JP6603997B2 - 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 urethane resins are rich in flexibility and can form tough cured films, as active energy ray-curable resins, for example, inks, paints, adhesives, coating agents, surface treatment agents, etc. Widely used.

  Generally, an unsaturated group-containing urethane resin is obtained by reacting a polyol component, an isocyanate component, and a radical polymerizable hydroxyl group-containing unsaturated monomer component. Here, as a polyol component, since polycarbonate diol has poor flexibility, polyether, polyester, or the like is generally used (see, for example, Patent Document 1).

  In recent years, an unsaturated group-containing urethane resin is required to have further improvements in flexibility and flexibility and durability such as water resistance and heat resistance for a cured film obtained from the resin.

  In order to improve the flexibility and flexibility of the unsaturated group-containing urethane resin, it is necessary to increase the molecular weight of the resin itself.

  However, increasing the molecular weight of the unsaturated group-containing urethane resin in an attempt to improve the flexibility and flexibility of the formed cured film will increase the viscosity of the resin, lower the handling properties, and deteriorate the low-temperature liquidity. There was a tendency to. Moreover, the cured film obtained from the resin has a tendency to bend and grip at low temperatures, and the water resistance and heat resistance are not sufficient.

JP 2003-40965 A

  The present invention has been made in view of the background art described above, and its purpose is to provide sufficient handling performance and low-temperature liquidity, as well as low-temperature flexibility, grip properties, water resistance and heat resistance of the formed cured film. An active energy ray-curable resin composition containing an unsaturated group-containing urethane resin is also provided.

  As a result of intensive studies to solve the above problems, the present inventors have found that an unsaturated group-containing urethane resin using a specific polycarbonate diol as a polyol component, and an active energy ray-curable resin composition containing the same. The present inventors have found that the above problems can be solved and have completed the present invention.

  That is, the present invention relates to an active energy ray-curable resin composition as shown below.

  [1] Polycarbonate diol (a) containing 3-methyl-1,5-pentanediol as a monomer unit, (meth) acrylate (b) containing one or more hydroxyl groups and one or more (meth) acryloyl groups And an active energy ray-curable resin composition containing an unsaturated group-containing polyurethane resin obtained by reacting polyisocyanate (c).

  [2] The active energy ray-curable resin composition according to [1], wherein the polycarbonate diol (a) has a number average molecular weight in the range of 300 to 5,000.

  [3] The active energy ray-curable resin composition according to any one of [1] or [2], wherein the molecular weight of the (meth) acrylate (b) is in the range of 100 to 3,000. object.

  [4] (Meth) acrylate (b) is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, ε-caprolactone adduct of 2-hydroxyethyl acrylate, β-methyl-valerolactone addition of 2-hydroxyethyl acrylate [1] to [1], which are at least one selected from the group consisting of a product, an ε-caprolactone adduct of 2-hydroxyethyl methacrylate, and a β-methyl-valerolactone adduct of 2-hydroxyethyl methacrylate. [3] The active energy ray-curable resin composition according to any one of [3].

  [5] The active energy ray according to any one of [1] to [4], wherein the polyisocyanate (c) is at least one selected from aliphatic diisocyanates and alicyclic diisocyanates. A curable resin composition.

  [6] The number average molecular weight of the unsaturated group-containing polyurethane resin is 1,000 to 200,000, and the degree of unsaturation is 0.1 to 1 mol / kg. 5] The active energy ray-curable resin composition according to any one of [5].

  [7] Any of [1] to [6], further comprising 0.01 to 15 parts by mass of a photopolymerization initiator with respect to 100 parts by mass of the unsaturated group-containing polyurethane resin composition. The active energy ray-curable resin composition described in 1.

  [8] A paint comprising the active energy ray-curable resin composition according to any one of [1] to [7].

  [9] A coating film formed using the active energy ray-curable resin composition according to any one of [1] to [7].

