JP6878941B2 - Active energy ray-curable resin composition - Google Patents

Description

The present invention relates to an active energy ray-curable resin composition.

Since unsaturated group-containing polyurethane resins are highly flexible and can form a tough cured film, they can be used as active energy ray-curable resins such as inks, paints, adhesives, coating agents, and surface treatment agents. Widely used.

The applicant has been able to perform active energy ray curing containing an unsaturated group-containing urethane resin having sufficient handling performance and low-temperature liquid properties, as well as excellent low-temperature flexibility, grip, water resistance and heat resistance of the cured film to be formed. A patent application has already been filed for the mold resin composition (see Patent Document 1).

However, in recent years, further studies have been required on the improvement of adhesion required for unsaturated group-containing polyurethane resins and the improvement of chemical resistance of the cured film.

Japanese Unexamined Patent Publication No. 2016-145275

The present invention has been made in view of the background art described above, and an object of the present invention is an active energy ray containing an unsaturated group-containing polyurethane resin having excellent adhesion to a substrate and chemical resistance of the cured film to be formed. It is to provide a curable resin composition.

As a result of diligent research to solve the above problems, the present inventors have found a polyol (A) having a specific number of hydroxyl group functional groups, a polyisocyanate (B), and a (meth) acrylate compound (C). The present invention has been completed by finding that an unsaturated group-containing polyurethane resin, which is a reaction product of the above, and an active energy ray-curable resin composition containing the same solve the above-mentioned problems.

That is, the present invention includes the following embodiments.

(1) An active energy ray-curable resin composition containing an unsaturated group-containing polyurethane resin which is a reaction product of a polyol (A), a polyisocyanate (B), and a (meth) acrylate compound (C). hand,
The polyol (A) contains a polycarbonate diol (a1) and a tris (2-hydroxyethyl) isocyanurate (a2), has an average number of hydroxyl functional groups of 2.3 to 2.9, and has a hydroxyl value of 50 to 150 mgKOH /. g, and the mass ratio of (a1) and (a2) is (a1) / (a2) = 95/5 to 75/25, and the number of (meth) acrylate compound (C) is one or more. An active energy ray-curable resin composition comprising a hydroxyl group and one or more (meth) acryloyl groups.

(2) The active energy ray-curable resin composition according to (1) above, wherein the number average molecular weight of the polycarbonate diol (a1) is in the range of 400 to 5,000.

(3) The active energy ray-curable resin composition according to (1) or (2) above, wherein the (meth) acrylate compound (C) has a molecular weight in the range of 100 to 3,000.

(4) The (meth) acrylate compound (C) is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, ε-caprolactone adduct of 2-hydroxyethyl acrylate, and β-methyl-valerolactone adduct of 2-hydroxyethyl acrylate. (1) to the above, which is at least one selected from the group consisting of a compound, an ε-caprolactone adduct of 2-hydroxyethyl methacrylate, and a β-methyl-valerolactone adduct of 2-hydroxyethyl methacrylate. The active energy ray-curable resin composition according to any one of (3).

(5) The active energy according to any one of (1) to (4) above, wherein the polyisocyanate (B) is at least one selected from the group consisting of an aliphatic diisocyanate and an alicyclic diisocyanate. Linear curable resin composition.

(6) The above-mentioned (1) to (5), wherein the unsaturated group-containing polyurethane resin has a number average molecular weight of 500 to 200,000 and an unsaturated degree of 0.1 to 5 mmol / g. The active energy ray-curable resin composition according to any one.

(7) The active energy ray according to any one of (1) to (6), which contains 0.01 to 15 parts by mass of a photopolymerization initiator with respect to 100 parts by mass of an unsaturated group-containing polyurethane resin. Curable resin composition.

(8) A coating material comprising the active energy ray-curable resin composition according to any one of (1) to (7) above.

(9) A coating film formed by using the active energy ray-curable resin composition according to any one of (1) to (7) above.

According to the present invention, an active energy ray-curable resin composition containing an unsaturated group-containing polyurethane resin, which has sufficient curing performance and the formed cured film also has excellent adhesion to a substrate and chemical resistance. Obtainable.

Hereinafter, the present invention will be described in detail.

