin (A) and the unsaturated compound (Ae) can be obtained, and these are dispersed in an aqueous medium. Aqueous dispersion.

In order to avoid unnecessary consumption of the polymerizable unsaturated bond, the step (A?) of obtaining the polyurethane resin (A) is preferably carried out in the presence of oxygen. Further, it is preferred to add a polymerization inhibitor to the reaction system as needed. In order to avoid unnecessary polymerization of the polymerizable unsaturated bond, the temperature of the step (A?) may be carried out at 0 to 120 ° C, preferably 0 to 100 ° C.

Examples of the acidic group neutralizing agent which can be used in the step (Aβ) of neutralizing the acidic group of the polyurethane resin (A) include trimethylamine, triethylamine, and triisopropylamine. Organic amines such as tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, dimethylethanolamine, diethylethanolamine, N-methylmorpholine, pyridine; sodium hydroxide, hydroxide Inorganic bases such as potassium; ammonia, etc. Among them, organic amines are preferred, and tertiary amines are preferred, and triethylamine is preferred. Here, the acidic group of the polyurethane resin (A) means a carboxylic acid group or a sulfonic acid group.

The amount of the acidic group neutralizing agent to be used is preferably from 0.8 to 1.5 in terms of moles with respect to the acidic group of the polyurethane resin (A). In this range, the dispersibility of the polyurethane resin (A) to water is not lowered, the storage stability of the obtained aqueous dispersion of the polyurethane resin is not lowered, and the odor of the aqueous dispersion of the polyurethane resin can be easily avoided. The situation of becoming stronger.

The step (Aγ) of dispersing the polyurethane resin (A) and the optional unsaturated compound (Ae) in an aqueous medium, as long as the polyurethane resin (A) and any unsaturated compound (Ae) can be dispersed in the aqueous medium The method, the procedure, and the like are not particularly limited, and examples thereof include a method in which an unsaturated compound (Ae) is mixed in a polyurethane resin (A) and dispersed in an aqueous medium; and an unsaturated compound (Ae) is mixed. a method for dispersing a polyurethane resin (A) in an aqueous medium; a method of mixing and dispersing the unsaturated compound (Ae) after dispersing the polyurethane resin (A) in an aqueous medium; and making the unsaturated compound (Ae) After dispersing in an aqueous medium, a method of mixing and dispersing the polyurethane resin (A); and dispersing each of the polyurethane resin (A) and the unsaturated compound (Ae) in an aqueous medium, and mixing them. When dispersed in an aqueous dispersion, if both the polyurethane resin (A) and the unsaturated compound (Ae) are present, the polyurethane resin (A) and the unsaturated compound (Ae) are combined to form an unsaturated compound (Ae). ) Easily dispersed in aqueous media.

The aqueous dispersion containing the polyurethane resin (A) and the unsaturated compound (Ae) and dispersed in the aqueous medium can also be obtained by mixing the unsaturated compound (Ae) in the production of the polyurethane resin (A). For example, in the step (Aα), the polyol (Aa), the acid group-containing polyol (Ab), the polyisocyanate (Ac), and the unsaturated compound (Ad) may be reacted in the presence of the unsaturated compound (Ae). Or, before, during or after the step (Aα), the unsaturated compound (Ae) is mixed.

In terms of dispersibility, it is preferred that the unsaturated compound (Ae) is present in the step (A?), and/or is present after the step (A?) and before the step (A?) is neutralized.

A well-known stirring device such as a homomixer or a homogenizer may be used for the above mixing or stirring or dispersion. Further, in order to adjust the viscosity, improve workability, and improve dispersibility, a hydrophilic organic solvent, water, or the like may be added in advance to the polyurethane resin (A) and the unsaturated compound (Ae) before mixing.

Further, in order to avoid unnecessary consumption of the polymerizable unsaturated bond, the above-mentioned mixing, stirring, or dispersion is preferably carried out in the presence of oxygen. Further, a polymerization inhibitor may be added in each step as needed. In order to avoid unnecessary consumption of the polymerizable unsaturated bond, the temperature at which the polyurethane resin (A) and the optional saturated compound (Ae) are mixed is preferably carried out at 0 to 100 ° C, and is carried out at 0 to 90 ° C. Preferably, it is more preferably carried out at 0 to 80 ° C, and particularly preferably at 50 to 70 ° C.

In the above production method, the step of neutralizing the acidic group of the polyurethane resin (A) (Aβ), and the step of dispersing the polyurethane resin (A) in the aqueous medium (A) γ), either one can be performed first or simultaneously. In this case, the polyurethane resin (A), any unsaturated compound (Ae), an aqueous medium, and an acidic base neutralizing agent may be mixed at once, or the acidic based neutralizing agent may be previously mixed into an aqueous medium or, as the case may be, unsaturated. After the compound (Ae), these are mixed with the polyurethane resin (A).

When the polyurethane resin (A) is used in the form of an aqueous dispersion, the ratio of the polyurethane resin (A) in the aqueous dispersion is preferably from 5 to 60% by weight, preferably from 15 to 50% by weight, more preferably from 25 to 40% by weight. Further, the number average molecular weight of the polyurethane resin (A) is preferably from 1,000 to 1,000,000.

<Polyurethane resin (B)>

The polyurethane resin (B) having no polymerizable unsaturated bond of the present invention reacts at least a polyol (Ba), an acid group-containing polyol (Bb), a polyisocyanate (Bc), and a chain extender (Bd). The obtained polyurethane resin is a polyurethane resin having an alicyclic structure content of 16 to 70% by weight in the aforementioned polyurethane resin (B).

As the polyol (Ba) (hereinafter also referred to as (Ba)) which can be used in the present invention, for example, a high molecular weight polyol (for example, a polycarbonate polyol, a polyester polyol, a polyether polyol, or the like) and a low molecular weight can be used. Polyol. In terms of easiness in producing the polyurethane resin (B), it is preferred to use a high molecular weight diol and a low molecular weight diol. Further, a polyol containing two or more hydroxyl groups and one or more acidic groups in one molecule is contained in the acid group-containing polyol (Bb).

The high molecular weight diol system is not particularly limited, and the number average molecular weight is preferably from 400 to 8,000. When the number average molecular weight is within this range, appropriate viscosity and good handleability can be easily obtained. Also, it is easy to ensure as soft When the coating film is formed by using the aqueous polyurethane resin dispersion containing the obtained polyurethane resin, it is easy to suppress the occurrence of cracks, and the reactivity with the polyisocyanate (Bc) is sufficient, and the polyurethane can be efficiently produced. Resin (B). The number average molecular weight of the polyol (Ba) is preferably from 400 to 4,000.

Examples of the high molecular weight diol include a polycarbonate diol, a polyester diol, and a polyether diol. The water-based polyurethane resin dispersion containing the obtained polyurethane resin and the coating film obtained by using the aqueous polyurethane resin dispersion have high light resistance, heat resistance, hydrolysis resistance, oil resistance, and alicyclic structure content. In particular, polycarbonate diol is preferred.

Further, among the polycarbonate diols, the diol component is preferably an aliphatic diol and/or an alicyclic diol, and the diol component is preferably an alicyclic diol.

