JP2010180363A - Urethane resin and coating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an urethane resin and a coating, capable of giving a coated film having an excellent performance on the surface of every members such as a natural leather, an imitation leather such as a synthetic imitation leather and an artificial leather, a TPO and a thermoplastic polyurethane for a slush molding. <P>SOLUTION: A siloxane-modified urethane resin containing at least a hydroxy group and a hydrophilic group in the same molecule is obtained by allowing a compound having at least one active hydrogen-containing group and a hydrophilic group other than a hydroxy group in a molecule, an amino alcohol having at least one hydroxy group and at least one amino group in a molecule, a polyol and/or a polyamine, a polysiloxane having at least one active hydrogen-containing group and a polyisocyanate to react so that all active hydrogen-containing group and isocyanate group may react by molar ratio of NCO/OH=0.9 to 1.1. The coating contains the resin. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel urethane resin and a paint containing the urethane resin. The paints of the present invention include natural leather used in vehicle seats, vehicle interior materials, furniture, shoes, bags, clothing, belts, wallets, synthetic artificial leather such as synthetic leather and artificial leather, and thermoplastic polyolefin (TPO). It is useful as a coating agent on the surface of all parts such as plastic sheet materials such as thermoplastic polyurethane for slush molding and vinyl chloride resin, various films, plastic molding, rubber molding, cloth, paper, wood, metal, etc. The film to be formed is abrasion resistance, substrate adhesion, flexibility, chemical resistance, oil resistance, slipperiness, flexibility, low temperature characteristics, leveling properties, durability (weather resistance, heat resistance, hydrolysis resistance) ) And antifouling property.

  Conventionally, surface finishing of natural leather has been performed for the purpose of improving functions such as designability, durability, wearability, and contamination of natural leather. As such a functional paint, a paint containing urethane resin, nitrified cotton lacquer, acrylic resin, ester resin, epoxy resin, acrylonitrile butadiene resin, or the like as a film forming component is used.

  In addition, many synthetic artificial leathers such as synthetic leather and artificial leather use polyurethane resins. Synthetic artificial leather can obtain a texture close to that of natural leather, and is therefore widely used in fields that require a high-class feeling such as clothing use, furniture, vehicle seats, and interior materials. In particular, in recent years, there has been a strong demand for the development of a high-performance synthetic artificial leather system made of environmentally friendly materials in addition to the above performance.

  Conventionally, synthetic artificial leather using a polyurethane-based resin has been manufactured by, for example, a wet method through the following main processes. First, for example, a solution of an organic solvent mainly composed of N, N-dimethylformamide (DMF), which is a polyurethane resin, is applied on a fibrous base material layer and solidified in water to form a microporous layer.

  Next, a polyurethane resin solution dissolved in various organic solvents is directly coated on the microporous layer with a coating machine such as a gravure and dried to form a skin layer (silver surface layer), or a polyurethane resin. There is a method in which a solution is applied on a release paper and dried to form an adhesive layer on the coating surface, and these layers are transferred to the microporous layer (Non-Patent Document 1).

  As described above, most of polyurethane-based resins for producing synthetic artificial leather are used as solutions dissolved in various organic solvents. Therefore, in the drying process, the organic solvent is released into the atmosphere. From the viewpoint of environmental problems (VOC countermeasures), safety and health, and fire fighting countermeasures, there is an increasing need for polyurethane resin aqueous dispersions that do not use organic solvents. ing.

  Conventional coating film made of polyurethane resin aqueous dispersion is used as a sheet material used for automobiles and furniture that require durability. Adhesion with substrate, flexibility, water resistance, especially against human sebum The required performance of synthetic artificial leather such as oil resistance, wear resistance, durability (weather resistance, hydrolysis resistance, heat resistance, etc.) is not fully satisfied, and improvements are required (Patent Document 1). .

  Other automotive interior materials include instrument panels, door trims, and console boxes. Conventionally, many vinyl chloride resins, which are materials with good flexibility, flame resistance, design, vacuum moldability, and cost balance, have been used. It had been. However, in recent years, a thermoplastic polyolefin called TPO and a thermoplastic polyurethane for slush molding are often used for the purpose of promoting dioxin countermeasures (dehalogenation) and recycling from the viewpoint of environmental protection.

  The vinyl chloride resin sheet has been transformed into dechlorinated vinyl because the toxic gas generated by incineration and the health safety due to bleed-out of the plasticizer and the durability decrease due to changes in physical properties, etc. . In addition, with the development of environmental regulations and the recovery trend of domestic capital investment, the market for thermoplastic polyurethane for TPO and slush molding continues to expand, and the track record as an automotive material leads to reliability. Replacement demand has been strong.

  TPO sheet is a material with excellent physical properties (weather resistance, chemical resistance, etc.) suitable for automobile materials, lightness control (low fuel consumption) and low recyclability, and excellent recyclability. Therefore, it is promising as an alternative material for vinyl chloride resin. However, automotive interior materials consisting of TPO sheets require string-proofing for the driver to travel safely and are designed for matte with a design for the purpose of giving a full matte (matte) tone. In addition to the need to apply surface paint, performance against wear resistance and oil resistance (human sebum, plastic paint, etc.) is inferior, and countermeasures must be taken.

  Therefore, in order to enhance the countermeasures and design properties of the above two items, after being treated with a solvent-type urethane resin paint, an automobile interior material is produced by vacuum molding. More specifically, a TPO sheet is surface-modified by corona discharge treatment to enhance adhesion, and after being coated with a chlorinated polypropylene layer and then treated with a solvent-type matte polyurethane resin paint, an automobile Molded as an interior material.

Patent Document 2 proposes an automobile interior material composed of a material having a vinyl chloride resin excellent in heat resistance as a skin and polyurethane foam. The above proposal is not preferable from the viewpoint of environmental protection because toxic gas is generated by incineration.
Edited by Keiji Iwata, Polyurethane resin handbook, pages 571-599, 15. Polyurethane leather (published by Nikkan Kogyo Shimbun, September 25, 1987) JP-A-5-5280 JP-A-6-297624

However, the above-mentioned proposed technique cannot satisfy all the performances, and a material for forming a surface with higher performance is demanded.
Accordingly, the object of the present invention is to provide wear resistance, substrate adhesion, flexibility, chemical resistance, oil resistance, slipperiness, flexibility, low temperature characteristics, leveling properties, durability (weather resistance, heat resistance, water resistance) It is an object of the present invention to provide a paint that gives a film excellent in decomposability and antifouling property, and further an environmentally friendly paint.

