Curable resin composition, coating material, and article

Abstract

The present invention provides a curable resin composition which is characterized by containing a polyester polyol (A) and an acrylic polyol (B) that are reaction products of a polycarboxylic acid (a1) and a polyol (a2), the polycarboxylic acid (a1) containing an aliphatic dicarboxylic acid (a1-1) having a linear alkyl group having 4-10 carbon atoms, and the polyol (a2) containing an aliphatic dicarboxylic acid (a1-1) having a linear alkyl group having 4-10 carbon atoms. The polyol (a2) contains one or more diols (a2-1) selected from the group consisting of ethylene glycol, diethylene glycol, 1, 2-propylene glycol, and 1, 3-propylene glycol, and also contains a trifunctional or higher alcohol (a2-2), and the polyester polyol (A) has an ester group concentration of 6-11 mmol / g. The curable resin composition can obtain a cured coating film having excellent appearance (fullness), adhesiveness, water resistance, and chemical resistance, and thus can be suitably used in various coatings.

Description

Technical Field

[0001] The present invention relates to a curable resin composition, a coating material and an article. Background Art

[0002] Acrylic resin compositions have traditionally been used in applications such as coatings, inks, adhesives, and synthetic leather due to their excellent chemical resistance, weather resistance, flexibility, and adhesion. In particular, coatings are used in the automotive, home appliance, and building material industries. In this field, there is a demand for coatings that exhibit not only excellent adhesion to plastic substrates and chemical resistance (sunscreen resistance and alcohol resistance) in realistic usage scenarios, but also excellent appearance (plump feel).

[0003] As a coating composition with a good saturated feel in the coating film, a two-component hybrid coating composition has been proposed (for example, see Patent Document 1) containing as a main component a copolymer comprising at least one of an oxidatively polymerizable unsaturated fatty acid and an alkyd resin having an oxidatively polymerizable group, an acrylic copolymer, and an organosilicon having at least one of a hydroxyl group and an alkoxysilyl group. However, systems using such unsaturated fatty acids and alkyd resins suffer from poor chemical resistance, such as sunscreen resistance.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent No. 5688523 Summary of the Invention

[0007] Problems to be solved by the invention

[0008] The problem to be solved by the present invention is to provide a curable resin composition, a coating material, and an article having a cured coating material of the coating material, which can produce a cured coating film having excellent appearance (plump feeling), adhesion, water resistance, and chemical resistance.

[0009] Means for solving problems

[0010] The present inventors have conducted intensive studies to solve the above-mentioned problems and have found that a curable resin composition containing a specific polyester polyol and an acrylic polyol can provide a cured coating film having excellent appearance (plumpness), adhesion, water resistance, and chemical resistance, thereby completing the present invention.

[0011] That is, the present invention relates to the following curable resin composition, characterized in that it contains a polyester polyol (A) which is a reaction product of a polycarboxylic acid (a1) and a polyol (a2), and an acrylic polyol (B), wherein the polycarboxylic acid (a1) contains 20 mol% or more of an aliphatic dicarboxylic acid (a1-1) having a linear alkyl group having 4 to 10 carbon atoms, and the polyol (a2) contains 20 mol% or more of one or more diols (a2-1) selected from ethylene glycol, diethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol, and contains 5 to 20 mol% of a trifunctional or higher alcohol (a2-2), and the ester group concentration of the polyester polyol (A) is 6 to 11 mmol / g.