The polycarbonate polyol can be obtained by reacting one or more kinds of polyol monomers with a carbonate or phosgene. It is preferable to use a polycarbonate polyol obtained by reacting one or more kinds of polyol monomers with a carbonate in terms of easy production and non-produced terminal chloride.

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

The aliphatic polyol monomer is not particularly limited, and examples thereof include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7. a linear aliphatic diol such as heptanediol, 1,8-octanediol or 1,9-nonanediol; 2-methyl-1,3-propanediol, 2-methyl-1,5-pentyl Branched chain aliphatic diol such as diol, 3-methyl-1,5-pentanediol, 2-methyl-1,9-nonanediol; 1,1,1-trimethylol A trifunctional or higher polyhydric alcohol such as propane or neopentyl alcohol.

The polyol monomer having an alicyclic structure is not particularly limited, and examples thereof include 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanediol. , 3-cyclopentanediol, 1,4-cycloheptanediol, 2,5-bis(hydroxymethyl)-1,4-di A diol having an alicyclic structure in the main chain, such as an alkane, 2,7-norbornanediol, tetrahydrofuran dimethanol or 1,4-bis(hydroxyethoxy)cyclohexane.

The aromatic polyol monomer is not particularly limited, and examples thereof include 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, and 4,4'-naphthalene dimethanol. 3,4'-naphthalene dimethanol and the like.

The polyester polyol monomer is not particularly limited, and examples thereof include polyester polyols of hydroxycarboxylic acids and diols such as polyester polyols of 6-hydroxycaproic acid and hexanediol, and adipic acid and hexane. A polyester polyol such as a polyester of a polyester such as a polyester polyol or a diol of a diol.

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

The carbonate is not particularly limited, and examples thereof include aliphatic carbonates such as dimethyl carbonate and diethyl carbonate; aromatic carbonates such as diphenyl carbonate; and cyclic carbonates such as ethyl carbonate. Further, phosgene or the like capable of producing a polycarbonate polyol can also be used. Among them, in view of the easiness of producing the above polycarbonate polyol, an aliphatic carbonate is preferred, and dimethyl carbonate is particularly preferred.

Examples of the method for producing a polycarbonate polyol from a polyol monomer and a carbonate include a carbonate added to a reactor and a polyol having an excess number of moles relative to the molar number of the carbonate. At a temperature of 160 to 200 After reacting at a temperature of about 50 mmHg for about 5 to 6 hours, the reaction is further carried out at a pressure of several mmHg or less at 200 to 220 ° C for several hours. In the above reaction, it is preferred to carry out the reaction while extracting the by-produced alcohol to the outside of the system. At this time, the remaining amount of carbonate may be added by azeotropy with the alcohol produced by the carbonate to the outside of the system. Further, in the above reaction, a catalyst such as titanium tetrabutoxide may also be used.

The polyester diol is not particularly limited, and examples thereof include polyethylene adipate diol, polybutylene adipate butyl diol, and poly(adipic acid) butyl butyl acrylate. Alcohol, polyhexamethylene isocyanate hexanoate diol, poly(ethyl succinate) condensate, polybutyl succinate butyl diol, poly(ethylene phthalate) diol, polyphthalic acid Polycondensation of butyl ester diol, poly-ε-caprolactone diol, poly(3-methyl-1,5-p-amyl adipate) diol, 1,6-hexanediol and dimer acid Things and so on.

The polyether diol is not particularly limited, and specific examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide and propylene oxide, ethylene oxide and butylene oxide. Random copolymers and block copolymers, and the like. Further, a polyether polyester polyol having an ether bond and an ester bond or the like can also be used.

The low molecular weight diol is not particularly limited, and examples thereof include 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 - an aliphatic diol having 2 to 9 carbon atoms such as methyl-1,8-octanediol, diethylene glycol, triethylene glycol or tetraethylene glycol; 1,4-cyclohexanedimethanol; 3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-bis(hydroxyethyl)cyclohexane, 2,7-norbornanediol, tetrahydrofuran dimethanol, 2,5-double (hydroxymethyl)-1,4-di A diol or the like having an alicyclic structure of 6 to 12 carbon atoms or the like. Further, a low molecular weight polyol such as trimethylolpropane, neopentyl alcohol or sorbitol may be used as the low molecular weight polyol.

The alicyclic structure of the polyol (Ba) has a content ratio of 16 to 70% by weight. When the content of the alicyclic structure is within this range, a coating film having excellent hardness can be easily obtained due to the presence of the alicyclic structure, and the viscosity in the production of the aqueous polyurethane resin dispersion is in an appropriate range, and the operation is also easy. The alicyclic structure content is preferably from 20 to 65% by weight, preferably from 30 to 55% by weight.

Here, the alicyclic structure content ratio means the weight ratio of the alicyclic group in the polyol (Ba). The weight ratio refers to, for example, an unsaturated heterocyclic residue such as a cyclohexane residue (a part of removing two hydrogen atoms from cyclohexane in the case of 1,4-hexanedimethanol) or a tetrahydrofuran residue (in tetrahydrofuran). In the case of dimethanol, the value calculated from the portion after removing two hydrogen atoms from tetrahydrofuran.

The polyol (Ba) may be used singly or in combination of plural kinds.

<Acid group-containing polyol (Bb)>

The acid group-containing polyol (Bb) which can be used in the present invention is not particularly limited as long as it has two or more hydroxyl groups and one or more acidic groups in one molecule. Examples of the acidic group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. In particular, as the acid group-containing polyol (Bb), a compound having two hydroxyl groups and one carboxyl group in one molecule is preferred. The acid group-containing polyol (Bb) may be used singly or in combination of plural kinds.

As the acid group-containing polyol (Bb), specifically 2,2-dihydroxyl Di-alkanol alkanoic acid, dimethylol alkanoic acid, such as propyl propionic acid, 2,2-dimethylol butyric acid; N,N-bishydroxyethylglycine, N,N-bishydroxyethyl propylamine An acid, 3,4-dihydroxybutanesulfonic acid, 3,6-dihydroxy-2-toluenesulfonic acid, an acid group-containing polyether polyol, an acid group-containing polyester polyol, and the like. Among them, from the viewpoint of easiness of availability, a dimethylol alkanoic acid having a carbon number of 4 to 12 containing two methylol groups is preferred, and among the dimethylol alkanoic acids, a 2,2-dihydroxy group is used. Methyl propionic acid is preferred.

In the present invention, the total number of hydroxyl groups of the polyol (Ba) and the acid group-containing polyol (Bb) is preferably from 100 to 400. When the number of hydroxyl equivalents is in this range, it is easy to produce an aqueous polyurethane resin dispersion containing the polyurethane resin (B), and it is also preferable in terms of storage stability. The hydroxyl equivalent is preferably from 150 to 300.

The hydroxyl equivalent can be calculated using the above formulas (1) and (2).

In the case of the polyurethane resin (B), the M system in the formula (2) represents [[the number of hydroxyl groups of the polyol (Ba) × the number of moles of the polyol (Ba)] + [the acid group-containing polyol (Bb) The number of hydroxyl equivalents × the number of moles of the acid group-containing polyol (Bb)]].

