JP2006124575A - Low voc urethan resin composition and its application - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low VOC urethan resin composition having low environmental load, high workability, and high physical properties of a coating film. <P>SOLUTION: The low VOC urethan resin composition is prepared which is composed of a polyol component (A) and a polyisocyanate component (B), wherein the polyol component (A) is composed of a low-molecular-weight polyol (A1) as a dilutant and a polymer polyol (A2). The polyol (A1) has a molecular weight of approximately 350 or less and is a 2-6C alkylene glycol, for example. The polymer polyol (A2) may be a polyether polyol, polyester polyol, polycarbonate polyol, acrylic polymer polyol, or the like. The ratio of the low-molecular-weight polyol (A1) to the polymer polyol (A2) ranges from approximately 1 to 100 parts by weight to 100 parts by weight, for example. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a low-VOC urethane-based resin composition that has a low environmental burden and is excellent in workability and uses thereof.

  Polyurethane resins are widely used as coating compositions or paints for buildings, building components, various vehicles, machinery, plastic products, textile products, etc. because of their high wear resistance, chemical resistance, flexibility, etc. . On the other hand, in recent years, regulations on the release of VOC (volatile organic compounds) into the atmosphere have become stricter in the paint field, and a paint that replaces the solvent-based paint that has been widely used in the past is also desired for urethane paints. Yes. Water-based paints and powder paints have been developed as low-VOC paints to replace solvent-based paints. However, since the water-based paint contains an emulsifier and a dispersant and the resin is hydrophilized, the water resistance of the coating film is not sufficient, and it takes a long time to dry the coating film. In the case of a powder paint, thick coating is difficult and the adhesion of the coating film is low. Accordingly, solvent-free urethane paints have been developed as non-solvent paints that improve these drawbacks.

  For example, Japanese Patent Application Laid-Open No. 10-292150 (Patent Document 1) describes a polyurethane paint that can be applied without a solvent, and can form a coating film that is excellent in water resistance, salt water shielding property, and followability. 2) a polyhydric alcohol having a dimer diol content of 50 to 100% by weight and a viscosity at 25 ° C. of 2000 cps or less, and (b) an aliphatic or alicyclic isocyanate having a viscosity at 25 ° C. of 200 to 2000 cps. A liquid polyurethane paint is disclosed. In the examples of this document, a mixture having a viscosity of 1200 cps composed of dimer diol and 3-methylpentanediol is used as the polyhydric alcohol (a). However, this urethane paint has low coatability and low coating film hardness.

Further, JP-A-9-221627 (Patent Document 2) discloses a polyol-modified acrylic resin comprising a polyol having two or more hydroxyl groups per molecule and an acrylic resin having a hydroxyl group and a glass transition temperature of 0 to 90 ° C. A solvent-free urethane coating composition for concrete coating mold plywood containing a polyisocyanate compound is disclosed. This document describes that a polyol-modified acrylic resin is prepared by radical copolymerization of an unsaturated monomer constituting the acrylic resin component in the presence of the polyol component. In this case, polyether polyol is used. However, even this urethane coating composition has a high viscosity and low coatability and handleability.
JP-A-10-292150 (Claim 1, paragraph numbers [0014] [0015]) JP-A-9-221627 (Claim 1, paragraph numbers [0024] [0032])

  Accordingly, an object of the present invention is to provide a low VOC urethane-based resin composition having a low environmental load and high workability and its use.

  Another object of the present invention is to provide a low VOC urethane-based resin composition capable of satisfying both coating film properties such as hardness and abrasion resistance and coating properties such as adhesion to a substrate and coating properties.

  Still another object of the present invention is to provide a low VOC urethane-based resin composition excellent in the balance between pot life and drying property (or curability) and its use.

  Another object of the present invention is excellent in the appearance of the coating film (designability, high glossiness, color developability, etc.) and various resistances (non-contamination, fire resistance, water resistance, weather resistance, chemical resistance, etc.). It is providing the outstanding low VOC urethane type resin composition and its use.

  As a result of diligent studies to achieve the above-mentioned problems, the present inventors have used a low molecular weight polyol as a diluent for a polymer polyol in a low VOC urethane-based resin composition such as a paint or an adhesive, and when combined with a polyisocyanate, It has been found that even a composition having a very low VOC content can reduce viscosity, improve paintability and workability, reduce the environmental load, and adjust the balance between pot life and drying (or curability). The present invention has been completed.

That is, the low VOC urethane resin composition of the present invention is a composition composed of a polyol component (A) and a polyisocyanate component (B), and the polyol component (A) has a low molecular weight as a diluent. It is composed of a polyol (A1) and a polymer polyol (A2). The polyol (A1) has a molecular weight of about 350 or less, and examples thereof include C _2-6 alkylene glycol. The polymer polyol (A2) may be, for example, a polyether polyol, a polyester polyol, a polycarbonate polyol, an acrylic polymer polyol, or the like. The ratio of the low molecular weight polyol (A1) is, for example, 5 to 100 parts by weight, preferably 7 to 80 parts by weight, and more preferably about 10 to 75 parts by weight with respect to 100 parts by weight of the polymer polyol (A2). . The polyisocyanate component may be a polyisocyanate derivative or a modified product (for example, a diisocyanate multimer). The low VOC urethane resin composition of the present invention may further contain a compound (C) having an epoxy group. The compound (C) having an epoxy group may be a compound having a plurality of glycidyl groups (for example, diglycidyl ether of an aliphatic diol). The ratio of the epoxy group-containing compound (C) is, for example, about 1 to 100 parts by weight with respect to a total of 100 parts by weight of the polyol component (A) and the polyisocyanate component (B). The ratio of the isocyanate group of the polyisocyanate component (B) was about 0.5 to 1.5 mol (particularly 0.7 to 1.3 mol) with respect to 1 mol of the hydroxyl group of the polyol component (A). May be. Such a low VOC urethane-based resin composition is suitable for a coating agent or an adhesive.

  In the present invention, since a low molecular weight polyol component is used as a diluent, even a low VOC urethane resin composition in which a polymer polyol and a polyisocyanate component are combined can reduce the viscosity and improve the paintability and workability. It can be improved and the environmental load can be reduced. In addition, by adjusting the types and quantitative ratios of low molecular weight polyols and polymer polyols as diluents, coating properties such as hardness and abrasion resistance, and paintability such as adhesion to substrates and coating properties can be achieved. Can be compatible. Moreover, it is excellent in the balance between pot life and drying property (curability). Furthermore, in addition to the appearance of the coating film (designability, high glossiness, color developability, etc.), various resistances (non-contamination, fire resistance, water resistance, weather resistance, chemical resistance, etc.) can be improved.

  The low VOC urethane resin composition of the present invention is composed of a polyol component (A) and a polyisocyanate component (B). This composition may further contain a compound having an epoxy group (epoxy group-containing compound) (C). Since the composition of the present invention has a very low VOC content, VOC generation and flammability are low.

[Polyol component (A)]
In the present invention, the polyol component (A) is composed of a low molecular weight polyol (A1) as a diluent and a polymer polyol (A2).

