JP5207530B2 - Plastic paint - Google Patents

Description

  The present invention relates to a plastic coating (hereinafter sometimes referred to simply as “paint”), and more specifically, an electron beam or ultraviolet curable (hereinafter sometimes referred to simply as “photocurable”) siloxane-modified urethane resin and polyurethane The present invention relates to a coating material used for an automotive member comprising gel particles and an aqueous crosslinking agent (particularly a photo-curable aqueous crosslinking agent and / or a water-dispersible reactive diluent). In particular, the resin is cured by light irradiation, which improves adhesion to plastic substrates, heat resistance of plastic molded products, light resistance, scratch resistance, hot water resistance, chemical resistance, etc. is there.

  General automotive interior materials include instrument panels, door trims, console boxes, glove boxes, etc., and vinyl chloride, a material that has traditionally been flexible, flame retardant, designable, vacuum formable, and cost-balanced. Many resins have been used as a material for the interior material.

  However, in recent years, thermoplastic polyolefins called TPO and thermoplastic polyurethanes for slush molding are often used instead of vinyl chloride resin for the purpose of promoting dioxin countermeasures (dehalogenation) and recycling from the viewpoint of environmental protection. .

  Molded vinyl chloride resin-based products have toxic gas generation due to incineration, deterioration of the durability due to changes in the environment and the human body due to the bleed-out of plasticizers, etc. It is changing. In addition, with the development of environmental regulations and domestic capital investment, the market for thermoplastic polyolefins and thermoplastic polyurethanes for slush molding continues to expand, and the track record as a material for automobiles leads to reliability, further replacing vinyl chloride resin. Demand acquisition is brisk.

  Thermoplastic polyolefin (TPO) has various physical properties (weather resistance, chemical resistance, etc.) that are suitable for automobile materials, and is flexible and low in density, so it can be reduced in weight (lower fuel consumption) and recyclable. It is considered a promising alternative material for vinyl chloride resin. However, automotive interior materials made of thermoplastic polyolefins require anti-glare properties for the driver to travel safely, and have a matte design with the aim of providing a full matte (matte) tone. There is a need to apply surface paint. Furthermore, the interior material is inferior in wear resistance and oil resistance (human sebum, cosmetics, etc.), and countermeasures must be taken.

  Therefore, in order to improve the countermeasures and design properties of the above two items, after processing a thermoplastic polyolefin base material with a solvent-type urethane-based resin paint, an interior material for automobiles is produced by vacuum forming the processed base material. More specifically, after a chlorinated polypropylene layer is formed on the surface of a thermoplastic polyolefin base material, it is treated with a solvent-type matte urethane resin paint as a molding base material, which is then molded into an automotive interior material. Processing.

  On the other hand, thermoplastic polyurethane for slush molding is designed as a skin material for instrument panels, etc., and the polyurethane is environmentally friendly and has design, mechanical properties, wear resistance, thermal stability, dimensional stability, low temperature In addition to excellent properties, flexibility, chemical resistance, etc., it also has excellent processability (fluidity and heat melting properties). Since the molded sheet has good design and various physical properties as an automobile interior material, surface treatment processing, which is a subsequent process, is not necessary, but a mold is required for processing, and various design properties are achieved. It is difficult to cope with and reduce costs.

  There is also a technique in which a matte paint is applied to a molded product, or a matte paint is sprayed on a mold having a design property, and then a resin (urethane resin, polypropylene, etc.) is molded. However, when urethane resin is selected as the molding material, there is no problem with the adhesion to the matte paint. However, when cost-effective polypropylene is selected, the adhesion with polypropylene is improved. In addition, a special production method is required through a special primer. In addition, as described above, use of a mold causes problems with various design properties and cost reduction.

There is a proposal to apply a paint for automobile interior materials containing chlorinated polyolefin and an acrylic emulsion to a TPO sheet that has not been surface-treated. This proposal is based on the idea of a one-coat system without pretreatment, and the effects of CO ₂ reduction, etc. are recognized by omitting the pretreatment process and simplifying the process, but the interior paint uses chlorinated polyolefin. Therefore, toxic gas is generated by incineration, which is not preferable from the viewpoint of environmental protection (Patent Document 1).

In addition, automobile interior materials composed of a material having a vinyl chloride resin excellent in heat resistance as a skin and polyurethane foam have been proposed. Since the interior material generates toxic gas by incineration, it is not preferable from the viewpoint of environmental protection (Patent Document 2).
JP 2001-2777 A JP-A-6-297624

  Therefore, the object of the present invention is to solve the above-mentioned problems, to give a plastic molded product a coating film with extremely improved wear resistance and vacuum moldability by soft touch, and further to the application of a volatile organic solvent (VOC) during coating. The objective is to provide plastic coatings that are suitable for the surface treatment of environmentally-friendly automotive interior materials that reduce emissions.

  The above object is achieved by the present invention described below. That is, the present invention contains an electron beam or ultraviolet curable (photocurable) siloxane-modified urethane resin (1), polyurethane gel particles (2), and an aqueous crosslinking agent (3) in an aqueous medium. A paint for plastics is provided.

  In the coating material of the present invention, the photocurable siloxane-modified urethane resin (1) has at least one active hydrogen-containing group and a hydrophilic group other than a hydroxyl group in the molecule (a) 0.01 ˜30% by weight, 0.01 to 30% by weight of the compound (b) having at least one active hydrogen-containing group and at least one unsaturated group, and the polyol and / or polyamine (c) (of a to d) The total amount of the compounds a to d), an amount of 0.01 to 50% by mass of the polysiloxane (d) having at least one active hydrogen-containing group, and the polyisocyanate (e). It is obtained by reacting all active hydrogen-containing groups with the isocyanate group of compound e at an equivalent ratio (OH / NCO) of 0.9 to 1.1, and the content of the siloxane segment is 0.01 to 50% by mass. Average molecule It is preferred but a resin of 2,000 to 500,000.

  In the coating material of the present invention, the polyurethane gel particle (2) is obtained by copolymerizing a polyisocyanate having at least one trifunctional or higher and a compound having an active hydrogen-containing group in the molecule. Polyurethane gel particles (particles C) comprising three-dimensionally crosslinked polyurethane gel particles (particles A) and polyurea colloid particles (particles B) coated from the polyurea colloid non-aqueous solvent solution covering the surface of the particles A. ) Is preferable.

  In the paint of the present invention, the particle B is composed of a solvated portion and a non-solvated portion with respect to the solvent, and the particle size of the non-solvated portion is 0.01 μm to 1 μm. A polyurea colloidal particle obtained by the reaction of an oil-modified polyol, a polyisocyanate, and a polyamine compound, wherein the non-solvated portion is composed of a hydrogen bond of a urea bond; The aqueous cross-linking agent (3) is preferably a photo-curable aqueous cross-linking agent and / or a photo-curable water-dispersible reactive diluent.

  In the paint of the present invention, a polyisocyanate crosslinking agent (including a block type), a melamine crosslinking agent, a carbodiimide crosslinking agent, an oxazoline crosslinking agent, an epoxy crosslinking agent, a silanol crosslinking agent, and an inorganic crosslinking agent. A crosslinking agent or a vinyl ether crosslinking agent can be included; the total amount of the photocurable siloxane-modified urethane resin (1), the polyurethane gel particles (2), and the aqueous crosslinking agent (3) is 100% by mass. It is preferable that the said resin (1) is 10-80 mass%, the said gel particle (2) is 10-80 mass%, and a water-system crosslinking agent (3) is 0.1-50 mass%.

  The coating film comprising the paint of the present invention has high design properties, soft touch and anti-glare properties, and has mechanical properties, bending resistance, slipping properties, heat resistance, low temperature properties, solvent resistance, chemical resistance, heat resistance. Excellent plasticity, light resistance, hydrolysis resistance, scratch resistance, water repellency, water resistance, and antifouling properties. Especially, the plastic substrate with the above coating film has soft wear and wear resistance and vacuum moldability. It has improved greatly.

  In addition to the above-mentioned matters, the paint of the present invention is a matte material suitable for painting environmentally friendly automobile interior materials considering the reduction of emission of volatile organic solvents (VOC) such as organic solvents used in painting. It is a paint, and the problems of the prior art are solved.

  Next, the present invention will be described in more detail by giving the best mode for carrying out the invention. The photocurable siloxane-modified urethane resin used in the present invention (hereinafter sometimes simply referred to as “the resin of the present invention”) has at least one active hydrogen-containing group and a hydrophilic group other than a hydroxyl group in the molecule. Compound (hereinafter sometimes referred to simply as “Compound a”) (Herein, the hydrophilic group other than hydroxyl group is, for example, a completely or partially neutralized carboxyl group or sulfonic acid group, completely or partially) A neutralized tertiary amino group), a compound (b) having at least one active hydrogen-containing group and at least one unsaturated group (hereinafter sometimes simply referred to as “compound b”), A polyol and / or a polyamine (hereinafter simply referred to as “compound c”) and a polysiloxane having at least one active hydrogen-containing group (hereinafter simply referred to as “compound d”). When polyisocyanate (hereinafter simply referred to as "Compound e") and obtained by reacting.