The active energy ray-curable resin composition of the present invention is an unsaturated group-containing polyurethane resin which is a reaction product with a polyol (A), a polyisocyanate (B), and a (meth) acrylate compound (C) (hereinafter simply "" An active energy ray-curable resin composition containing (also referred to as "unsaturated group-containing polyurethane resin").
The polyol (A) contains a polycarbonate diol (a1) and a tris (2-hydroxyethyl) isocyanurate (a2), has a hydroxyl value of 50 to 150 mgKOH / g, and has a mass ratio of (a1) and (a2). Is (a1) / (a2) = 95/5 to 75/25, and the (meth) acrylate compound (C) contains one or more hydroxyl groups and one or more (meth) acryloyl groups. Is its feature.

The polyol (A) in the present invention contains a polycarbonate diol (a1) and a tris (2-hydroxyethyl) isocyanurate (a2).

Examples of the polycarbonate diol (a1) include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, alkylene carbonates such as ethylene carbonate and propylene carbonate, diphenyl carbonate, dinaphthyl carbonate, dianthryl carbonate, diphenanthryl carbonate, and diinda. It can be obtained by reacting glycols with carbonates such as diaryl carbonates such as nal carbonate and tetrahydronaphthyl carbonate.

Examples of the glycol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol. 1,6-Hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylol heptane, diethylene glycol, dipropylene glycol, neopentyl glycol, Low molecular weight diols such as cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, ethylene oxide and propylene oxide adduct of bisphenol A, bis (β-hydroxyethyl) benzene, and xylylene glycol. Selected from. These may be used alone or in combination of two or more.

As the polycarbonate diol (a1) in the present invention, it is preferable to use alkylene carbonate as the carbonates and 1,6-hexanediol as the glycols from the viewpoint of availability and chemical resistance.

The mass ratio of the polycarbonate diol (a1) to the tris (2-hydroxyethyl) isocyanurate (a2) is in the range of (a1) / (a2) = 95/5 to 75/25, and (a1) / (a2) = The range of 90/10 to 80/20 is preferable.

By setting the mass ratio within these ranges, it is possible to improve both adhesion to the substrate and chemical resistance by balancing the cohesive force of the polycarbonate diol, the urethane group concentration, and the tris (2-hydroxyethyl) isocyanurate content. it can.

The polyol (A) may be used by simply mixing the polycarbonate diol (a1) and the tris (2-hydroxyethyl) isocyanurate (a2), but since they are difficult to be compatible with each other, they can be obtained by a transesterification reaction. By using the copolymer polyol, not only the adhesion to the base material and the chemical resistance are compatible, but also the solubility in the solvent is improved.

The average number of hydroxyl group functional groups of the polyol (A) is 2.3 to 2.9, preferably in the range of 2.6 to 2.8. When the average number of hydroxyl group functional groups is less than the lower limit, the chemical resistance is lowered due to the decrease in crosslink density, and when the average number of hydroxyl group functional groups exceeds the upper limit, the adhesion to the substrate is lowered due to the increase in the crosslink density.

The average hydroxyl value of the polyol (A) is 50 to 150 mgKOH / g, more preferably 80 to 130 mgKOH / g. When the average hydroxyl value is less than the lower limit, the urethane group concentration is lowered and the adhesion to the substrate is improved, but the chemical resistance is lowered. When the average hydroxyl value exceeds the upper limit, the urethane group concentration is increased and the urethane group resistance is increased. The chemical properties are improved, but the adhesion to the substrate is reduced.

The average number of functional groups in the present invention was calculated by the following formula based on the nominal number of functional groups.
Average number of functional groups = ((number of functional groups of polycarbonate diol (a1) x number of mols of polycarbonate diol (a1)) + (number of functional groups of tris (2-hydroxyethyl) isocyanurate (a2) x number of functional groups of tris (2-hydroxyethyl) isocyanate) Nurate (a2) mol number)) / ((Polycarbonate diol (a1) mol number) + (Tris (2-hydroxyethyl) isocyanurate (a2) mol number)).

Further, in the present invention, the number average molecular weight of the polycarbonate diol (a1) is preferably 400 to 5,000, more preferably 800 to 3,500 in consideration of ease of synthesis and ease of handling.