  The above object is achieved by the present invention described below. That is, the present invention comprises a compound having at least one active hydrogen-containing group and a hydrophilic group (anionic group or cationic group) other than a hydroxyl group in the molecule (hereinafter sometimes referred to as “compound a”), An amino alcohol having at least one hydroxyl group and at least one amino group in the molecule (hereinafter sometimes referred to as “compound b”), a polyol and / or a polyamine (hereinafter sometimes referred to as “compound c”); , A polysiloxane having at least one active hydrogen-containing group (hereinafter referred to as “compound d”) and a polyisocyanate (hereinafter sometimes referred to as “compound e”), wherein all active hydrogen-containing groups and isocyanate groups are converted into NCO / OH = 0.9-1.1 molar ratio (however, the hydroxyl group of the compound b is not included), which is obtained by reacting at least hydroxy in the same molecule And siloxane-modified urethane resin containing a hydrophilic group (hereinafter sometimes referred to as "resins of the present invention").

  The number average molecular weight of the resin of the present invention is 2,000 to 500,000; the content of the segment consisting of compound a is 0.01 to 30% by mass, and the content of the segment consisting of compound b is 0.00. 01 to 30% by mass, the content of the segment consisting of compound c is 10 to 80% by mass, and the content of the segment consisting of compound d is 0.01 to 50% by mass (provided that the total of a to d is 100% by mass) The numerical values of a to d are preferably selected in a combination in which the total is 100% by mass).

  The present invention also provides the production of the resin of the present invention, wherein the compound a, the compound c, the compound d, and the compound e are reacted to produce a terminal isocyanate prepolymer, and then the compound b is reacted. A method and a paint containing the resin of the present invention are provided. The paint may further contain other film forming components.

  The paint of the present invention further comprises a polyisocyanate (hereinafter sometimes referred to as “compound e ′”) in which at least one of the compounds is trifunctional or more, and a compound having an active hydrogen-containing group in the molecule (hereinafter “compound”). c ′ ”in some cases) and three-dimensionally crosslinked polyurethane gel fine particles (hereinafter also referred to as“ particle A ”) composed of a copolymerized compound, and the surface of the fine particles precipitated from the polyurea colloid non-aqueous solvent solution. It is preferable to contain polyurethane gel fine particles (hereinafter sometimes referred to as “particle C”) composed of polyurea colloidal particles (hereinafter also referred to as “particle B”).

  Moreover, in the coating material of this invention, the said particle | grains B are comprised from the part solvated with respect to a solvent, and the non-solvated part, and the particle diameter of a non-solvated part is 0.01 micrometer-1 .. Particles B are polyurea colloidal particles obtained by the reaction of oil-modified polyol, polyisocyanate, and polyamine, and the non-solvated part consists of hydrogen bonds of urea bonds; The diameter is in the range of 0.5 to 100 μm, the circularity is in the range of 0.9 to 1.0, the compressive strength is in the range of 0.01 to 50 MPa, the recovery rate is in the range of 50 to 100%, and the thermal softening point temperature is It is preferable that it is 200 degreeC or more.

  In addition, the coating material of the present invention further includes silica, silicone-modified urethane resin fine particles, nylon resin fine particles, ester resin fine particles, silicone resin fine particles, fluorine resin fine particles, acrylic resin fine particles, polyolefin resin fine particles, or reaction. A polyisocyanate (including a block type) crosslinking agent, an oxazoline crosslinking agent, a carbodiimide crosslinking agent, a melamine crosslinking agent, a radical polymerization crosslinking agent ((meth) acryloyl group-containing crosslinking agent), It is preferable to include a crosslinking agent selected from a cationic polymerization crosslinking agent (epoxy, oxetane, vinyl ether crosslinking agent) and an organometallic complex crosslinking agent.

  As a result of intensive studies to achieve the above object, the present inventors can use the resin of the present invention to design an environment-friendly paint and introduce a hydrophilic group into the resin of the present invention. Since a polar group (hydrophilic group) is oriented at the interface with the substrate, a coating film having excellent adhesion can be obtained. Furthermore, the hydrophilic group (carboxyl group) reacts with a polyoxazoline-based crosslinking agent or a polycarbodiimide-based crosslinking agent, and can be used to improve various physical properties of the coating film.

  Moreover, the urethane resin which contains a hydroxyl group in a molecule | numerator is obtained from the competitive reaction of an amino group and a hydroxyl group by using the compound b as a part of raw material. When the resin of the present invention contains a hydroxyl group, the hydrophilicity is increased, and the leveling property is improved in the formation of a coating film. Furthermore, when a water-dispersed isocyanate crosslinking agent is used, the reactivity between the resin and the crosslinking agent is increased. High, low deactivation of the isocyanate component of the crosslinking agent, and a high-performance coating film can be obtained. Moreover, when a block isocyanate type crosslinking agent is used, the specification of 1 liquid coating material is attained.

  Further, the resin of the present invention has poor compatibility between the siloxane segment and the polyurethane segment in the molecule, and a coating film is formed in which the siloxane segment and the polyurethane segment are microphase-separated during coating. That is, the siloxane segment is a mechanism that is oriented from the surface tension to the air side and exhibits the characteristics of the siloxane segment (sliding property, wear resistance, heat resistance, antifouling property, non-adhesiveness, etc.). Furthermore, the use of a crosslinking agent has the effect of suppressing the migration of the siloxane segment, while providing further characteristics of the siloxane segment covered with the surface.

  Since the surface tension (20.3 dyn / cm) of the siloxane segment is significantly smaller than the value of the surface tension (30.4 dyn / cm) of the polyurethane segment, the surface of the coating film made of the resin of the present invention is in the polyurethane domain. The siloxane segment formed in the island shape is considered to be oriented on the surface, and is supported also from the value of the surface tension.

  With the resin of the present invention, a coating film excellent in the required specifications of the paint can be obtained by adjusting the amount of each segment component comprising the compounds a to d.

The present invention is described in further detail below.
In the present invention, the “resin of the present invention” is a general term for polyurethane, polyurea, and polyurethane-polyurea. Further, the “active hydrogen-containing group” in the present invention refers to a group having active hydrogen such as a hydroxyl group, a mercapto group, a carboxyl group, and an amino group that is reactive with an isocyanate group.

  The resin of the present invention is obtained by reacting compounds a to e. The raw material components of the resin of the present invention will be described below. As the compound a, a sulfonic acid-based, carboxylic acid-based, phosphoric acid-based, amine-based compound, or the like can be used.

For example, if it is a sulfonic acid type compound, the following compounds and derivatives thereof may be mentioned.

  In addition, if it is a carboxylic acid compound, dimethylolpropanoic acid, dimethylolbutanoic acid and their alkylene oxide low-mole adducts (number-average molecular weight less than 500) or γ-caprolactone low-mole adducts (number-average molecular weight less than 500). And half esters derived from an acid anhydride and glycerin, and compounds derived from free radical reaction of a monomer containing a hydroxyl group and an unsaturated group and a monomer containing a carboxyl group and an unsaturated group.