  In the above, compound a to e are used in an amount of 0.01 to 30% by mass, preferably 1 to 15% by mass of compound a, 0.01 to 30% by mass of compound b, preferably 1 to 15% by mass, and compound. c is an amount such that the total of a to d is 100% by mass, for example, 10 to 80% by mass, preferably 20 to 70% by mass, and compound d is 0.01 to 50% by mass, preferably 1 to 20% by mass. And the compound e is used such that the total active hydrogen-containing group of the compounds a to d and the isocyanate group of the compound e are equivalent ratios (OH / NCO) of 0.9 to 1.1, preferably 1.0. Amount. The compounds a to d are used in such a ratio that the total amount of the compounds a to d is 100% by mass within the above range.

  In the resin of the present invention, the content of the segment composed of the compound a is preferably 0.01 to 30% by mass when the entire resin is 100% by mass. More preferably, it is 1-15 mass%. If the content is less than 0.01% by mass, it is insufficient in terms of the emulsification stability of the resin and the adhesion to the substrate. On the other hand, if the content exceeds 30% by mass, the water resistance of the resin is insufficient. Causes a decrease.

  Moreover, it is preferable that content of the segment which consists of the said compound b is 0.01-30 mass% when the whole resin is 100 mass%. More preferably, it is 1-15 mass%. When the content is less than 0.01% by mass, the film does not have the desired coating performance when irradiated with light to undergo intramolecular / intermolecular crosslinking or a curing reaction with a crosslinking agent, while the content is 30% by mass. When it exceeds%, the crosslinking density of the coating film increases, and cracks occur in the coating film when the plastic substrate having the coating film is vacuum-molded.

  Moreover, it is preferable that content of the polysiloxane segment which consists of the said compound d is 0.01-50 mass% when the whole resin is 100 mass%. More preferably, it is 1-20 mass%. When the content is less than 0.01% by mass, it is insufficient in terms of resin lubricity and blocking resistance. On the other hand, when the content exceeds 50% by mass, it is based on the resin substrate (TPO, etc.). It may cause poor adhesion and contamination due to migration of siloxane components.

  In addition, content of the said segment of ad is used in the ratio from which the total amount of compound ad is 100 mass% within the said range. The number average molecular weight (GPC measurement, standard polystyrene conversion) of the resin is preferably 2,000 to 500,000. More preferably, it is 10,000-200,000. If the molecular weight is less than 2,000, the water resistance and weather resistance of the resin are inadequate, and on the other hand, if the molecular weight exceeds 500,000, the resin of the present invention is used as a paint. Inferior paintability and cause poor curing.

  As said compound a, compounds, such as a sulfonic acid type, a carboxylic acid type, a phosphoric acid type, and an amine type, can be used. The compound a has an effect of imparting adhesion of the resin of the present invention to a plastic substrate, and imparts dispersibility in water and self-emulsification to the resin of the present invention.

Examples of the sulfonic acid compound a include the following compounds and derivatives thereof.

  Further, as the carboxylic acid-based compound a, dimethylolpropanoic acid, dimethylolbutanoic acid and their alkylene oxide low-mole adducts (number average molecular weight less than 500), and γ-caprolactone low-mole adducts of these compounds (several numbers) (Average molecular weight less than 500), half esters derived from acid anhydride and glycerin, compounds derived from free radical reaction of monomers containing hydroxyl and unsaturated groups and monomers containing carboxyl and unsaturated groups, etc. Is mentioned. Particularly preferred compounds a are dimethylolpropanoic acid, dimethylolbutanoic acid, N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid (the acid value of the resin of the present invention is 5 to 40 mgKOH / g). It is preferable to use within a range.

  The above are examples of the preferred compound a used in the present invention, and the present invention is not limited to these exemplified compounds. Accordingly, not only the exemplified compounds described above but also any other compound a that is currently commercially available and can be easily obtained from the market can be used in the present invention.

  When the resin of the present invention containing the segment of the compound a is anionic (sulfonic acid type, carboxylic acid, etc.) when the segment of the compound a is used for dispersion in water or emulsification of the resin in use, for example, Organic amines (ammonia, ethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, N- Methyl morpholine, 2-amino-2-ethyl-1-propanol, etc.), alkali metals (lithium, potassium, sodium, etc.), inorganic alkalis (lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.) Neutralized by addition, in the case segment of compound a is cationic (tertiary amine), for example, organic acids, e.g., neutralized formic acid, lactic acid, and the like acetic acid.

  The compound b is not particularly limited, and one or more of known compounds can be used. When the active hydrogen-containing group of compound b is a hydroxyl group, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycerin monoallyl ether , Trimethylolpropane diallyl ether, pentaerythritol triallyl ether, glycerin monomethacrylate and the like. Particularly preferred compounds are those having one unsaturated group and two hydroxyl groups.

  When the active hydrogen-containing group of compound b is an amino group, for example, allylamine, diallylamine, N, N′-methylenebisacrylamide, N-methylacrylamide, diacetone acrylamide, N-methylol acrylamide, 2-acrylamide- Examples include 2-methylpropanesulfonic acid.

  The polyol as the compound c is preferably a conventionally known one such as a short chain diol, a polyhydric alcohol and a polymer polyol conventionally used for polyurethane production, and a polyamine is conventionally used for polyurethane production. The short chain diamine etc. currently used can be used. These are not particularly limited. Each compound will be described below.

  Examples of the short-chain diol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, and neopentyl. Aliphatic glycols such as glycols and alkylene oxide low-mole adducts thereof (number average molecular weight less than 500), alicyclic glycols such as 1,4-bishydroxymethylcyclohexane and 2-methyl-1,1-cyclohexanedimethanol And its alkylene oxide low molar adduct (number average molecular weight less than 500), aromatic glycols such as xylylene glycol and its alkylene oxide low molar adduct (less than number average molecular weight 500), bisphenol A, thiobisphenol and Bisphenols and alkylene oxide low molar adducts of such fine sulfone bisphenol (number average molecular weight of less than 500), and compounds such as alkyl dialkanolamines, such as alkyl diethanolamine of C1~C18 thereof.

  Examples of the polyhydric alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, tris- (2-hydroxyethyl) isocyanurate, 1,1,1-trimethylolethane, and 1,1,1- Examples include trimethylolpropane. These can be used alone or in combination of two or more.

Examples of the polymer polyol include the following.
(1) Polyether polyols such as those obtained by polymerizing or copolymerizing alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) and / or heterocyclic ethers (tetrahydrofuran, etc.) are specifically exemplified. Are polyethylene glycol, polypropylene glycol, polyethylene glycol-polytetramethylene glycol (block or random), polytetramethylene ether glycol and polyhexamethylene glycol,

(2) Polyester polyols such as aliphatic dicarboxylic acids (eg succinic acid, adipic acid, sebacic acid, glutaric acid and azelaic acid) and / or aromatic dicarboxylic acids (eg isophthalic acid and terephthalic acid) And low molecular weight glycols (for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, neopentyl glycol) And 1,4-bishydroxymethylcyclohexane) and the like, specifically, polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyneopentyl adipate di Lumpur, polyethylene / butylene adipate diol, polyneopentyl / hexyl adipate diol, poly-3-methylpentane adipate diol, and polybutylene isophthalate diol, etc.,

(3) Polylactone polyols such as polycaprolactone diol and poly-3-methylvalerolactone diol,
(4) Polycarbonate diol, such as polyhexamethylene carbonate diol, polytetramethylene carbonate diol,
(5) Polyolefin polyol, such as polybutadiene glycol and polyisoprene glycol, or a hydride thereof,
(6) Polymethacrylate diols such as α, ω-polymethylmethacrylate diol and α, ω-polybutylmethacrylate diol are exemplified.

  The structure and molecular weight of these polyols are not particularly limited, but usually the number average molecular weight is preferably about 500 to 4,000, and these polyols can be used alone or in combination of two or more.

  Preferred polyamines as the polyamine include, for example, short chain diamines, aliphatic, aromatic diamines, long chain diamines and hydrazines. Examples of the short-chain diamine include aliphatic diamine compounds such as ethylene diamine, trimethylene diamine, hexamethylene diamine and octamethylene diamine, phenylene diamine, 3,3′-dichloro-4,4′-diaminodiphenylmethane, and 4,4 ′. -Aromatic diamine compounds such as methylene bis (phenylamine), 4,4'-diaminodiphenyl ether and 4,4'-diaminodiphenyl sulfone, cyclopentanediamine, cyclohexyldiamine, 4,4-diaminodicyclohexylmethane, 1,4-diamino And alicyclic diamine compounds such as cyclohexane and isophorone diamine.

  Examples of the long-chain diamine include those obtained by polymerizing or copolymerizing alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.), and specific examples include polyoxyethylene diamine and polyoxypropylene diamine. Further, hydrazines such as hydrazine, carbohydrazide, adipic acid dihydrazide, sebacic acid dihydrazide and phthalic acid dihydrazide can be mentioned. These can be used alone or in combination of two or more. As the polyol and polyamine, polyether-based diol compounds and diamine compounds such as ethylene oxide and propylene oxide are preferable.

  The compound d is contained as a polysiloxane segment in the resin of the present invention, and the polysiloxane segment is contained in the main chain of the resin or in a branched state. That is, if the compound d as a raw material is reactive at both ends, the segment of the compound d is from the backbone of the main chain of the resin, and if the compound d is one end or branched reaction type, from the main chain of the resin. It will be contained in a branched state.

