TW202006067A - Curing resin composition, film of the curing resin composition, and molded article of the film - Google Patents

Abstract

The purpose of the present invention is to provide a curable resin composition that is capable of forming a cured coating film which has high chemical resistance, while having an elongation that does not interfere with injection molding. A curable resin composition according to the present invention contains (A) a polyurethane (meth)acrylate compound which has a urethane bond equivalent weight of 210 g/mol or less, (B) a polymerization initiator and (C) an aprotic polar solvent.

Description

Curable resin composition, film using the same, and molded product using the film

The present invention relates to a curable resin composition. Furthermore, the present invention relates to a molded film and a molded product using a cured coating film obtained by curing a curable resin composition.

The surface of resin molded products or plastic molded products such as automotive interiors, automotive exteriors, electrified products, etc. is required to have scratch resistance that is not or difficult to cause damage due to impact. Therefore, in order to improve the scratch resistance of the surface of these molded products, a scratch-resistant protective layer is widely provided. In the past, after obtaining a resin molded product or a plastic molded product by injection molding or the like, a scratch-resistant component is applied to provide a scratch-resistant protective layer. However, if a resin molded product or a plastic molded product having a scratch-resistant protective layer can be obtained by injection molding at a time, the molding process steps are reduced, which is economically advantageous. Therefore, attempts have been made to develop a curable composition that can form a protective layer that can withstand higher elongation and scratch resistance of the injection molding method.

Japanese Patent No. 6123428 discloses an active energy ray-curable resin composition that can form a cured film that has flexibility, breaking strength and mechanical strength, damage repairability, and scratch resistance that can follow deformation during three-dimensional processing. The active energy ray-curable resin composition is characterized in that it contains a low urethane (meth)acrylate as a reactant of polyisocyanate, polycarbonate polyol and hydroxyalkyl (meth)acrylate. The tensile modulus of elasticity of the polymer and the cured film has a specific value.

[Problems to be solved by the invention]

The active energy ray-curable resin composition of Patent Document 1 can form a soft and scratch-resistant cured film as described above, but there is a problem that it becomes white when contacted with chemicals. Therefore, an object of the present invention is to provide a curable resin composition that can form a high elongation that is resistant to deformation in the injection molding method including the insert molding method and scratch resistance, and has chemical resistance together Hardening coating. [Technical means to solve the problem]

The curable resin composition in the embodiment of the present invention includes a polyurethane (meth)acrylate compound (A) having a urethane bond equivalent weight of 210 g/mol or less and a polymerization initiator (B), and the curable resin composition of the aprotic polar solvent (C). Here, the polyurethane (meth)acrylate compound (A) is characterized by the following compounds: a polyisocyanate compound (a1) and a C1-C6 polyol compound (a2) and A compound obtained by reacting a hydroxyalkyl (meth)acrylate compound (a3). Another embodiment of the present invention is a formed film having a cured film formed by curing a curable resin composition and a base material. Still another embodiment of the present invention is a molded product having a cured film obtained by curing a curable resin composition and a cured film obtained by curing the curable resin composition on the surface. [Effect of invention]

The formed film formed using the curable resin composition of the present invention has sufficient elongation in thermoforming such as injection molding. In addition, the molded film of the present invention is used for processing the surface of a resin molded product or a plastic molded product. A cured film is closely adhered to the surface of the molded product, thereby effectively protecting the surface.

The embodiments of the present invention will be described below. An embodiment of the present invention is a curable resin composition comprising a polyurethane (meth)acrylate compound (A) having an urethane bond equivalent weight of 210 g/mole or less, polymerized Starting agent (B), and aprotic polar solvent (C).

In the present embodiment, the curable resin composition means that it is in a liquid state when it exists at room temperature, and the curing reaction starts by the opportunity of irradiation of active energy such as ultraviolet rays, infrared rays, X-rays, the application of thermal energy, and the addition of chemical substances. A mixture of resin or plastic or these raw material monomers as the main component that can form a hardened material or hardened film. The curable resin composition is used for a wide range of applications such as paints, sealing materials, sealing materials, and adhesives, and needs to satisfy various required performances according to its use. The cured product of the curable resin composition of this embodiment can be used as a film for processing or decorating the surface of molded products such as resins, plastics, metals, etc. The cured coating is closely attached to the surface of the molded product and is not easily peeled, which can prevent Damage caused by external impact.