[0012] Effects of the Invention

[0013] The curable resin composition of the present invention can produce a cured coating film having excellent appearance (plump feel), adhesion, water resistance, and chemical resistance. Therefore, it can be suitably used in various coatings for automobile exteriors, automobile repairs, plastics, industrial machinery, building materials, wood flooring, and the like. DETAILED DESCRIPTION

[0014] The curable resin composition of the present invention contains a polyester polyol (A) which is a reaction product of a polycarboxylic acid (a1) and a polyol (a2), and an acrylic polyol (B), wherein the polycarboxylic acid (a1) contains 20 mol% or more of an aliphatic dicarboxylic acid (a1-1) having a linear alkyl group having 4 to 10 carbon atoms, and the polyol (a2) contains 20 mol% or more of one or more diols (a2-1) selected from ethylene glycol, diethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol, and contains 5 to 20 mol% of a trifunctional or higher alcohol (a2-2), and the ester group concentration of the polyester polyol (A) is 6 to 11 mmol / g.

[0015] The polyester polyol (A) is a reaction product of a polycarboxylic acid (a1) and a polyol (a2), and can be obtained by a known condensation reaction.

[0016] From the viewpoint of obtaining a coating film having excellent plumpness, it is important that the polycarboxylic acid (a1) contains 20 mol % or more of an aliphatic dicarboxylic acid (a1-1) having a linear alkyl group having 4 to 10 carbon atoms.

[0017] Examples of the aliphatic dicarboxylic acid (a1-1) having a linear alkyl group having 4 to 10 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, and the like, and their methyl esters and acid chlorides, with succinic acid and sebacic acid being more preferred. It should be noted that these aliphatic dicarboxylic acids (a1-1) may be used alone or in combination of two or more.

[0018] It should be noted that, in the present invention, dicarboxylic acid includes anhydrides of dicarboxylic acid.

[0019] As the polycarboxylic acid (a1), other polycarboxylic acid (a1-2) other than the dicarboxylic acid (a1-1) may be used in combination.

[0020] Examples of the other polycarboxylic acids (a1-2) include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, etc. other than the dicarboxylic acids (a1-1). These polycarboxylic acids (a1-2) may be used alone or in combination of two or more.

[0021] Examples of the aliphatic dicarboxylic acid other than the dicarboxylic acid (a1-1) include decanedicarboxylic acid and dimer acid.

[0022] Examples of the alicyclic dicarboxylic acid include 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid.

[0023] Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, trimellitic acid, and pyromellitic acid.

[0024] The content of the aliphatic dicarboxylic acid (a1-1) having a linear alkyl group having 4 to 10 carbon atoms in the polycarboxylic acid (a1) is preferably 30 to 90 mol % in order to further improve the plumpness of the resulting coating film.

[0025] From the viewpoint of obtaining a coating film having excellent plumpness, it is important that the polyol (a2) contains 20 mol % or more of one or more diols (a2-1) selected from ethylene glycol, diethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol.

[0026] Furthermore, it is important that the polyol (a2) contains 5 to 20 mol % of a trifunctional or higher functional alcohol (a2-2) in order to obtain a coating film having excellent chemical resistance.

[0027] Examples of the trifunctional or higher alcohol (a2-2) include aliphatic polyol compounds such as trimethylolethane, trimethylolpropane, glycerol, hexanetriol, and pentaerythritol; aromatic polyol compounds such as trihydroxybenzene; and polyether-modified polyol compounds obtained by ring-opening polymerization of cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether with the aliphatic polyol compounds or aromatic polyol compounds. It should be noted that these trifunctional or higher alcohols (a2-2) may be used alone or in combination of two or more.

[0028] As the polyol (a2), other polyols (a2-3) other than the diol (a2-1) and the trifunctional or higher-functional alcohol (a2-2) may be used in combination.

[0029] Examples of the other polyols (a2-3) include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-ethyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2-ethyl-2-methyl-1,3-propanediol, 2-ethylbutane-1,4-butanediol, 2,3-dimethyl-1,4-butanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1 Aliphatic diols such as 2,5-pentanediol, 3,3-dimethylpentane-1,5-diol, 2,2-diethyl-1,3-propanediol, 3-propylpentane-1,5-diol, 2,2-diethyl-1,4-butanediol, 2,4-diethyl-1,5-pentanediol, 2,2-dipropyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, and 2,5-diethyl-1,6-hexanediol; diol compounds containing an alicyclic structure such as cyclohexanediol and cyclohexanediol (Japanese: シクロヘキサンジアルコール); diol compounds containing an aromatic ring such as biphenol and bisphenol; polyether diols; and polycarbonate diols. It should be noted that these other polyols (a2-3) may be used alone or in combination of two or more.