  Examples of the compound a which is an amino compound include N-alkyldialkanolamines such as N-methyldiethanolamine and N-ethyldiethanolamine, and N-alkyldiaminoalkylamines such as N-methyldiaminoethylamine and N-ethyldiaminoethylamine. .

  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.

  In the present invention, the compound a may be used in an unneutralized or neutralized state. When the compound a has an anionic group (sulfonic acid type, carboxylic acid type, etc.) when used as a neutralization salt, for example, ethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanol Amine, N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, N-methylmorpholine, 2-amino-2-ethyl-1-propanol, trimethylamine, triethylamine, tripropylamine , Organic amines such as tributylamine, N-methyldiethanolamine and triethanolamine, alkali metals such as lithium, potassium and sodium, sodium hydroxide, potassium hydroxide , Calcium hydroxide, potassium hydroxide, and inorganic bases can be mentioned such as ammonia, which can be used in combination. These are used in an amount necessary to neutralize some or all of the carboxyl groups or sulfonic acid groups.

  On the other hand, as a neutralizing agent when the compound a has a cationic group (tertiary amino group) as a hydrophilic group, for example, formic acid, acetic acid, propionic acid, butyric acid, lactic acid, malic acid, malonic acid, adipic acid, etc. Organic acids and inorganic acids such as hydrochloric acid, phosphoric acid and nitric acid can be mentioned, and these can be used in combination. These neutralizing agents are used in an amount necessary to neutralize some or all of the tertiary amino groups.

  Examples of the compound b used in the present invention include 2- (hydroxymethylamino) ethanol, aminopropanol, aminobutanol, 4-methylaminobutanol, 2-hydroxyethylaminopropanol, diethanolaminopropylamine, and 1-aminopropanediol. 1- (methylamino) propanediol, N-methyldiethanolamine, N-methylethanolamine, N-ethylethanolamine, Nn-butylethanolamine, Nt-butylethanolamine, N- (β-aminoethyl) Ethanolamine), aliphatic amino alcohols such as N- (β-aminoethyl) isopropanolamine, and hydroxyethylpiperazine such as 3-piperazinemethanol, 2-piperazineethanol and 4-piperazinol Compound may be mentioned. These can be used alone or in combination of two or more.

  The compound d used in the present invention is a polysiloxane having at least one active hydrogen-containing group, and for example, it is preferable to use the following compounds (in which the active hydrogen-containing group is used for modification). The epoxy-modified polysiloxane prepared is included because it reacts with the isocyanate group and is contained in the polyurethane resin).

  The siloxane segment derived from the compound d is contained in the resin of the present invention, and contained in the main chain of the urethane resin or in a branched state. That is, if the compound d as a raw material is a double-end reactive type, it is contained in the trunk portion which is the main chain of the urethane resin, and if it is a single-end or branched reaction type, it is contained in a state branched from the main chain of the urethane resin. Become.

  As the compound d used in the present invention, for example, the following compounds can be used.

(1) Amino-modified polysiloxane

(2) Epoxy-modified polysiloxane

  The above epoxy compounds can be used by reacting with polyols, polyamides, polyamines, polycarboxylic acids and the like so as to have terminal active hydrogen.

(3) Alcohol-modified polysiloxane

(4) Mercapto-modified polysiloxane

  The polysiloxanes having active hydrogen-containing groups listed above are the preferred compounds d used in the present invention, but the present invention is not limited to these exemplified compounds. Accordingly, not only the compound d exemplified above, but also any other compound d which is currently commercially available and can be easily obtained from the market can be preferably used in the present invention. Particularly preferred compound d in the present invention is a polysiloxane having two hydroxyl groups or amino groups.

  In addition to these, polylactone (polyester) -polysiloxane obtained by modifying polysiloxane with lactone, polyethylene oxide-polysiloxane modified with ethylene oxide or propylene oxide, and polypropylene oxide-polysiloxane are also preferably used. Particularly preferably, a polylactone-polysiloxane obtained by modifying a polysiloxane having one or more active hydrogen-containing groups in the molecule with a lactone, and a polysiloxane having one or more active hydrogen-containing groups in the molecule are ethylene oxide, propylene oxide, or the like. A polyether-polysiloxane modified with ether.

  Preferred lactones used here are β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, 7-heptanolide, 8-octanolide, γ-valerolactone, γ-caprolactone and δ-caprolactone. .

  In order to obtain the molecular chain of the oxyalkylene polymer, alkylene oxide, specifically, ethylene oxide, propylene oxide, α-butylene oxide, β-butylene oxide, hexene oxide, cyclohexene oxide, styrene oxide, α-methyl Examples thereof include styrene oxide, which can be obtained by ring-opening polymerization in the presence of various catalysts.

  In the present invention, the polylactone-polysiloxane, that is, a polylactone-polysiloxane obtained by modifying a polysiloxane having one or more active hydrogen-containing groups in the molecule with a lactone is one or more active in the molecule. It can be obtained by subjecting a siloxane having a hydrogen-containing group, such as an amino group, a hydroxyl group, or a carboxyl group, to ring-opening polymerization of a lactone with the active hydrogen-containing group and then subjecting it to reduced pressure treatment.

  The compound c used in the present invention includes conventionally known polyols such as short-chain diols and polymer polyols conventionally used in the production of polyurethane, and polyamines conventionally used in the production of polyurethane. Although the short chain diamine etc. which are used from 1 can be used, these are not specifically limited.

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

  Examples of the polyhydric alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, tris- (2-hydroxyethyl) isocyanurate, 1,1,1-trimethylolethane, 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, for example, those obtained by polymerizing or copolymerizing alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) and / or heterocyclic ethers (tetrahydrofuran, etc.), specifically polyethylene glycol , Polypropylene glycol, polyethylene glycol-polytetramethylene glycol (block or random), polytetramethylene ether glycol, polyhexamethylene glycol, etc.

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

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

  The molecular weight of these polyols is not particularly limited, but the number average molecular weight is usually about 500 to 2,000. Moreover, these polyols can be used individually or in combination of 2 or more types.

  Examples of the polyamine used as the compound c include short-chain diamine, aliphatic, aromatic diamine, hydrazine and the like. Examples of the short-chain diamine include aliphatic diamines such as methylene diamine, ethylene diamine, trimethylene diamine, hexamethylene diamine, and octamethylene diamine; phenylene diamine, 3,3′-dichloro-4,4′-diaminodiphenyl methane, 4, Aromatic diamines such as 4′-methylenebis (phenylamine), 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone; cyclopentadiamine, cyclohexyldiamine, 4,4-diaminodicyclohexylmethane, 1,4- And alicyclic diamines such as diaminocyclohexane and isophoronediamine. Further, hydrazine such as hydrazine, carbodihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, phthalic acid dihydrazide, and the like can be given. These can be used alone or in combination of two or more. As the polyol and polyamine, diol or diamine is preferable.