The curable resin composition of this embodiment contains a polyurethane (meth)acrylate compound (A) having a urethane bond equivalent weight of 210 g/mole or less. Polyurethane (meth)acrylate compound refers to a polymerization having a urethane bond in the molecule and having a polymer group selected from acryl or metaacryl Substances, that is, polymers or oligomers. The polyurethane (meth)acrylate compound (A) contains an acrylic group (acryl) or methyl group that starts to undergo free radical polymerization by irradiating active energy rays, applying heat, or adding a polymerization initiator. Methacrylic acid (metaacryl). The urethane bond equivalent of the polyurethane (meth)acrylate compound (A) is 210 g/mole or less. Here, the urethane bond equivalent refers to the weight average molecular weight of the polyurethane (meth)acrylate compound (A) (that is, 1 mole of polyurethane (meth)acrylate The ratio of the weight of compound (A)) to the number of urethane bonds present in the polyurethane (meth)acrylate compound (A), the unit is g/mol. The smaller value of the urethane bond equivalent means that there are more urethane bonds in the molecule of the polyurethane (meth)acrylate compound (A).

If a polyurethane (meth)acrylate compound having a smaller value of urethane bond equivalent is used as (A), in the cured film polymer obtained by curing the curable resin composition There are more urethane bonds. If the urethane bond equivalent of the polyurethane (meth)acrylate compound (A) is 210 g/mole or less, sufficient amino acid can be ensured to impart chemical resistance to the cured film Number of ester bonds.

In the embodiment, the polyurethane (meth)acrylate compound as the component (A) is preferably a polyisocyanate compound (a1), a C1-C6 polyol compound (a2) and (a Group) hydroxyalkyl acrylate compound (a3) reacted compound. The polyisocyanate compound (a1) refers to a compound having two or more isocyanate groups (-N=C=O) in one molecule. The polyisocyanate compound (a1) is particularly preferably a diisocyanate compound having two isocyanate groups in the molecule. Here, examples of the diisocyanate compound include bis(isocyanatomethyl)cyclohexane, cyclohexane diisocyanate, diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), Toluene/Tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), cyclohexyl diisocyanate, dicyclohexylmethane 4,4'-diisocyanate, etc., One or more of these can be used.

The polyol compound (a2) refers to a compound having two or more hydroxyl groups (-OH) in one molecule. In the embodiment, the polyol compound (a2) preferably has 1 to 6 carbon atoms. By using a polyol compound with a relatively low molecular weight as (a2), the number of urethane bonds in the polyurethane (meth)acrylate compound (A) can be increased. That is, the urethane bond equivalent of the polyurethane (meth)acrylate compound (A) can be adjusted by adjusting the carbon number of the polyol compound (a2). Examples of such polyol compounds include methylene glycol, ethylene glycol, n-propylene glycol, isopropylene glycol, n-butanediol, isobutanediol, third butanediol, n-pentanediol, and n-hexanediol. Aliphatic or cycloaliphatic diol compounds such as dihydroxycyclohexane; aliphatic or cycloaliphatic triol compounds such as 1,2,4-butanetriol; catechol, resorcinol, hydroquinone Etc. aromatic diol compounds; and aromatic triol compounds such as pyrogallol, phloroglucinol, pyrogallol, etc. One or more of these can be used.

The hydroxyalkyl (meth)acrylate compound (a3) refers to a compound having a hydroxyalkyl group (alkyl group having a hydroxy group), and acryl or methacryl group in one molecule. Examples of hydroxyalkyl (meth)acrylate compounds include hydroxymethyl acrylate, hydroxymethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, pentaerythritol diacrylate, and pentaerythritol dimethacrylate. , Pentaerythritol triacrylate, pentaerythritol trimethacrylate, etc., one or more of them can be used.