In the present invention, the polyisocyanate (B) is not particularly limited, and is appropriately selected from various conventionally known polyisocyanates such as aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, and aromatic aliphatic diisocyanates. Can be done.

<Alphatic diisocyanate>
Examples of the aliphatic diisocyanate include hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, and lysine diisocyanate.

<Alicyclic diisocyanate>
Examples of the alicyclic diisocyanate include isophorone diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated tetramethylxylene diisocyanate.

<Aromatic diisocyanate>
Examples of the aromatic diisocyanis include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4, 4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4, 4'-diphenylpropane diisocyanis, m-phenylenediisocyanis, p-phenylenediisocyanate, naphthylene-1,4-diisocyanis, naphthylene-1,5-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate and the like. be able to.

<Aromatic aliphatic diisocyanate>
Examples of the aromatic aliphatic diisocyanate include xylylene-1,4-diisocyanate and xylylene-1,3-diisocyanate.

Among these, aliphatic diisocyanates and alicyclic diisocyanates are preferable, and isophorone diisocyanates are particularly preferable.

These diisocyanates may be used alone or in combination of two or more.

Next, the (meth) acrylate compound (C) in the present invention contains one or more hydroxyl groups and one or more (meth) acryloyl groups. Examples of such an acrylate compound include 2-hydroxyethyl acrylate, hydroxypropyl acrylate, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, ε-caprolactone adduct of 2-hydroxyethyl acrylate, and β- of 2-hydroxyethyl acrylate. Methyl-valerolactone adduct, acrylates such as glycerol monoacrylate, glycerol diacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, polyethylene glycol monoacrylate, polypropylene glycol monomethacrylate, ε-caprolactone of 2-hydroxyethyl methacrylate Additives, β-methyl-valerolactone adduct of 2-hydroxyethyl methacrylate, methacrylates such as glycerol monomethacrylate and glycerol dimethacrylate, allyl compounds such as allyl alcohol, glycerol monoallyl ether and glycerol diallyl ether, etc. Can be done.

Of these, preferred are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, ε-caprolactone adduct of 2-hydroxyethyl acrylate, β-methyl-valerolactone adduct of 2-hydroxyethyl acrylate, 2-. The ε-caprolactone adduct of hydroxyethyl methacrylate and the β-methyl-valerolactone adduct of 2-hydroxyethyl methacrylate are preferable, and 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are particularly preferable.

These (meth) acrylate compounds (C) may be used alone or in combination of two or more.

The molecular weight of the (meth) acrylate compound (C) is preferably 100 to 3,000, more preferably 100 to 2,000, and most preferably 100 to 1,000.

In the present invention, the unsaturated group-containing polyurethane resin preferably has a number average molecular weight of 500 to 200,000, more preferably 800 to 5,000. If the number average molecular weight is less than the lower limit, the adhesion and chemical resistance of the cured film formed from the resin to the substrate may be insufficient, and if it exceeds the upper limit, the crystallinity becomes stronger and the viscosity becomes higher. Therefore, it may be difficult to ensure manufacturing stability.

Further, in the present invention, the unsaturated group-containing polyurethane resin preferably has an unsaturated degree of 0.1 to 5 mmol / g, more preferably 0.3 to 2 mmol / g. Here, the degree of unsaturation is defined as α mol as the number of moles of the component (C) required for producing 1 g of the resin, and β as the number of radically polymerizable unsaturated bonds contained in one molecule of the component (C). If so, it is the number of mmol calculated by α × β. If the degree of unsaturation is less than the lower limit, the crosslink density of the cured film becomes small, so that sufficient surface curability may not be obtained. If the degree of unsaturation exceeds the upper limit, sufficient surface curability can be obtained, but the cured film is hard. In some cases, flexibility and elongation may be poor.

In the present invention, the unsaturated group-containing polyurethane resin can be produced, for example, by reacting the above-mentioned components (A) to (C). Further, an organic solvent may be added.