  The polyol (A1) has a low molecular weight, and the molecular weight of the polyol (A1) is, for example, 350 or less (for example, 50 to 330), preferably 62 to 300 (for example, 62 to 200), and more preferably 76 to 150 ( In particular, it is about 76 to 120).

Examples of the polyol (A1) include aliphatic diols (ethylene glycol, 1,2- or 1,3-propylene glycol, 1,4-, 1,3- or 1,2-butanediol, 2-methyl-1 , 3-propanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 2,2,4-trimethylpentane C _2- such as -1,3-diol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-undecanediol, etc. ₁₂ alkanediol), polyalkylene glycols (diethylene glycol, triethylene glycol, dipropylene glycol, DOO Propylene glycol, di-methylene ether glycol, such as di- or tri-C _2-4 alkylene glycol such as di tetramethylene ether glycol), aliphatic polyols (glycerol, trimethylolpropane, trimethylolethane, C _3-12 fats such as pentaerythritol Aliphatic polyols), cycloaliphatic diols (cycloalkanediols such as cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, hydrogenated xylylenediol, and C _2-4 alkylene oxide adducts of these cycloalkanediols), aromatic diols (xylylenediol, bisphenol a, bisphenol S, catechol, resorcinol, an aromatic diol such as hydroquinone, C _2-4 alkylene oxide adducts of the aromatic diol Etc.), and the like. These polyol components can be used alone or in combination of two or more.

Among these polyol components, aliphatic diols (for example, C _2-6 alkylene glycols such as propylene glycol, butanediol, neopentyl glycol, hexanediol), aliphatic polyols (for example, trimethylolethane, trimethylolpropane, etc.) (Poly) C _2-4 alkylene glycol (such as di-C _2-3 alkylene glycol such as dipropylene glycol) is preferred.

  Furthermore, a polyol having a branched chain, for example, propylene glycol, dipropylene glycol, and the like may exhibit high solubility in the polymer polyol.

  The low molecular weight polyol component (A1) is usually a liquid at room temperature (15 to 25 ° C.). In addition, even if it is a compound solid at room temperature, it can be used as a liquid polyol by combining with another polyol. The viscosity of the polyol component is 500 cps (mPa · s) or less (for example, 1 to 500 cps), preferably 3 to 300 cps (for example, 3 to 200 cps), more preferably 5 to 100 cps (particularly 10 to 100 cps) at 25 ° C. Degree.

  In the present invention, by using such a low molecular weight polyol as a part of the polyol component, the low molecular weight polyol acts as a solvent (reactive diluent) even though the VOC content is extremely small. The viscosity can be lowered and the workability and paintability can be improved. Furthermore, by increasing the proportion of the low molecular weight polyol, it is possible to form a coating film having high hardness and wear resistance, and it is possible to suppress a decrease in thickness (thinning) due to foaming or drying of the coating film even when thickly applied. Therefore, the occurrence of cracks and the like in the coating film can be suppressed, and a coating film having a smooth surface can be formed. Furthermore, it has excellent appearance characteristics, stain resistance (dirt resistance) and fire resistance on the surface of the coating.

  Examples of the polymer polyol (A2) include polyether polyol, polyester polyol, polycarbonate polyol, and acrylic polymer polyol. These polymer polyols can be used alone or in combination of two or more.

Examples of the polyether polyol include alkylene oxide homopolymers or copolymers [poly (C _2-4 alkylene glycol) such as polyethylene glycol, polypropylene glycol, polytrimethylene ether glycol, polytetramethylene ether glycol], bisphenol A or Examples thereof include alkylene oxide adducts of hydrogenated bisphenol A. These polyether polyols can be used alone or in combination of two or more.

Examples of the polyester polyol include a reaction product of the low molecular weight diol (A1) and a dicarboxylic acid or a reactive derivative thereof (lower alkyl ester, acid anhydride), and a lactone (butyrolactone, valerolactone, caprolactone, laurolactone). And derivatives (ring-opening polymers) from C _3-12 lactones and the like.

Examples of the dicarboxylic acid include aliphatic dicarboxylic acids (eg, aliphatic C _4-14 aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid), and alicyclic dicarboxylic acids ( Examples thereof include tetrahydrophthalic acid, tetrahydroisophthalic acid, tetrahydroterephthalic acid, etc.) and aromatic dicarboxylic acids (eg, phthalic acid, terephthalic acid, isophthalic acid, etc.). These dicarboxylic acids can be used alone or in combination of two or more. If necessary, the dicarboxylic acid may be used in combination with a polyvalent carboxylic acid such as trimellitic acid or pyromellitic acid.

  These polyester polyols can be used alone or in combination of two or more.

Examples of the polycarbonate polyol include the low molecular weight diol (A1), dialkyl carbonate (diC _1-4 alkyl carbonate such as dimethyl carbonate) and diaryl carbonate (di C _6-12 aryl carbonate such as diphenyl carbonate) and the like. The reaction product of is mentioned. These polycarbonate polyols can be used alone or in combination of two or more.

  The acrylic polymer polyol may be an acrylic polymer polyol in which a hydroxyl group is introduced by modifying an acrylic polymer. Usually, a hydroxyl group is formed by polymerizing a (meth) acrylic monomer having a hydroxyl group. It is a (meth) acrylic polymer polyol introduced.

Examples of the (meth) acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) Examples include (meth) acrylic acid hydroxy C _2-4 alkyl esters such as 4-hydroxybutyl acrylate, poly C _2-4 alkylene glycol (meth) acrylates such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate. It is done. These hydroxyl group-containing (meth) acrylic monomers can be used alone or in combination of two or more. Among these hydroxyl group-containing (meth) acrylic monomers, (meth) acrylic acid hydroxy C _2-4 alkyl esters such as (meth) acrylic acid 2-hydroxyethyl and (meth) acrylic acid 2-hydroxypropyl are preferable.

The (meth) acrylic monomer having a hydroxyl group may be copolymerized with another copolymerizable monomer. Other copolymerizable monomers include, for example, (meth) acrylic acid, (meth) acrylic ester [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) (Meth) acrylic acid C _1-20 alkyl ester such as hexyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate , Benzyl (meth) acrylate, glycidyl (meth) acrylate, etc.], vinyl cyanide monomers such as acrylonitrile, α-olefins (α-C _2-10 olefins such as ethylene and propylene), aromatic vinyls (styrene) Vinyl toluene, α-methylstyrene, etc.), carboxylic acid vinyl esters (vinyl acetate, etc.), etc. Other copolymerizable monomers can be used alone or in combination of two or more. Of these other copolymerizable monomers, (meth) acrylic acid esters such as (meth) acrylic acid alkyl esters, glycidyl (meth) acrylic acid, styrene and other aromatic vinyls, especially methyl (meth) acrylate And (meth) acrylic acid C _1-4 alkyl esters such as butyl (meth) acrylate are preferred.

  The ratio (weight ratio) between the hydroxyl group-containing acrylic monomer and the other copolymerizable monomer can be appropriately selected according to the hydroxyl value of the acrylic polymer polyol. For example, the former / the latter = 100/0. ˜1 / 99, preferably 80/20 to 3/97, more preferably about 50/50 to 5/95 (particularly 30/70 to 10/90).