Polyurethanes can be formed by reacting the isocyanate groups present in (a1) above with the hydroxyl groups present in (a2) and the hydroxyl groups present in (a3) to form a carbamate bond ( Methacrylate compound (A). Preferably, the component (a1) and the component (a2) are reacted first, and then the component (a3) is added, thereby generating the polyurethane (meth)acrylate compound (A). In the polyurethane (meth)acrylate compound (A), there is a radical polymerizable group (acryl or metaacryl) derived from (a3). The reaction of the radical polymerizable group contributes to the curing of the curable resin composition of the embodiment.

、乙基蒽醌)、產生陽離子活性種之光陽離子聚合起始劑(例如六氟磷酸雙(4-第三丁基苯基)錪、三氟甲磺酸雙(4-氟苯基)錪、六氟磷酸二苯基錪、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三𠯤、4-硝基苯重氮鎓四氟硼酸鹽)、產生陰離子活性種之光陰離子聚合起始劑(苯乙酮-O-苯甲醯肟、環己基胺基甲酸1,2-雙(4-甲氧基苯基)-2-側氧乙酯、硝苯地平)。作為光聚合起始劑，可使用Irgacure(BASF)等市售品。可使用Irgacure184(1-羥基環己基苯基酮)、Irgacure907(2-甲基-1-(4-(甲硫基)苯基)-2-嗎啉基丙烷-1-酮)、Lucirin TPO(2,4,6-三甲基苯甲醯基二苯基氧化膦)等。又，該等可單獨使用或混合2種以上使用。The curable resin composition of the embodiment includes a polymerization initiator (B) in addition to the polyurethane (meth)acrylate compound (A). The polymerization initiator is a compound that initiates the polymerization reaction of the monomer in response to stimuli such as light irradiation and heat application. In the curable resin composition of the embodiment, it is preferable to use a photopolymerization initiator that initiates polymerization by irradiation of light including ultraviolet rays, electron beams, and visible light. As a photopolymerization initiator, a photoradical polymerization initiator that generates free radical active species by irradiation of light (for example, acetophenone, dimethoxybenzyl, dibenzoyl, benzoyl) Marriage, benzophenone, benzoyl benzoic acid, bis(dimethylamino) benzophenone, bis(diethylamino) benzophenone, chloro 9-oxythio

, Ethylanthraquinone), photocationic polymerization initiators that generate cationic active species (such as bis(4-third butylphenyl) hexafluorophosphate, bis(4-fluorophenyl) chlorotrifluoromethanesulfonate , Diphenylphosphonium hexafluorophosphate, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-tris, 4-nitro Phenyldiazonium tetrafluoroborate), photoanionic polymerization initiator that produces anionic active species (acetophenone-O-benzoyl oxime, cyclohexylaminocarbamic acid 1,2-bis(4-methoxybenzene) Radical)-2-oxoethyl ester, nifedipine). As the photopolymerization initiator, commercially available products such as Irgacure (BASF) can be used. Irgacure 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure 907 (2-methyl-1-(4-(methylthio) phenyl)-2-morpholinylpropane-1-one), Lucirin TPO ( 2,4,6-trimethylbenzyl diphenylphosphine oxide), etc. Moreover, these can be used individually or in mixture of 2 or more types.

The curable resin composition of the embodiment includes an aprotic polar solvent (C). Aprotic polar solvents refer to polar solvents that do not have proton donating groups in the molecule. Examples of aprotic polar solvents include ethers such as diethyl ether and tetrahydrofuran; ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate and ethyl acetate; and dimethyl sulfoxide, N, N -Dimethylformamide, triamine hexamethylphosphate, etc. As the aprotic polar solvent (C), one of these or two or more of them may be used in combination. From the viewpoint of dielectric constant, it is preferably composed of N,N-dimethylformamide and dimethyl At least one of arrogance. By including the aprotic polar solvent (C) in the curable resin composition, the interaction between the molecules of the polyurethane (meth)acrylate compound (A) contained in the curable resin composition can be suppressed effect. Therefore, the polyurethane (meth)acrylate compound (A) is uniformly distributed in the curable resin composition. If such a curable resin composition is cured, a uniform cured film can be formed. Furthermore, when the curable resin composition is cured, the aprotic polar solvent (C) volatilizes. This embodiment of the present embodiment uses a combination of a polyurethane (meth)acrylate compound (A) having a specific value of a urethane bond equivalent as described above and an aprotic polar solvent (C) The hardenable resin composition can form a hardened and hardened coating.