In the case where the polyurethane resin (B) is obtained, when the total amount of the polyurethane resin (B) is 100 parts by weight, the polyol (Ba) is preferably 20 to 85 parts by weight, and the acid group-containing polyol (Bb) It is preferably 2 to 14 parts by weight. When the polyol (Ba) is in the above range, the polyurethane resin (B) has good dispersibility in water, and the aqueous polyurethane resin dispersion containing the polyurethane resin (B) can easily obtain excellent film formability. The polyol (Ba) is preferably 25 to 80 parts by weight, preferably 30 to 75 parts by weight, particularly preferably 35 to 70 parts by weight. When the acid group-containing polyol (Bb) is in the aforementioned range, it is distinguished from the aqueous polyurethane resin. The water resistance of the coating film obtained by the monomer is good, and the dispersibility of the polyurethane resin (B) in an aqueous medium is good. The acid group-containing polyol (Bb) is preferably from 2.5 to 12 parts by weight, preferably from 3.0 to 10 parts by weight, particularly preferably from 3.5 to 8 parts by weight.

<polyisocyanate (Bc)>

The polyisocyanate (Bc) which can be used in the present invention is not particularly limited, and examples thereof include an aromatic polyisocyanate, an aliphatic polyisocyanate, and an alicyclic polyisocyanate.

Specific examples thereof include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-methylphenylene diisocyanate (TDI), and 2,6-methylphenylene. Isocyanate, 4,4'-diphenylene diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl -4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-anthranyl diisocyanate, 4, Aromatic polyisocyanates such as 4',4"-triphenylmethane triisocyanate, meta-isocyanylphenylsulfonyl isocyanate, p-isocyanatophenylsulfonyl isocyanate; ethyl diisocyanate, tetra Methyl diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate , phthalic acid diisocyanate, 2,6-diisocyanatomethyl hexanoate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) An aliphatic polyisocyanate such as carbonate, 2-isocyanatoethyl-, 6-diisocyanatohexanoate ; Isophorone diisocyanate (IPDI), 4,4'- dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methyl cyclohexylene diisocyanate (hydrogenated TDI), bis (2- Isocyanatoethyl)-4-dicyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, alicyclic polyisocyanate such as 2,6-norbornane diisocyanate, etc. .

The polyisocyanate usually has two isocyanato groups per molecule, and the polyurethane resin of the present invention may also have an isocyanate group having three or more, such as triphenylmethane triisocyanate, in the range of no gelation. Polyisocyanate.

Among the polyisocyanates, 4,4'-diphenylene diisocyanate (MDI), isophorone diisocyanate (IPDI), 4,4'-di are used from the viewpoints of control of reactivity and imparting strength. Cyclohexylmethane diisocyanate (hydrogenated MDI) is preferred. In terms of the ease of increasing the content of the alicyclic structure, isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI) is preferred, 4,4'-bicyclic ring Hexyl methane diisocyanate (hydrogenated MDI) is more preferred.

These polyisocyanates may be used singly or in combination of two or more.

When the polyurethane resin (B) is obtained, the molar ratio of the isocyanate group of the polyisocyanate (Bc) to the molar number of the total hydroxyl groups of the polyol (Ba) and the acidic group-containing polyol (Bb), It is preferably from 1.1 to 2.5. In this range, the problem that the reaction time becomes long due to the excessive number of moles of the hydroxyl group can be easily avoided, and it is easy to prevent the unreacted polyol (Ba) and the acid group-containing polyol (Bb) from remaining in a large amount. The problem of reduced storage stability. The number of moles of the isocyanato group of the polyisocyanate (Bc) is preferably from 1.2 to 2.2, particularly preferably from 1.3 to 2.0, relative to the molar number of the total hydroxyl groups of the polyol component.

<chain elongation agent (Bd)>

The chain extender (Bd) is not particularly limited as long as it is reactive with an isocyanate group, and examples thereof include ethylenediamine and 1,4-tetramethylenediamine (1,4-tetramethylenediamine). ), 2-methyl-1,5-pentanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-hexamethylenediamine, 3-Aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis(aminomethyl)cyclohexane, Xylylenediamine, Piper , adipoyl hydrazide, hydrazine, 2,5-dimethylper An amine compound such as diethylenetriamine or triamethylenetetramine; a glycol compound such as ethylene glycol, propylene glycol, 1,4-butanediol or 1,6-hexanediol; represented by polyethylene glycol A polyalkylene glycol, water or the like is preferably obtained, and among them, a first-grade diamine compound is preferred. These lines may be used alone or in combination.

The amount of the chain extender (Bd) to be added is preferably the same as the equivalent of the isocyanate group as the starting point of the chain elongation in the obtained amine ester prepolymer, preferably 0.7 to 0.99 equivalents of the isocyanate group. . In this range, the molecular weight of the elongated amine ester polymer can be easily prevented from being lowered, and the strength of the coating film obtained by coating the obtained aqueous polyurethane resin dispersion can be lowered. The chain extender (Bd) may be added after the amine ester prepolymer is dispersed in water, or may be added in the dispersion. Chain elongation can also be carried out by water. At this time, the water system as a dispersion medium also serves as a chain extender.

<Polyurethane resin (B)>

In the present invention, the polyurethane resin (B) can also be used in the form of being dispersed in an aqueous medium. Examples of the aqueous medium include water, a mixed medium of water and a hydrophilic organic solvent, and the like.

Examples of the water include fresh water, ion-exchanged water, distilled water, and ultrapure water. Among them, taking into account the ease of acquisition, the influence of salt will cause particles It is not stable, and ion exchange water is preferred.

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

In the present invention, the acid value of the polyurethane resin (B) is preferably from 10 to 55 mgKOH/g. When the acid value is in this range, the dispersibility of the obtained aqueous polyurethane resin dispersion is good, and it is also preferable in terms of the water resistance of the coating film. The acid value is preferably from 12 to 42 mgKOH/g, more preferably from 14 to 35 mgKOH/g.

The acid value of the polyurethane resin (B) refers to the average content of the acidic groups in the so-called solid fraction after removing the solvent and the neutralizing agent, and can be derived according to the following formula (3'); the solvent is a polyurethane resin. (B) The user may use the neutralizing agent to disperse the polyurethane resin (B) in an aqueous medium as the case may be.

[Acid Value of Polyurethane Resin (B)] = [Mole Number of Acid Group of Acid Group-Containing Polyol (Bb)] × 56.11 / [Polyol (Ba), Acid Group-Based Polyol (Bb), Poly Total weight of isocyanate (Bc) and chain extender (Bd)]. . . (3’)

The polyol (Ba), the polyisocyanate (Bc), and the acidic group-containing polyol (Bb) are reacted to obtain a prepolymer, and then dispersed in an aqueous medium and chain-extended (Bd) to carry out chain elongation to be aqueous. When the form of the dispersion is obtained as the polyurethane resin (B), the acid value is synonymous with the acid value of the prepolymer.

<Method for Producing Polyurethane Resin (B)>

Next, a method of producing the polyurethane resin (B) will be described.

When the polyurethane resin (B) is used in the form of an aqueous dispersion, the aqueous dispersion can be obtained by a production method comprising the following steps: at least a polyol (Ba), an acid group-containing polyol (Bb), and a polyisocyanate ( Bc) a step of reacting to obtain a polyurethane prepolymer (Bα); a step of neutralizing the acidic group of the aforementioned amine ester prepolymer (Bβ); a step of dispersing the aforementioned amine ester prepolymer in an aqueous medium (Bγ); And a step (Bσ) of reacting the aforementioned amine ester prepolymer with a chain extender (Bd).