  As the compound e used in the present invention, any of those conventionally used for producing polyurethane can be used, and is not particularly limited. For example, preferred are 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, tolidine diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, Aromatic diisocyanates such as benzidine diisocyanate, o-nitrobenzidine diisocyanate, 4,4′-diisocyanate dibenzyl;

  Aliphatic diisocyanates such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 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, hydrogenated XDI, etc., or these diisocyanate compounds with low molecular weight polyols or polyamines so that the terminal is isocyanate. Naturally, polyurethane prepolymers and the like can also be used.

  The resin of the present invention comprises compound a (preferably a compound having two active hydrogen-containing groups and preferably one hydrophilic group other than a hydroxyl group), compound b, compound c, compound d, Obtained by reacting with compound e.

  The method for producing the resin of the present invention is not particularly limited, and a conventionally known method for producing polyurethane can be used. For example, in the presence or absence of an organic solvent that does not contain active hydrogen in the molecule, compound a, compound c, compound d, and compound e, and optionally a low molecular diol as a chain extender And an equivalent ratio (NCO / OH) of the isocyanate group and the active hydrogen-containing group of 0.9 to 1.1, preferably 1.0, and is usually 20 by a one-shot method or a multistage method. A prepolymer of terminal isocyanate is produced by reacting at ˜150 ° C., preferably 60-110 ° C. until the theoretical isocyanate% is obtained, and this is emulsified in water with a neutralizing agent, and then with compound b (if necessary The resin of the present invention can be obtained through a solvent-removing step as necessary, by subjecting the prepolymer to chain extension with a polyamine and reacting until there are almost no isocyanate groups. Thus, by using the compound b, a hydroxyl group can be introduced into the resin of the present invention.

  In the present invention, a catalyst can be used as necessary in the urethane synthesis. For example, as catalysts, dibutyltin laurate, dioctyltin laurate, stannous octoate, zinc octylate, salts of organic and inorganic acids such as tetra n-butyl titanate, and organic amines such as organometallic derivatives and triethylamine And diazabicycloundecene catalysts.

  In the present invention, the urethane synthesis may be performed without a solvent, or may be performed using an organic solvent if necessary. Preferred solvents as organic solvents include those that are inert to isocyanate groups or less active than isocyanate groups. 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 solvent)), aliphatic hydrocarbon solvent (n-hexane etc.), alcohol solvent (methanol, ethanol, isopropanol etc.), ether solvent (dioxane, tetrahydrofuran etc.), ester type 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, ethyl-3 Ethoxypropionate, etc.), amide solvents (dimethylformamide, dimethyl acetamide), lactam solvent (N- methyl-2-pyrrolidone, etc.). Of these, methyl ethyl ketone, ethyl acetate, acetone, tetrahydrofuran and the like are preferable in consideration of recovery, solubility during urethane synthesis, reactivity, boiling point, and emulsification dispersibility in water.

  In the present invention, in the urethane 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 the reaction can be easily controlled.

  When the resin of the present invention is produced, the compound a is 0.01 to 30% by mass, preferably 1 to 15% by mass, and the compound b is 0.01 to 30% by mass, preferably 0.05. To 15% by weight, 10 to 80% by weight of compound c, preferably 20 to 70% by weight, and 0.01 to 50% by weight, preferably 1 to 15% by weight of compound d (however, the total of these reaction components) The amount is 100% by mass, and the amount of each component is a combination in which the total amount is 100% by mass). These reaction components a to d and compound e are combined such that all active hydrogen-containing groups and isocyanate groups in these reaction components are NCO / OH = 0.9 to 1.1, preferably equimolar (provided that If necessary, the reaction is carried out in the presence of an appropriate amount of a chain extender (in an amount that gives the desired molecular weight). Thereafter, it is dispersed in water, preferably ion-exchanged water, with a neutralizing agent as described above to form a self-emulsifying type stable aqueous urethane resin.

  The molecular weight of the resin of the present invention thus obtained preferably has a number average molecular weight (measured by GPC, converted to standard polystyrene) in the range of 2,000 to 500,000.

  When all the compounds other than the compound c among the above raw material components are compounds having two active hydrogen-containing groups, the structural formula of the resin of the present invention is represented by the following general formula. The units A to D in the general formula are as follows. Moreover, ad is a content rate of each unit, and is calculated from the usage-amount of each said compound ad which comprises each unit, and the quantity of the reacted compound e.

A unit: a unit introduced from compound a.
B unit: a unit introduced from compound b.
C unit: a unit introduced from compound c.
D unit: a unit introduced from compound d.

Structural formula of the resin of the present invention excluding the segment of compound e-(A) _a- (B) _b- (C) _c- (D) _d- (1)
ad is a content ratio of each unit. a is 0.01 to 30% by mass, preferably 1 to 15% by mass, b is 0.01 to 30% by mass, preferably 0.05 to 15% by mass, and c is 0.01 to 50% by mass, preferably 1 to 15% by mass, d is 10 to 80% by mass, preferably 20 to 70% by mass (provided that the total amount of these reaction components is 100% by mass, and ad is 100% by mass in total) Selected in combination.).

  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 particle C used in the present invention is composed of a part in which the particle B covering the particle A is solvated with respect to a solvent and a non-solvated part, and a non-solvated part. The particle B is a particle obtained by a reaction between an oil-modified polyol, a compound e ′ and a polyamine, and the non-solvated part is a hydrogen bond with a urea bond. Preferably, the particle C has a particle size in the range of 0.5 to 100 μm.

  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 perimeter actually captured). 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 addition, in the case of the particle C having a circularity of less than 0.9, it is not spherical and loses its stable dispersibility, and the coating material containing the particle C has a problem in that the paintability is deteriorated and the smoothness of the coating surface is inferior. Occurs.

  Furthermore, the compressive strength of the particles C is preferably 0.01 to 50 MPa, and the recovery rate is preferably in the range of 50 to 100%. In terms of compressive strength, since the particles C are polyuntan gel particles in which the particles A are coated with the particles B, a sufficient dry feeling can be obtained at 0.01 MPa or more, and the coating strength, environmental friendliness (light resistance) The compressive strength of the particles C is preferably 50 MPa or less from the viewpoint of properties, heat resistance, and water resistance.

  Furthermore, 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 the chipping resistance is improved due to the elasticity and deformation recovery of the particles C. In order to improve, it is preferable that it is in the range of 50 to 100%. Here, the compressive strength and the recovery rate are the load and 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 expressed by the equation [recovery rate (%) = L2 / L1 × 100] from the distance (L1) displaced when a pressure of 50 mN is applied to the particle and the distance (L2) displaced when the pressure is released. Is a value calculated by. The compressive strength and recovery rate of the particles C can be adjusted by controlling the types and blending amounts of the compound e ′ and the compound c ′ which are constituents of the particles A.