The acrylic polymer polyol may be modified with fluorine depending on the application. Although the modification method by fluorine is not particularly limited, it is usually a method for preparing a modified fluorine copolymer by polymerizing a fluorine-containing vinyl monomer as a copolymerizable monomer. Examples of fluorine-containing vinyl monomers include fluorine-containing C _2-6 olefin monomers such as tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, dichlorodifluoroethylene, vinyl fluoride, hexafluoropropylene, and trifluoromethyl vinyl ether. And perfluoro C _1-4 alkyl vinyl ether. These fluorine-containing vinyl monomers can be used alone or in combination of two or more. Of these monomers, fluorine-containing C _2-4 olefins such as tetrafluoroethylene, vinylidene fluoride, vinyl fluoride, and hexafluoropropylene are preferable.

  The proportion of the fluorine-containing vinyl monomer is, for example, about 1 to 80% by weight, preferably 3 to 60% by weight, and more preferably 5 to 50% by weight (particularly 10 to 40% by weight) in all monomers. .

  Among these polymer polyols, acrylic polymer polyols are preferable because various functions are easily imparted depending on applications.

  These polymer polyols may have a functional group for improving weather resistance such as light resistance. For example, the acrylic polymer polyol may be an acrylic monomer having a photostable group [for example, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy- (Meth) acryloyloxy-alkylpiperidine such as 1,2,2,6,6-pentamethylpiperidine and (meth) acryloyl such as 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine Amino-alkyl piperidines, etc.], acrylic monomers having UV-absorbing groups [2- (2'-hydroxy-5 '-(meth) acryloxyethylphenyl) -2H-benzotriazole and other hydroxy- (meth) And a copolymer with acryloxyalkyl-phenylbenzotriazole and the like]. The proportion of the monomer having a functional group is, for example, about 0.1 to 30% by weight, preferably about 0.5 to 20% by weight, and more preferably about 1 to 10% by weight with respect to all monomers. is there. As described above, by incorporating the ultraviolet absorbing group into the polymer polyol, bleed-out can be suppressed and the effect of light resistance can be maintained for a long period of time as compared with the case where the ultraviolet absorber is added.

  The hydroxyl value of the polymer polyol is, for example, about 10 to 400 KOH mg / g, preferably 20 to 300 KOH mg / g, more preferably about 30 to 250 KOH mg / g (particularly 50 to 200 KOH mg / g), and usually 20 to 200 KOH mg / g. Degree.

  The ratio of the low molecular weight polyol (A1) to the polymer polyol (A2) is, for example, 100 parts by weight of the polymer polyol (A2), depending on the viscosity, paintability, coating film characteristics, etc. The range can be selected from about 1 to 100 parts by weight, for example, 5 to 100 parts by weight, preferably 7 to 80 parts by weight, more preferably 10 to 75 parts by weight, 10 to 60 parts by weight, and 15 to 50 parts by weight. is there. The proportion of the low molecular weight polyol (A1) is, for example, about 3 to 80 parts by weight, preferably about 5 to 50 parts by weight (particularly 10 to 30 parts by weight) with respect to 100 parts by weight of the polymer polyol (A2). Good.

[Polyisocyanate component (B)]
Examples of the polyisocyanate component (B) include aliphatic polyisocyanates [propylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMDI), lysine diisocyanate (LDI), and the like. Aliphatic diisocyanates, aliphatic triisocyanates such as 1,6,11-undecane triisocyanate methyloctane, 1,3,6-hexamethylene triisocyanate], alicyclic polyisocyanates [cyclohexane 1,4-diisocyanate, isophorone diisocyanate ( IPDI), hydrogenated xylylene diisocyanate, hydrogenated bis (isocyanatophenyl) methane, and other alicyclic diisocyanates, Cycloaliphatic triisocyanates such as cycloheptane triisocyanate], aromatic polyisocyanates [phenylene diisocyanate, tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), naphthalene diisocyanate (NDI) , Aromatic diisocyanates such as bis (isocyanatophenyl) methane (MDI), toluidine diisocyanate (TODI), 1,3-bis (isocyanatophenyl) propane, and the like.

  These polyisocyanate components include derivatives such as multimers (dimers, trimers, tetramers, etc.), adducts, modified products (burette modified products, allophanate modified products, urea modified products, etc.) It may be a urethane oligomer having an isocyanate group.

  In addition, these polyisocyanate components are usually hydrophobic polyisocyanates, but hydrophilic groups [for example, nonionic groups (hydroxyl groups, (poly) oxyethylene groups, alkylphenyl (poly) oxyethylene groups, etc.), Hydrophilic polyisocyanates into which an anionic group (carboxyl group, sulfonic acid group, etc.) or cationic group (tertiary amino group, etc.) is introduced may be used. Hydrophilic polyisocyanates are, for example, from Nippon Polyurethane Industry Co., Ltd., trade names “Aquanate 100 (AQ-100)”, “AQ-110”, “AQ-120”, “AQ-200”, “AQ-”. 210 ".

  These polyisocyanate components can be used alone or in combination of two or more.

  Of these polyisocyanate components, modified polyisocyanates or derivatives, urethane oligomers having a plurality of isocyanate groups, and the like are preferable. Among these, from the viewpoint of weather resistance, non-yellowing polyisocyanates (for example, modified products or derivatives of polyisocyanates such as aliphatic polyisocyanates and alicyclic polyisocyanates), particularly aliphatic isocyanates or derivatives thereof (for example, hexamethylene) Diisocyanate or trimer thereof) is preferred.

  Examples of modified polyisocyanates or derivatives include adducts of polyisocyanates (such as aliphatic polyisocyanates such as hexamethylene diisocyanate) and polyhydric alcohols (such as trimethylolpropane and pentaerythritol), and burettes of the above polyisocyanates. The polyisocyanate multimer can be preferably used. From the viewpoint of coating properties such as appearance and strength, polyisocyanate (for example, aliphatic polyisocyanate) multimers (for example, polyisocyanate having an isocyanurate ring such as hexamethylene diisocyanate trimer) are particularly preferable. Such polyisocyanates are available, for example, from Mitsui Takeda Chemical Co., Ltd. under the trade names “Takenate D-170N”, “Takenate D-170HN”, and “Takenate D-177N”.

  The molecular weight of the polyisocyanate component can be selected from the range of about 150 to 3000, preferably 250 to 2000, more preferably about 300 to 1500 (particularly 300 to 1000).

  The viscosity of the polyisocyanate component (viscosity at 25 ° C.) can be selected from the range of about 100 to 5000 cps, depending on the viscosity of the polyol component and the epoxy group-containing compound described later, for example, 150 to 3000 cps, preferably 200 to 3000 cps, More preferably, it is about 250-2500 cps (especially 500-2500 cps).

  The proportion of the polyol component (A) and the polyisocyanate component (B) is such that the isocyanate group of the polyisocyanate component (B) is approximately equivalent to the hydroxyl group of the polyol component (A), for example, the proportion of the isocyanate group. However, it may be 0.5 to 1.5 mol, preferably 0.7 to 1.3 mol, and more preferably about 0.8 to 1.2 mol with respect to 1 mol of the hydroxyl group.