The step (Bα) of obtaining the amine ester prepolymer can be carried out at 0 to 120 ° C, preferably at 40 to 100 ° C.

A catalyst (Bα) for obtaining an amine ester prepolymer may be a catalyst, and examples thereof include a catalyst such as a tin catalyst exemplified in the paragraph of the production of the polyurethane resin (A). Further, it may be carried out without a solvent, or may be carried out by adding an organic solvent. In this case, examples of the organic solvent include organic solvents exemplified in the paragraphs for producing the polyurethane resin (A).

The acid-based neutralizing agent which can be used as a step of neutralizing the acidic group of the amine ester prepolymer (Bβ), and examples thereof include trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, and N-methyl. Organic amines such as diethanolamine, N-phenyldiethanolamine, dimethylethanolamine, diethylethanolamine, N-methylmorpholine, pyridine; inorganic bases such as sodium hydroxide and potassium hydroxide; ammonia, and the like. Among them, organic amines are preferably used, and a tertiary amine is preferably used, and triethylamine is preferably used.

Here, the acidic group of the amine ester prepolymer means a carboxylic acid group or a sulfonic acid group.

The amount of the acidic base neutralizer used relative to the acidic group of the amine ester prepolymer It is preferably used in a form of from 0.8 to 1.5 in terms of a molar number. When the amount of the acidic base neutralizing agent used is less than the amount, the dispersibility of the amine ester prepolymer to water is lowered, and the storage stability of the aqueous polyurethane resin dispersion is lowered. When the amount of the acidic base neutralizing agent used is larger than this amount, the odor of the aqueous polyurethane resin dispersion may become strong.

The step (Bγ) of dispersing the amine ester prepolymer in the aqueous medium is not particularly limited as long as the amine ester prepolymer can be dispersed in the aqueous medium, and examples thereof include, for example, A method in which an amine ester prepolymer is added to an aqueous medium and dispersed, and a method in which an aqueous medium is added to an amine ester prepolymer and dispersed.

The step (Bσ) of reacting the amine ester prepolymer with the chain extender (Bd) is not particularly limited as long as the isocyanate group of the amine ester prepolymer is reacted with the chain extender, and the method and the operation sequence thereof are not particularly limited. For example, a method of performing (Bσ) after performing (Bα), (Bβ), and (Bγ) in an arbitrary order; performing (Bα) and (Bβ) in an arbitrary order, performing (Bσ), and then performing (Bσ) The method of Bγ); and the method of performing (Bσ) and then performing (Bβ) and (Bγ) in an arbitrary order after performing (Bα).

A well-known stirring device such as a homomixer or a homogenizer can be used for mixing, stirring, and dispersing as described above. Further, in order to adjust the viscosity, improve the workability, and improve the dispersibility, the polyurethane resin (B) can also be previously added with the hydrophilic organic solvent, water, or the like before mixing.

The proportion of the polyurethane resin in the aqueous dispersion of the polyurethane resin (B) is preferably from 5 to 60% by weight, preferably from 15 to 50% by weight, more preferably from 25 to 40% by weight. Also, the number average molecular weight is from 1,000 to 1,000,000 It is better.

The alicyclic structure of the polyurethane resin (B) has a alicyclic structure content of 16 to 70% by weight. In this range, good coating film adhesion and non-stickiness are obtained, and the polyurethane resin (B) has good dispersibility in water, and deterioration in storage stability can be avoided. The alicyclic structure content is preferably from 29 to 60% by weight, more preferably from 39 to 50% by weight. The alicyclic structure content rate was calculated in the following manner. For example, in the case where 1,4-cyclohexanedimethanol is used as the polycarbonate polyol of the polyol monomer, the cyclohexane ring is an alicyclic structure, and the cyclohexane is removed from the cyclohexane. The weight (molecular weight) of the alkane residue, that is, the proportion occupied by the weight (number average molecular weight) of the polyurethane resin.

<Aqueous polyurethane resin dispersion>

The present invention relates to an aqueous polyurethane resin dispersion in which a polyurethane resin (A) and a polyurethane resin (B) are dispersed in an aqueous medium, and a polyurethane resin (A aqueous polyurethane resin dispersion of A) is dispersed in an aqueous medium. The water-based medium is dispersed with the aqueous polyurethane resin dispersion of the polyurethane resin (B), and then it is preferably produced by mixing the aqueous polyurethane resin dispersions.

The mixing method of the aqueous polyurethane resin dispersion is not particularly limited. For example, it is preferred to add a small amount of another aqueous polyurethane resin dispersion in small portions when stirring the aqueous polyurethane resin dispersion.

The aqueous polyurethane resin dispersion of the present invention may contain other polyurethane resin, viscosity modifier, stabilizer, antioxidant, preservative, antifungal agent, pH modulation in addition to the polyurethane resin (A) and the polyurethane resin (B). Additives such as agents and wettability improvers.

As the polyurethane resin (A), it contains a polyurethane resin (A) and is unsaturated. The compound (Ae), when the aqueous dispersion dispersed in an aqueous medium is used, the aqueous polyurethane resin dispersion of the present invention contains an unsaturated compound (Ae).

In the aqueous polyurethane resin dispersion of the present invention, the mixing ratio of the polyurethane resin (A) and the polyurethane resin (B) is not particularly limited, and is based on the weight ratio (polyamine resin (A): polyurethane resin (B), solid content). It is preferably 90:10 to 50:50. When the ratio of the polyurethane resin (A) to the polyurethane resin (B) is too small, the hardness of the obtained coating film may be lowered or the adhesion may be lowered; the polyurethane resin may be used. When the ratio of (A) is too large, there is a case where the non-stickiness is lowered and the adhesion is lowered. It is preferably 80:20 to 60:40.

The aqueous polyurethane resin dispersion of the present invention is prepared by mixing an aqueous polyurethane resin dispersion (A) in which an aqueous polyurethane resin (A) is dispersed in an aqueous medium, and an aqueous polyurethane resin dispersion (B) in which an aqueous polyurethane medium (B) is dispersed in an aqueous medium. In the case of the original, the aqueous polyurethane resin dispersion (A): aqueous polyurethane resin dispersion (B) is preferably 80:20 to 30:70 by weight, preferably 80:20 to 50:50.

In the aqueous polyurethane resin dispersion of the present invention, a photopolymerization initiator may be added. As the photopolymerization initiator, a usual user can be used, for example, a photofragmentation type and/or a hydrogen abstraction type which can be easily cleaved by irradiation of ultraviolet rays to generate two radicals can be used. Or use these to mix and use. Examples of such a photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, diphenylketone, and 2-chlorodiphenyl ketone. ,p,p'-double (two Amino)diphenyl ketone, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin n-butyl ether, benzoin dimethyl ketal, Thioxanthone, p-isopropyl-α-hydroxyisobutylbenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2, 4,6,-trimethyldiphenyl ketone, 4-methyldiphenyl ketone, 2,2-dimethoxy-1, 2-diphenylethanone, and the like. Preferred is hydroxycyclohexyl phenyl ketone.