[0030] From the perspective of achieving a balance between the chemical resistance of the resulting coating film and compatibility with the acrylic polyol (B), it is important that the ester group concentration of the polyester polyol (A) is 6 to 11 mmol / g.

[0031] The ester group concentration (mmol / g) refers to the number of millimoles of ester groups in 1 g of the polyester polyol (A), and is determined, for example, as a calculated value based on the input amount.

[0032] The hydroxyl value of the polyester polyol (A) is preferably 50 to 250 mgKOH / g in order to further improve the balance between the chemical resistance of the resulting coating film and the compatibility with the acrylic polyol (B).

[0033] Furthermore, the number average molecular weight of the polyester polyol (A) is preferably 800 to 5000 from the viewpoint of further improving the balance between the chemical resistance of the resulting coating film and the compatibility with the acrylic polyol (B).

[0034] The hydroxyl value and acid value in the present invention are measured according to JIS test method K 0070-1992, and the average molecular weight is a value obtained by measuring by gel permeation chromatography (hereinafter, abbreviated as "GPC") and converting it into polystyrene.

[0035] The acrylic polyol (B) can be obtained by copolymerizing, for example, an unsaturated monomer (b1) having a hydroxyl group and another unsaturated monomer (b2).

[0036] Examples of the unsaturated monomer (b1) having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxy-n-butyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-n-butyl (meth)acrylate, 3-hydroxy-n-butyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, glycerol mono(meth)acrylate, polyoxyethylene mono(meth)acrylate, polyoxypropylene mono(meth)acrylate, polyoxybutylene mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, and polycaprolactone-modified hydroxyethyl mono(meth)acrylate. It should be noted that these unsaturated monomers (b1) having a hydroxyl group may be used alone or in combination of two or more.

[0037] As the above-mentioned other unsaturated monomers (b2), for example, there can be mentioned unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, β-carboxyethyl (meth)acrylate, ω-carboxy-polycaprolactone mono(meth)acrylate, 2-(meth)acryloyloxyethyl succinate, and 2-(meth)acryloyloxyethyl hexahydrophthalate; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, or unsaturated monomers having a carboxyl group such as half esters of these unsaturated dicarboxylic acids; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylate) (Meth)acrylates having a hydrocarbon group, such as nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, behenyl (meth)acrylate, cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and benzyl (meth)acrylate; acrylamide, N,N-dimethyl (meth)acrylamide, (meth)acrylonitrile, 3-(meth)acryloylpropyltrimethoxysilane, N,N-dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2-(meth)acryloyloxyethyl acid phosphate, styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene. It should be noted that these other unsaturated monomers (b2) may be used alone or in combination of two or more.

[0038] From the viewpoint of further improving the balance between chemical resistance and adhesion, the content of the unsaturated monomer (b1) having a hydroxyl group in the unsaturated monomer raw material of the acrylic polyol (B) is preferably 0.5 to 40% by mass, more preferably 1.5 to 35% by mass.

[0039] From the viewpoint of further improving chemical resistance, the content of the unsaturated monomer having a carboxyl group in the unsaturated monomer raw material of the acrylic polyol (B) is preferably 0.1 to 15% by mass.

[0040] In the present invention, "(meth)acrylic acid" refers to one or both of methacrylic acid and acrylic acid, "(meth)acrylate" refers to one or both of methacrylate and acrylate, and "(meth)acryloyl" refers to one or both of methacryloyl and acryloyl.

[0041] The acrylic polyol (B) can be produced by using the hydroxyl group-containing monomer (b1) and the other monomer (b2) as raw materials by a known polymerization method. Solution radical polymerization is preferred because of its simplicity.