Examples of the organic solvent include aliphatic hydrocarbons such as octane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, acetic acid-n-propyl and isopropyl acetate. Esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, ethylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate , Glycol ether esters such as ethyl-3-ethoxypropionate, ethers such as dioxane, halogenated hydrocarbons such as methylene iodide and monochlorobenzene, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, Examples thereof include polar aproton solvents such as hexamethylphosphonylamide. These solvents can be used alone or in combination of two or more.

Here, the reaction temperature is usually 20 to 200 ° C, preferably in the range of 30 to 150 ° C.

The reaction may be appropriately carried out until the isocyanate residue disappears, and the reaction time is usually 5 minutes to 72 hours.

At the time of this reaction, a reaction catalyst of a hydroxyl group and an isocyanate group can be added if necessary. Examples of such reaction catalysts include lead oleate, tetrabutyltin, antimony trichloride, triphenylaluminum, trioctylaluminum, zinc naphthenate, zirconium naphthenate, dibutyltin dilaurate, dioctyltin dilaurate, and tetra-n-butyl-1. , 3-Diacetyloxydistanoxane, 1,4-diaza [2.2.2] bicyclooctane, N-ethylmorpholin and the like.

When a reaction catalyst is used, it is usually used in the range of 0.005 to 1.0 parts by mass with respect to 100 parts by mass of the total measurement (solid content) of the components (A) to (C).

The active energy ray-curable resin composition of the present invention preferably contains 0.01 to 15 parts by mass of a photopolymerization initiator with respect to 100 parts by mass of the above-mentioned unsaturated group-containing polyurethane resin, and contains active energy rays. A cured product can be obtained by irradiating.

The photopolymerization initiator is not particularly limited, but is, for example, acetophenone, methoxyacetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, α-hydroxy. Acetophenones such as -α, α'-dimethylacetophenone, 2-hydroxy-2-cyclohexylacetophenone, 2-methyl-1 [4- (methylthio) phenyl] -2-monforinopropanone-1, benzoin, benzoinmethyl Benzoin ethers such as ether, benzoin ethyl ether, benzoin isopropylbutyl ether, benzophenone, 2-chlorobenzophenone, p, p'-dichlorobenzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone, 4- (2) Ketones such as -hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, phosphine such as bisacylphosphine oxide and benzoylphosphine oxide. Examples thereof include oxides, ketals such as benzyldimethyl ketal, and quinones such as phenyl-2,3-dione and acetophenone quinone. These photopolymerization initiators can be used alone or in combination of two or more.

The active energy ray for curing the active energy ray-curable resin composition of the present invention is not particularly limited, but for example, electron beam, ultraviolet light, visible light, laser light (near infrared ray, visible light laser, ultraviolet laser). Etc.). The irradiation amount may be adjusted as necessary.

In addition to the above-mentioned components (A) to (C), the active energy ray-curable resin composition of the present invention contains, if necessary, an organic solvent, a coloring pigment, an extender pigment, an additive for paint, and the like. You may.

Examples of the organic solvent include organic solvents that can be used in the reactions of the above components (A) to (C).

The coloring pigment is not particularly limited, but is, for example, an inorganic pigment such as titanium oxide, zinc oxide, carbon black, ferric oxide (bengala), yellow lead, yellow iron oxide, ocher, ultramarine blue, and cobalt green. Organic pigments such as azo-based, naphthol-based, pyrazolone-based, anthraquinone-based, perylene-based, quinacridone-based, disazo-based, isoindolinone-based, benzoimidazole-based, phthalocyanine-based, and quinophthalone-based.

The extender pigment is not particularly limited, and examples thereof include heavy calcium carbonate, clay, kaolin, talc, precipitated barium sulfate, barium carbonate, white carbon, and diatomaceous earth.

The additive for paint is not particularly limited, but for example, a plasticizer, a catalyst, an antifungal agent, a defoamer, a leveling agent, a pigment dispersant, an anti-sedimentant, an anti-dripping agent, a thickener, and a gloss Examples thereof include an eraser, a light stabilizer, and an ultraviolet absorber.

The active energy ray-curable resin composition of the present invention can be suitably used for various coating applications such as inks, paints, adhesives, coating agents, and surface treatment agents. The coating method of the resin composition is not particularly limited and may be appropriately selected from known methods. Further, the coating amount, the thickness of the coating film, the irradiation amount of active energy rays, and the like may be appropriately adjusted according to the material of the surface to be coated and the like.