  Examples of the compound d used in the present invention include the following compounds. Among these, epoxy-modified polysiloxanes modified using active hydrogen-containing groups are included, but they are included because they react with isocyanate groups and are contained in polyurethane resins.

(1) Amino-modified polysiloxane

(2) Epoxy-modified polysiloxane

  The above epoxy compound can be used by reacting with a polyol, polyamide, polycarboxylic acid or the like to have a terminal active hydrogen-containing group.

(3) Alcohol-modified polysiloxane

(4) Mercapto-modified polysiloxane

  The polysiloxanes having active hydrogen-containing groups listed above are preferred compounds for use in the present invention, but the present invention is not limited to these exemplified compounds. The listed polysiloxanes are dimethylpolysiloxane compounds, but other phenyl polysiloxane compounds and vinyl polysiloxanes that are cured by electron beams or ultraviolet rays (light) can also be used. Therefore, not only the compounds exemplified above, but also any other compounds that are currently commercially available and can be easily obtained from the market can be used in the present invention. In addition to these, particularly preferred compounds in the present invention are polysiloxanes having two hydroxyl groups or amino groups.

  Besides these, polylactone (polyester) -polysiloxane obtained by modifying polysiloxane with lactone, polyalkylene oxide-polysiloxane modified with alkylene oxide, and the like are also preferably used. Preferred lactones used here are β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, 7-heptanolide, 8-octanolide, γ-valerolactone, γ-caprolactone and δ-caprolactone. . Examples of the alkylene oxide include ethylene oxide, propylene oxide, α-butylene oxide, β-butylene oxide, hexene oxide, cyclohexene oxide, styrene oxide, α-methylstyrene oxide, and the like.

  As the compound e, any of those conventionally used for producing polyurethane can be used and is not particularly limited. Preferred examples of the compound e include, for example, toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-Butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanate diphenyl ether, 4,4′-methylenebis (phenylene isocyanate) (MDI), durylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate (XDI), 1,5 Aromatic diisocyanates such as naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate and 4,4'-diisocyanate dibenzyl, methylene diisocyanate 1,4-tetramethylene diisocyanate, aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate and 1,10-decamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), Obtained by reacting 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, alicyclic diisocyanates such as hydrogenated MDI and hydrogenated XDI, or these diisocyanate compounds with low molecular weight polyols and polyamines so that the ends are isocyanates. Naturally, polyurethane prepolymers and the like can also be used.

  The method for producing the resin of the present invention using the compounds a to e is not particularly limited, and conventionally known methods for producing polyurethane can be used. For example, in the presence or absence of an organic solvent that does not contain an active hydrogen-containing group in the molecule, the compound a, the compound b, the compound c, the compound d, and the compound e are combined with an isocyanate group and an active hydrogen-containing group. The equivalent ratio (OH / NCO) is usually 1.0 or around (0.9 to 1.1), and is usually 20 to 150 ° C., preferably by the one-shot method or multistage method, It reacts at 60-110 ° C. until the product reaches theoretical NCO%, and the resulting resin is emulsified with water and a neutralizing agent. Accordingly, the resin of the present invention (or its emulsion in water) can be obtained through a solvent removal step.

  In the present invention, a catalyst can be used as necessary in the urethane synthesis. For example, salts of metals and organic and inorganic acids such as dibutyltin laurate, dioctyltin laurate, stannous octoate, lead octylate, tetra-n-butyl titanate, and organic metal derivatives, organic amines such as triethylamine, diaza Bicycloundecene catalysts and the like can be mentioned.

  The resin of the present invention may be synthesized without a solvent, or may be synthesized using an organic solvent if necessary. Preferred solvents as organic solvents include those that are inert to isocyanate groups or less active than the reaction components. For example, ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), aromatic hydrocarbon solvents (toluene, xylene, swazol (aromatic hydrocarbon solvents manufactured by Cosmo Oil Co., Ltd.)), Solvesso (Exxon Chemical Co., Ltd.) Company-made aromatic hydrocarbon solvents), aliphatic hydrocarbon solvents (n-hexane, etc.), alcohol solvents (methyl alcohol, ethyl alcohol, isopropyl alcohol, etc.), ether solvents (dioxane, tetrahydrofuran, etc.) , Ester solvents (ethyl acetate, butyl acetate, isobutyl acetate, etc.), glycol ether ester solvents (ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate) Over DOO, such as ethyl 3-ethoxypropionate), amide solvents (dimethylformamide, dimethyl acetamide), lactam solvent (N- methyl-2-pyrrolidone, etc.). Of these, methyl ethyl ketone, ethyl acetate, acetone, and tetrahydrofuran are preferable in consideration of solvent recovery, solubility during urethane synthesis, reactivity, boiling point, and emulsification dispersibility in water.

  In the present invention, in the resin synthesis step, when an isocyanate group remains at the polymer terminal, an isocyanate terminal termination reaction may be added. For example, not only monofunctional compounds such as monoalcohols and monoamines, but also compounds having two kinds of functional groups having different reactivities with respect to isocyanate can be used. Monoalcohols such as alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol; monoethylamine, n-propylamine, diethylamine, di-n-propylamine, di-n -Monoamines such as butylamine; alkanolamines such as monoethanolamine and diethanolamine, and the like. Among these, alkanolamines are preferable because of easy reaction control.

  In the production of the resin of the present invention, additives may be added as necessary. For example, antioxidants (hindered phenols, phosphites, thioethers, etc.), light stabilizers (hindered amines, etc.), UV absorbers (benzophenones, benzotriazoles, etc.), gas discoloration stabilizers (hydrazines, etc.) ), Metal deactivators and the like, and two or more of these.

  Next, the polyurethane gel particles ((2) or particles C) used in the present invention will be described. In the particle C, the particle B covering the particle A is composed of a part solvated with a solvent and a non-solvated part, and the particle size of the non-solvated part is 0. 0.01 μm to 1.0 μm, and the particle B is a particle obtained by a reaction of an oil-modified polyol, a polyisocyanate, and a polyamine, and the non-solvated portion is formed of a hydrogen bond of a urea bond. Preferably, the particle C has a particle diameter in the range of 0.5 to 100 μm.

  The above particles C consist of a polyisocyanate solution (hereinafter sometimes referred to as “compound e ′”) and a compound having an active hydrogen-containing group (hereinafter sometimes referred to as “compound c ′”) as a raw material. It can be obtained by emulsifying and dispersing (dispersed liquid of particle B) in an inert solvent as a dispersant. At this time, it is important that the polyurea colloid solution easily emulsifies the compound e ′ and compound c ′ as raw materials in an inert solvent in the form of particles.

  In this state, the compound e ′ and the compound c ′ are polymerized to generate particles A, and the particles B precipitated from the polyurea colloid solution are uniformly attached around the generated particles A. In a state where the particles C are separated from the dispersion solvent, the particles A are uniformly coated with the particles B.

  Further, in the conventional process of synthesizing the particles A or C, a significant increase in viscosity usually occurs. However, when the particle A is synthesized in the presence of a polyurea colloid solution, a significant increase in the viscosity of the polymerization solution does not occur in the synthesis process. The produced particles C are characterized by maintaining excellent dispersion stability without agglomeration. This action is fundamentally different from conventionally known organic emulsifiers and dispersion stabilizers.

  The particles C used in the present invention can be obtained by the above-described method, but a preferable method is that a polyurea colloid solution is charged into an inert solvent in a jacket-type synthesis kettle equipped with a stirrer or an emulsifier, and at least one of them is added. A method of synthesizing particles C by adding and emulsifying compound e ′ and compound c ′, one of which is trifunctional or higher, into an inert solvent solution and reacting these synthesis raw materials, or at least one of which is trifunctional or higher A compound e ′ and a compound c ′ are separately emulsified in an inert solvent in the presence of a polyurea colloid solution, and these are reacted.

  Although the synthesis temperature in the said synthesis method is not specifically limited, A preferable temperature is 40 to 140 degreeC. In addition, the polyurea colloid solution used at the time of synthesis is used in an amount of 0.01 mass parts or more per 100 mass parts of the compound e ′ and the compound c ′ each having at least one of three or more functional groups as the solid content. Can be used, and it is preferably 0.1 to 20 parts by mass. When the amount used is less than 0.01 parts by mass, the stability of the generated particles C is insufficient, and large aggregates of the particles A are generated during the synthesis process, making it difficult to obtain a target particle C dispersion. On the other hand, when the amount used exceeds 20 parts by mass, there is no problem with the emulsifiability of the polyurethane raw material (compound e ′ and compound c ′), and a dispersion of particles C can be produced. As an excessive amount, there is no particular advantage. The lower the concentration of the compound e 'and the compound c' in the inert solvent, the easier it is to obtain particles C having a smaller particle diameter. However, a preferable concentration is 20 to 70 parts by mass for productivity.

  Examples of the polyol as the compound c ′ used for the synthesis of the particle A include conventionally known ones such as a short-chain diol, a polyhydric alcohol, and a polymer polyol similar to the compound c. The molecular weights of these polyols are not particularly limited, but all those that react with the compound e 'can be used, and the number average molecular weight is usually preferably about 500 to 3,000. Moreover, these polyols can be used individually or in combination of 2 or more types. As the polyol, a polyol having two or more active hydrogen-containing groups is preferable, and a polyol having three or more active hydrogen-containing groups is particularly preferable.