  In the present invention, “(meth) acryloyl group” refers to acryloyl group or methacryloyl group, and “(meth) acrylate” refers to acrylate or methacrylate.

  According to the present invention, an unsaturated group-containing urethane resin having sufficient resin handling properties, low-temperature liquidity, and curing performance, and also having a low-temperature flexibility and gripping property, and an activity including the same. An energy beam curable resin composition can be provided.

  Hereinafter, the present invention will be described in detail.

  The active energy ray-curable resin composition of the present invention includes a polycarbonate diol (a) containing 3-methyl-1,5-pentanediol as a monomer unit, one or more hydroxyl groups, and one or more (meth) acryloyl groups. It is characterized by containing an unsaturated group-containing polyurethane resin obtained by reacting (meth) acrylate (b) containing polyisocyanate (c).

  In the present invention, the polycarbonate diol (a) has a polymer chain in which a hydrocarbon group derived from a polyol is linked via a carbonate bond, and a hydroxyl group bonded to both ends of the polymer chain. And having a structural unit represented by the following formula (A).

  The polycarbonate diol (a) used in the present invention is 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, It can be obtained by dealcoholization reaction or dephenol reaction of carbonates such as diaryl carbonates such as diindanyl carbonate and tetrahydronaphthyl carbonate and 3-methyl-1,5-pentanediol.

  In the present invention, polycarbonate diol (a) may be used in combination with 3-methyl-1,5-pentanediol and glycols other than 3-methyl-1,5-pentanediol.

  Examples of glycols other than 3-methyl-1,5-pentanediol include, but are not limited to, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3,3-dimethylolheptane, Diethylene glycol, dipropylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, ethylene oxide or propylene oxide adduct of bisphenol A, bis ( β-hydro Shiechiru) benzene, xylylene glycol, glycerin, trimethylol propane, may be mentioned low molecular weight polyol such as pentaerythritol.

  Mole ratio of 3-methyl-1,5-pentanediol and other glycol, which is a raw material for producing polycarbonate diol (a) ([3-methyl-1,5-pentanediol]: [other glycol] ) Is preferably 100: 0 to 1:99, and if 3-methyl-1,5-pentanediol is less than 1 mol%, the liquidity may deteriorate.

  In the present invention, the number average molecular weight of the polycarbonate diol (a) is preferably in the range of 300 to 5,000 in view of ease of synthesis and ease of handling.

  In the present invention, the (meth) acrylate (b) containing one or more hydroxyl groups and one or more (meth) acryloyl groups is not particularly limited, but has a molecular weight of 100 to 3,000, preferably The range is from 100 to 2,000, more preferably from 100 to 1,000. For example, ε of 2-hydroxyethyl acrylate, hydroxypropyl acrylate, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, 2-hydroxyethyl acrylate -Caprolactone adduct, β-methyl-valerolactone adduct of 2-hydroxyethyl acrylate, acrylates such as glycerol monoacrylate, glycerol diacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl meta Methacrylates such as acrylate, polyethylene glycol monoacrylate, polypropylene glycol monomethacrylate, ε-caprolactone adduct of 2-hydroxyethyl methacrylate, β-methyl-valerolactone adduct of 2-hydroxyethyl methacrylate, glycerol monomethacrylate, glycerol dimethacrylate, etc. And allyl compounds such as allyl alcohol, glycerol monoallyl ether, and glycerol diallyl ether.

  Among these, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, ε-caprolactone adduct of 2-hydroxyethyl acrylate, β-methyl-valerolactone adduct of 2-hydroxyethyl acrylate, An ε-caprolactone adduct of hydroxyethyl methacrylate and a β-methyl-valerolactone adduct of 2-hydroxyethyl methacrylate are preferable, and 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are particularly preferable. In addition, as the component (b), the above-described one type of compound may be used alone, or two or more types may be used in combination.