[Compound having epoxy group (C)]
The urethane-based resin composition of the present invention may contain a compound having an epoxy group (epoxy group-containing compound) (C). When an epoxy group-containing compound is used, the pot life becomes longer and the workability is improved. Moreover, it can suppress that a coating film becomes cloudy or foams under high humidity, and transparency and smoothness fall by using an epoxy-group containing compound. Further, by thick coating, even if the thickness of the coating film is large, a decrease in thickness due to foaming or drying and clouding can be suppressed, and a coating film having a smooth surface can be formed. However, since the light resistance of the coating film tends to be slightly lowered, it is preferably used in combination with an ultraviolet-absorbing polymer polyol or an ultraviolet absorber in applications requiring light resistance.

  The compound having an epoxy group includes a compound having a glycidyl group and an alicyclic epoxy compound, and a compound having a glycidyl group is usually used. Examples of the compound having a glycidyl group include a glycidyl ether compound, a glycidyl ester compound, and a glycidyl amine compound. These epoxy group-containing compounds can be used alone or in combination of two or more.

Examples of glycidyl ether compounds include aliphatic diol glycidyl ethers (for example, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, butanediol glycidyl ether, neopentyl glycol glycidyl ether, 1,5-pentanediol glycidyl ether, 1,6 -Hexanediol glycidyl ether, 1,7-heptanediol glycidyl ether, 2,2,4-trimethylpentane-1,3-diol glycidyl ether, 1,8-octanediol glycidyl ether, 1,10-decanediol glycidyl ether, etc. C _2-20 alkanediol mono or diglycidyl ether of), polyether diol glycidyl ether (diethylene glycol glycidyl ether, Triethylene glycol glycidyl ethers, such as di- or tri-C _2-4 alkylene glycol mono or diglycidyl ethers, such as dipropylene glycol glycidyl ether), aliphatic polyol glycidyl ethers (e.g., glycerine triglycidyl ether, trimethylolpropane triglycidyl ether, trimethylol ethane C _3-12 aliphatic polyol mono to tetraglycidyl ether such as glycidyl ether and pentaerythritol glycidyl ether), alicyclic diol glycidyl ether (for example, cyclohexanediol glycidyl ether, cyclohexanedimethanol glycidyl ether), aromatic diol glycidyl Ethers (eg, resorcing ricidyl ether), heterocyclic polyol glycidyl ethers [For example, (iso) cyanuric acid glycidyl ether] and the like. These glycidyl ether compounds can be used alone or in combination of two or more.

The glycidyl ester compounds, for example, aliphatic saturated carboxylic acid glycidyl ester (acetate glycidyl, glycidyl propionate, glycidyl butyrate, glycidyl caprate, C _4-20 aliphatic carboxylic acid glycidyl such as lauric acid glycidyl), aliphatic unsaturated saturated carboxylic acid glycidyl esters [(meth) glycidyl acrylate, aliphatic dicarboxylic acid glycidyl ester (glycidyl acid, glycidyl glutaric acid, glycidyl adipate, C _5-20 aliphatic dicarboxylic acid mono- or di-like sebacic acid glycidyl Glycidyl ester, etc.). These glycidyl ester compounds can be used alone or in combination of two or more.

  Examples of the glycidylamine compound include tetraglycidyldiaminodiphenylmethane, triglycidylaminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidylxylylenediamine, diglycidyltribromoaniline, tetraglycidylbisaminomethylcyclohexane, and the like. These glycidylamine compounds can be used alone or in combination of two or more.

Among these epoxy group-containing compounds, aliphatic glycidyl ether compounds having a plurality of glycidyl groups, for example, C _2-12 alkanediol diglycidyl such as neopentyl glycol diglycidyl ether and 1,6-hexanediol diglycidyl ether Ether, (poly) C _2-3 alkylene glycol diglycidyl ether is preferred. Furthermore, the epoxy group-containing compound may have a hydroxyl group from the viewpoint of improving the appearance and physical properties of the coating film. Examples of the epoxy group-containing compound having a hydroxyl group (or a compound having a plurality of glycidyl groups and hydroxyl groups) include glycerin diglycidyl ether, trimethylol propane diglycidyl ether, trimethylol ethane diglycidyl ether, pentaerythritol di or tri Aliphatic polyol glycidyl ethers such as glycidyl ether are preferred. Furthermore, you may use combining the epoxy group containing compound which does not have a hydroxyl group, and the epoxy group containing compound which has a hydroxyl group.

  The epoxy equivalent of the epoxy group-containing compound is not particularly limited, but is, for example, about 50 to 1000 g / eq, preferably 70 to 500 g / eq, more preferably 100 to 300 g / eq (particularly 100 to 250 g / eq). .

  The molecular weight of the epoxy group-containing compound can be selected from the range of about 110 to 1000, preferably 120 to 700, and more preferably 150 to 500 (particularly 150 to 300).

  The viscosity of the epoxy group-containing compound is preferably low from the viewpoint of coating workability, for example, 200 cps or less (for example, 1 to 200 cps) at 25 ° C., preferably 1 to 100 cps (for example, 2 to 100 cps). More preferably, it is about 3-50 cps (especially 5-30 cps).

  The proportion of the epoxy group-containing compound (C) is, for example, 1 to 100 parts by weight, preferably 3 to 80 parts by weight, based on 100 parts by weight of the total of the polyol component (A) and the polyisocyanate component (B). Preferably it is about 5-80 weight part (especially 5-50 weight part).

  In the urethane resin composition of the present invention, a urethanization catalyst may be added to promote the urethanization reaction. As the urethanization catalyst, a conventional organometallic catalyst such as a tin-based catalyst such as dibutyltin dilaurate (DBTDL), dibutyltin marker peptide, dioctyltin marker peptide, dibutyltin dimaleate, dibutyltin thiocarboxylate, or the like can be used. . These urethanization catalysts can be used alone or in combination of two or more. The proportion of the urethanization catalyst can be used in the range of 5 parts by weight or less (0 to 5 parts by weight) with respect to 100 parts by weight of the total of the polyol component (A) and the polyisocyanate component (B). The amount is about 001 to 1 part by weight, preferably about 0.005 to 0.1 part by weight, and more preferably about 0.005 to 0.05 part by weight. When the ratio of the urethanization catalyst is too large, bubbles are generated or the pot life is shortened.

  The urethane-based resin composition of the present invention further includes conventional pigment components such as inorganic pigments (white pigments such as titanium oxide, yellow pigments such as titanium yellow, red pigments such as iron oxide red, and green pigments such as chrome green). , Blue pigments such as cobalt blue, black pigments such as carbon black), organic colorants (azo dyes, phthalocyanine dyes, lake dyes, etc.), extenders (calcium carbonate, barium sulfate, aluminum hydroxide, mica, Talc, alumina, bentonite, magnesium oxide, etc.), luster pigment (metal foil such as stainless steel flake, metal powder such as aluminum, zinc, copper, glass powder, glass sphere, glass flake, glass fiber, graphite, etc.) Also good. The pigment component may be a rust preventive pigment (for example, an aluminum-containing compound such as aluminum powder, zinc powder, or condensed aluminum phosphate). These pigment components can be used alone or in combination of two or more.