  In addition, as the polyamine as the compound c ′, a short-chain diamine, a high molecular polyamine and the like similar to the compound c can be used. As these polyamines, polyamines having 2 or more active hydrogen-containing groups are preferable, and polyamines having 3 or more active hydrogen-containing groups are particularly preferable.

  As the compound e ′ used for the synthesis of the particles A, any of those similar to the compound e can be used and is not particularly limited. In addition, a compound having a polyfunctional isocyanate group in which the compound e ′ is an isocyanurate, burette, adduct, or polymer and having a polyfunctional isocyanate group can be used without any particular limitation. For example, dimer of 2,4-toluylene diisocyanate, triphenylmethane triisocyanate, tris- (p-isocyanatephenyl) thiophosphite, polyfunctional aromatic isocyanate, polyfunctional aromatic aliphatic isocyanate, polyfunctional aliphatic Examples thereof include blocked polyisocyanates such as isocyanate, fatty acid-modified polyfunctional aliphatic isocyanate, and blocked polyfunctional aliphatic isocyanate, and polyisocyanate prepolymers.

  Of these, it is possible to use either an aromatic or aliphatic type, preferably a modified product such as diphenylmethane diisocyanate and tolylene diisocyanate for an aromatic type, hexamethylene diisocyanate and isophorone diisocyanate for an aliphatic type, and a molecule. A urethane prepolymer obtained by reacting a polyisocyanate multimer or an adduct with another compound, or a low molecular weight polyol or polyamine so as to be a terminal isocyanate is preferable. Etc. are also preferably used. These are exemplified below with structural formulas, but are not limited thereto.

  The types, amounts and ratios of the above-mentioned compound e 'and compound c' are determined depending on the purpose of use of the particles C to be obtained, but any one of the components must be trifunctional or more. For example, when the compound e ′ is bifunctional, the compound c ′ is trifunctional or higher, and when the compound c ′ is bifunctional, the trifunctional or higher functional compound e ′ is required. Select the number of functional groups to be used according to the purpose of use. Of course, all the components may be trifunctional or more. The NCO / OH ratio is determined by the performance required for the raw material compound to be used and the particles C to be obtained, but is preferably in the range of 0.5 to 1.2.

  The inert solvent used for the synthesis reaction of the particles C and forming the continuous phase of the dispersion of the generated particles C is substantially non-solvent with respect to the generated particles A and has no active hydrogen-containing group. Is. Examples include pentane, hexane, heptane, octane, decane, petroleum ether, petroleum benzine, ligroin, petroleum spirit, cyclohexane, methylcyclohexane, toluene, xylene, ethylcyclohexane, dimethylcyclohexane, etc. having the structure of alicyclic hydrocarbons. Hydrocarbon, dimethylpolysiloxane, etc. may be used alone or as a mixture, and these inert solvents have a boiling point of 150 ° C. or less in terms of productivity in the separation process of the particles C synthesized with the inert solvent. Is preferred. In the synthesis of the particles A, a known catalyst may be used at a low temperature, but a reaction temperature of 40 ° C. or higher is preferable from the work surface.

  The particles B in the polyurea colloid solution used as an emulsifier during the synthesis of the particles A are composed of a solvated part and a non-solvated part, and the particle size of the non-solvated part is preferred. Is a particle of 0.01 μm to 1.0 μm, and such a polyurea colloid solution is obtained by, for example, mixing an oil-modified polyol, a compound e ′ (or a terminal NCO prepolymer comprising these compounds) and a polyamine in a non-aqueous solvent. Obtained by reaction.

  In this reaction, as the reaction proceeds, hydrogen bonds between urea bonds form an insoluble urea domain in the solvent, and at the same time, the oil-modified polyol chain is solvated in the solvent, thereby insoluble urea. The enlarging of the particle B due to domain aggregation or the like is prevented, and a stable polyurea colloid solution can be easily obtained.

  Furthermore, the oil-modified polyol used has little crystallinity in a non-aqueous solvent, and the polymer chain mainly composed of the oil-modified polyol can move to some extent in the solvent even in the process of polymerization that occurs as the reaction proceeds. Therefore, separation of the non-soluble crystal portion and the soluble non-crystalline portion is easily performed, and a urea domain having the non-soluble crystal portion due to hydrogen bonding between urea bonds as the center of the particle B is formed, and the periphery thereof is formed. The solvated polymer chains are regularly ordered outward. This is a fundamentally different action from the surfactant in a known method for producing a colloidal solution obtained by polymerization in the conventional micelle.

  The method for producing the polyurea colloid solution will be described more specifically. First, the oil-modified polyol and the compound e ′ are first reacted in a non-aqueous solvent or without a solvent to synthesize a prepolymer having an NCO group. Next, this prepolymer is charged into a jacket-type synthesis kettle equipped with a stirrer, and the concentration is adjusted by adding a non-aqueous solvent so that the concentration becomes 5 to 70% by mass. While stirring this solution, a polyamine solution adjusted to a concentration of 1 to 20% by mass in advance is gradually added to react to produce a polyurea colloid solution in the polyureaization reaction.

  In addition to the above method, the polyamine may be added by adding the prepolymer or a solution thereof to the polyamine solution. The temperature for polymer synthesis is not particularly limited, but a preferred temperature is 20 to 120 ° C. The reaction concentration for polymer synthesis, temperature, stirrer form, stirring power, polyamine solution and prepolymer or addition rate of the prepolymer are not particularly limited, but the reaction between the polyamine and the isocyanate group of the prepolymer is fast, It is preferable to control the reaction so that a rapid reaction is not performed.

  The oil-modified polyol used for the production of the polyurea colloid solution is a polyol having 2 or less functional groups, and a preferred molecular weight is 700 to 3,000, but is not limited thereto. Specific examples of the oil-modified polyol include, for example, various fats and oils by alcoholysis using a lower alcohol or glycol, a method of partially saponifying fats and oils, a method of esterifying a hydroxyl group-containing fatty acid with glycol, and the like. Those containing two or less hydroxyl groups are preferred, and examples of the hydroxyl group-containing fatty acid include ricinoleic acid, 12-hydroxystearic acid, castor oil fatty acid, hydrogenated castor oil fatty acid, and the like.

  The reaction between the oil-modified polyol and the compound e ′ is carried out under the condition of 1 <NCO / OH ≦ 2, and the molecular weight of the solvated prepolymer chain is controlled. The molecular weight of the prepolymer synthesized in this way is not particularly limited, but a preferred range is about 500 to 15,000. Examples of the compound e 'used above include all known polyisocyanates. Particularly preferred are aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, water-added TDI, water-added MDI, isophorone diisocyanate, and hydrogenated XDI.

  As the non-aqueous solvent used for the production of the polyurea colloidal solution, any non-aqueous solvent that dissolves the oil-and-fat-modified polyol, diisocyanate and polyamine used as raw materials and does not have an active hydrogen-containing group can be used. . Particularly preferred are pentane, hexane, heptane, octane, decane, petroleum ether, petroleum benzine, ligroin, petroleum spirit, cyclohexane, methylcyclohexane, toluene, xylene, ethylcyclohexane and dimethylcyclohexane having an alicyclic hydrocarbon structure. A hydrocarbon, dimethylpolysiloxane or the like may be used alone or as a mixture. In the present invention, “dissolution” includes both dissolution at normal temperature and high temperature.

  Examples of the polyamine used for the production of the polyurea colloid solution include the polyamine used for the production of the resin or particles A of the present invention, and these can be used alone or in combination of two or more.

  The purpose of controlling the size and stability of the particle B in the solvent used is the type, amount and ratio of the oil-modified polyol, polyisocyanate, polyamine and the resulting prepolymer used in the production of the polyurea colloid solution. Determined by That is, the particles B in the polyurea colloid solution are formed of a urea domain in a crystal part that is not solvated in the solvent and a polymer chain that extends from the urea domain and is solvated in the solvent.

  The size of the urea domain of particle B in the polyurea colloid solution and the size and morphology of the solvated polymer chain influence the properties of the polyurea colloid solution. Thus, the particle B formed of the urea domain and the solvated polymer chain is a polyurea colloidal solution that is stable in the solvent, and the particle size of the urea domain of the particle B in the solution is usually 0.00. The molecular weight of one solvated polymer chain is about 500 to 15,000, and the mass ratio of both is 0.5 for the urea domain (urea bond or polyamine) / polymer chain. A range of ˜30 is preferred. When the ratio of the urea bond is less than the above range, the non-solvating urea domain in the obtained particle B is hardly formed, the particle B is easily dissolved in the non-aqueous solvent, and a good polyurea colloid solution is not generated. On the other hand, when the ratio of the urea bond exceeds the above range, the non-solvating urea domain is increased, the stability of the resulting polyurea colloid solution is lowered, and the aggregation of the particles B is likely to occur.

  The form in the solvent of the particle | grains B used by this invention is imagined as shown in FIG. Regarding the control of the particle size of the particle B, it is possible to control both the size of the entire particle B including the solvated polymer portion and the urea domain, and the size of each of the solvated polymer portion and the urea domain. is there. The particle size of the particle B described above represents a urea domain portion.

  In order to produce a stably controlled polyurea colloidal solution, it is desirable that the solvated polymer part and the urea domain part are clearly phase-separated as shown in FIG. It is necessary to manufacture such that the chain and the urea domain of the crystal part are not mixed. For this purpose, a synthesis condition is required in which the polymer part solvated in the synthesis process and the urea domain part are easily separated.