[0042] As a method for producing the above-mentioned acrylic polyol (B) by the above-mentioned solution radical polymerization method, there can be mentioned a method in which each monomer serving as a raw material is dissolved in a solvent and / or the above-mentioned polyester polyol (A), and a polymerization reaction is carried out in the presence of a polymerization initiator. From the viewpoint of improving compatibility, it is preferred to carry out the polymerization reaction in the presence of the above-mentioned polyester polyol (A).

[0043] Examples of the solvent include hydrocarbon solvents such as toluene, xylene, cyclohexane, n-hexane, and octane; alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, and ethylene glycol monomethyl ether; ester solvents such as methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, and amyl acetate; and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. These solvents may be used alone or in combination of two or more.

[0044] Examples of the polymerization initiator include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), and azobiscyanovaleric acid; organic peroxides such as t-butyl peroxypivalate, t-butyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate, di-t-butyl peroxide, cumene hydroperoxide, benzoyl peroxide, and t-butyl hydroperoxide; and inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate. These polymerization initiators may be used alone or in combination of two or more. The polymerization initiator is preferably used in an amount of 0.1 to 10% by mass relative to the total amount of the monomers used as raw materials for the acrylic polyol (A).

[0045] Furthermore, if necessary, a chain transfer agent such as lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid, or α-methylstyrene dimer may be used together with the above-mentioned polymerization initiator.

[0046] The weight average molecular weight (Mw) of the mixture of the polyester polyol (A) and the acrylic polyol (B) is preferably 8,000 to 150,000.

[0047] The curable resin composition of the present invention contains the polyester polyol (A) and the acrylic polyol (B). From the perspective of improving the balance between fullness and chemical resistance, the mass ratio (A / B) of the polyester polyol (A) to the acrylic polyol (B) is preferably 10 / 90 to 70 / 30, and more preferably 15 / 85 to 60 / 40.

[0048] Furthermore, from the viewpoint of further improving the balance between chemical resistance and adhesion, the solid content hydroxyl value of the curable resin composition of the present invention is preferably 30 to 150 mg KOH / g.

[0049] From the viewpoint of further improving the balance among chemical resistance, adhesion, and water resistance, the solid content acid value of the curable resin composition of the present invention is preferably 0.5 to 20 mg KOH / g.

[0050] The method for mixing the polyester polyol (A) and the acrylic polyol (B) is not particularly limited, but a method of synthesizing the acrylic polyol (B) in the presence of the polyester polyol (A) is preferred from the viewpoint of improving compatibility.

[0051] The coating of the present invention contains the curable resin composition of the present invention, and as other compounding agents, inorganic pigments, organic pigments, extender pigments, coloring pigments, highlighter pigments, cellulose derivatives, waxes, surfactants, stabilizers, flow regulators, dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, plasticizers, antistatic agents, defoaming agents, viscosity regulators, light stabilizers, weather stabilizers, heat stabilizers, pigment dispersants, curing agents, etc. can be used.

[0052] By using a polyisocyanate compound (C) as the curing agent, the coating film properties can be further improved. Examples of the polyisocyanate compound (C) include aromatic diisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, m-xylylene diisocyanate, and m-phenylenebis(dimethylmethylene) diisocyanate; and aliphatic or alicyclic diisocyanate compounds such as pentamethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, 4,4'-dicyclohexylmethane diisocyanate, and isophorone diisocyanate.