The curable resin composition of the embodiment may further contain an ethylenically unsaturated compound (D) having one or more radical polymerizable groups in the molecule. Here, the ethylenically unsaturated compound refers to a compound having at least one ethylenically unsaturated group (-C=C-). The ethylenically unsaturated compound (D) preferably has one or more radical polymerizable groups in the molecule. The radical polymerizable group is represented by vinyl, acryl, methacryl, metaacryl, acryl, methacryl, allyl, etc. as described above. The energy ray either imparts heat or adds a polymerization initiator to cleave the double bond or triple bond that initiates free radical polymerization. Examples of such ethylenically unsaturated compound (D) include ethoxylated glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and trimethylol. Propylene tri (meth) acrylate, dimethylol propane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate is represented by multifunctional (meth) acrylate compounds; (meth) acrylic acid (Meth)acrylic monomers represented by hydroxybutyl ester, hydroxypropyl (meth)acrylate, and hydroxyethyl (meth)acrylate; and (meth)acrylamide, dimethyl (meth)acrylic acid Acetamide is the representative (meth)acrylamide. As long as it does not affect the embodiment, a polymer having at least one ethylenically unsaturated group can be used as the ethylenically unsaturated compound (D). By making various changes to the ethylenically unsaturated compound (D), the elongation, hardness, adhesion to the substrate, etc. of the cured film can be changed. Therefore, the ethylenically unsaturated compound (D) may or may not be used depending on the type of base material to which the cured coating is applied, the molding method, and the use of the finished molded product.

In addition to the above-mentioned components, the curable resin composition of the embodiment can also be formulated with additives (such as dyes, pigments, plasticizers, dispersants, preservatives, matting agents, and antistatic agents) generally contained in the curable resin composition. , Flame retardants, ultraviolet absorbers, light stabilizers, antifouling agents, anti-blocking agents, antibacterial agents, inorganic particles).

The curable resin composition of the embodiment can be prepared by using a protic polar solvent for dilution according to the application. As the protic polar solvent, one kind of alcohols such as methanol, ethanol, 1-propanol, isopropanol, ethylene glycol methyl ether, propylene glycol monomethyl ether, or two or more kinds can be used in combination. In addition, in the present specification, those obtained by diluting the curable resin composition of the embodiment with a protic polar solvent are sometimes referred to as "curable resin composition".

The preferred curable resin composition can be produced by preparing a polyurethane (meth)acrylate compound (A), and a polymerization initiator (B), according to the curable resin composition An appropriate amount of an aprotic polar solvent (C) and an ethylenically unsaturated compound (D) as appropriate depending on the purpose are mixed, and then diluted with a protic polar solvent as appropriate.

Here, the content of the polyurethane (meth)acrylate compound (A) (non-volatile matter) is based on the weight of the curable resin composition (ie, component (A), component (B), component (C ), the total weight of component (D) is 15 to 50% based on the standard, preferably 20 to 45%. In addition, the content of the polymerization initiator (B) is 0.5 to 5%, preferably 1 to 3%, based on the weight of the curable resin composition. The content of the aprotic polar solvent (C) is 40% to 80% based on the weight of the curable resin composition, preferably 45% to 75%. The content of the ethylenically unsaturated compound (D) is 5 to 20% based on the weight of the curable resin composition, preferably 10 to 20%. Furthermore, the curable resin composition of the embodiment can be prepared by diluting a protic polar solvent according to the application. In this case, the component (A), component (B), and component (C) can be diluted by a protic polar solvent in an amount of 1.1 times to 5 times, preferably 1.3 times to 3 times 1. The curable resin composition of component (D). That is, the content of the polyurethane (meth)acrylate compound (A) (non-volatile matter) may include the total weight of the curable resin composition of the solvent (ie, component (A), component (B), component (C), the total weight of the component (D) and the diluted solvent) is set to 5 to 30% based on the standard, preferably 10 to 25%. The content of the polymerization initiator (B) is 0.1 to 3% based on the total weight of the curable resin composition containing a solvent, preferably 0.5 to 2%. The content of the aprotic polar solvent (C) is 20% to 60% based on the total weight of the curable resin composition containing the solvent, preferably 25% to 60%. The content of the ethylenically unsaturated compound (D) is 3 to 15%, preferably 5 to 10%, based on the total weight of the curable resin composition containing the solvent.