  The proportion of these pigment components can be adjusted according to the application, for example, can be selected from a range of about 1 to 1000 parts by weight with respect to a total of 100 parts by weight of the polyol component and the polyisocyanate component. The amount is about 500 parts by weight, preferably about 5 to 300 parts by weight, and more preferably about 10 to 100 parts by weight.

  The urethane resin composition of the present invention further includes conventional additives such as fillers, thixotropic agents, viscosity modifiers, dispersants, wetting agents, plasticizers, defoamers, crosslinking agents, couplings. Add agents (silane coupling agents, titanium coupling agents, etc.), curing accelerators, leveling agents, lubricants, flame retardants, stabilizers (antioxidants, UV absorbers, heat stabilizers), antistatic agents, etc. Also good. In particular, when an organic powdered granular waste such as wood powder, cork powder, or plastic powder is used as a filler, heat retention and cushioning properties can be improved, and resources can be effectively used. These additives can be used alone or in combination of two or more.

  In particular, when the polymer polyol component (A2) does not have a UV-absorbing group when used for an application requiring light resistance, a benzotrizol-based UV absorber [2- (2 ′ -Hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole and other hydroxyl group and alkyl group substituted aryl benzotriazoles Cyanoacrylate ultraviolet absorbers [2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate, cyano group-containing diaryl acrylates such as ethyl-2-cyano-3,3′-diphenyl acrylate, etc.], benzophenone UV absorber [2,4-dihydroxybenzophenone, 2-hydroxy-4 Hydroxy and / or alkoxy-substituted benzophenone such as octoxybenzophenone and 2-hydroxy-4-methoxybenzophenone], salicylic acid-based UV absorber [aryl salicylates such as phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate Etc.] may be added. These ultraviolet absorbers can be used alone or in combination of two or more.

  The method for preparing the urethane resin composition of the present invention is not particularly limited, and the urethane resin composition can be prepared by a conventional method of mixing each component. In preparing the composition, each component may be added all at once or in any order. For example, you may add any component of a polyol component (A) and a polyisocyanate component (B), without adding each component collectively.

  Furthermore, the polyol (A) may be prepared by separately using the low molecular weight polyol (A1) and the polymer polyol (A2), and constitutes the polymer polyol (A2) in the low molecular weight polyol (A1). A mixture of the two may be prepared by polymerizing the monomer. When the polymer polyol (A2) is commercially available as a solution containing an organic solvent, the low molecular weight polyol (A1) having a boiling point higher than that of the organic solvent is added to the organic solvent solution of the polymer polyol. The solvent is replaced (exchanged) by removing the organic solvent by heating at a temperature not lower than the boiling point of the organic solvent and not higher than the boiling point of the low molecular weight polyol (A1) (preferably heating under reduced pressure). And a mixture of the two may be prepared.

  The urethane resin composition of the present invention can be used for various applications such as adhesives and coating agents (paints). As a method of applying the urethane resin composition of the present invention to a substrate such as an object to be coated or an object to be coated, a conventional method such as brush, roll coating, spray coating, air spray, airless spray, dipping, etc. This method can be used. The coating thickness (after drying) is not particularly limited, and can be selected from the range of about 5 μm to 50 mm depending on the application, for example, 10 to 5000 μm, preferably 30 to 3000 μm, more preferably 50 to 1000 μm (particularly 100 to 500 μm). ) In this invention, even if it coats thickly, while being able to suppress generation | occurrence | production of a foam, the reduction | decrease (thinness thinning) of the coating film thickness by drying can be suppressed. Therefore, it is useful for forming a coating film having a large film thickness and high surface smoothness.

  The urethane-based resin composition of the present invention can be cured to form a coating film by coating the base material and then curing at room temperature or warming (for example, warming at about 50 to 100 ° C.). In addition, in this invention, it can harden | cure rapidly also at normal temperature (for example, about 15-25 degreeC). The urethane resin composition of the present invention can secure a sufficient pot life, has a quick drying or curing time, and has high workability.

  Since the urethane-based resin composition of the present invention is excellent in adhesion to a substrate and various coating film properties, it can be used for coating and adhesion of various substrates. As a base material, the base material comprised by organic materials, such as inorganic materials, such as a metal, ceramics, glass, mortar, concrete, a synthetic resin, and a natural material (wood etc.), can be mentioned, for example. Furthermore, when the polymer polyol has a UV-absorbing group, the coating film has excellent light resistance, and is therefore suitable for outdoor use.

  The urethane-based resin composition of the present invention is used in various applications, for example, for surface finishing of buildings and structures, for surface finishing of machinery and equipment, for surfaces and inner surfaces of various pipes such as sewers and gases, and home appliances. For surface finishing of products, furniture, daily necessities, etc., for finishing of textile products, etc., for surfaces and inner surfaces of containers, containers, etc., for protective finishing of various types of vehicle exterior panels, coarse grains of various natural stones and artificially colored coarse grains It can be used for various finishes of concrete floors blended with, for heat insulation and heat insulation finish blended with fine pieces such as foamed urethane, or for bonding these products to each other or between these products and other products.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

  The contents of the components used in the examples and comparative examples, and methods for evaluating the properties of the compositions and coating films are shown below.

(1) Content of each component [Polyol component (A)]
Low molecular weight polyol A1-1: propylene glycol, manufactured by Showa Denko KK, industrial, molecular weight 76.1, specific gravity (25 ° C.) 1.038, viscosity (25 ° C.) 43 mPa · s
Low molecular weight polyol A1-2: Dipropylene glycol, manufactured by Kishida Chemical Co., Ltd., reagent grade 1, molecular weight 134.2, specific gravity 1.025, viscosity (25 ° C.) 73 mPa · s
Low molecular weight polyol A1-3: 1,4-butanediol, manufactured by Mitsubishi Chemical Corporation, molecular weight 90.1, specific gravity (25 ° C.) 1.015, viscosity (25 ° C.) 68 mPa · s
Polymer polyol A2-1: Acrylic polyol, manufactured by Nippon Shokubai Co., Ltd., trade name “Udouble H-4818”, nonvolatile content: 70% by weight, viscosity (25 ° C.) Z _{3 to} Z ₅ (Gardner) (4630 to 9850 cSt) , Hydroxyl value (value in the form of varnish) 70 KOH mg / g, solution containing xylene and butyl acetate Polymer polyol A2-2: UV-absorbing acrylic polyol, manufactured by Nippon Shokubai Co., Ltd., trade name “Hals Hybrid GP1034-3” Non-volatile content 40% by weight, viscosity (25 ° C.) 80 mPa · s, hydroxyl value (varnish) 36 KOH mg / g, ethyl acetate-containing solution Polymer polyol A2-3: highly weather-resistant acrylic polyol, manufactured by Rohm and Haas Name “Paraloid UCD-750”, viscosity (25 ° C.) 5000 mPa · s, specific gravity (25 ) 1.04, hydroxyl group equivalent (solid) 400, heating residue (wt%) 80, n-butyl acetate containing solution Polymer polyol A2-4: Polyester polyol, trade name “Takelac U118A” manufactured by Mitsui Takeda Chemical Co., Ltd. , Non-volatile content 97%, viscosity (25 ° C.) 3500 mPa · s, specific gravity (25 ° C.) 1.04, hydroxyl value 219
Polymer polyol A2-5: Polyester polyol, manufactured by Mitsui Takeda Chemical Co., Ltd., trade name “MT Olester C-1000”, non-volatile content 100%, viscosity (25 ° C.) U to V (Gardner), hydroxyl value 161, iodine Price 86.