  The synthesis of the polyurea colloidal solution gives better results as the concentration of both the prepolymer solution containing NCO groups and the polyamine solution is lower, and the addition rate of adding the other solution to one solution is lower, and the stirring is better. Propeller mixer agitation is sufficient. Further, when the concentration of the raw material solution is high or when the addition rate of the solution is high, it is preferable to synthesize while mixing with a high shearing force by using a homogenizer or the like. Although the reaction temperature is determined by the type of solvent used and the solubility of the urea domain in the solvent, the preferred temperature is 20 to 120 ° C. at which the synthesis can be easily controlled, but is not particularly limited to this temperature range. The formation of the urea domain may be a method of forming in the synthesis process, or a method of forming a synthesis at a high temperature in the cooling process.

  The important factors of the particles B in the polyurea colloid solution are the type and concentration of the surface groups, and further the dispersibility and the dispersed particle size in an inert solvent. That is, the action of the polyurea colloid solution as an emulsifier is a W / O, O / O type emulsifier, and the correlation between the hydrophilicity and hydrophobicity of the polyisocyanate and the compound having an active hydrogen-containing group and the inert solvent. Acts on sex. As a result of considering these conditions, it is possible to control the particle size of the particles C by adjusting the amount of polyurea colloid solution added to the polyisocyanate and the compound having an active hydrogen-containing group. In this range, the larger the amount added, the smaller the particle size, and the smaller the amount, the larger the particle size.

  The particles C are obtained by separating the inert solvent from the dispersion solution of the particles C obtained from the raw materials as described above under normal pressure or reduced pressure. Any known device such as a spray dryer, a vacuum dryer with a filtration device, a vacuum dryer with a stirring device, a shelf dryer, etc. can be used as a device for particle formation, and the preferred drying temperature is the vapor pressure of an inert solvent, gel particles Although it is influenced by the softening temperature, particle size, etc., it is preferably 40 to 130 ° C. under reduced pressure.

  The particle C thus produced has a true spherical shape with a particle size of 0.5 μm to 100 μm and a circularity of 0.9 to 1.0. The control of the particle size depends on the emulsification type of the synthetic kettle (propeller type, saddle type, homogenizer, spiral band type, etc.) and the stirring force when the composition of the polyurethane is the same, but especially in an inert solvent. It is influenced by the concentration of the polyisocyanate and the compound having an active hydrogen-containing group, the type of polyurea colloid solution and the amount added. The mechanical agitation and shearing force for emulsifying the polyisocyanate and the compound having an active hydrogen-containing group are determined in the initial stage of emulsification, and the stronger this is, the smaller the particle size of the dispersion. Subsequent stirring and shear forces are not significantly affected. On the other hand, if the force is too strong, aggregation of the dispersions is promoted, which is not preferable.

  These particles C are almost perfectly spherical particles as shown in the electron micrograph (magnification 500 times) in FIG. 2, and polyurea colloids are formed on the surfaces of the individual particles A as shown in the imaginary view of FIG. Particles B deposited from the solution are attached or coated, and particles B are excellent in non-adhesiveness and heat resistance. Therefore, the particles C are highly fluid by simply removing the particles C from the dispersion solvent. In the formation of particles, there are various advantages such as no complicated and costly pulverization process and classification operation as in the prior art.

  Further, it is preferable that the particle C has a circularity of 0.9 to 1.0 represented by [circularity = peripheral length of circle obtained from equivalent circle diameter / peripheral length of particle projection]. Here, the circularity is calculated by the above equation by the particle shape image analysis apparatus PITA-1 of Seishin Co., Ltd., and the circularity is equivalent to a circle-equivalent diameter (the same projected area as the actually captured perimeter). It is defined as a value obtained by dividing the perimeter calculated from the diameter of the perfect circle by the perimeter of the actually imaged particle, and becomes 1 for a perfect circle, and becomes a smaller value as the shape becomes more complex. For this reason, particles with extremely high sphericity with a circularity of 0.9 or more are preferable, and the dispersion in which the particles are dispersed in water or the like is very stably dispersed due to charge repulsion. Has dispersion stability and thickening effect. In the case of the particles C having a circularity of less than 0.9, the particles C are not spherical and lose the stable dispersibility, and the coating composition containing the particles C has a rough feeling.

  Further, the compressive strength of the particles C is preferably 0.01 to 1.0 MPa, and the recovery rate is preferably in the range of 60 to 100%. As for the compressive strength, since the particle C is a polyuntan gel particle in which the particle A is coated with the particle B, a sufficient dry feeling can be obtained at 0.01 MPa or more, soft touch feeling, slipperiness, slime feeling From the viewpoint of obtaining the above, the compressive strength of the particles C is preferably 1 MPa or less.

  Further, the recovery rate of the particles C is required to be restored to the original shape at the same time as the force is released when deformed by pressure, and is preferably in the range of 60 to 100%. Here, the compression strength and the recovery rate are the load and the particle diameter when the resin particles are subjected to a compression test with a microcompression tester MCT-W500 manufactured by Shimadzu Corporation and deformed by 10% with respect to the particle diameter. From the equation [compressive strength (MPa) = 2.8 × load (N) / {π × particle diameter (mm) × particle diameter (mm)}].

  Further, the recovery rate of the particle C is obtained by applying the equation [recovery rate (%) = L2 / L1 × 100 from a distance (L1) displaced when a pressure of 50 mN is applied to the particle and a distance (L2) displaced when the pressure is released. ] Is calculated. The compressive strength and recovery rate of the resin particles can be adjusted by controlling the types and blending amounts of the compound e 'and the compound c' that are the constituent components of the particles A.

  Next, the aqueous crosslinking agent (3) used in the present invention will be described. The aqueous crosslinking agent (3) crosslinks a coating film made of the resin of the present invention. The crosslinking is carried out by blending a reactive diluent and / or a photocurable crosslinking agent and a photopolymerization initiator (only in the case of an ultraviolet curing system) with the above-described resin of the present invention, and then applying light. Then, the coating film can be cured.

  Examples of the reactive diluent and / or photo-curable crosslinking agent used here include radical polymerization monofunctional acrylate compounds, polyfunctional acrylate compounds, and cationic polymerization compounds, but water-soluble radical polymerization. Type monofunctional acrylate compounds are preferred, for example, methoxytriethylene glycol acrylate, methoxypolyethylene glycol acrylate, vinyl caprolactam, ethyl carbitol acrylate, N-vinylformamide, N, N-dimethylaminoethyl acrylate, methoxytetraethylene glycol ( (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methoxyethyl (meth) acrylate Rate, N- vinyl-2-pyrrolidone, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N, N- dimethylacrylamide, N- isopropylacrylamide, acryloylmorpholine, and the like glycerine monoallyl ether. Also, commercially available hydrophobic radical polymerization monofunctional acrylate compounds can be used.

  Examples of water-soluble polyfunctional acrylate compounds include triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, diethylene glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. . Examples of the hydrophobic polyfunctional acrylate compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol hexa (meth) acrylate, trimethylolpropane di (meth) acrylate, pentatrithritol tetra (meth) acrylate. Etc. Examples of the cationic polymerization diluent include an epoxy compound, an oktacene compound, a vinyl ether compound, and the like.

  In addition, a photocurable crosslinking agent obtained by reacting a polyfunctional polyisocyanate and an active hydrogen group-containing (meth) acrylate compound, or a photocurable urethane containing a hydrophilic group and one or more unsaturated groups in one molecular chain. System crosslinking agents can also be used. These crosslinking agents are used in an amount of 120 parts by mass or less, preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resin of the present invention.

  Furthermore, a thermosetting crosslinking agent can be used in combination with the photocurable crosslinking agent. Examples of these crosslinking agents include polyisocyanate crosslinking agents (including block type), melamine crosslinking agents, carbodiimide crosslinking agents, oxazoline crosslinking agents, epoxy crosslinking agents, inorganic crosslinking agents, and cationic polymerization crosslinking agents. Agents (epoxy, oxetane, vinyl ether crosslinking agent) and the like. In particular, in the present invention, a crosslinking method utilizing the reactivity of a hydrophilic group such as a urethane group and / or a carboxyl group is preferable, but is not particularly limited.

  Examples of the crosslinking method using a urethane group include crosslinking with a polyisocyanate crosslinking agent, but the polyisocyanate crosslinking agent is not particularly limited, and any conventionally known one can be used. For example, water-dispersed polyfunctional aromatic isocyanates, water-dispersed polyfunctional aliphatic isocyanates, water-dispersed fatty acid-modified polyfunctional aliphatic isocyanates, water-dispersed blocked polyfunctional aliphatic isocyanates and other block-type polyisocyanates, water-dispersed Type polyisocyanate prepolymer. These polyisocyanate cross-linking agents are effective in improving the adhesion between the coating film and the plastic substrate if they are in an appropriate amount, but if the amount used is too large, unreacted isocyanate remains and becomes a problem. When using a crosslinking agent together, it is preferable that it exists in the range of 0.5-50 mass parts with respect to 100 mass parts of the said water-system crosslinking agent (3).