[0053] In addition, as the above-mentioned polyisocyanate compound, the following can also be used: a prepolymer having an isocyanate group obtained by subjecting the above-mentioned diisocyanate compound to an addition reaction with a polyol; a compound having an isocyanurate ring obtained by cyclotrimerization of the above-mentioned diisocyanate compound; a polyisocyanate compound having a urea bond or a biuret bond obtained by reacting the above-mentioned diisocyanate compound with water; a homopolymer of an acrylic monomer having an isocyanate group, such as 2-isocyanatoethyl (meth)acrylate, 3-isopropenyl-α,α-dimethylbenzyl isocyanate, or (meth)acryloyl isocyanate; a copolymer having an isocyanate group obtained by copolymerizing the above-mentioned acrylic monomer having an isocyanate group with other acrylic monomers, vinyl ester compounds, vinyl ether compounds, aromatic vinyl monomers, fluoroolefins, or the like; and the like.

[0054] The polyisocyanate compounds (C) may be used alone or in combination of two or more.

[0055] Regarding the amount of the polyisocyanate compound (C) used, the equivalent ratio (NCO / OH) of the isocyanate group (NCO) of the polyisocyanate compound (C) to the hydroxyl group (OH) of the curable resin composition is preferably in the range of 0.2 to 2, and more preferably in the range of 0.5 to 1.5.

[0056] Biomass raw materials may also be used as the above-mentioned raw materials used in the curable resin composition and coating material of the present invention.

[0057] The coating method of the coating of the present invention varies depending on the article to be coated, and examples thereof include gravure coaters, roll coaters, comma coaters, knife coaters, air knife coaters, curtain coaters, kiss coaters, spray coaters, wheel coaters, spin coaters, dipping, screen printing, spraying, applicators, rod coaters, brushes, and the like.

[0058] Furthermore, the coating of the present invention may be diluted with an organic solvent to adjust the viscosity to a suitable viscosity for the above-mentioned coating method. Examples of such organic solvents include aromatic hydrocarbon solvents such as toluene and xylene; alcohol solvents such as methanol, ethanol, isopropyl alcohol, tert-butyl alcohol, propylene glycol monomethyl ether, propylene glycol n-propyl ether, ethylene glycol monobutyl ether, and diacetone alcohol; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, n-propyl acetate, propylene glycol monomethyl ether acetate, and ethyl 3-ethoxypropionate; and ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone. These solvents may be used alone or in combination of two or more.

[0059] The coating material of the present invention can provide a cured coating film having excellent appearance and various coating properties on the surfaces of various articles.

[0060] The coating composition of the present invention may be applied directly to an article to be coated, or the coating composition of the present invention may be applied after applying a primer coating material suitable for the article to be coated.

[0061] Examples of materials for articles to be coated include various metals such as iron, copper, zinc, aluminum, and magnesium, and their alloys; various plastics such as polycarbonate, acrylonitrile-butadiene-styrene copolymer, PC-ABS polymer alloys, polymethyl methacrylate, polyethylene terephthalate, polyamide, and polypropylene, and fiber-reinforced plastics obtained by adding fillers such as glass fiber to these plastics; and wood.

[0062] Examples of articles having a cured coating film formed using the coating of the present invention include interior and exterior finishing materials for various vehicles such as automobiles and railway vehicles; interior and exterior finishing materials for buildings such as industrial machinery, exterior walls, roofs, glass, decorative panels, and wooden floors; civil engineering components such as soundproof walls and drainage gutters; housings for home appliances such as televisions, refrigerators, washing machines, and air conditioners; housings for electronic devices such as personal computers, smartphones, mobile phones, digital cameras, and game consoles; and housings for office automation equipment such as printers and fax machines.

[0063] Example

[0064] The present invention will be described in more detail below with reference to specific examples. It should be noted that the hydroxyl value and acid value were measured according to JIS test method K 0070-1992. The average molecular weight (Mw) was measured under the following GPC measurement conditions.

[0065] [GPC measurement conditions]

[0066] Measuring device: High-speed GPC device (Tosoh Corporation "HLC-8220GPC")

[0067] Column: The following columns manufactured by Tosoh Corporation were connected in series and used.