[Polyisocyanate component (B)]
Polyisocyanate B-1: Trade name “Takenate D-170N”, manufactured by Mitsui Takeda Chemical Co., Ltd., hexamethylene diisocyanate trimer, molecular weight 504, specific gravity (25 ° C.) 1.16, viscosity (25 ° C.) 2000 mPa · s
Polyisocyanate B-2: trade name “Takenate D-170HN”, manufactured by Mitsui Takeda Chemical Co., Ltd., hexamethylene diisocyanate trimer, specific gravity (25 ° C.) 1.14, viscosity (25 ° C.) 600 mPa · s
Polyisocyanate B-3: Trade name “Takenate D-177N”, manufactured by Mitsui Takeda Chemical Co., Ltd., hexamethylene diisocyanate trimer, specific gravity (25 ° C.) 1.10, viscosity (25 ° C.) 250 mPa · s.

[Epoxy group-containing compound (C)]
Glycidyl ether: Hexamethylene glycol diglycidyl ether, trade name “Denacol EX212”, manufactured by Nagase ChemteX Corporation, molecular weight 230, epoxy equivalent 150 g / eq, specific gravity (25 ° C.) 1.06, viscosity (25 ° C.) 20 mPa · s.

[Other additives]
DBTDL: Dibutyltin dilaurate, trade name “L101-V”, manufactured by Tokyo Fine Chemical Co., Ltd. Silane coupling agent: γ-glycidoxypropyltrimethoxysilane, trade name “NUCA 187”, manufactured by Nippon Unicar Co., Ltd., specific gravity ( 25 ° C) 1.07, boiling point 290 ° C, flash point 135 ° C.

(2) Evaluation method of each characteristic The obtained urethane type resin composition was lightly ground with sandpaper # 240 and washed with toluene (the tin plate described in JIS-K-5410 2- (3), SPTE 1505003) was coated with a brush on one side, and after curing for 5 days indoors, the coated products were subjected to the following characteristic evaluation tests. In the case of water resistance, acid resistance, and alkali resistance tests, the surfaces not to be coated were all subjected to each test after being bonded and sealed with a commercially available electrical insulating tape (black).

[VOC]
It calculated | required by calculation from the composition of the compounding component.

[viscosity]
Measured at a temperature of 25 ° C. using a B-type viscometer [pot life]
After preparing the urethane-based resin composition, the paintable time at 25 ° C. was measured.

[Brush painting workability]
The obtained urethane-based resin composition was applied to one side of a flexible asbestos board (length 70 mm x width 150 mm x thickness 3 mm) by alternately returning the brush 5 times in each of the vertical and horizontal directions. The degree of difficulty was evaluated according to the following criteria.

◎: Good ○: Slightly heavy △: Very heavy

[Drying time]
According to JIS-K-5400 6.5, the drying time at 25 ° C. was measured and evaluated according to the following criteria.

A: Dried for less than 5 hours B: Dried for 5 hours or more and less than 12 hours Δ: Dried for 12 hours or more and less than 24 hours X: Dried for 24 hours or more.

[State of coating film]
The gloss, clarity, and leveling level of the dried coating film were observed with the naked eye and evaluated according to the following criteria.

A: Gloss, sharpness, and leveling are high. B: Gloss, sharpness, and leveling are normal. X: Gloss, sharpness, and leveling are low.

[Film thickness]
The film thickness was measured at five locations with a micrometer, and the average value was obtained.

[Pencil hardness]
It measured according to JIS-K-5400 8.4.2.

[Adhesion]
A cross-cut test was conducted according to JIS-K-5400 8.5.2, and the following criteria were evaluated.

A: Coating film peeling is less than 10% B: Coating film peeling is 10% or more and less than 50% Δ: Coating film peeling is 50% or more and less than 90% ×: Coating film peeling is 90% or more.

[Flexibility]
Using a mandrel having a diameter of 3 mm, evaluation was performed according to the following criteria according to JIS-K-5400 8.1.

◎: No abnormality ○: Shallow cracks ×: Peeling.

[water resistant]
After immersing the coating film in water at 20 ° C. for 10 days, the state of the coating film surface was visually observed and evaluated according to the following criteria.

A: No change on the coating film surface O: Slight swelling on the coating film surface X: Most of the coating film surface was eluted or peeled off.

[Acid resistance]
After being immersed in 10% by weight sulfuric acid at room temperature for 10 days, the state of the coating film surface was visually observed and evaluated according to the following criteria.

A: No change on coating film surface O: Slight swelling on coating film surface X: Swelling occurs on most coating film surface

[Alkali resistance]
After being immersed in saturated lime water at room temperature for 10 days, the state of the coating film surface was visually observed and evaluated according to the following criteria.

A: No change on coating film surface O: Slight swelling on coating film surface X: Swelling occurs on most coating film surface

[Light resistance]
The obtained urethane-based resin composition was coated once with a brush on one side of a polycarbonate plate (length 80 mm × width 150 mm × thickness 2 mm), cured indoors (room temperature) for 5 days, and then the size of 33 mm length × 45 mm width. After being irradiated for 48 hours with an ultraviolet irradiation machine (trade name “Super UV Tester SUV-F11, manufactured by Iwasaki Electric Co., Ltd.”), the degree of change in the appearance of the coating film was visually compared with that before irradiation. Evaluated according to the following criteria,
A: There was very little discoloration. B: There was considerable discoloration. B: Significant discoloration.

[Cleanability]
Mark the surface of the paint film with a commercially available oil-based magic pen (black), wipe it off with Kimwipe S200 (made by Crecia Co., Ltd.) wetted with toluene after 24 hours, and evaluate the degree of cleaning according to the following criteria did.

◎: ○ mark completely disappeared ○: Most of ○ mark disappeared △: Only a small part of ○ mark disappeared ×: ○ mark did not disappear.

[Paintability to Styrofoam]
The obtained urethane-based resin composition was coated once with a brush on one side of a polystyrene foam plate (length 100 mm × width 100 mm × thickness 30 mm), and the finished state was visually observed and evaluated according to the following criteria.

A: The film could be formed without dissolving the substrate. B: Some of the substrate was dissolved, but the film could be formed. X: The substrate was dissolved.