When the photopolymerization initiator is added, the order of mixing is not particularly limited, but it is preferably added after mixing the polyurethane resin (A) and the polyurethane resin (B).

The amount of the photopolymerization initiator to be added is preferably from 0.5 to 5% by weight based on the total solid content of the aqueous polyurethane resin dispersion.

Further, the aqueous polyurethane resin dispersion of the present invention may be added as needed: tackifier, photosensitizer, hardening catalyst, ultraviolet absorber, light stabilizer, antifoaming agent, plasticizer, surface conditioner, anti-precipitation Additives such as agents. The additives may be used singly or in combination of plural kinds. The aqueous polyurethane resin dispersion of the present invention preferably contains no protective colloid, emulsifier or surfactant in terms of hardness and chemical resistance of the obtained coating film.

<Coating composition and coating composition>

The present invention also relates to a coating composition and a coating composition comprising the aqueous polyurethane resin dispersion.

In the coating composition and the coating composition of the present invention, in addition to the aqueous polyurethane resin dispersion described above, other resins may be added. As before Examples of the other resin include a polyester resin, an acrylic resin, a polyether resin, a polycarbonate resin, a polyurethane resin, an epoxy resin, an alkyd resin, and a polyolefin resin. These lines may be used alone or in combination.

Further, the other resin preferably has one or more hydrophilic groups. Examples of the hydrophilic group include a hydroxyl group, a carboxyl 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 usually be produced by an esterification reaction or a transesterification reaction of an acid component with an alcohol component. As the acid component, a compound which is usually used as an acid component in the production of a polyester resin can be used. As the acid component, for example, an aliphatic polybasic acid, an alicyclic polybasic acid, an aromatic polybasic acid or the like can be used.

The hydroxyl value of the polyester resin is preferably from about 10 to 300 mgKOH/g, more preferably from about 50 to 250 mgKOH/g, still more preferably from about 80 to 180 mgKOH/g. The acid value of the polyester resin is preferably from about 1 to 200 mgKOH/g, more preferably from about 15 to 100 mgKOH/g, still more preferably from about 25 to 60 mgKOH/g.

The weight average molecular weight of the polyester resin is preferably from 500 to 500,000, more preferably from 1,000 to 300,000, still more preferably from 1,500 to 200,000.

The acrylic resin is preferably a hydroxyl group-containing acrylic resin. The 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 an organic solvent. Known methods such as solution polymerization method and emulsion polymerization method performed in water The method is carried out by copolymerization.

The hydroxyl group-containing polymerizable unsaturated monomer is a compound having one or more of a hydroxyl group and a polymerizable unsaturated bond in one molecule. For example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. (methyl) a monoester of acrylic acid with a carbon number of 2 to 8; an ε-caprolactone modified body of the monoester; N-hydroxymethyl (meth) acrylamide; allyl alcohol; having a molecule A (meth) acrylate or the like of a polyoxyethylene chain having a hydroxyl group at the end.

The hydroxyl group-containing acrylic resin preferably has an anionic functional group. The hydroxyl group-containing acrylic resin having an anionic functional group is, for example, a polymerizable unsaturated monomer which can be used as a polymerizable unsaturated monomer by using an anionic functional group having a carboxylic acid group, a sulfonic acid group or a phosphoric acid group. Kind to manufacture.

The hydroxyl value of the hydroxyl group-containing acrylic resin is preferably from about 1 to 200 mgKOH/g, and from 2 to 100 mgKOH/ from the viewpoints of storage stability of the aqueous polyurethane resin dispersion and water resistance of the obtained coating film. Preferably, g is preferably about 3 to 60 mgKOH/g.

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 from about 1 to 200 mgKOH/g from the viewpoint of water resistance of the obtained coating film, and the like. It is preferably about 150 mgKOH/g, more preferably about 5 to 100 mgKOH/g.

The weight average molecular weight of the more suitable hydroxyl group-containing acrylic resin is preferably from 1,000 to 200,000, more preferably from 2,000 to 100,000, still more preferably from 3,000 to 50,000.

As the polyether resin, a polymer having an ether bond or copolymerization is exemplified. Examples of the material include polyethers derived from aromatic polyhydroxy compounds such as polyoxyethylene polyethers, polyoxypropylene polyethers, polyoxybutylene polyethers, bisphenol A or bisphenol F.

Examples of the polycarbonate resin include a polymer produced from a bisphenol compound, and examples thereof include bisphenol A/polycarbonate.

The polyurethane resin may be a resin having an amine ester bond obtained by a reaction of various polyol components such as acrylic acid, polyester, polyether, or polycarbonate with a polyisocyanate.

The epoxy resin may, for example, be a resin obtained by reacting a bisphenol compound with epichlorohydrin. Examples of the bisphenol include bisphenol A and bisphenol F.

Examples of the alkyd resin include a modifier such as a fat or oil/fat fatty acid (soybean oil, linseed oil, coconut oil, or stearic acid) or a natural resin (rosin, amber, etc.). An alkyd resin obtained by reacting a polybasic acid such as an acid or succinic acid with a polyhydric alcohol.

The polyolefin resin may be a polyolefin resin obtained by polymerizing or copolymerizing an olefin-based monomer and an appropriate other monomer according to a usual polymerization method, and water-dispersing or olefin-based by using an emulsifier. A resin obtained by emulsion polymerization of a monomer together with a suitable other monomer. Further, as the case may be, a so-called chlorinated polyolefin-modified resin obtained by chlorinating the above-mentioned polyolefin resin may be used.

Examples of the olefin-based monomer include ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, and 3-methyl-1-pentene. -α-olefins such as heptene, 1-hexene, 1-decene, 1-dodecene; butadiene, ethylene decene, dicyclopentadiene, 1,5-hexadiene, benzene a conjugated diene such as ethylene or Non-conjugated dienes and the like; these single systems may be used singly or in combination of plural kinds.

Examples of other monomers copolymerizable with the olefin-based monomer include vinyl acetate, vinyl alcohol, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, and y. For the anhydride or the like, the single systems may be used singly or in combination of plural kinds.

By including the curing agent in the coating composition and the coating composition of the present invention, the coating film or the coating film using the coating composition or the coating composition, the water resistance of the coating film, and the like can be improved.

As the curing agent, for example, an amine resin, a polyisocyanate, a blocked polyisocyanate, a melamine resin, a carbodiimide or the like can be used. The hardener may be used alone or in combination of plural kinds.

The amine-based resin may, for example, be a partially or completely methylolated amine-based resin obtained by reacting an amine-based component with an aldehyde component. Examples of the amine-based component include melamine, urea, benzoguanamine, acetamide, spiro-guanamine, and dicyandiamide. Examples of the aldehyde group component include formaldehyde (formic aldehyde), paraformaldehyde, acetaldehyde, benzaldehyde, and the like.

The polyisocyanate may, for example, be a compound having two or more isocyanate groups in one molecule, and examples thereof include hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.