  As a crosslinking method using a hydrophilic group, for example, a carboxyl group, a carbodiimide-based crosslinking agent, an oxazoline-based crosslinking agent, an epoxy-based crosslinking agent, an oxetane-based crosslinking agent, a vinyl ether-based crosslinking agent, or a metal complex-based crosslinking agent has been conventionally used. The well-known thing used can be used and it does not specifically limit. For example, as an epoxy-type crosslinking agent, conventionally well-known commercially available epoxy resins, such as "Epicoat" (made by Yuka Shell Epoxy), are mentioned.

  As the carbodiimide-based cross-linking agent, a commercially available product under the trade name “Carbodilite” (manufactured by Nisshinbo) can be used. The crosslinking agent reacts with a carbodiimide group and a carboxyl group to form N-acyl urea, thereby improving the coating film performance. As the oxazoline-based crosslinking agent, commercially available products such as “Epocross” trade name (manufactured by Nippon Shokubai Co., Ltd.), WS-300, WS-500, W-700, and WS-R10 can be obtained and used. These crosslinking agents take a crosslinked structure by reacting the oxazoline group of the crosslinking agent and the carboxyl group of the resin to form an amide ester.

Moreover, as an oxetane type crosslinking agent, the commercial item of the brand name (made by Ube Industries) of "Ethanacol" can be obtained and used. As the vinyl ether-based crosslinking agent, commercially available products such as BASF, IPS Japan, Maruzen Petrochemical, Nippon Shokubai, etc. can be obtained and used. The crosslinking agent reacts by cationic polymerization or forms an alkoxyester by Michael addition reaction.
When using the above crosslinking agent together, it is preferable that it exists in the range of 0.5-50 mass parts with respect to 100 mass parts of the said water-system crosslinking agent (3).

  As the metal complex-based crosslinking agent, titanium organic compound-based, zirconium organic compound-based commercially available under the trade name of “Orgatyx” (manufactured by Matsumoto Pharmaceutical Co., Ltd.) are available, and aluminum, chromium, cobalt, copper, Iron, nickel, vanadium, zinc, indium, calcium, magnesium, manganese, yttrium, cerium, strontium, palladium, barium, molybdenium, lanthanum, tin sold under the trade name "Narsem" (manufactured by Nippon Kagaku Sangyo Co., Ltd.) An acetylacetone complex can be obtained and used.

Moreover, in the silanol type crosslinking agent (silyl type crosslinking agent), coating film performance is improved by self-condensation. As this silane coupling crosslinking agent, it is marketed by the brand name (made by Shin-Etsu Chemical Co., Ltd.) of "KBM-, KBE-series".
When using the above crosslinking agent together, it is preferable that it exists in the range of 0.5-50 mass parts with respect to 100 mass parts of the said water-system crosslinking agent (3).

  In the present invention, a photopolymerization initiator is used only in the case of an ultraviolet curing system. As the photopolymerization initiator, one that generates a radical by light and reacts with the polymerizable unsaturated compound is desirable. Although not particularly limited, for example, benzophenone, acetophenone, benzoin, benzoin isobutyl ether, benzoin isopropyl ether, benzoin ethyl ether, 2,4-dimethylthioxanthone, 2-chlorothioxanthone, ethylanthraquinone, 4,4′-bisdimethyl Examples include aminobenzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and benzylmethylketanol. Examples of the cationic polymerization initiator include diazonium salt type compounds, sulfonium salt type compounds, iodonium salt type compounds, and the like. These compounds may be used in combination. However, it is easy to use the thing of the structure which can be used also for a water system, or a liquid thing.

  The paint of the present invention is preferably obtained by adding or dissolving or dispersing the resin of the present invention, the polyurethane gel particles and the water-based cross-linking agent in an aqueous medium, more preferably in ion-exchanged water. The content of the component in the paint solid content is 10 to 80% by mass of the resin of the present invention, more preferably 20 to 70% by mass, and 10 to 80% by mass of the polyurethane gel particle C, preferably 15 to 75%. The mass% and the water-based crosslinking agent are 0.1 to 50 mass%, preferably 1 to 40 mass%. In addition, according to the resin standard of the present invention, the polyurethane gel particles are 10 to 60 parts by mass and the aqueous crosslinking agent is 0.5 to 20 parts by mass per 100 parts by mass of the resin of the present invention. In addition, although the solid content of the prepared coating material is not specifically limited, Usually, it is about 1-95 mass%.

  The essential components of the paint of the present invention are as described above. However, as long as the object of the present invention is not hindered, conventionally known resins and various additives such as antioxidants (hindered phenols, phosphites) , Thioethers, etc.), light stabilizers (hindered amines, etc.), UV absorbers (benzophenones, benzotriazoles, etc.), gas discoloration stabilizers (hydrazines, etc.), metal deactivators, etc. Is mentioned. Furthermore, designability imparting agents (organic fine particles, inorganic fine particles), antifungal agents, flame retardants and other additives can be used as appropriate. Examples of the organic fine particles and inorganic fine particles may include silica, silicone resin fine particles, fluororesin fine particles, acrylic resin fine particles, urethane resin fine particles, silicone-modified urethane resin fine particles, polyethylene fine particles, and reactive siloxane.

  Examples of plastics to which the paint of the present invention is applied include olefin resins (polyethylene, polypropylene, etc.), ethylene propylene diene resins, styrene acrylonitrile resins, polysulfone resins, polyphenylene ether resins, acrylic resins, silicones. Resin, fluorine resin, polyester resin, polyamide resin, polyimide resin, polystyrene resin, polyurethane resin, polycarbonate resin, norbornene resin, cellulose resin, polyvinyl alcohol resin, polyvinyl formal resin, polyvinyl Conventionally known various materials such as butyral resin, polyvinyl pyrrolidone resin, polyvinyl acetal resin, polyvinyl acetate resin, vinyl chloride, engineer plastic, and biodegradable plastic Plastic molding can be mentioned a thermoplastic polyolefins used, polyurethane, plastic moldings such as polypropylene and the like, especially as interior materials for automobiles. For example, in the case of a TPO base sheet, a two-component water-based urethane resin is applied onto a corona discharge-treated TPO base sheet, and the paint of the present invention is further applied thereon by spray coating or gravure coating. Later, the instrument panel for automobiles can be manufactured by vacuum forming.

  Also useful are a method of directly applying the paint of the present invention to a plastic molded product, and a mold molding method in which polypropylene or urethane resin or the like is placed in a mold after the paint of the present invention is spray-coated on a mold. . However, when the paint of the present invention is applied to a polypropylene molded product having poor adhesion, it is preferable to preliminarily treat the surface of the plastic molded product.

  After coating the coating material of the present invention on a TPO sheet (solid content thickness: 3 to 25 μm), drying at 90 to 120 ° C. for 1 to 3 minutes, and then vacuum forming at 160 to 220 ° C., the coating material of the present invention An automotive instrument panel having a coating film formed of is obtained.

  The above-described paint of the present invention does not contain a volatile organic solvent (VOC) such as an organic solvent used for painting, and is a paint suitable for an environment-friendly automobile interior material. However, as is well known, an organic solvent can be used in combination for the purpose of improving the paintability and drying property. In addition, the plastic molded product obtained as described above has good low friction properties, anti-blocking properties, slidability, elasticity, wear resistance, low temperature characteristics, and weather resistance due to the coating film of the present invention. Yes, and mechanical properties, stretchability, recoverability, adhesion to substrates, flex resistance, slipperiness, heat resistance, low temperature characteristics, solvent resistance, chemical resistance, hydrolysis resistance, scratch resistance, Excellent water repellency, water resistance, antifouling properties, and heat insulation, especially with a combination of photocurable siloxane-modified urethane resin and polyurethane gel particles, with soft touch, anti-blocking, wear resistance and slidability, Provided is a plastic coated product with significantly improved water resistance, chemical resistance, scratch resistance, low temperature characteristics, elasticity, and deformation recovery.

  Hereinafter, the present invention will be described more specifically with reference to synthesis examples, examples, comparative examples, and usage examples, but the present invention is not limited thereto. Moreover, in the following sentence, “part” indicates mass part, and “%” indicates mass%.