  In the present invention, the polyisocyanate (c) is not particularly limited, and can be appropriately selected from conventionally known various polyisocyanates. For example, aliphatic isocyanates such as hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, lysine diisocyanate; isophorone diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene Alicyclic diisocyanates such as diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylene diisocyanate; 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-ni Lodiphenyl-4,4′-diisocyanate, 2,2′-diphenylpropane-4,4′-diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, 4,4′-diphenylpropane diisocyanate, m Aromatic aromatics such as -phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate; xylylene-1,4 -Aroaliphatic diisocyanates such as diisocyanate and xylylene-1,3-diisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, aliphatic isocyanate and alicyclic diisocyanate are preferable. Of these isocyanates, isophorone diisocyanate is preferable.

  In the present invention, the unsaturated group-containing urethane resin preferably has a number average molecular weight of 1,000 to 200,000. If the number average molecular weight is less than the above range, the flexibility and elongation of the cured film formed from the resin tends to be insufficient, and if it exceeds the above range, the crystallinity and the viscosity become very high, so that the production stability is improved. It tends to be difficult to secure. A more preferred number average molecular weight is 10,000 to 50,000.

  In the present invention, the unsaturated group-containing urethane resin preferably has an unsaturation degree of 0.1 to 1 mol / kg. Here, the degree of unsaturation means that the number of moles of component (b) necessary for producing 1 kg of resin is α mol, and the number of radical polymerizable unsaturated bonds contained in one molecule of component (b) is β. In this case, the value is calculated by α × β. If the degree of unsaturation is less than the above range, the curing performance is insufficient, or the crosslinking density of the cured film formed from the resin is small, and there is a tendency that sufficient surface curability cannot be obtained. Although sufficient surface curability can be obtained, the cured film tends to be hard and tend to be poor in flexibility and elongation. A more preferable range is 0.1 to 0.5 mol / kg.

  In the present invention, the unsaturated group-containing urethane resin can be produced, for example, by introducing the above-described components (a) to (c) into an organic solvent and allowing them to react.

  Here, reaction temperature is 20-200 degreeC normally, and the range of 30-150 degreeC is preferable. Further, the reaction may be carried out as appropriate until the isocyanate residue disappears, and the reaction time is usually 10 minutes to 48 hours. Examples of the organic solvent include aliphatic hydrocarbons such as octane, cycloaliphatic hydrocarbons such as cyclohexane and methylcyclohexane, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, acetic acid-n-propyl, 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, ethyl- Glycol ether esters such as 3-ethoxypropionate, ethers such as dioxane, halogenated hydrocarbons such as methylene iodide and monochlorobenzene, N-methylpyrrolidone, dimethylformamide, dimethyl ester Ruasetoamido, dimethylsulfoxide, polar aprotic solvents such as hexamethylphosphoric phosphonyl amides. These solvents can be used alone or in combination of two or more.

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

  Further, the ratio of the component (a), the component (b), and the component (c) may be determined according to the degree of unsaturation and the number average molecular weight required for the unsaturated group-containing urethane resin, and is particularly limited. However, for example, in order to produce an unsaturated group-containing urethane resin having a number average molecular weight of 1,000 to 200,000 and an unsaturation degree of 0.1 to 1 mol / kg, (a) to (c ) When the total measurement (solid content) of the component is 100% by mass, the component (a) is 50 to 90% by mass, the component (b) is 2 to 20% by mass, and the component (c) is 5 to 40% by mass. It is preferable that Moreover, when using a reaction catalyst, it is normally used in 0.005-1.0 mass part with respect to 100 mass parts of total measurement (solid content) of (a)-(c) component.

  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 unsaturated group-containing urethane resin. By doing so, a cured product is obtained.