  Furthermore, the thermal softening point of the particles C is preferably 200 ° C. or higher. When the thermal softening point is low, when the paint containing the particles C is baked, it is processed in an environment of 140 ° C. to 180 ° C. for about 30 minutes, so that problems such as melting of the particles C at high temperatures may occur. The thermal softening point of the particles C was measured by using a thermomechanical analyzer (TMA, Rigaku Corporation) to produce a sheet having the same resin composition as the particles.

  The above particles C are polymerized by emulsifying and dispersing compound e ′ and compound c ′ as raw materials in an inert solvent using a polyurea colloid solution (dispersion of particles B) described later as a dispersant. can get. At this time, the polyurea colloid solution easily emulsifies the compound e ′ and the compound c ′ as raw materials in the form of particles in an inert solvent, and the compound e ′ and the compound c ′ are polymerized in this state. Then, the particles A are generated, and the particles B precipitated from the polyurea colloid solution are uniformly attached around the generated particles A. In the state where the particles C are separated from the dispersion solvent, the particles A are The particles B are uniformly coated.

  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 contained therein. A method in which compound e ′ and compound c ′, one of which is trifunctional or higher, is added and emulsified in an inert solvent solution and these synthesis raw materials are reacted to synthesize particles C, or at least one of which is trifunctional or higher. A method of emulsifying compound e ′ and compound c ′ separately in an inert solvent in the presence of a polyurea colloid solution and reacting them may be mentioned.

  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 parts by mass or more per 100 parts by mass of compound e ′ and compound c ′ each having at least one of three or more functional groups. Preferably, it is 0.1-20 mass parts. 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 in the emulsifying properties of compound e ′ and compound c ′, and a dispersion of particles C can be produced. 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, the preferred concentration is 20 to 70 parts by mass for productivity.

  The polyol as the compound c ′ used for the synthesis of the particles A is preferably a conventionally known one such as a short-chain diol, a polyhydric alcohol and a polymer polyol conventionally used in the production of polyurethane. As the polyamine as the compound c ′, a short-chain diamine, a high-molecular polyamine and the like conventionally used in the production of polyurethane can be used, but these are not particularly limited. Each compound used below is described. The compound c ′ is the same as the compound c, the compound e ′ is the same as the compound e, and further includes the following compound e ′.

  A compound having a polyfunctional isocyanate group such as an isocyanurate body, a burette body, an adduct body, or a polymer body of compound e, which is conventionally used, can be used and is not particularly limited. 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. Preferred are those containing 3 or more isocyanate groups, and a urethane prepolymer obtained by reacting a multimer of the compound e, an adduct with another compound, or a low molecular weight polyol or polyamine so as to be a terminal isocyanate. Etc. are also preferably used. These are exemplified below with structural formulas, but are not limited thereto.

  The type, amount and ratio of compound e 'and compound c' are determined depending on the purpose of use of the resulting particles C, 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 to be used and the obtained particles C, 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 compounds e ′. 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 colloid solution, any non-aqueous solvent that does not have active hydrogen can be used, which dissolves the oil-and-fat-modified polyol, the compound e ′, and the polyamine that are used raw materials. . 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 a short-chain diamine, an aliphatic polyamine, an alicyclic polyamine, an aromatic polyamine, and hydrazine. Short chain diamines and aliphatic polyamines include, for example, methylene diamine, ethylene diamine, diaminopropane, diaminobutane, trimethylene diamine, trimethyl hexamethylene diamine, hexamethylene diamine, octamethylene diamine, polyoxypropylene diamine and polyoxypropylene triamine. Aliphatic polyamines such as phenylenediamine, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 4,4′-methylenebis (phenylamine), 4,4′-diaminodiphenyl ether and 4,4′-diaminodiphenyl Aromatic polyamines such as sulfone, cyclopentanediamine, cyclohexyldiamine, 4,4-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, bis-amino Propyl piperazine, thiourea, methyl iminobispropylamine, and alicyclic diamines, such as norbornane diamine and isophorone diamine. Further, hydrazine such as hydrazine, carbohydrazide, adipic acid dihydrazide, sebacic acid dihydrazide and phthalic acid dihydrazide can be used. These can be used alone or in combination of two or more.

  The oil-modified polyol, compound e ′, polyamine, the type of prepolymer obtained, the amount used and the ratio used in the production of the polyurea colloid solution control the size and stability of the particles B in the solvent used. Determined by purpose. 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 acts by the correlation between the hydrophilicity and hydrophobicity of the compounds e ′ and c ′ and the inert solvent. To do. As a result of considering these conditions, it is possible to control the particle size of the particles C by adjusting the amount of the polyurea colloid solution added to the compounds e ′ and c ′. 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 compound e ′ and the compound c ′, the type of polyurea colloid solution and the amount added. The mechanical agitation and shearing force for emulsifying the compound e 'and the compound c' 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.

  In the present invention, in the production of the particles C, at least a part or all of the raw materials are colorants such as dyes and pigments, aluminum, mica, pearl, ultraviolet absorption and / or ultraviolet cut components, antioxidants, It is also possible to obtain particles C suitable for various coating applications by mixing polyurethane and various additives such as extender pigments and synthesizing polyurethane.

  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.

  Next, as a crosslinking agent used in 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, an inorganic crosslinking agent, Examples include radical polymerization crosslinking agents ((meth) acryloyl group-containing crosslinking agents), cationic polymerization crosslinking agents (epoxy, oxetane, vinyl ether crosslinking agents), silanol crosslinking agents, 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.

  As a crosslinking method using a urethane group and / or a hydroxyl group, for example, crosslinking with a polyisocyanate-based crosslinking agent can be mentioned, but as the polyisocyanate-based crosslinking agent, conventionally known ones can be used and are particularly limited. Not. 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-based crosslinking agents are effective in improving the adhesion between the coating film and the base sheet if they are in an appropriate amount. However, if the amount used is too large, unreacted isocyanate remains and becomes a problem. It is 120 mass parts or less with respect to 100 mass parts of resin of invention, Preferably it exists in the range of 1-50 mass parts. Moreover, in the silanol type crosslinking agent (silyl type crosslinking agent), the coating film performance is improved by self-condensation.

  Conventional crosslinking methods using hydrophilic groups such as carboxyl groups include epoxy crosslinking agents, carbodiimide crosslinking agents, oxazoline crosslinking agents, oxetane crosslinking agents, vinyl ether crosslinking agents, and metal complex crosslinking agents. 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 crosslinking agent, a commercially available product having a trade name of “Carbodilite” (manufactured by Nisshinbo Co., Ltd.) can be obtained and used. The crosslinking agent reacts with a carbodiimide group and a carboxyl group to form N-acyl urea, thereby improving the coating film performance.