[Synthesis Examples 1 to 5]
The synthesis examples 1-5 of the urethane type resin used for this invention and a photocurable siloxane modification urethane type resin are shown.
After replacing the reaction vessel equipped with a stirrer, reflux condenser, thermometer, nitrogen blowing tube and manhole with nitrogen gas, hydrophilic group-containing compound (compound a), unsaturated group-containing compound (compound b), polymer diol ( Compound c), polysiloxane having a hydroxyl group at both ends or one end (compound d), and acetone were added in predetermined amounts and uniformly dissolved to adjust the solution concentration. Subsequently, hexamethylene diisocyanate (compound e) was added at an equivalent ratio of a predetermined amount (NCO / OH = 2.0) and reacted at 80 ° C., reacted until the predetermined NCO% was reached, cooled to 50 ° C., Add a predetermined amount of ion-exchanged water and 20% of the solid content and a neutralizing agent (an amount equivalent to the hydrophilic group -COOH) to uniformly emulsify the system, and an ethylenediamine component (equal to the remaining NCO%). The chain was extended. Finally, acetone in the system was recovered by vacuum degassing. Table 1 shows the raw material composition of the polyurethane resin.

note)
Compound a
A-1: dimethylolbutanoic acid a-2: dimethylolpropanoic acid

Compound b
・ GMAE: Glycerol monoallyl ether (Daiso)
・ GMA: Glycerin monomethacrylate (manufactured by NOF Corporation)

Compound c
PCD: Plaxel CD220, polycarbonate diol (Daicel Chemical Industries, average molecular weight 2,000)
PBD: NISSO PB GI1000, water-added polybutadiene diol (manufactured by Nippon Soda, average molecular weight 1,500)

Compound d
D-1: (both terminal polysiloxane diol, n is an integer, average molecular weight 1,900)
D-2: (one-end polysiloxane diol, n is an integer, average molecular weight 3,000)

TEA: triethylamine HDI: hexamethylene diisocyanate EDA: ethylenediamine

The synthesis examples 6-9 of the urethane gel particle used for this invention are shown.
(Preparation of polyurea colloid solution)
[Synthesis Example 6]
100 parts of a bifunctional oil- and fat-modified polyol having a hydroxyl value of 119.5 (URIC Y-202 manufactured by Ito Oil Co., Ltd.) and 100 parts of n-octane were charged into a synthetic kettle equipped with a stirrer, and the polyol was dissolved. While stirring, the temperature was controlled at 50 ° C., 47.3 parts of isophorone diisocyanate prepared in advance so that NCO / OH = 2 was gradually added over 1 hour, and the reaction was continued for 3 hours under these conditions. The reaction was performed at 3 ° C. for 3 hours. Next, the concentration was adjusted to 50% with n-octane to obtain a prepolymer solution (PP-1) containing 3.0% of NCO groups. Its molecular weight is 1,383.

  40% of the above PP-1 and 60 parts of n-octane were charged and dissolved in a synthetic kettle equipped with a stirrer, while the temperature was controlled at 70 ° C. while stirring, 10% of n-octane of isophoronediamine prepared in advance. 24.3 parts of the solution was gradually added over 5 hours to complete the reaction, and (polyamine (urea bonding part) / prepolymer chain) × 100 = 12.15% polyurea colloid solution (solid content 18.0%) ) (C-1) was obtained. This solution was a blue opalescent stable solution.

[Synthesis Example 7]
100 parts of a bifunctional oil- and fat-modified polyol having a hydroxyl value of 119.5 (URIC Y-202 manufactured by Ito Oil Co., Ltd.) and 100 parts of n-octane were charged into a synthetic kettle equipped with a stirrer, and the polyol was dissolved. While stirring, the temperature was controlled at 50 ° C., 26.0 parts of isophorone diisocyanate prepared in advance so that NCO / OH = 1.1 was gradually added over 1 hour, and the reaction was continued for 3 hours under these conditions. Further, the reaction was carried out at 80 ° C. for 4 hours for synthesis. Next, the concentration was adjusted to 50% with n-octane to obtain a prepolymer solution (PP-2) containing 0.36% of NCO groups. Its molecular weight is 11,834.

  20 parts of the above PP-2 and 80 parts of n-octane were charged into a synthetic kettle equipped with a stirrer to dissolve the prepolymer. While controlling the temperature at 70 ° C. while stirring, 14.4 parts of a 1% solution of n-octane of isophoronediamine prepared in advance was gradually added over 8 hours to complete the reaction, and (polyamine / prepolymer chain) ) × 100 = 1.44% polyurea colloid solution (solid content: 8.9%) (C-2) was obtained. This solution was a blue opalescent stable solution.

(Production of polyurethane gel particles C)
[Synthesis Example 8]
20 parts of polybutylene adipate having an average molecular weight of 1,000 is dissolved at 60 ° C., and isocyanurate polyisocyanate of hexamethylene diisocyanate represented by the following structural formula (Duranate TPA-100 manufactured by Asahi Kasei Kogyo Co., Ltd., NCO% = 23) .1) Add 7.3 parts and mix uniformly. This was gradually added to a mixture of 5.0 parts of polyurea colloid solution (C-1) of Synthesis Example 6 and 25 parts of n-octane prepared in advance in a 1 liter stainless steel container, and emulsified with a homogenizer for 15 minutes. . This emulsion was a stable emulsion having an average dispersoid particle size of 5 μm and no separation.

  Next, this was charged into a reaction kettle equipped with a vertical stirrer, the temperature was raised to 80 ° C. while rotating at 400 rpm, the reaction for 6 hours was completed, and a solution of polyurethane gel particles (particle C) was obtained. This solution was vacuum dried at 100 Torr to separate n-octane to obtain particles C (1). This was a spherical white powder having an average particle diameter of 5 μm and a circularity of 0.92. The compressive strength was 0.35 MPa and the recovery rate was 89%.

[Synthesis Example 9]
In a 500 ml separable flask, 4 parts of polyurea colloid solution (C-2) and 150 parts of isooctane were charged and mixed. Next, 100 parts of a trifunctional polylactone polyol having an average molecular weight of 785, which was preheated to 50 ° C., was gradually added and emulsified while mixing this solution with a homomixer. Furthermore, 68.3 parts of hexamethylene diisocyanate adduct polyisocyanate represented by the following structural formula (Duranate 24A-100 manufactured by Asahi Kasei Kogyo Co., Ltd., NC 0% = 23.5) was gradually added.

  Next, while rotating the homomixer, the temperature was raised to 80 ° C., and after reaction for 3 hours, 0.005 part of dibutyltin dilaurate was added as a reaction catalyst, and the reaction was further performed for 4 hours to obtain a dispersion of particles C. . Particles C (2) were obtained from this dispersion in the same manner as in the above example. This was a spherical white powder having an average particle diameter of 15 μm and a circularity of 0.94. The compressive strength was 0.60 MPa, and the recovery rate was 92%.

[Examples 1-3, Comparative Examples 1-2]
The polyurethane-based resin obtained in the synthesis example, the particles C, and the crosslinking agent are blended in ion-exchanged water at the following ratios, and the paints 1 to 3 of Examples 1 to 3 and Comparative Examples 1 and 2 having a solid content of 20%, respectively. 5 was obtained. The paint 4 was a non-electron beam or non-ultraviolet curable water-based paint, and the other was a photo-curable water-based paint.

Initiator; benzophenone aqueous cross-linking agent;
-S-1: Water-dispersed isocyanate WB40-100 (manufactured by Asahi Kasei Chemicals Corporation, NCO% = 16.5, nonvolatile content = 100%) reacted with 2-hydroxybutyl acrylate at a 40% equivalent ratio to the total NCO% After the remaining NCO is reacted with ethanol, the crosslinking agent is dispersed in an aqueous medium having a non-volatile content of 30%.
S-2; TEGDBE; triethylene glycol divinyl ether S-3; PTMGDA; polytetramethylene glycol diacrylate

(Usage example 1)
Spray coating of the paint 1 (paint for forming a surface treatment layer for TPO) on an olefin-based thermoplastic (TPO) sheet having a hardness (JIS-A) 75 that has been surface-modified (50 mN / m) by corona discharge treatment (Coating amount: 10 μm · dry) and dried at 90 ° C. for 90 seconds. Next, a metal halide lamp was irradiated from above the coated surface with ultraviolet rays under conditions of peak illuminance of 380 mW / cm ² (irradiation intensity = 425 mj / cm ² ) with a roll heated to 230 ° C. with a sheet heated to 230 ° C. (Surface side; painted / unprocessed original; back side) A sheet is laminated to produce a laminated sheet. Furthermore, various evaluation tests were conducted on molded products obtained by female drawing of a mold containing a texture (pattern) at 220 ° C. for 10 seconds.

(Usage example 2)
The paint 2 is applied by gravure coating (coating amount: 10 μm · dry) on an olefin-based thermoplastic (TPO) sheet having a hardness (JIS-A) 75 that has been surface-modified (50 mN / m) by corona discharge treatment. After the work, it was dried at 90 ° C. for 90 seconds. Next, an electron beam was irradiated from above the coated surface with an EB facility under an acceleration voltage of 100 KV to form a laminated sheet. Further, a laminated sheet is prepared by laminating sheets (surface side: painted / unprocessed original; back side) with a roll heated to 230 ° C. Furthermore, various evaluation tests were conducted on molded products obtained by female drawing of a mold containing a texture (pattern) at 220 ° C. for 10 seconds.

(Usage example 3)
After spray coating (coating amount; 10 μm · dry) of the paint 3 on an olefinic thermoplastic (TPO) sheet having a hardness (JIS-A) 75 that has been surface-modified (50 mN / m) by corona discharge treatment Then, the sheet obtained by drying at 90 ° C. for 90 seconds was irradiated with an electron beam under the condition of an acceleration voltage of 100 KV using an EB facility from the coated surface to form a laminated sheet. Furthermore, after molding a leather-like pattern with an embossing roll containing a wrinkle (pattern) heated to 220 ° C, the molded product obtained by male drawing under conditions of 160 ° C for 10 seconds Various evaluation tests were conducted.

(Usage example 4)
On the olefin-based thermoplastic (TPO) sheet of hardness (JIS-A) 75 not subjected to corona discharge treatment, the paint 2 was applied by gravure coating (application amount: 10 μm · dry), and then at 90 ° C. for 90 seconds. Dried. Next, an electron beam was irradiated from above the coated surface with an EB facility under an acceleration voltage of 100 KV to form a laminated sheet. Further, a laminated sheet is prepared by laminating sheets (surface side: painted / unprocessed original; back side) with a roll heated to 230 ° C. Furthermore, various evaluation tests were conducted on molded products obtained by female drawing of a mold containing a texture (pattern) at 220 ° C. for 10 seconds.