  The photopolymerization initiator is not particularly limited. 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-montolinopropanone-1, benzoin, benzoin Benzoin ethers such as methyl ether, benzoin ethyl ether, benzoin isopropyl butyl ether, benzophenone, 2-chlorobenzophenone, p, p′-dichlorobenzophenone, N, N′-tetramethyl-4,4′-diaminobenzofe , Ketones such as 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, bisacylphosphine oxide, Examples include phosphine oxides such as benzoylphosphine oxide, ketals such as benzyldimethyl ketal, and quinones such as camphane-2,3-dione and phenanthrenequinone. 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. For example, an electron beam, an ultraviolet ray, a visible ray, a laser beam (near infrared ray, visible ray laser, ultraviolet ray laser) Etc.). The irradiation amount may be adjusted as necessary.

  The active energy ray-curable resin composition of the present invention contains, in addition to the above-described components (a) to (c), an organic solvent, a color pigment, an extender pigment, a paint additive, and the like as necessary. May be.

  Examples of the organic solvent include aliphatic hydrocarbons such as octane, cycloaliphatic hydrocarbons such as cyclohexane and methylcyclohexane, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, acetic acid-n-propyl, 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, ethyl- Glycol ether esters such as 3-ethoxypropionate, ethers such as dioxane, halogenated hydrocarbons such as methylene iodide and monochlorobenzene, N-methylpyrrolidone, dimethylformamide, dimethyl ester Ruasetoamido, dimethylsulfoxide, polar aprotic solvents such as hexamethylphosphoric phosphonyl amides.

  Although it does not specifically limit as a coloring pigment, For example, inorganic pigments, such as a titanium oxide, a zinc oxide, carbon black, ferric oxide (Bengara), yellow lead, yellow iron oxide, ocher, ultramarine, and cobalt green Organic pigments such as azo, naphthol, pyrazolone, anthraquinone, perylene, quinacridone, disazo, isoindolinone, benzimidazole, phthalocyanine, and quinophthalone.

  The extender 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 coating is not particularly limited, but examples thereof include plasticizers, catalysts, fungicides, antifoaming agents, leveling agents, pigment dispersants, anti-settling agents, anti-sagging agents, thickeners, and gloss. Examples 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 application method of the resin composition is not particularly limited, and may be appropriately selected from known methods. Moreover, what is necessary is just to make a coating amount, the thickness of a coating film, an active energy ray irradiation amount, etc. appropriate according to the material etc. of the surface to be coated.

  The coating film formed using the active energy ray-curable resin composition of the present invention is suitably used for various applications that require low-temperature flexibility, grip properties, water resistance, and heat resistance for the formed cured film. The

Production Example 1
[Production of polycarbonate diol 1]
To a reaction apparatus including a stirrer, a thermometer, a heating device, and a distillation tower, 3-methyl-1,5-pentanediol (hereinafter abbreviated as MPD) and 1,6-hexanediol (hereinafter referred to as 1,6-hexane) are used as glycols. HG is abbreviated as MPD / 1,6-HG = 3/7, and this glycol is added to diethyl carbonate (hereinafter abbreviated as DEC) at a molar ratio of 1.06. MPD 300 g, 1,6-HG 700 g and DEC 939 g are charged, and 0.05 g of tetrabutyl titanate (hereinafter abbreviated as TBT) is added as a reaction catalyst, and the temperature is gradually increased to 190 ° C. under a nitrogen stream. Raised. When the distillation of ethanol slows down and the top temperature of the distillation column becomes 50 ° C. or lower, the pressure is gradually reduced to 1.3 kPa while maintaining the reaction temperature at 190 ° C., and further at a pressure of 1.3 kPa for 7 hours. Reacted. Furthermore, the reaction was continued under a reduced pressure of 1.3 kPa or less at a reaction temperature of 190 ° C. until the hydroxyl value of the reaction product became 35 to 40 (mg-KOH / g), to obtain a polycarbonate diol (Polyol-1). The resulting polyol compound had a hydroxyl value of 37.4 mg-KOH / g (number average molecular weight (hereinafter Mn) = 3,000).