  Also, the oxazoline-based cross-linking agent has a slow reaction in the low temperature region (80 to 100 ° C.) when the paint is dried, while the reaction is completed in the high temperature region during the heat treatment. . As the oxazoline-based crosslinking agent, commercially available products such as “Epocross” trade name (manufactured by Nippon Shokubai Co., Ltd.), WS-300, WS-500, WS-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.

  As the oxazoline-based crosslinking agent, those having a Tg of −5 to 90 ° C. and an oxazoline group equivalent of about 100 to 400 can be used. Particularly preferred is Tg = −5 to 25 ° C. (room temperature or lower), and an oxazoline group equivalent of 200-350. When Tg is lower than the above range, there is a concern about blocking, while when Tg is higher than the above range, the coating is cracked. Also, if the oxazoline group equivalent is lower than the above range, the effect of the intended performance will not be manifested unless the addition amount of the crosslinking agent is increased, while if the oxazoline group equivalent is higher than the above range, the oxazoline group is adjacent. As a result, the reactivity decreases and an unreacted oxazoline group remains. These oxazoline-based crosslinking agents are within a range of 0.1 to 50 parts by mass, preferably 1 to 40 parts by mass with respect to 100 parts by mass of the resin of the present invention. If the amount of the crosslinking agent used is lower than the above range, the effect of the crosslinking agent cannot be obtained. On the other hand, if the amount of the crosslinking agent used is higher than the above range, occurrence of blocking, reduction in film formability and cost increase Become.

  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. As the oxetane-based cross-linking agent, a commercial product of “ETANACOL” under the trade name (manufactured by Ube Industries) can be obtained and used. Commercially available products such as BASF, IPS Japan, Maruzen Petrochemical, Nippon Shokubai Co., Ltd. can be used as the vinyl ether crosslinking agent. The crosslinking agent reacts by cationic polymerization or forms an alkoxyester by Michael addition reaction.

  Moreover, as a silane coupling crosslinking agent, it is marketed by the brand name (made by Shin-Etsu Chemical Co., Ltd.) of "KBM-, KBE-series". These crosslinking agents are particularly effective for improving the durability if they are in an appropriate amount. However, if the amount used is too large, it will significantly shorten the working life and cause the coating to become brittle. 40 parts by mass or less, preferably 0.5 to 20 parts by mass.

  Moreover, the vinyl ether type crosslinking agent which is a cationic polymerization type crosslinking agent can react with a urethane group or a carboxyl group. Of course, it can be cured by irradiation with an electron beam.

  The paint of the present invention may be prepared without a solvent, but is preferably dissolved or dispersed in an aqueous medium, more preferably by adding the resin of the present invention and the aqueous cross-linking agent in ion-exchanged water. can get. The content of the component in the solid content of the paint is 10 to 80% by mass of the resin of the present invention, more preferably 20 to 70% by mass, and 0.1 to 50% by mass of the crosslinking agent, preferably 1 to 40% by mass. In addition, although the solid content of the prepared coating material is not specifically limited, Usually, it is about 5-100 mass%.

  Furthermore, designability imparting agents (organic fine particles, inorganic fine particles), antibacterial agents, antifungal agents, flame retardants and other additives can be used as appropriate. Examples of organic fine particles and inorganic fine particles include silica, silicone modified urethane resin fine particles, nylon resin fine particles, ester resin fine particles, silicone resin fine particles, fluorine resin fine particles, acrylic resin fine particles, silicone modified urethane resin fine particles, It may contain polyolefin resin fine particles, reactive siloxane, and the like.

  The film forming components other than the urethane resin used in the present invention are not particularly limited. For example, conventionally known siloxane resins, polyester resins, polyamide resins, polyimide resins, polystyrene resins, polyurethane resins, polycarbonate resins, norbornene resins, cellulose resins, polyvinyl alcohol resins, polyvinyl formal resins , Polyvinyl butyral resin, polyvinyl pyrrolidone resin, polyvinyl acetate resin, polyvinyl acetal resin, and the like. Although the usage-amount of these resin is not specifically limited, Usually, it is 900 mass parts or less with respect to 100 mass parts of this polyurethane resin, Preferably it is the range of 5-400 mass parts.

  In addition, when forming the surface treatment layer of a coating material by this invention, the surface treatment layer formation coating material which contains the resin of the said this invention as a film formation component is used. The coating material may be prepared with ion-exchanged water or may be prepared using a small amount of organic solvent. As the organic solvent, for example, methanol, ethanol, isopropyl alcohol, butanol and the like can also be used. Although the solid content of the coating material prepared using ion-exchanged water or an organic solvent is not particularly limited, it is usually about 3 to 45% by mass.

Next, the present invention will be described more specifically with reference to synthesis examples, examples and comparative examples. In the text, “part” or “%” is based on mass unless otherwise specified.
[Synthesis Examples 1 to 6: Synthesis of Resins of the Present Invention and Comparative Examples]
After replacing the reaction vessel equipped with a stirrer, reflux condenser, thermometer, nitrogen blowing tube, and manhole with nitrogen gas, compound a, compound c, chain extender (short chain diol component), compound d and acetone (nonvolatile content) Is 70%). Subsequently, a predetermined amount of hexamethylene diisocyanate was added as compound e, and the reaction was carried out at 80 ° C. using dibutyltin dilaurate as a catalyst until the NCO% of the resin reached the theoretical value. Next, the obtained reaction product was cooled to 50 ° C., and a predetermined amount of triethylamine as a neutralizing agent was added to 30% of the solid content, and the mixture was emulsified under stirring conditions until uniform. . Compound b and polyamine were each diluted with an equal amount of water to the obtained urethane water dispersion and reacted with the NCO group of the urethane water dispersion. The reaction was continued until the absorption due to the free isocyanate group at 2,270 cm ⁻¹ disappeared in the infrared absorption spectrum. Finally, acetone in the system was recovered by vacuum degassing.

註)
Compound a
DMPA: dimethylolpropanoic acid compound c
PCD:
Plaxel CD220: Polycarbonate diol (Daicel Chemical Industries, average molecular weight 2,000)

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

TEA: triethylamine HDI: hexamethylene diisocyanate EDA: ethylenediamine

[Synthesis Example 7: Synthesis of Urethane Resin for Microporous Layer]
After replacing the reaction vessel equipped with a stirrer, reflux condenser, thermometer, nitrogen blowing tube and manhole with nitrogen gas, carbonate diol (hydroxyl value = 56) 150 parts, ethylene glycol 10 parts and 1,4-butylene glycol 10 The part was dissolved in a predetermined amount of N, N-dimethylformamide (DMF) to adjust the solution concentration. Subsequently, 4,4′-methylenebis (phenylene isocyanate) (MDI) was added in a predetermined amount (NCO / OH = 1.0) and reacted at 80 ° C. until the NCO% disappeared in the IR spectrum. A high molecular weight type urethane resin solution (A-1) for a microporous layer was obtained. The solution had a nonvolatile content of 30% and a viscosity of 1,200 dPa · s.