The blocked polyisocyanate is obtained by adding a blocking agent to the polyisocyanate of the polyisocyanate, and examples of the terminal blocking agent include a phenol system such as phenol or cresol. ; aliphatic alcohols such as methanol and ethanol Department; active methylene series such as dimethyl malonate or acetamidine acetone; thiol series such as butyl thiol and dodecyl thiol; acid amide series such as acetanilide and acetamide; An indoleamine such as indoleamine or δ-valeroinamide; an acid iodide such as succinimide or succinimide; acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, etc. A blocking agent such as an amine system such as diphenylaniline, aniline or ethylenimine.

Examples of the melamine resin include methylol melamine such as dimethylol melamine or trimethylol melamine; an alkyl etherate or condensate of the methylol melamine; and an alkyl etherate of methylol melamine. Condensate, etc.

The coating composition and the coating composition of the present invention may contain a coloring pigment, an extender pigment, and a gloss pigment.

Examples of the coloring pigment include titanium oxide, zinc white, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinophthalone pigment, isoporphyrin pigment, Threne is a pigment, a perylene pigment, and the like. These lines may be used alone or in combination. As the coloring pigment, titanium oxide and/or carbon black are particularly preferred.

Examples of the extender pigment include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, and aluminum white. These lines may be used alone or in combination. In particular, as the extender pigment, barium sulfate and/or talc is preferably used, and barium sulfate is preferably used.

The gloss pigment may be, for example, alumina coated with aluminum, copper, zinc, brass, nickel, alumina, mica, titanium oxide or iron oxide, and titanium oxide. Or mica coated with iron oxide.

The coating composition and the coating composition of the present invention can contain a tackifier, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a plasticizer, a surface conditioner, an antiprecipitant, etc., as needed. A common additive for coatings. These lines may be used alone or in combination.

The method for producing the coating composition and the coating composition of the present invention is not particularly limited, and a known production method can be used. In general, the coating composition and the coating composition can be produced by mixing the aqueous polyurethane resin dispersion with the above various additives, adding an aqueous medium, and adjusting the viscosity depending on the coating method.

Examples of the material to be coated of the coating material or the coating composition of the coating composition include metals, plastics, inorganic materials, and wood. The coating composition and the coating composition of the present invention have high adhesion to plastics, and particularly have high adhesion to ABS resins. Therefore, it is preferable that the material to be coated and the material to be coated are ABS resin.

The coating method of the coating composition or the coating method of the coating composition may, for example, be a Bell coating, a spray coating, a roll coating, a shower coating, or a dip coating.

The aqueous polyurethane resin dispersion, coating composition and coating composition of the present invention are coated or coated, coated, coated or coated after the desired substrate, under heating or non-heating, After evaporating at least a portion of the aqueous medium, it is preferred to harden it by irradiation with an active energy ray. Examples of the active energy ray include free radiation such as electron rays, ultraviolet rays, or γ rays, and among them, ultraviolet rays are preferred.

The light source of the ultraviolet light is not particularly limited as long as it emits light in an ultraviolet region or a light source, and for example, a xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh 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 the type of the compound having a polymerizable unsaturated bond, the type of the photopolymerization initiator, the thickness of the film, and the ultraviolet source. In terms of workability, it is preferred to irradiate for 1 to 60 seconds. In order to further complete the hardening reaction, it is also possible to carry out heat treatment after ultraviolet irradiation.

The irradiation amount of ultraviolet rays used for curing the aqueous polyurethane resin dispersion, the coating composition, the coating composition, and the like of the present invention is 300 to 3,000 mJ/cm ² from the viewpoint of quick-curing property and workability. good.

In order to harden, an electron beam or the like can be used in addition to ultraviolet rays. When it is hardened by an electron beam, it is preferable to use an electron beam accelerating device having an energy of 100 to 500 eV without adding a photopolymerization initiator.

The thickness of the hardened film is not particularly limited, and is preferably from 1 to 100 μm. It is preferred to form a hardened film having a thickness of 3 to 50 μm.

(Example)

Next, the present invention will be described in more detail by way of examples and comparative examples. Production Examples 1 to 3 are examples of production of an aqueous dispersion of the polyurethane resin (A), and Production Examples 4 to 9 are examples of production of an aqueous dispersion of the polyurethane resin (B).

[Manufacturing Example 1]

In a reaction apparatus equipped with a stirrer and a heater, ETERNACOLL (registered trademark) PH100 (manufactured by Ube Industries; number average molecular weight 1054; hydroxyl value 106 mgKOH/g; polyol component is 1,5-penta Alcohol: 1,6-hexanediol = 1:1 molar ratio of polyol mixture obtained by reacting with carbonate to obtain polycarbonate diol, 41.0 g), 2,2-dimethylolpropionic acid (14.4) g) Isophorone diisocyanate (56.7 g), heated in N-ethylpyrrolidone (45.9 g) in the presence of dibutyltin dilaurate (0.2 g) at 80 to 90 ° C under nitrogen atmosphere 3 hour. 2,6-Di-t-butyl-4-methylphenol (0.4 g) and 4-methoxyphenol (0.4 g) were added, and the atmosphere was air. Furthermore, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (DPHA, dipentaerythritol pentaacrylate ratio of 50 to 60 mol%, hydroxyl value 95 mgKOH/g, 181 g) is placed. Heat at 90 ° C for 7 hours. The NCO group content at the end of the amine esterification reaction was 0.23% by weight. Among the reaction mixture, 48.3 g was extracted and cooled to 70 ° C, and ethylene oxide-modified neopentaerythritol pentaacrylate (EOPETA, from 4 moles of neopentyl alcohol to 4 moles of ethylene oxide) was added/mixed. Tetraacrylate derived from alcohol, 10.8 g), and triethylamine (2.3 g). The reaction mixture was cooled to 45 ° C, and water (107 g) was slowly added while stirring to obtain an aqueous polyurethane resin dispersion.

[Manufacturing Example 2]

In a reaction apparatus equipped with a stirrer and a heater, ETERNACOLL (registered trademark) PH100 (manufactured by Ube Industries; number average molecular weight: 1054; hydroxyl value: 106 mgKOH/g; and polyol component: 1,5-pentanediol: 1, 6-hexanediol = 1:1 molar ratio of polyol mixture obtained by reacting with carbonate to obtain polycarbonate diol, 80.3 g), 2,2-dimethylolpropionic acid (28.2 g), different The ketone diisocyanate (111 g) was heated in an N-ethylpyrrolidone (94.1 g) in the presence of dibutyltin dilaurate (0.2 g) at 80 to 90 ° C for 3 hours under a nitrogen atmosphere. Add 2,6-di-tert-butyl-4-methylphenol (0.5 g) and 4-methoxyphenol (0.5 g), and the environment was air. Furthermore, a mixture of neopentyl alcohol triacrylate and neopentyl alcohol tetraacrylate (PETA, dipentaerythritol pentaacrylate ratio of 50 to 60 mol%, hydroxyl value 95 mgKOH/g, 179 g) is placed. Heat at 90 ° C for 13 hours. The NCO group content at the end of the amine esterification reaction was 0.62% by weight. 10.0 g of the reaction mixture was extracted and cooled to room temperature, and triethylamine (0.5 g) was added/mixed. Water (29.9 g) was added to the reaction mixture and stirred to obtain an aqueous polyurethane resin dispersion.