[0068] "TSKgel G5000" (7.8mm I.D. × 30cm) × 1 piece

[0069] "TSKgel G4000" (7.8mm I.D. × 30cm) × 1 piece

[0070] "TSKgel G3000" (7.8mm I.D. × 30cm) × 1 piece

[0071] "TSKgel G2000" (7.8mm I.D. × 30cm) × 1 piece

[0072] Detector: RI (differential refractometer)

[0073] Column temperature: 40°C

[0074] Eluent: tetrahydrofuran (THF)

[0075] Flow rate: 1.0 mL / min

[0076] Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 4 mg / mL)

[0077] Standard sample: The following monodisperse polystyrene was used to prepare a calibration curve.

[0078] (monodisperse polystyrene)

[0079] Tosoh Corporation "TSKgel Standard Polystyrene A-500"

[0080] Tosoh Corporation "TSKgel Standard Polystyrene A-1000"

[0081] Tosoh Corporation "TSKgel Standard Polystyrene A-2500"

[0082] Tosoh Corporation "TSKgel Standard Polystyrene A-5000"

[0083] Tosoh Corporation "TSKgel Standard Polystyrene F-1"

[0084] Tosoh Corporation "TSKgel Standard Polystyrene F-2"

[0085] Tosoh Corporation "TSKgel Standard Polystyrene F-4"

[0086] Tosoh Corporation "TSKgel Standard Polystyrene F-10"

[0087] Tosoh Corporation "TSKgel Standard Polystyrene F-20"

[0088] Tosoh Corporation "TSKgel Standard Polystyrene F-40"

[0089] Tosoh Corporation "TSKgel Standard Polystyrene F-80"

[0090] Tosoh Corporation "TSKgel Standard Polystyrene F-128"

[0091] Tosoh Corporation "TSKgel Standard Polystyrene F-288"

[0092] Tosoh Corporation "TSKgel Standard Polystyrene F-550"

[0093] (Synthesis Example 1: Production of Polyester Polyol (A-1))

[0094] In a reaction vessel equipped with a stirrer, condenser, and thermometer, 61 parts by mass of ethylene glycol, 314 parts by mass of diethylene glycol, 92 parts by mass of trimethylolpropane, 379 parts by mass of succinic acid, and 154 parts by mass of isophthalic acid were added. An esterification reaction was carried out at 200-250°C for 12 hours while stirring under a nitrogen stream. 148.9 parts by mass of condensation water was removed to obtain polyester polyol (A-1). This polyester polyol (A-1) had a number average molecular weight (Mn) of 1416, a hydroxyl value of 115 mgKOH / g, and an acid value of 7.1 mgKOH / g.

[0095] Ester group concentration [mmol / g]

[0096] =(number of moles of carboxyl groups [mol]) / (mass of polyester polyol [g]) × 1000

[0097] =8.273 / 851.1×1000[mmol / g]

[0098] =9.72[mmol / g]

[0099] (Synthesis Examples 2 to 6: Production of Polyester Polyols (A-2) to (A-6))

[0100] Polyester polyols (A-2) to (A-6) were obtained in the same manner as in Synthesis Example 1 except that the respective raw materials used in Synthesis Example 1 were changed as shown in Table 1.

[0101] (Synthesis Examples 7 to 10: Production of Polyester Polyols (RA-1) to (RA-4))

[0102] Polyester polyols (RA-1) to (RA-4) were obtained in the same manner as in Synthesis Example 1 except that the raw materials used in Synthesis Example 1 were changed as shown in Table 2.

[0103] Tables 1 and 2 show the resin compositions and property values of the polyester polyols (A-1) to (A-6) obtained above.

[0104] [Table 1]

[0105]

[0106] [Table 2]

[0107]

[0108] Table 3 shows the resin compositions and property values of the polyester polyols (RA-1) to (RA-4) obtained above.