Production Example 2
[Production of polycarbonate diol 2]
In the same production method as in Production Example 1, MPD was added in an amount of 300 g, 1,6-, so that the molar ratio was MPD / 1,6-HG = 3/7, and the blending ratio with respect to DEC was 1.08. A polycarbonate diol (Polyol-2) having a hydroxyl value of 56.1 mg-KOH / g (Mn = 2,000) was obtained in the same manner except that 700 g of HG and 926.1 g of DEC were charged.

Production Example 3
[Production of polycarbonate diol 3]
In the same production method as in Production Example 1, MPD was added in an amount of 300 g, 1,6-, so that the molar ratio was MPD / 1,6-HG = 3/7, and the blending ratio with respect to DEC was 1.16. A polycarbonate diol (Polyol-3) having a hydroxyl value of 112.2 mg-KOH / g (Mn = 1,000) was synthesized by the same method except that 700 g of HG and 862.2 g of DEC were charged.

Production Example 4
[Production of polycarbonate diol 4]
In the same production method as in Production Example 1, MPD was added in an amount of 500 g, 1,6-, so that the molar ratio was MPD / 1,6-HG = 5/5, and the blending ratio with respect to DEC was 1.08. A polycarbonate diol (Polyol-4) having a hydroxyl value of 56.1 mg-KOH / g (Mn = 2,000) was obtained in the same manner except that 500 g of HG and 926.1 g of DEC were charged.

Production Example 5
[Production of polycarbonate diol 5]
In the same production method as in Production Example 1, MPD was 900 g, 1,6-, so that the molar ratio was MPD / 1,6-HG = 9/1 and the blending ratio with respect to DEC was 1.08. A polycarbonate diol (Polyol-5) having a hydroxyl value of 37.4 mg-KOH / g (Mn = 3,000) was obtained by synthesizing in the same manner except that 100 g of HG and 938.7 g of DEC were charged.

Production Example 6
[Production of polycarbonate diol 6]
In the same production method as in Production Example 1, MPD was 900 g, 1,6-, so that the molar ratio was MPD / 1,6-HG = 9/1 and the blending ratio with respect to DEC was 1.08. A polycarbonate diol (Polyol-6) having a hydroxyl value of 56.1 mg-KOH / g (Mn = 2,000) was obtained by synthesizing in the same manner except that 100 g of HG and 926.1 g of DEC were charged.

Production Example 7
[Production of polycarbonate diol 7]
In the same production method as in Production Example 1, MPD was 900 g, 1,6-, so that the molar ratio was MPD / 1,6-HG = 9/1 and the blending ratio with respect to DEC was 1.38. A polycarbonate diol (Polyol-7) having a hydroxyl value of 224.0 mg-KOH / g (Mn = 500) was obtained by synthesizing in the same manner except that 100 g of HG and 725.0 g of DEC were charged.

Production Example 8
[Production of polycarbonate diol 8]
In the same production method as in Production Example 1, MPD was 1000 g, 1,6-, so that the molar ratio was MPD / 1,6-HG = 10/0 and the blending ratio with respect to DEC was 1.08. A polycarbonate diol (Polyol-8) having a hydroxyl value of 56.1 mg-KOH / g (Mn = 2,000) was obtained in the same manner except that 0 g of HG and 926.1 g of DEC were charged.

Production Example 9
[Production of polycarbonate diol 9]
In the same production method as in Production Example 1, MPD was changed to 0 g, 1,6-, so that the molar ratio was MPD / 1,6-HG = 0/10, and the blending ratio with respect to DEC was 1.08. A polycarbonate diol (Polyol-9) having a hydroxyl value of 37.4 mg-KOH / g (Mn = 3,000) was obtained by synthesizing in the same manner except that 1000 g of HG and 938.7 g of DEC were charged.

Production Example 10
[Production of polycarbonate diol 10]
In the same production method as in Production Example 1, MPD was changed to 0 g, 1,6-, so that the molar ratio was MPD / 1,6-HG = 0/10, and the blending ratio with respect to DEC was 1.08. A polycarbonate diol (Polyol-10) having a hydroxyl value of 56.1 mg-KOH / g (Mn = 2,000) was obtained by synthesizing in the same manner except that 1000 g of HG and 926.1 g of DEC were charged.