[Manufacturing Example 3]

In a reaction apparatus equipped with a stirrer and a heater, ETERNACOLL (registered trademark) PH100 (manufactured by Ube Industries; number average molecular weight: 1054; hydroxyl value: 106 mgKOH/g; and polyol component: 1,5-pentanediol: 1, a polycarbonate diol obtained by reacting a mixture of a molar ratio of 6-hexanediol = 1:1 with a carbonate, 41.0 g), 2,2-dimethylolpropionic acid (14.4 g), and The ketone diisocyanate (56.7 g) was heated in an N-ethylpyrrolidone (45.9 g) in the presence of dibutyltin dilaurate (0.2 g) at 80 to 90 ° C for 3 hours under a nitrogen atmosphere. 2,6-Di-t-butyl-4-methylphenol (0.4 g) and 4-methoxyphenol (0.4 g) were added, and the atmosphere was air. Furthermore, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (DPHA, dipentaerythritol pentaacrylate ratio of 50 to 60 mol%, hydroxyl value 95 mgKOH/g, 181 g) is placed. Heat at 90 ° C for 7 hours. The NCO group content at the end of the amine esterification reaction was 0.23% by weight. 60.4 g of the reaction mixture was extracted, and triethylamine (2.9 g) was added/mixed. The reaction mixture was cooled to 45 ° C, and water (111 g) was slowly added while stirring to obtain an aqueous polyamine. Ester resin dispersion.

[Manufacturing Example 4]

ETERNACOLL UC100 (manufactured by Ube Industries, Ltd.; number average molecular weight 1,030; hydroxyl value 109 mgKOH/g; reaction of 1,4-cyclohexanedimethanol with carbonate) Carbonate diol, 85.0 g), PTMG (quantitative molecular weight 2,030, 14.9 g), 2,2-dimethylolpropionic acid (12.1 g), hydrogenated MDI (91.1 g), in N-ethylpyrrolidone (146 g) was heated at 80 to 90 ° C for 6 hours in the presence of dibutyltin dilaurate (0.2 g) under nitrogen. The reaction mixture was cooled to 80 ° C, and after adding/mixing triethylamine (8.9 g), 239 g was extracted and added to water (310 g) with vigorous stirring. Subsequently, a 35 wt% aqueous solution of 2-methyl-1,5-pentanediamine (41.0 g) was added to obtain an aqueous polyurethane resin dispersion.

[Manufacturing Example 5]

In a reaction vessel equipped with a stirrer, a reflux cooling tube and a thermometer inserted, ETERNACOLL UM90 (3/1) (manufactured by Ube Industries; number average molecular weight 916; hydroxyl value 123 mg KOH/g; polyol component 1,4- Cyclohexanedimethanol: 1,6-hexanediol = 3:1 molar ratio of a mixture of polyols and a polycarbonate diol obtained by reacting a carbonate, 1500 g), 2,2-dimethylolpropane The acid (220 g) and hydrogenated MDI (1450 g) were heated in N-methylpyrrolidone (1,350 g) in the presence of dibutyltin dilaurate (2.6 g) at 80 to 90 ° C for 6 hours under nitrogen. The reaction mixture was cooled to 80 ° C, and triethylamine (149 g) was added/mixed. 4360 g was extracted from the reaction mixture and added to water (6900 g) with vigorous stirring. Subsequently, adding 35% by weight of 2-methyl-1,5- An aqueous solution of pentamethylenediamine (626 g) gave an aqueous polyurethane resin dispersion.

[Manufacturing Example 6]

In a reaction apparatus equipped with a stirrer and a heater, ETERNACOLL UM90 (3/1) (manufactured by Ube Industries; number average molecular weight 916; hydroxyl value 123 mg KOH/g; making the polyol component 1,4-cyclohexanedimethanol : 1,6-hexanediol = 3:1 molar ratio of polyol mixture of polycarbonate to carbonate diol, 175 g), 2,2-dimethylolpropionic acid (26.0 g) Isophorone diisocyanate (142 g) was heated in an N-methylpyrrolidone (137 g) in the presence of dibutyltin dilaurate (0.3 g) at 80 to 90 ° C for 6 hours under a nitrogen atmosphere. The reaction mixture was cooled to 80 ° C, and after adding/mixing triethylamine (19.6 g), 404 g was extracted and added to water (535 g) with vigorous stirring. Subsequently, a 35 wt% aqueous solution of 2-methyl-1,5-pentanediamine (60.9 g) was added to obtain an aqueous polyurethane resin dispersion.

[Manufacturing Example 7]

In a reaction vessel equipped with a stirrer, a reflux cooling tube and a thermometer inserted, ETERNACOLL UM90 (1/3) (manufactured by Ube Industries; number average molecular weight 916; hydroxyl value 123 mg KOH/g; polyol component 1,4- Cyclohexanedimethanol: 1,6-hexanediol = 1:3 molar ratio of polyol mixture and polycarbonate diol obtained by reaction with carbonate, 150 g), 2,2-dimethylol Acid (22.0 g), hydrogenated MDI (145 g), heated in N-methylpyrrolidone (135 g) in the presence of dibutyltin dilaurate (0.3 g) at 80 to 90 ° C for 6 hours under nitrogen atmosphere . The reaction mixture was cooled to 80 ° C, and triethylamine (14.9 g) was added/mixed. 436 g of the reaction mixture was extracted and added to water (690 g) with vigorous stirring. Subsequently, adding 35% by weight of 2-methyl-1,5- An aqueous solution of pentamethylenediamine (62.6 g) gave an aqueous polyurethane resin dispersion.

[Manufacturing Example 8]

In a reaction apparatus equipped with a stirrer and a heater, ETERNACOLL (registered trademark) UH200 (manufactured by Ube Industries, Ltd.; number average molecular weight: 2,000; hydroxyl value: 57 mgKOH/g; reaction of 1,6-hexanediol with carbonate) Polycarbonate diol, 101 g), 2,2-dimethylolpropionic acid (11.8 g), hydrogenated MDI (71.4 g), in N-methylpyrrolidone (73.0 g), dibutyltin dilaurate In the presence of (0.2 g), it was heated at 80 to 90 ° C for 3 hours under a nitrogen atmosphere. The reaction mixture was cooled to 80 ° C, triethylamine (8.8 g) was added/mixed thereto, and 230 g was extracted from the reaction mixture, and added to water (382 g) with vigorous stirring. Subsequently, a 35 wt% aqueous solution of 2-methyl-1,5-pentanediamine (5.8 g) was added to obtain an aqueous polyurethane resin dispersion.

[Manufacturing Example 9]

In a reactor equipped with a stirrer and a heater, ETERNACOLL (registered trademark) UH200 (manufactured by Ube Industries, Ltd.; number average molecular weight: 2,000; hydroxyl value: 56 mgKOH/g; reaction of 1,6-hexanediol with carbonate) Polycarbonate diol, 301 g), 2,2-dimethylolpropionic acid (16.3 g), isophorone diisocyanate (90.0 g), in N-ethylpyrrolidone (132 g), dilauric acid In the presence of dibutyltin (0.3 g), it was heated at 80 to 95 ° C for 5 hours under a nitrogen atmosphere. The reaction mixture was cooled to 80 ° C, and after adding/mixing triethylamine (12.0 g), 506 g was added to water (816 g) with vigorous stirring. Subsequently, a 35 wt% aqueous solution of 2-methyl-1,5-pentanediamine (31.3 g) was added to obtain an aqueous polyurethane resin dispersion.