The coating film formed by using the active energy ray-curable resin composition of the present invention is suitably used for various applications in which the formed cured film is required to have adhesion to a substrate and chemical resistance.

Hereinafter, examples of the present invention will be described, but the present invention is not construed as being limited to these examples.

[Manufacturing of polyol 1]
The molar ratio of 1,6-hexanediol (hereinafter abbreviated as 1,6-HG) to diethyl carbonate (hereinafter abbreviated as DEC) in a reaction device incorporating a stirrer, a thermometer, a heating device, and a distillation column is a molar ratio. In addition to charging 826 g of 1,6-HG and 787 g of DEC, 0.05 g of tetrabutyl titanate (hereinafter abbreviated as TBT) was charged as a reaction catalyst and gradually added under a nitrogen stream. The temperature was raised to 190 ° C. When the distillation of ethanol became slow and the top temperature of the distillation column became 50 ° C or lower, the reaction temperature remained at 190 ° C, the pressure was gradually reduced to 1.3 kPa, and the pressure was 1.3 kPa for another 7 hours. It was reacted. Further, the reaction was continued at a reaction temperature of 190 ° C. under a reduced pressure of 1.3 kPa or less until the hydroxyl value of the reaction product became 35 to 40 (mg-KOH / g) to obtain a polyol (Polyol-A). The hydroxyl value of the obtained polyol was 37.4 (mg-KOH / g).

[Manufacturing of polyol 2]
824 g of 1,6-HG and 800 g of DEC in a reaction device including a stirrer, a thermometer, a heating device, and a distillation column so that the mixing ratio of 1,6-HG to DEC is 1.03 in terms of molar ratio. Along with the charge, 0.05 g of TBT was further charged as a reaction catalyst, and the temperature was gradually raised to 190 ° C. under a nitrogen stream. When the distillation of ethanol became slow and the top temperature of the distillation column became 50 ° C or lower, the reaction temperature remained at 190 ° C, the pressure was gradually reduced to 1.3 kPa, and the pressure was 1.3 kPa for another 7 hours. It was reacted. Further, the reaction was continued at a reaction temperature of 190 ° C. under a reduced pressure of 1.3 kPa or less until the hydroxyl value of the reaction product became 20 to 25 (mg-KOH / g) to obtain a polyol (Polyol-B). The hydroxyl value of the obtained polyol was 22.4 (mg-KOH / g).

[Manufacturing of polyol 3]
Preparation of Polyol 850 g of Polyol-A obtained in 1 and 150 g of tris (2-hydroxyethyl) isocyanurate were charged, and a transesterification reaction was carried out at 190 ° C. for 5 hours to add 15 mass of tris (2-hydroxyethyl) isocyanurate. A polyol containing% was obtained (Polyol-1). The hydroxyl value of the obtained polyol was 128.5 (mg-KOH / g).

[Manufacturing of polyol 4]
850 g of Polyol-B obtained in Production of Polyol 2 and 150 g of tris (2-hydroxyethyl) isocyanurate were charged, and a transesterification reaction was carried out at 190 ° C. for 5 hours to add 15 mass of tris (2-hydroxyethyl) isocyanurate. A polyol containing% was obtained (Polyol-2). The hydroxyl value of the obtained polyol was 115.8 (mg-KOH / g).

[Manufacturing of polyol 5]
Preparation of Polyol 900 g of Polyol-A obtained in 1 and 100 g of tris (2-hydroxyethyl) isocyanurate were charged, and a transesterification reaction was carried out at 190 ° C. for 5 hours to add 10 mass of tris (2-hydroxyethyl) isocyanurate. % Was obtained (Polyol-3). The hydroxyl value of the obtained polyol was 98.2 (mg-KOH / g).

[Manufacturing of polyol 6]
900 g of Polyol-B obtained in Production of Polyol 2 and 100 g of tris (2-hydroxyethyl) isocyanurate were charged, and a transesterification reaction was carried out at 190 ° C. for 5 hours to add 10 mass of tris (2-hydroxyethyl) isocyanurate. % Was obtained (Polyol-4). The hydroxyl value of the obtained polyol was 84.7 (mg-KOH / g).