Production Example 11
[Production of polycarbonate diol 11]
In the same production method as in Production Example 1, MPD was 0 g, 1,6-, so that the molar ratio was MPD / 1,6-HG = 0/10, and the blending ratio with respect to DEC was 1.16. A polycarbonate diol (Polyol-11) having a hydroxyl value of 112.2 mg-KOH / g (Mn = 1,000) was obtained by synthesizing in the same manner except that 1000 g of HG and 862.2 g of DEC were charged.

Production Example 12.
[Production 12 of polycarbonate diol]
In the same production method as in Production Example 1, the molar ratio was 1,5-pentanediol / 1,6-HG = 5/5, and the blending ratio with respect to DEC was 1.08 so that the molar ratio was 1.08. -It was synthesized by the same method except that 531.7 g of pentanediol, 468.3 g of 1,6-HG, and 868.6 g of DEC were prepared, and the hydroxyl value was 56.1 mg-KOH / g (Mn = 2,000). Polycarbonate diol (Polyol-12) was obtained.

  In addition, in the following comparative examples, Nippon Solar 4010 (poly 1,4-butylene adipate, hydroxyl value 56.1 mg-KOH / g (Mn = 2,000)) manufactured by Tosoh Corporation was used as Polyol-13. As Poly-14, PTG-2000SN (polytetramethylene glycol, hydroxyl value 56.1 mg-KOH / g (Mn = 2,000)) manufactured by Hodogaya Chemical Co., Ltd. was used.

Example 1.
[Production of unsaturated group-containing urethane resin]
In a 2 L four-necked flask with a stirrer, thermometer, and heating device, Polyol-1, 443.4 g, isophorone diisocyanate (hereinafter abbreviated as IPDI) 43.7 g, and dioctyltin dilaurate (hereinafter abbreviated as DOTDL) 0 .2 g and 500 g of methyl ethyl ketone (hereinafter abbreviated as MEK) were added and stirred at 70 ° C. for about 12 hours for reaction. Thereafter, 12.7 g of 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA) was added, and the mixture was stirred and reacted at 70 ° C. for about 12 hours.

  Upon completion of the reaction, it was confirmed by the infrared absorption spectrum that no isocyanate residue was observed. In this way, a resin solution containing 50% by mass of an unsaturated group-containing urethane resin having a number average molecular weight of 30,000 and an unsaturation of 0.20 mol / kg as a solid content was obtained. About the obtained resin solution, handling property and low-temperature liquid property were evaluated by the following method. The results are shown in Tables 1 and 2.

[Film production using active energy ray-curable resin composition]
1.5 parts by mass of a photopolymerization initiator (Irgacure 184, 1-hydroxycyclohexyl-phenylketone manufactured by Ciba Specialty Chemicals Co., Ltd.) with respect to 100 parts by mass of the unsaturated group-containing urethane resin solid content in the obtained resin solution. In addition, a resin composition was prepared, and this resin composition was coated on a release paper with a film thickness of about 200 μm (PET substrate was used for grip property evaluation). Thereafter, the film was left at 40 ° C. for 24 hours to completely volatilize the organic solvent, and then irradiated with ultraviolet rays at 100 mJ / cm ² to form a film (cured film). The cured film was evaluated for low-temperature flexibility (flexibility), grip properties, hot water resistance, and heat resistance by the following evaluation methods. The results are shown in Tables 1 and 2.

〔Evaluation methods〕
(1) Handling property.
The handling properties of the obtained unsaturated group-containing urethane resin solution were evaluated in the following three stages.
Using a 200 μm applicator, the appearance immediately after coating at a coating speed of 5 cm / s was evaluated in three stages. A smooth and smooth object was indicated with “◎”, an object with unevenness was indicated with “×”, an intermediate part between them was indicated with “◯”, and “◎” and “O” were accepted.