[Production of pencil hardness and adhesion evaluation]

Each of the aqueous polyurethane resin dispersions of the above Production Examples 1 to 3 and the aqueous polyurethane resin dispersions of the above Production Examples 4 to 9 were mixed so as to have a weight ratio in Table 1. A 5% by weight/solids polymerization initiator (IRGACURE 500, manufactured by CIBA SPECIALTY CHEMICALS) was added and sufficiently stirred to obtain a coating composition. Each of the coating composition was uniformly coated on the PMMA resin so that the film thickness after drying became about 20 μm. Next, a coating film (before ultraviolet irradiation) was obtained by drying at 60 ° C for 30 minutes. The obtained dried coating film was supplied to a non-stick test. Further, the coating film obtained in the same manner (before ultraviolet irradiation) was passed through a high-pressure mercury lamp (illumination once, and the amount of ultraviolet irradiation was 1000 mJ/cm ² ) to obtain an ultraviolet-curable coating film. The obtained polyurethane resin coating film was supplied to a pencil hardness measurement and adhesion evaluation test. The results are shown in Table 1.

(non-stick evaluation)

The coating film obtained above (before ultraviolet irradiation) was pressed by the finger, and the state of the coating film was observed.

The state of the coating film was evaluated using the following four stages.

×: The coating film is in contact with the hand, △: the fingerprint is applied to the coating film, ○: the fingerprint is hardly applied to the coating film, and ◎: the fingerprint is not applied to the coating film.

(Evaluation of hardness)

The evaluation was carried out by measuring the pencil hardness of the polyurethane resin coating film.

[Determination of pencil hardness]

The pencil hardness of the resin coating film was measured by the method of JIS K 5600-5-4 on the polyurethane resin coating film on the PMMA resin obtained above.

(assessment of adhesion)

The polyurethane resin coating film on the PMMA resin obtained above was evaluated by a checkerboard peeling method. That is, 25 4 mm ² squares were fabricated on the test piece using a cutter, and peelability was investigated by a cellophane tape.

In Table 1, the mixing ratio of the polyurethane resin (A) and the polyurethane resin (B) is the mixing ratio of the aqueous polyurethane resin dispersion obtained in each of Production Examples 1 to 9.

It is understood that Examples 1 to 9 corresponding to the composition of the present invention are excellent non-tacky coating films before being cured by irradiation with active energy rays, and at the same time, by hardening after irradiation with active energy rays, Various plastics have high adhesion. In particular, when Examples 1 to 6 in which the same amount of the polyurethane resin (A) were used in the same amount, the alicyclic structure of the polyurethane resin (B) contained Examples 1 to 5 in the range of 29 to 60% by weight. It is particularly excellent in adhesion, and Examples 1 to 4 using a polycarbonate polyol having an alicyclic structure content of 20 to 65% by weight as the polyurethane resin (B) are also excellent in non-tackiness.

On the other hand, Comparative Example 1 lacking the polyurethane resin (B) was remarkably inferior in tackiness; Comparative Example 2 lacking the polyurethane resin (A) was remarkably inferior in hardness and adhesion after hardening; The polyurethane resin (A) and (B) are contained, but the alicyclic structure of the polyurethane resin (B) is lower than the range of the present invention, and neither of the non-stickiness nor the adhesion is inferior to the present invention. An embodiment.

(industrial availability)

The aqueous polyurethane resin dispersion system of the present invention can be widely used as a raw material of a coating material, a coating composition, and the like.

Claims (16)

An aqueous polyurethane resin dispersion which is an aqueous polyurethane resin dispersion in which at least a polyurethane resin (A) having a polymerizable unsaturated bond and a polyurethane resin (B) having no polymerizable unsaturated bond are dispersed in an aqueous medium; The polyurethane resin (B) is obtained by reacting at least a polyol (Ba), an acid group-containing polyol (Bb), a polyisocyanate (Bc), and a chain extender (Bd), and the polyurethane of the polyurethane resin (B). The ring structure content is 16 to 70% by weight. The aqueous polyurethane resin dispersion according to claim 1, wherein the polyol (Ba)-based polycarbonate polyol. The aqueous polyurethane resin dispersion according to claim 2, wherein the polyol (Ba) is a polycarbonate polyol having an alicyclic structure content of 20 to 65% by weight. The aqueous polyurethane resin dispersion according to any one of claims 1 to 3, wherein the aqueous polyurethane resin dispersion of the polyurethane resin (A) is dispersed in an aqueous medium, and the polyurethane is dispersed in the aqueous medium. The aqueous polyurethane resin dispersion of the resin (B) is mixed. The aqueous polyurethane resin dispersion according to the invention of claim 4, wherein the aqueous polyurethane resin dispersion in which the polyurethane resin (A) is dispersed in the aqueous medium and the aqueous polyurethane in which the polyurethane resin (B) is dispersed in the aqueous medium The weight ratio of the resin dispersion is from 80:20 to 30:70. The aqueous polyurethane resin dispersion according to any one of claims 1 to 5, wherein the polyurethane resin (B) has an alicyclic structure content of 29 to 60% by weight. The aqueous polyurethane resin dispersion according to any one of claims 1 to 6, wherein the polyurethane resin (A) is at least a polyol (Aa), an acid group-containing polyol (Ab), and a poly An isocyanate (Ac) and a compound (Ad) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups are reacted. The aqueous polyurethane resin dispersion according to claim 7, wherein the polyurethane resin (A) is supplied as an aqueous polyurethane, and the aqueous polyurethane is dispersed in the aqueous medium with the polyurethane resin (A) and has 1 One or more compounds having a polymerizable unsaturated bond (Ae). The aqueous polyurethane resin dispersion according to the seventh or eighth aspect of the invention, wherein the compound (Ad) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups has three or more polymerizable properties. A compound having an unsaturated bond and one or more hydroxyl groups. The aqueous polyurethane resin dispersion according to claim 9, wherein the compound (Ad) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups has five or more polymerizable properties. A compound having a saturated bond and one or more hydroxyl groups. The aqueous polyurethane resin dispersion according to any one of claims 7 to 10, wherein the compound (Ad) having one or more polymerizable unsaturated bonds and one or more hydroxyl groups is two The mixture of pentaerythritol hexaacrylate and dipentaerythritol pentaacrylate The style is supplied. The aqueous polyurethane resin dispersion according to any one of the items 7 to 11, wherein the polyurethane resin (A) has one or more polymerizable unsaturated bonds and one or more hydroxyl groups. The weight ratio of the compound (Ad) is 55 to 75% by weight. The aqueous polyurethane resin dispersion according to any one of claims 7 to 12, wherein the polyol (Aa) is a polycarbonate polyol. A photocurable composition comprising the aqueous polyurethane resin dispersion according to any one of claims 1 to 13 and a photopolymerization initiator. A coating composition comprising the aqueous polyurethane resin dispersion according to any one of claims 1 to 13. A coating composition comprising the aqueous polyurethane resin dispersion according to any one of claims 1 to 13.