[Synthesis Example 8: Solvent-free reactive urethane adhesive]
A reaction vessel equipped with a stirrer, reflux condenser, thermometer, nitrogen blowing tube and manhole was replaced with nitrogen gas, and then 20 parts of adipic acid, 30 parts of terephthalic acid and 53 parts of 1,6-hexanediol were charged up to 210 ° C. The temperature was raised. The reaction was carried out for 3 hours after reaching 200 ° C. After cooling to 100 ° C., a predetermined amount (NCO / OH = 2.0) of isophorone diisocyanate was added, and the reaction was further carried out for 3 hours. The obtained reactive urethane-modified ester resin had a non-volatile content of 100% and a melting point of 93 ° C. This is a urethane-modified reactive ester resin for adhesives.

(Preparation of polyurea colloid solution)
[Synthesis Example 9]
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. The molecular weight of this product is 1,383.

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

[Synthesis Example 10]
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. The molecular weight of this product 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%) (B-2) was obtained. This solution was a blue opalescent stable solution.

(Production of polyurethane gel particles C)
[Synthesis Example 11]
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 product was gradually added to a mixed solution of 5.0 parts of polyurea colloid solution (B-1) of Synthesis Example 9 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 12]
In a 500 ml separable flask, 4 parts of a polyurea colloid solution (B-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. . Particle C-2 was obtained from this dispersion in the same manner as described above. 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%.
Paint formulation examples 1-8 (Examples of paint preparation)
Coating formulation examples 1 to 8 used in Examples and Comparative Examples with the formulations shown in Table 2 below were prepared.

Water-based crosslinking agent, colorant;
X: Carbodilite V-02 (Nisshinbo Co., Ltd., carbodiimide-based crosslinking agent)
Y: Epocros WS-500 (manufactured by Nippon Shokubai Co., Ltd., oxazoline-based crosslinking agent)
Z: WB40-100 (Asahi Kasei Chemicals, water-dispersed isocyanate)
Colorant: Seika Seven DW-794 Black (Daiichi Seika Kogyo Co., Ltd., water dispersion type colorant)

Example 1 (Surface treatment agent for natural leather; glossy)
The raw leather of the cowhide was salted, the salt and filth were washed away to make a raw hide, and the hair was removed using slaked lime. After processing with tanning tanning agent, shaving the back side of the leather to adjust the thickness, adding dyes and oils and fats to give the specified softness, skin, color, etc., washing with water and drying Thus, a natural leather sheet as a base was produced. The paint composition example 2 was spray-coated on the natural leather sheet (coating amount: 10 μm · dry) and dried at 100 ° C. for 120 seconds to produce a natural leather sheet expressing a soft and deep gloss. Various evaluation tests were performed on the sheet.

Example 2 (Surface treatment agent for natural leather; glossy)
A coating composition example 4 is spray-coated on the natural leather sheet subjected to the pretreatment process of Example 1 (application amount: 10 μm · dry), dried at 100 ° C. for 120 seconds, and has good wear resistance and deep gloss. Were produced, and various evaluation tests were performed on the obtained sheets.

Example 3 (surface treatment agent for natural leather; matte tone)
Spray coating (coating amount: 10 μm · dry) of paint composition example 3 on the natural leather sheet subjected to the pretreatment process of Example 1 and drying at 100 ° C. for 120 seconds to give a matte tone with good flexibility and wear resistance The expressed natural leather sheet was produced, and various evaluation tests were performed on the obtained sheet.

Example 4 (surface treatment agent for TPO sheet)
The coating composition example 3 was spray-coated on a olefinic thermoplastic (TPO) primer-treated (easy-adhesion-treated) sheet having a corona-treated hardness (JIS-A) of 75 and then dried at 90 ° C. for 90 seconds. The sheet is further laminated with a roll heated to 230 ° C. (front side; painted original / untreated original / untreated original; back side) to produce a laminated sheet. Furthermore, various evaluation tests were performed on molded products obtained by female drawing of a mold containing a texture (pattern) at 220 ° C. for 10 seconds.

Example 5 (surface treatment agent for TPO sheet)
After coating Corona-treated hardness (JIS-A) 75 olefinic thermoplastic (TPO) primer-treated (easy-adhesion-treated) sheet with paint formulation example 5 by gravure coating, it was dried at 90 ° C. for 90 seconds. The sheet obtained was further leather-patterned with an embossing roll containing a texture (pattern) heated to 220 ° C., and then the mold was male-drawn at 160 ° C. for 10 seconds. Various evaluation tests were performed on the obtained molded product.

Example 6 (Surface treatment agent for plastic member)
Various evaluation tests were performed on molded products obtained by spray-coating the water-based matte paint described in Paint Formulation Example 6 on a die-molded member and drying at 90 ° C. for 90 seconds.

Example 7 (Surface layer of synthetic artificial leather)
On the dough, 1,000 g / m ² · wet of a mixed solution diluted with 100 parts of DMF is applied to 100 parts of urethane-based resin for microporous layer (Synthesis Example 7; A-1), and a solidified layer (DMF / water) is applied. = 5/95), solidified for 10 minutes, washed with water / mangle, passed through the DMF process 5 times, then dried at 130 ° C. for 10 minutes to finish the microporous layer. Various evaluation tests were performed on the molded products obtained by applying and drying at 120 ° C. for 3 minutes.
-A system was adopted in which all DMF solvent was recovered by a recovery device.

Example 8 (Treatment agent for surface treatment of synthetic artificial leather)
Various evaluation tests were performed on the sheet obtained by applying the coating composition example 6 on the sheet prepared in Example 7 by gravure coating and then drying at 90 ° C. for 90 seconds.

Example 9 (surface layer of synthetic artificial leather)
On the release paper, coating composition example 1 was applied (20 μm · Dry amount), dried (120 ° C., 3 minutes drying), and then the adhesive composition of Synthesis Example 8 previously heated to 100 ° C. was applied. (Amount to be 120 μm · Dry) After that, the coated product and the fabric were bonded together with a laminator and aged for 2 days at 40 ° C., and various evaluation tests were performed on the sheets produced synthetic leather.
Release paper transfer: The release paper is EV130 TPD-R8 (manufactured by Lintec).

Example 10 (treatment agent for surface treatment of synthetic artificial leather)
Various evaluation tests were performed on the sheet obtained by applying Paint Formulation Example 6 by gravure coating on the sheet prepared in Example 9 and then drying at 90 ° C. for 90 seconds.