[0109] [Table 3]

[0110]

[0111] (Example 1: Production of curable resin composition (1))

[0112] In a flask equipped with a condenser, a thermometer, a dropping funnel, and a stirrer, 200 parts by mass of polyester polyol (A-1) and 600 parts by mass of n-butyl acetate were added, and the internal temperature was raised to 100°C. Subsequently, a mixture of 370.4 parts by mass of methyl methacrylate, 160.0 parts by mass of n-butyl methacrylate, 245.6 parts by mass of 2-hydroxyethyl methacrylate, 24.0 parts by mass of methacrylic acid, 160 parts by mass of n-butyl acetate, and 32 parts by mass of tert-butyl peroxy-2-ethylhexanoate was added dropwise over 3 hours. Polymerization reaction was then carried out for 15 hours while maintaining the internal temperature at 100°C. Subsequently, 250 parts by mass of n-butyl acetate was added to obtain the target curable resin composition (1). The obtained resin had a weight-average molecular weight (Mw) of 25540, a solid content hydroxyl value of 128 mgKOH / g, and a solid content acid value of 17.1 mgKOH / g.

[0113] (Examples 2 to 6: Production of curable resin compositions (2) to (6))

[0114] Curable resin compositions (2) to (6) were obtained in the same manner as in Example 1 except that the respective raw materials used in Example 1 were changed as shown in Table 4.

[0115] (Comparative Examples 1 to 4: Production of Curable Resin Compositions (R1) to (R4))

[0116] Curable resin compositions (R1) to (R4) were obtained in the same manner as in Example 1 except that the respective raw materials used in Example 1 were changed as shown in Table 5.

[0117] Table 4 shows the resin compositions and property values of the curable resin compositions (1) to (6) obtained above.

[0118] [Table 4]

[0119]

[0120] Table 5 shows the resin compositions and property values of the curable resin compositions (R1) to (R4) obtained above.

[0121] [Table 5]

[0122]

[0123] The abbreviations in the table are as follows.

[0124] MMA: Methyl Methacrylate

[0125] BMA: n-butyl methacrylate

[0126] HEMA: 2-Hydroxyethylmethyl methacrylate

[0127] MAA: Methacrylic acid

[0128] [Preparation of coating]

[0129] The curable resin composition obtained above and the curing agent ("Desmodur N-3300", a polyisocyanate compound manufactured by Sumika Covestro Urethane Co., Ltd.) were uniformly mixed. It should be noted that the mixing ratio of the curable resin composition and the curing agent was set to an amount such that the equivalent of the hydroxyl group in the curable resin composition and the equivalent of the isocyanate group in the curing agent were 1:1. Next, the mixture was diluted with a mixed solvent (butyl acetate / diacetone alcohol / isobutyl acetate / ethyl acetate = 30 / 30 / 10 / 10 (mass ratio)) so that the viscosity was 9 to 10 seconds (23°C) using a "viscosity cup NK-2" manufactured by Anest Iwata Co., Ltd., to prepare a coating.

[0130] [Preparation of Cured Coating Film X for Evaluation]

[0131] The obtained coating was spray-coated onto an ABS (acrylonitrile-butadiene-styrene copolymer) substrate (50 mm × 70 mm × 1 mm) to a film thickness of 15 to 25 μm after drying. The coating was then dried in a dryer at 80°C for 30 minutes and then at 25°C for 7 days to produce a cured coating film X for evaluation.

[0132] [Preparation of Cured Coating Film Y for Evaluation]

[0133] The obtained coating was spray-coated on a PC (polycarbonate) substrate (50 mm × 70 mm × 1 mm) to a film thickness of 20 to 30 μm after drying, and dried in a dryer at 80° C. for 30 minutes and then at 25° C. for 7 days to prepare a cured coating film Y for evaluation.

[0134] [Evaluation of Adhesion]

[0135] A 1 mm wide cut was made in the cured coating film for evaluation using a knife, creating 100 checkered squares. Cellophane tape was then applied to cover all the checkered squares and quickly peeled off four times. The number of remaining checkered squares was used to evaluate adhesion according to the following criteria.