[Manufacturing of polyol 7]
841 g of 1,6-HG and 723 g of DEC in a reaction device including a stirrer, a thermometer, a heating device, and a distillation column so that the mixing ratio of 1,6-HG to DEC is 1.16 in terms of molar ratio. Along with the charge, 0.05 g of TBT was further charged as a reaction catalyst, and the temperature was gradually raised to 190 ° C. under a nitrogen stream. When the distillation of ethanol became slow and the top temperature of the distillation column became 50 ° C or lower, the reaction temperature remained at 190 ° C, the pressure was gradually reduced to 1.3 kPa, and the pressure was 1.3 kPa for another 7 hours. It was reacted. Further, the reaction was continued at a reaction temperature of 190 ° C. under a reduced pressure of 1.3 kPa or less until the hydroxyl value of the reaction product became 110 to 114 (mg-KOH / g) to obtain a polyol (Polyol-5). The hydroxyl value of the obtained polyol was 112.2 (mg-KOH / g).

[Manufacturing of polyol 8]
Preparation of Polyol 700 g of Polyol-A obtained in 1 and 300 g of tris (2-hydroxyethyl) isocyanurate were charged, and a transesterification reaction was carried out at 190 ° C. for 5 hours to add 30 mass of tris (2-hydroxyethyl) isocyanurate. A polyol containing% was obtained (Polyol-6). The hydroxyl value of the obtained polyol was 193.5 (mg-KOH / g).

[Manufacturing of polyol 9]
Preparation of Polyol 970 g of Polyol-A obtained in 1 and 30 g of tris (2-hydroxyethyl) isocyanurate were charged, and a transesterification reaction was carried out at 190 ° C. for 5 hours to add 3 mass of tris (2-hydroxyethyl) isocyanurate. A polyol containing% was obtained (Polyol-7). The hydroxyl value of the obtained polyol was 55.6 (mg-KOH / g).

In addition, the raw materials used in the present invention are shown below.
PCL-210 Polycaprolactone diol (Molecular weight = 1000, hydroxyl value = 112, number of functional groups = 2) Daicel PCL-308 Polycaprolactone triol (Molecular weight = 870, hydroxyl value = 193.5, number of functional groups = 3) Daicel ..

Example 1.
[Manufacture of unsaturated group-containing polyurethane resin]
429 g of Polyol-1, 230 g of isophorone diisocyanate (hereinafter abbreviated as "IPDI"), and 0.08 g of dioctyltin dilaurate (hereinafter abbreviated as DOTDL) in a 1 L 4-neck flask equipped with a stirrer, a thermometer, and a heating device. , 200 g of methyl ethyl ketone (hereinafter abbreviated as MEK) was added, and the mixture was stirred and reacted at 70 ° C. for about 5 hours. Then, 0.16 g of 4-methoxyphenol (hereinafter abbreviated as MEHQ) and 141 g of 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA) were added, and the mixture was stirred and reacted at 70 ° C. for about 5 hours. The reaction was terminated when isocyanate residues were no longer observed in the infrared absorption spectrum. In this way, a resin solution containing an unsaturated group-containing polyurethane resin having a number average molecular weight of 1,930 and an unsaturated degree of 1.35 mmol / g as a solid content in an amount of 80% by mass was obtained.

The unsaturated group-containing polyurethane resins of Examples 2 to 4 and Comparative Examples 1 to 5 were obtained by the same production method as in Example 1. The obtained resin solution was evaluated for adhesion to a substrate and chemical resistance. The results are shown in the table.

[Preparation of cured film using active energy ray-curable resin composition]
To 100 parts by mass of the unsaturated group-containing polyurethane resin solid content in the obtained resin solution, 5 parts by mass of a photopolymerization initiator (1-hydroxycyclohexyl-phenylketone; Irgacure 184 manufactured by Ciba Speciality Chemicals) was added. A resin composition was prepared, and the resin composition was coated on a substrate with a thickness of about 80 μm (base materials: ABS, PET, PC). Then, it was left at 50 ° C. for 1 hour to completely volatilize the organic solvent, and then ^{irradiated with ultraviolet rays at 1,200 mJ / cm 2} to form a film (cured film). The cured film was evaluated for adhesion to a substrate and chemical resistance by the following evaluation method. The results are shown in Table 1.