(Usage example 5)
After spray coating (coating amount; 10 μm · dry) on the olefinic thermoplastic (TPO) sheet of hardness (JIS-A) 75 that has not been subjected to corona discharge treatment, it is dried at 90 ° C. for 90 seconds. Next, the obtained sheet was irradiated with an electron beam under the condition of an accelerating voltage of 100 KV with an EB facility from the coated surface to form a laminated sheet. Furthermore, after molding a leather-like pattern with an embossing roll containing a wrinkle (pattern) heated to 220 ° C, the molded product obtained by male drawing under conditions of 160 ° C for 10 seconds Various evaluation tests were conducted.

(Comparative use example 1)
The following primer 1 (chlorine TPO primer) is spray-coated (coating amount) on an olefinic thermoplastic (TPO) sheet of hardness (JIS-A) 75 that has been surface-modified (50 mN / m) by corona discharge treatment. 3 μm · dry), and then spray-coated with a water-based paint according to the paint 4 of the present invention (application amount: 10 μm · dry) on a sheet obtained by drying at 90 ° C. for 90 seconds, and at 90 ° C. The sheet dried for 90 seconds was aged at 40 ° C. for 1 day. Next, a laminated sheet is prepared by laminating sheets (surface side: painted original fabric / untreated original fabric / untreated original fabric; back side) with a roll heated to 230 ° C. Furthermore, various evaluation tests were conducted on molded products obtained by female drawing of a mold containing a texture (pattern) at 220 ° C. for 10 seconds.

(Primer 1)
・ Chlorinated PP 100 parts ・ Ion-exchanged water 200 parts Total 300 parts Chlorinated PP; Hardren EZ-2000 (Toyo Kasei Kogyo, NV = 30%)

(Comparative use example 2)
The paint 5 is applied by gravure coating (coating amount: 10 μm · dry) on an olefin-based thermoplastic (TPO) sheet having a hardness (JIS-A) 75 that has been surface-modified (50 mN / m) by corona discharge treatment. After the work, it was dried at 90 ° C. for 90 seconds. Next, an electron beam was irradiated from above the coated surface with an EB facility under an acceleration voltage of 100 KV to form a laminated sheet. Furthermore, after molding a leather-like pattern with an embossing roll containing a wrinkle (pattern) heated to 220 ° C, the molded product obtained by male drawing under conditions of 160 ° C for 10 seconds Various evaluation tests were conducted.

The molded items produced in Use Examples 1 to 3 and Comparative Use Examples 1 and 2 were evaluated on the following items.
<Adhesion test>
A 180-degree peeling force was measured using HEIDON-14DR manufactured by Shinto Kagaku Co., Ltd., on the test piece in which the coated surfaces were bonded with an adhesive.
Evaluation criteria;
×: Less than 1 kg / cm ○; 1 kg / cm or more

<Abrasion test>
The number of wear until the appearance of the coated surface was changed with a No. 6 canvas and a load of 500 g was measured using a flat wear tester.
Evaluation criteria;
×: Less than 1000 times Δ; 1000 to less than 2000 times ○; 2000 times or more

<Vacuum formability test>
The surface of the sample piece before and after vacuum molding at a development rate of 200% was observed visually and with a digital scope (100 times) to confirm the presence or absence of appearance defects (change in aperture, whitening, cracks, etc.).
Evaluation criteria;
×: Appearance failure occurred ○: No appearance failure

<Glossiness>
Using a direct reading haze computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd., the glossiness (60 ° incident light / 60 ° reflected light) of each sheet was measured. As an automobile interior material, the glossiness is preferably 1.2 or less.

<Scratch resistance test>
The coating of the matte layer of the various sheets was rubbed 100 times with a Scotch Bright (manufactured by Sumitomo 3M Co., Ltd.) at a load of about 1 kg / cm ² , and scratches on the surface were visually confirmed.
○: 0 or more and less than 5 scratches that can be confirmed Δ: 5 or more and less than 10 scratches that can be confirmed ×: 10 or more scratches that can be confirmed

<Weather resistance test>
After forming the multilayer coating film under the above conditions, a weather resistance test was performed, and a weather resistance acceleration test was performed with a xenon weatherometer to confirm the appearance change of the coating film.
Weather resistance test conditions: Xenon weatherometer irradiation conditions were illuminance (50 to 150 w / m ² , 300 to 400 nm), black panel temperature 90 ° C., and irradiation time 8 weeks (2000 kj).
Light resistance test (appearance) evaluation criteria;
○: No discoloration, choking, cracks or cracks.
×: Discoloration, choking, cracks, cracks, etc.

<Heat resistance test>
After the formation of the interior material for automobiles under the above conditions, a heat resistance test was conducted by setting the test conditions in an oven at 120 ° C. for 400 hours to confirm changes in the appearance of the coating film.
Heat resistance test (appearance) evaluation criteria;
○: No yellow discoloration, choking, cracks, cracks, etc. ×: Yellow discoloration, choking, cracks, cracks, etc.

<Hydrolysis resistance test>
After forming the automotive interior material under the above conditions, the adhesive strength with the base material after the jungle test (temperature: 70 ° C., relative humidity 95%, 8 weeks) was measured and compared with the initial strength.
○: Retention rate is 70% or more Δ; Less than 70% to 40%
×: Less than 40%

  ADVANTAGE OF THE INVENTION According to this invention, the water-based matte paint suitable for the interior of a VOC corresponding | compatible vehicle interior which can be used for the olefin type thermoplastic sheet etc. which are environmental measures goods in consideration of recycling is provided. The coating film made of the paint has excellent adhesion to the substrate, and the plastic molded product having the coating film has good wear resistance, chemical resistance, vacuum moldability, glossiness, scratch resistance, and the like. .

The imaginary figure of the cross section of the polyurea colloid particle B in the polyurea colloid solution used by this invention. The photograph of the polyurethane gel particle C used by this invention. The imaginary figure of the cross section of the polyurethane gel particle C used by this invention.

Explanation of symbols

1: Solvated polymer chain (oil segment)
2: Unsolvated urea domain 3: Polyurethane gel particle A
4: Polyurea colloidal particle B

Claims (8)

A plastic coating comprising an electron beam or ultraviolet curable polysiloxane-modified urethane resin (1), polyurethane gel particles (2), and an aqueous crosslinking agent (3) in an aqueous medium,
The electron beam or ultraviolet curable polysiloxane-modified urethane resin (1)
In a ratio where the total amount of the following compounds (a) to (d) is 100% by mass,
0.01 to 30% by mass of a compound (a) having at least one active hydrogen-containing group and a hydrophilic group other than a hydroxyl group in the molecule;
0.01 to 30% by mass of compound (b) having at least one active hydrogen-containing group and at least one unsaturated group;
A polyol and / or a polyamine (c) (amount in which the total of a to d is 100% by mass);
0.01-50% by mass of polysiloxane (d) having at least one active hydrogen-containing group;
Polyisocyanate (e),
It is obtained by reacting the total active hydrogen-containing groups of the compounds a to d with the isocyanate group of the compound e at an equivalent ratio (OH / NCO) of 0.9 to 1.1, and the content of the siloxane segment is 0.01. A plastic paint characterized by being a resin having a number average molecular weight of 2,000 to 500,000 at -50% by mass.   The ratio of the compound (b) having at least one active hydrogen-containing group and at least one unsaturated group is 1 to 15% by mass, and the polysiloxane (d) having the at least one active hydrogen-containing group The paint according to claim 1, wherein the ratio is 1 to 20% by mass.   The polyurethane gel particles (2) are three-dimensionally crosslinked polyurethane gel particles (particles) obtained by copolymerizing a polyisocyanate having at least one of three or more functional groups and a compound having an active hydrogen-containing group in the molecule. 3. A polyurethane gel particle (particle C) comprising A) and polyurea colloid particles (particle B) deposited from a polyurea colloid nonaqueous solvent solution covering the surface of the particle A. Paint. The particle B is composed of a solvated portion with respect to a solvent and a non-solvated portion, and the particle size of the non-solvated portion is 0.01 μm to 1.0 μm. The paint according to claim 3, wherein the polyurea colloidal particles are obtained by a reaction between an isocyanate and a polyamine compound, and the unsolvated part is composed of a hydrogen bond of a urea bond. The paint according to claim 3 or 4 , wherein a particle diameter of the particles C is in a range of 0.5 to 100 µm.   The paint according to any one of claims 1 to 5, wherein the water-based cross-linking agent (3) is an electron beam or an ultraviolet curable water-based cross-linking agent and / or a water-dispersible reactive diluent.   In addition, polyisocyanate crosslinking agent (including block type), melamine crosslinking agent, carbodiimide crosslinking agent, oxazoline crosslinking agent, epoxy crosslinking agent, silanol crosslinking agent, inorganic crosslinking agent or vinyl ether crosslinking agent The paint according to any one of claims 1 to 6.   When the total amount of the electron beam or ultraviolet curable polysiloxane-modified urethane resin (1), the polyurethane gel particles (2), and the aqueous crosslinking agent (3) is 100% by mass, the resin (1) The paint according to any one of claims 1 to 7, wherein 10 to 80% by mass of the gel particles (2) is 10 to 80% by mass and the water-based crosslinking agent (3) is 0.1 to 50% by mass. .