Example 1
6. In a container, 67 parts by weight of low molecular weight polyol A1-2, 433 parts by weight of polymer polyol A2-1 (303 parts by weight of solid content), 151 parts by weight of glycidyl ether, and DBTDL (2% by weight xylene solution) After adding 5 parts by weight and stirring uniformly using a desktop stirrer, the agent A is prepared by removing the solvent in the polymer polyol A2-1 under conditions of a temperature of 80 ° C. and a pressure of 6 to 20 mmHg. did. The solid content concentration of agent A before the solvent exchange was 46.1% by weight, and the solid content concentration of agent A after the solvent exchange was 58.1% by weight. Moreover, the viscosity of this A agent is 5000 mPa * s at the temperature of 25 degreeC, and the composition is 22 weight% of low molecular weight polyol A1-2 with respect to 100 weight part polymer polyol A2-1 in conversion of solid content. About 50 parts by weight of glycidyl ether.

  Next, 166 parts by weight of polyisocyanate B-1 as B agent was added to 172 parts by weight of this A agent, and the mixture was further uniformly stirred to obtain a target urethane resin composition. The miscibility of A agent and B agent was favorable, and the viscosity immediately after mixing was 3050 mPa * s at the temperature of 25 degreeC. About this urethane type resin composition, while showing the composition (solid content) in Table 1, the result of having evaluated various characteristics is shown in Table 1.

Example 2
In a container, 38 parts by weight of low molecular weight polyol A1-1, 350 parts by weight of polymer polyol A2-2 (140 parts by weight of solid content), 75.5 parts by weight of glycidyl ether, and DBTDL (2% by weight xylene solution) After adding 3 parts by weight and stirring uniformly using a desktop stirrer, the agent A is prepared by removing the solvent in the polymer polyol A2-2 under conditions of a temperature of 80 ° C. and a pressure of 6 to 10 mmHg. did. The solid content concentration of Agent A before the solvent exchange was 30% by weight, and the solid content concentration of Agent A after the solvent exchange was 55.2% by weight. The viscosity of the agent A is 6500 mPa · s at a temperature of 25 ° C., and its composition is 27 parts by weight of low molecular weight polyol A1-1 based on 100 parts by weight of polymer polyol A2-2 in terms of solid content. The glycidyl ether was about 54 parts by weight.

  Next, 160 parts by weight of polyisocyanate B-2 as a B agent was added to 181 parts by weight of the A agent, and the mixture was further uniformly stirred to obtain a target urethane resin composition. The miscibility between agent A and agent B was somewhat difficult, and the viscosity immediately after mixing was 3200 mPa · s at a temperature of 25 ° C. About this urethane type resin composition, while showing the composition (solid content) in Table 1, the result of having evaluated various characteristics is shown in Table 1.

Example 3
In a container, 11 parts by weight of low molecular weight polyol A1-3, 125 parts by weight of polymer polyol A2-3 (solid content 100 parts by weight), 18 parts by weight of glycidyl ether, and 1 part by weight of DBTDL (2% by weight xylene solution) A part was added and the A agent was prepared by stirring uniformly using a desktop stirrer. To this A agent, 143 parts by weight of polyisocyanate B-1 was added as a B agent, followed by uniform stirring to obtain a desired urethane resin composition. The miscibility of A agent and B agent was favorable, and the viscosity immediately after mixing was 1200 mPa * s at the temperature of 25 degreeC. About this urethane type resin composition, while showing the composition (solid content) in Table 1, the result of having evaluated various characteristics is shown in Table 1.

Example 4
Add 38 parts by weight of low molecular weight polyol A1-1, 1000 parts by weight of polymer polyol A2-4, and 2 parts by weight of DBTDL (2% by weight xylene solution) to the container, and stir uniformly using a desktop stirrer. By doing this, the agent A was prepared. To this agent A, 284 parts by weight of polyisocyanate B-1 was added as agent B, and the mixture was then stirred uniformly to obtain the desired urethane resin composition. The miscibility of agent A and agent B was good, and the viscosity immediately after mixing was 1150 mPa · s at a temperature of 25 ° C. About this urethane type resin composition, while showing the composition (solid content) in Table 1, the result of having evaluated various characteristics is shown in Table 1.

Example 5
Add 11 parts by weight of low molecular weight polyol A1-1, 100 parts by weight of polymer polyol A2-4, 58 parts by weight of glycidyl ether, and 2 parts by weight of DBTDL (2% by weight xylene solution) to a container, The agent A was prepared by using and stirring uniformly. To this A agent, 437 parts by weight of polyisocyanate B-1 was added as a B agent, and the mixture was then stirred uniformly to obtain the desired urethane resin composition. The miscibility of agent A and agent B was good, and the viscosity immediately after mixing was 750 mPa · s at a temperature of 25 ° C. About this urethane type resin composition, while showing the composition (solid content) in Table 1, the result of having evaluated various characteristics is shown in Table 1.

Comparative Example 1
By adding 142.9 parts by weight of polymer polyol A2-1 (solid content: 100 parts by weight) and 1 part by weight of DBTDL (2% by weight xylene solution) to a container, and stirring uniformly using a desktop stirrer , A agent was prepared. To this agent A, 36 parts by weight of polyisocyanate B-3 was added as agent B, followed by stirring to obtain the desired urethane resin composition. The miscibility of agent A and agent B was good, and the viscosity immediately after mixing was 2150 mPa · s at a temperature of 25 ° C. About this urethane type resin composition, while showing the composition (solid content) in Table 1, the result of having evaluated various characteristics is shown in Table 1.

Comparative Example 2
By adding 250 parts by weight of polymer polyol A2-2 (solid content of 100 parts by weight) and 1 part by weight of DBTDL (2% by weight xylene solution) to a container, and stirring uniformly using a desktop stirrer, A An agent was prepared. 33 parts by weight of polyisocyanate B-2 was added as a B agent to this A agent, followed by stirring to obtain the desired urethane resin composition. The miscibility of agent A and agent B was good, and the viscosity immediately after mixing was 100 mPa · s at a temperature of 25 ° C. About this urethane type resin composition, while showing the composition (solid content) in Table 1, the result of having evaluated various characteristics is shown in Table 1.

Comparative Example 3
By adding 125 parts by weight of polymer polyol A2-3 (solid content: 100 parts by weight) and 2 parts by weight of DBTDL (2% by weight xylene solution) to a container, and stirring uniformly using a table stirrer, A An agent was prepared. To this A agent, 52 parts by weight of polyisocyanate B-3 was added as a B agent, followed by stirring to obtain the desired urethane resin composition. The miscibility of A agent and B agent was favorable, and the viscosity immediately after mixing was 2800 mPa * s at the temperature of 25 degreeC. About this urethane type resin composition, while showing the composition (solid content) in Table 1, the result of having evaluated various characteristics is shown in Table 1.

Comparative Example 4
Add 125 parts by weight of polymer polyol A2-3 (solid content: 100 parts by weight), 30 parts by weight of silane coupling agent, and 2 parts by weight of DBTDL (2% by weight xylene solution) to a container, and use a desktop stirrer. The agent A was prepared by stirring uniformly. To this A agent, 173 parts by weight of polyisocyanate B-1 was added as a B agent, followed by stirring to obtain the desired urethane resin composition. The miscibility of agent A and agent B was good, and the viscosity immediately after mixing was 3100 mPa · s at a temperature of 25 ° C. About this urethane type resin composition, while showing the composition (solid content) in Table 1, the result of having evaluated various characteristics is shown in Table 1.