〔Evaluation method〕
1. 1. Adhesion to base material The obtained coating film was subjected to an adhesion test by the cross-cut method according to JIS K5600-5-6.
Classification 0 to 1: ○
Classification 2-5: ×.

2. Chemical resistance 2-1. Ultraviolet absorber resistance A 3% solution of glycerin of the following compound was prepared, one drop of each preparation solution was dropped on the coating film, left at 55 ° C. for 4 hours, and then wiped off and the appearance was visually evaluated.

<Compound>
(1) 2-Hydroxy-4-methoxybenzophenone (2) 2-Ethylhexyl salicylate (3) Salicylic acid 3,3,5-trimethylcyclohexyl (4) 4-tert-butylbenzoyl (4-methoxybenzoyl) methane (5) 3 , 2-Ethylhexyl 3-diphenyl-2-cyanoacrylate.

<Evaluation criteria>
・ Those with no change in the coating film and those with slight blisters to the extent that dripping marks remain (evaluation: ○)
・ Wrinkles on most of the coating film (evaluation: △)
-Most of the coating film has swelling, wrinkles, and dissolution (evaluation: x).

2-2. Prepare a 10% ethanol solution of insect repellent DEET (N, N-diethyl-3-methylbenzamide), add 1 drop of the preparation solution to the coating film, leave it at 55 ° C. for 4 hours, and then wipe it off and visually evaluate the appearance. did.

<Evaluation criteria>
-Those with no change in the coating film, those with slight blisters to the extent that dripping marks remain (evaluation: ○)
・ Wrinkles on most of the coating film (evaluation: △)
・ Most of the coating film has swelling, wrinkles, and dissolution (evaluation: ×)

Claims (9)

An active energy ray-curable resin composition containing an unsaturated group-containing polyurethane resin which is a reaction product of a polyol (A), a polyisocyanate (B), and a (meth) acrylate compound (C).
The polyol (A) contains a polycarbonate diol (a1) and a tris (2-hydroxyethyl) isocyanurate (a2), has an average number of hydroxyl functional groups of 2.3 to 2.9, and has a hydroxyl value of 50 to 150 mgKOH /. g, and the mass ratio of (a1) and (a2) is (a1) / (a2) = 95/5 to 75/25, and the number of (meth) acrylate compound (C) is one or more. An active energy ray-curable resin composition comprising a hydroxyl group and one or more (meth) acryloyl groups. The active energy ray-curable resin composition according to claim 1, wherein the number average molecular weight of the polycarbonate diol (a1) is in the range of 400 to 5,000. The active energy ray-curable resin composition according to claim 1 or 2, wherein the molecular weight of the (meth) acrylate compound (C) is in the range of 100 to 3,000. The (meth) acrylate compound (C) is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, ε-caprolactone adduct of 2-hydroxyethyl acrylate, β-methyl-valerolactone adduct of 2-hydroxyethyl acrylate, 2 Any of claims 1 to 3, which is at least one selected from the group consisting of the ε-caprolactone adduct of −hydroxyethyl methacrylate and the β-methyl-valerolactone adduct of 2-hydroxyethyl methacrylate. The active energy ray-curable resin composition according to. The active energy ray-curable resin composition according to any one of claims 1 to 4, wherein the polyisocyanate (B) is at least one selected from the group consisting of an aliphatic diisocyanate and an alicyclic diisocyanate. .. The activity according to any one of claims 1 to 5, wherein the unsaturated group-containing polyurethane resin has a number average molecular weight of 500 to 200,000 and an unsaturated degree of 0.1 to 5 mmol / g. Energy ray curable resin composition. The active energy ray-curable resin composition according to any one of claims 1 to 6, wherein the photopolymerization initiator is contained in an amount of 0.01 to 15 parts by mass with respect to 100 parts by mass of the unsaturated group-containing polyurethane resin. .. A coating material comprising the active energy ray-curable resin composition according to any one of claims 1 to 7. A coating film formed by using the active energy ray-curable resin composition according to any one of claims 1 to 7.