(2) Low temperature liquidity.
The liquid properties after the obtained unsaturated group-containing urethane resin solution was allowed to stand at −5 ° C. for 1 week were evaluated in the following three stages. “◎” indicates that the liquid is not turbid or suspended, “◯” indicates that the liquid is turbid or suspended, “×” indicates that it is solidified, and “×” indicates that it is solid.

(3) Low temperature flexibility (flexibility).
Based on JIS K 6542, the test piece cut out from the obtained cured film was bent 25,000 times at −10 ° C., and the appearance was evaluated in the following three stages. A specimen in which no change was observed was designated as “◎”, a specimen remaining after bending was designated as “◯”, a specimen in which the specimen was cracked was designated as “x”, and “◎” was designated as acceptable.

(4) Grip properties.
The cured film obtained on the PET substrate was fixed on a horizontal flat table with the upper side facing up. A circular weight (1 g) having a radius of 10 mm was placed on the cured film, and an angle (θ) at which the weight slides when the flat table is tilted was determined and evaluated in the following three stages. θ> 30 ° was “◎”, 15 ° ≦ θ ≦ 30 ° was “◯”, θ <15 ° was “×”, and “◎” was acceptable.

(5) Hot water resistance.
The cured film and distilled water obtained were put in a sample bottle and allowed to stand at 80 ° C. for 2 weeks, and the appearance of the cured film was evaluated in the following two stages. “◎” indicates that there was no change before and after the test, “×” indicates that the sample was dissolved after the test, and “◎” indicates a pass.

(6) Heat resistance.
The obtained cured film was allowed to stand at 110 ° C. for 2 weeks, and the appearance of the cured film was evaluated in the following two stages.
“◎” indicates that there was no change before and after the test, “×” indicates that the sample was dissolved after the test, and “◎” indicates a pass.

Example 2 , 4-6, 8, Reference Examples 3, 7, and Comparative Examples 1-6.
The unsaturated group was changed in the same manner as in Example 1 except that the types and masses of the components charged into a 2 L four-necked flask equipped with a thermometer, a condenser, and a stirrer were changed as shown in Tables 1 and 2. A containing urethane resin was produced, and a film (cured film) was similarly formed and evaluated. The results are shown in Tables 1 and 2.

Claims (7)

Polycarbonate diol (a) containing 3-methyl-1,5-pentanediol as a monomer unit, (meth) acrylate (b) containing one or more hydroxyl groups and one or more (meth) acryloyl groups, An active energy ray-curable resin composition containing an unsaturated group-containing polyurethane resin which is a reaction product with an isocyanate (c) , wherein the polycarbonate diol (a) has a number average molecular weight of 2,000 or more and 3,000 The active energy ray-curable type, wherein the unsaturated group-containing polyurethane resin has a number average molecular weight of 1,000 to 200,000 and an unsaturation degree of 0.1 to 1 mol / kg. Resin composition . 2. The active energy ray-curable resin composition according to claim 1 , wherein the molecular weight of the (meth) acrylate (b) is in the range of 100 to 3,000. The (meth) acrylate (b) is 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 2-hydroxyethyl methacrylate and at least one selected from the group consisting of β-methyl-valerolactone adduct of 2-hydroxyethyl methacrylate are described in claim 1 or 2 . Active energy ray-curable resin composition. The active energy ray-curable resin composition according to any one of claims 1 to 3 , wherein the polyisocyanate (c) is at least one selected from aliphatic diisocyanates and alicyclic diisocyanates. object. Furthermore, 0.01-15 mass parts of photoinitiators are contained with respect to 100 mass parts of said unsaturated group containing polyurethane resin compositions, The activity in any one of the Claims 1 thru | or 4 characterized by the above-mentioned. Energy ray curable resin composition. A paint comprising the active energy ray-curable resin composition according to any one of claims 1 to 5 . The coating film formed using the active energy ray hardening-type resin composition in any one of Claims 1 thru | or 5 .