Comparative example 1 (surface treatment agent for natural leather; gloss)
A natural leather sheet was obtained by spray-coating paint formulation example 7 (coating amount; 10 μm · dry) on a natural leather sheet that had been subjected to a pretreatment step in the same manner as in Example 1 and drying at 100 ° C. for 120 seconds. Various evaluation tests were performed on the sheet.

Comparative example 2 (surface treatment agent for natural leather; gloss)
A natural leather sheet was obtained by spray-coating paint formulation example 8 (coating amount: 10 μm · dry) on a natural leather sheet that had been subjected to a pretreatment step in the same manner as in Example 1 and drying at 100 ° C. for 120 seconds. Various evaluation tests were performed on the sheet.

Comparative Example 3
The same tests as in Example 4 were performed for various evaluation tests with the powder 3 in the paint 3 replaced with commercially available urethane beads.
For powder: Art Pearl P-800T Average particle size 7 μm (Negami Kogyo Co., Ltd.)

Here, the contents of each test item and the evaluation criteria are shown.
<Measures against VOC>
○: When the solvent used is 0 Δ: Less than 5% ×: 5% or more

<Appearance>
○: Sensitive to see and close to natural leather tone ×; Others <texture>
○: Volumey and soft △: Slightly hard ×: Hard

<Hydrolysis resistance>
The adhesion strength with the substrate after the jungle test (temperature: 70 ° C., relative humidity 95%, 3 weeks) was measured and compared with the initial strength.
○: Retention rate is 70% or more △; 69-40%
×: Less than 40%

<Light resistance>
The adhesion strength with the base material after the sunshine weatherometer test (temperature: 63 ° C., no water, 120 hours) was measured and compared with the initial strength.
○: Retention rate is 70% or more △; 69-40%
×: Less than 40%

<Heat resistance>
The test was carried out in a gear oven, the temperature was 120 ° C., the adhesive strength with the substrate after 150 hours was measured, and compared with the initial strength.
○: Retention rate is 70% or more △; 69-40%
×: Less than 40%

<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.
○: 1.2 kg / cm or more Δ; 0.8 kg / cm or more and less than 1.2 kg / cm ×; less than 1 kg / cm

<Cold-resistant bending>
The test was conducted at 0 ° C. and 20,000 times of flexing with a flexo testing machine.
○: No change △; Some cracks ×: Severe cracks

<Abrasion resistance 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.
○: 2000 times or more Δ; 1000 to less than 2000 times ×; less than 1000 times

  As described above, according to the present invention, artificial leather such as natural leather, synthetic artificial leather, artificial leather, TPO, plastic sheet-like materials such as thermoplastic polyurethane for slush molding and vinyl chloride resin, various films, plastic molded products Abrasion resistance, adhesion to base material, flexibility, chemical resistance, oil resistance, slipperiness, flexibility, low temperature characteristics, leveling properties on the surface of all parts such as rubber molding, cloth, paper, wood and metal Urethane resins and paints are provided that provide coatings having performances such as durability (weather resistance, heat resistance, hydrolysis resistance) and antifouling properties.

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.

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

Claims (12)

  A compound having at least one active hydrogen-containing group in the molecule and a hydrophilic group (anionic group or cationic group) other than a hydroxyl group (hereinafter sometimes referred to as “compound a”), and at least one in the molecule An amino alcohol (hereinafter sometimes referred to as “compound b”) having a hydroxyl group and at least one amino group, a polyol and / or a polyamine (hereinafter sometimes referred to as “compound c”), and an active hydrogen-containing group. A polysiloxane having at least one (hereinafter referred to as “compound d”) and a polyisocyanate (hereinafter sometimes referred to as “compound e”) are formed by converting all active hydrogen-containing groups and isocyanate groups to NCO / OH = 0.9˜ Contains at least a hydroxyl group and a hydrophilic group in the same molecule obtained by reacting at a molar ratio of 1.1 (excluding the hydroxyl group of the compound b) That siloxane-modified urethane resin (hereinafter sometimes referred to as "resins of the present invention").   The urethane resin according to claim 1, wherein the number average molecular weight is 2,000 to 500,000.   The content of the segment consisting of the compound a is 0.01 to 30% by mass, the content of the segment consisting of the compound b is 0.01 to 30% by mass, the content of the segment consisting of the compound c is 10 to 80% by mass, and The content of the segment consisting of compound d is 0.01 to 50% by mass (however, the total of a to d is 100% by mass, and the numerical values of a to d are selected in a combination that makes the total 100% by mass) The urethane resin according to claim 1.   The compound a, the compound c, the compound d, and the compound e are reacted, and after the terminal isocyanate prepolymer is produced, the compound b is reacted. Production method of urethane resin.   A paint comprising the urethane resin according to any one of claims 1 to 3.   Furthermore, the coating material of Claim 5 containing another film forming component.   Furthermore, a polyisocyanate (hereinafter sometimes referred to as “compound e ′”) in which at least one compound is trifunctional or more, and a compound having an active hydrogen-containing group in the molecule (hereinafter referred to as “compound c ′”). Three-dimensionally crosslinked polyurethane gel fine particles (hereinafter sometimes referred to as “particle A”) composed of a compound obtained by copolymerization with a polyurea colloidal particle (hereinafter referred to as “particle A”) precipitated from the polyurea colloid non-aqueous solvent solution. The paint according to claim 5, comprising polyurethane gel fine particles (hereinafter sometimes referred to as “particle C”).   The paint according to claim 7, wherein the particle B is composed of a part solvated with respect to the solvent and a non-solvated part, and the particle size of the non-solvated part is 0.01 µm to 1.0 µm. .   The paint according to claim 7, wherein the particles B are polyurea colloidal particles obtained by a reaction of an oil-and-fat-modified polyol, polyisocyanate, and polyamine, and the non-solvated portion is composed of urea-bonded hydrogen bonds.   Particle C has a particle size in the range of 0.5 to 100 μm, circularity in the range of 0.9 to 1.0, compressive strength in the range of 0.01 to 50 MPa, recovery rate in the range of 50 to 100%, and heat The paint according to claim 7, wherein the softening point temperature is 200 ° C or higher.   Furthermore, it contains silica, silicone-modified urethane resin fine particles, nylon resin fine particles, ester resin fine particles, silicone resin fine particles, fluorine resin fine particles, acrylic resin fine particles, polyolefin resin fine particles, or reactive siloxane. The paint described.   Furthermore, polyisocyanate (including block type) crosslinking agents, oxazoline crosslinking agents, carbodiimide crosslinking agents, melamine crosslinking agents, radical polymerization crosslinking agents ((meth) acryloyl group-containing crosslinking agents), cationic polymerization crosslinking agents ( The coating material according to claim 5, comprising a crosslinking agent selected from epoxy, oxetane, vinyl ether crosslinking agent) and organometallic complex crosslinking agent.