[0136] ○: 100

[0137] △: 70 to 99

[0138] ×: Less than 69

[0139] [Evaluation of water-resistant adhesion]

[0140] The cured coating film for evaluation obtained above was immersed in water at 40° C. for 240 hours, and then the same operation as in the above-mentioned adhesion evaluation was performed to evaluate water-resistant adhesion according to the following criteria.

[0141] ○: 100

[0142] △: 70 to 99

[0143] ×: Less than 69

[0144] [Evaluation of chemical resistance]

[0145] On the cured coating film for evaluation obtained above, 20 mg / cm 2 After applying a chemical (Neutrogena, UltraSheer Dry Touch Sunscreen, SPF 55), the film was dried in a dryer at 55°C for 4 hours. The film was then washed with a neutral detergent and allowed to stand at room temperature for 24 hours. The chemical resistance was evaluated according to the following criteria.

[0146] ◎: No trace

[0147] ○: There are some traces

[0148] △: There are traces

[0149] ×: The texture of the base material is exposed

[0150] [Appearance evaluation]

[0151] The plumpness of the cured coating film for evaluation obtained above was visually evaluated.

[0152] ◎: Very strong sense of fullness

[0153] ○: Strong sense of fullness

[0154] △: Weak sense of fullness

[0155] ×: No feeling of fullness

[0156] Table 6 shows the results of the coating materials (1) to (6) obtained above.

[0157] [Table 6]

[0158]

[0159] Table 7 shows the results of the coating materials (R1) to (R4) obtained above.

[0160] [Table 7]

[0161]

[0162] It was confirmed that the cured coating films obtained from the curable resin compositions of the present invention in Examples 1 to 6 were excellent in appearance (plump feeling), adhesion, water resistance, and chemical resistance.

[0163] On the other hand, in Comparative Example 1, the content of the trifunctional or higher alcohol (a2-2) in the polyol (a2) was less than the lower limit of the present invention, and it was confirmed that the chemical resistance of the cured coating film was insufficient.

[0164] Comparative Example 2 is an example in which the ester group concentration of the polyester polyol (A) is higher than the upper limit of the present invention. It was confirmed that the compatibility with the acrylic polyol (B) is poor, and the appearance of the cured coating film is insufficient.

[0165] Comparative Example 3 is an example in which the diol (a2-1) in the polyol (a2) is less than the lower limit of the present invention, and it was confirmed that the appearance of the cured coating film was insufficient.

[0166] Comparative Example 4 is an example in which the aliphatic dicarboxylic acid (a1-1) in the polycarboxylic acid (a1) is less than the lower limit of the present invention, and it was confirmed that the appearance of the cured coating film was insufficient.

Claims

1. A curable resin composition, characterized in that A polyester polyol (A) which is a reaction product of a polycarboxylic acid (a1) and a polyol (a2) and an acrylic polyol (B), wherein the polycarboxylic acid (a1) contains 20 mol% or more of an aliphatic dicarboxylic acid (a1-1) having a linear alkyl group having 4 to 10 carbon atoms, the polyol (a2) contains 20 mol% to 80 mol% of one or more diols (a2-1) selected from ethylene glycol, diethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol, and contains 5 mol% to 20 mol% of a trifunctional or higher alcohol (a2-2), and the polyester polyol (A) has an ester group concentration of 6 mmol / g to 11 mmol / g.

2. The curable resin composition according to claim 1, wherein The mass ratio of the polyester polyol (A) to the acrylic polyol (B), ie, A / B, is 10 / 90 to 70 / 30.

3. The curable resin composition according to claim 1, wherein The curable resin composition has a solid content hydroxyl value of 30 mgKOH / g to 150 mgKOH / g. 4 . A coating material comprising the curable resin composition according to claim 1 , and a polyisocyanate compound (C).

5. An article, characterized in that A cured coating film comprising the coating material according to claim 4.

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