Comparative Example 5
The agent A was prepared by adding 100 parts by weight of the polymer polyol A2-4 and 2 parts by weight of DBTDL (2% by weight xylene solution) to the container and stirring uniformly using a desktop stirrer. To this A agent, 77 parts by weight of polyisocyanate B-1 was added as a B agent, followed by stirring to obtain the desired urethane resin composition. The miscibility of A agent and B agent was favorable, and the viscosity immediately after mixing was 2875 mPa * s at the temperature of 25 degreeC. About this urethane type resin composition, while showing the composition (solid content) in Table 1, the result of having evaluated various characteristics is shown in Table 1.

Comparative Example 6
The agent A was prepared by adding 100 parts by weight of the polymer polyol A2-4 and 2 parts by weight of DBTDL (2% by weight xylene solution) to the container and stirring uniformly using a desktop stirrer. To this A agent, 92 parts by weight of polyisocyanate B-1 was added as a B agent, followed by stirring to obtain the desired urethane resin composition. The miscibility of agent A and agent B was good, and the viscosity immediately after mixing was 2525 mPa · s at a temperature of 25 ° C. About this urethane type resin composition, while showing the composition (solid content) in Table 1, the result of having evaluated various characteristics is shown in Table 1.

Comparative Example 7
The agent A was prepared by adding 100 parts by weight of the polymer polyol A2-4 and 2 parts by weight of DBTDL (2% by weight xylene solution) to the container and stirring uniformly using a desktop stirrer. To this A agent, 82 parts by weight of polyisocyanate B-3 was added as a B agent, followed by stirring to obtain the desired urethane resin composition. The miscibility of A agent and B agent was favorable, and the viscosity immediately after mixing was 2200 mPa * s at the temperature of 25 degreeC. About this urethane type resin composition, while showing the composition (solid content) in Table 1, the result of having evaluated various characteristics is shown in Table 1.

Comparative Example 8
The agent A was prepared by adding 100 parts by weight of the polymer polyol A2-4 and 2 parts by weight of DBTDL (2% by weight xylene solution) to the container and stirring uniformly using a desktop stirrer. To this A agent, 98 parts by weight of polyisocyanate B-3 was added as a B agent, followed by stirring to obtain a target urethane resin composition. The miscibility of agent A and agent B was good, and the viscosity immediately after mixing was 2000 mPa · s at a temperature of 25 ° C. About this urethane type resin composition, while showing the composition (solid content) in Table 1, the result of having evaluated various characteristics is shown in Table 1.

Comparative Example 9
The agent A was prepared by adding 100 parts by weight of the polymer polyol A2-5 and 3 parts by weight of DBTDL (2% by weight xylene solution) to the container and stirring uniformly using a desktop stirrer. To this A agent, 58 parts by weight of polyisocyanate B-1 was added as a B agent, followed by stirring to obtain a target urethane resin composition. The miscibility of agent A and agent B was good, and the viscosity immediately after mixing was 1300 mPa · s at a temperature of 25 ° C. About this urethane type resin composition, while showing the composition (solid content) in Table 1, the result of having evaluated various characteristics is shown in Table 1.

Comparative Example 10
The agent A was prepared by adding 100 parts by weight of the polymer polyol A2-5 and 3 parts by weight of DBTDL (2% by weight xylene solution) to the container and stirring uniformly using a desktop stirrer. To this A agent, 60 parts by weight of polyisocyanate B-3 was added as a B agent, followed by stirring to obtain the desired urethane resin composition. The miscibility of A agent and B agent was favorable, and the viscosity immediately after mixing was 575 mPa * s at the temperature of 25 degreeC. About this urethane type resin composition, while showing the composition (solid content) in Table 1, the result of having evaluated various characteristics is shown in Table 1.

Comparative Example 11
To a container, add 60 parts by weight of polymer polyol A2-4, 40 parts by weight of polymer polyol A2-5, and 3 parts by weight of DBTDL (2% by weight xylene solution), and stir uniformly using a desktop stirrer. The A agent was prepared by this. To this A agent, 71 parts by weight of polyisocyanate B-1 was added as a B agent, followed by stirring to obtain a target urethane resin composition. The miscibility of agent A and agent B was good, and the viscosity immediately after mixing was 2250 mPa · s at a temperature of 25 ° C. About this urethane type resin composition, while showing the composition (solid content) in Table 1, the result of having evaluated various characteristics is shown in Table 1.

  As is clear from the results in Table 1, the urethane resin compositions of the examples have good workability and physical properties of the coating film. On the other hand, the urethane-based resin composition of the comparative example does not have sufficient properties such as workability, physical properties of the coating film, and various resistances.

Claims (11)

  A composition comprising a polyol component (A) and a polyisocyanate component (B), wherein the polyol component (A) comprises a low molecular weight polyol (A1) and a polymer polyol (A2) as diluents. Low VOC urethane resin composition.   The urethane resin composition according to claim 1, wherein the low molecular weight polyol (A1) is a polyol having a molecular weight of 350 or less.   The urethane resin composition according to claim 1, wherein the proportion of the low molecular weight polyol (A1) is 5 to 100 parts by weight with respect to 100 parts by weight of the polymer polyol (A2).   The urethane resin composition according to claim 1, wherein the polymer polyol (A2) is at least one selected from polyether polyol, polyester polyol, polycarbonate polyol, and acrylic polymer polyol.   The urethane resin composition according to claim 1, wherein the polyisocyanate component (B) is a derivative or modified product of polyisocyanate.   The ratio of the isocyanate group of the polyisocyanate component (B) is 0.5 to 1.5 mol with respect to 1 mol of the hydroxyl group of the polyol component (A), and the ratio of the low molecular weight polyol (A1) is the polymer polyol. (A2) The urethane-based resin composition according to claim 1, which is 7 to 80 parts by weight with respect to 100 parts by weight.   Furthermore, the urethane type resin composition of Claim 1 containing the compound (C) which has an epoxy group.   The urethane-based resin composition according to claim 7, wherein the compound (C) having an epoxy group is a compound having a plurality of glycidyl groups.   8. The urethane-based resin composition according to claim 7, wherein the proportion of the compound (C) having an epoxy group is 1 to 100 parts by weight with respect to 100 parts by weight as a total of the polyol component (A) and the polyisocyanate component (B). . A composition comprising a polyol component composed of a C _2-6 alkylene glycol and an acrylic polymer polyol, a diisocyanate multimer, and a diglycidyl ether of an aliphatic diol, wherein the ratio of isocyanate groups in the diisocyanate multimer Is 0.7 to 1.3 moles with respect to 1 mole of hydroxyl groups of the polyol component, and the proportion of C _2-6 alkylene glycol is 10 to 75 parts by weight with respect to 100 parts by weight of the acrylic polymer polyol. A low VOC urethane-based resin composition. The urethane resin composition according to claim 1, which is a coating agent or an adhesive.