The curable resin composition of the embodiment can be applied to the surface of a suitable substrate and cured on it to form a cured film. The thickness of the cured coating can be changed according to the application, but it is generally 1 to 20 μm, preferably 1 to 10 μm. Examples of the substrate for curing the curable resin composition include glass, plastic, and metal. The curable resin composition of the embodiment can be particularly suitable for curing on plastic to form a cured film. As the base material, for example, acrylic resin or polycarbonate resin whose outermost layer is covered with acrylic resin can be used. The coating of the curable resin composition on the surface of the base material can be appropriately performed by the previous coating method. The applied curable resin composition can be heated to form a cured film. Regarding the heating of the curable resin composition, as long as it is heated to initiate the polyurethane (meth)acrylate compound (A) by the action of the polymerization initiator (B) in the curable resin composition, and A sufficient temperature required for the polymerization or copolymerization of the ethylenically unsaturated compound (D) according to circumstances. The heating temperature varies according to the types of (A) and (D) and the polymerization initiator (B) used, and usually the copolymerization reaction can be initiated by heating to about 80 to 150°C, preferably about 100 to 150°C. The coating material of the curable resin composition may be heated by a heating device such as a burner or an oven, or may be heated by a heating method such as a dryer using hot air.

In addition, the curable resin composition of the embodiment may be applied to the surface of the base material, and the coated surface is irradiated with active energy rays to initiate the polyurethane (meth)acrylate compound (A) and optionally Polymerization or copolymerization of ethylenically unsaturated compound (D). Examples of the active energy rays to be irradiated include visible light, ultraviolet light, infrared light, α-rays, β-rays, γ-rays, and X-rays.

In this way, the curable resin composition of the embodiment can be cured on a plastic substrate to form a cured film, thereby forming a molded film. The formed film of the embodiment can be used as a film for processing the surface of molded products such as plastic. The formed film of the embodiment may have patterns, patterns, patterns, colors, etc., or may be transparent. A formed film having a pattern or the like is called a decorative film, and is preferably used to apply a pattern or the like to the surface of a molded product. The molded film of the embodiment can be filled into an injection molding die, and the cured film can be attached to the molded product at the same time as the injection molding (embedded molding method). In addition, the formed film of the embodiment can be attached to the surface of the formed product, the base material can be peeled off, and a hardened film with a pattern or pattern applied can be transferred (transfer method). The cured film obtained by curing the curable resin composition of the embodiment can form a strong film having heat resistance for the injection molding method and sufficient elongation that can follow the surface of the molded product and is closely adhered to the surface of the molded product . [Example]

(1) Preparation of curable resin composition (1-1) Synthesis of Polyurethane (Meth)acrylate Compound (A-1) In a 300 mL eggplant flask, add 30.0 parts by weight of dicyclohexylmethane-4,4'-diisocyanate as (a1) component, 6.9 parts by weight of ethylene glycol as (a2) component, and (C) component 98.7 parts by weight of N,N-dimethylformamide and 0.024 parts by weight of dioctyltin dilaurate as a catalyst were reacted at 70°C for 6 hours while stirring. After completion of the reaction, 5.4 parts by weight of pentaerythritol triacrylate (manufactured by East Asia Synthesizing Co., Ltd., trade name: ARONIX M-306) as a component (a3) was added, and reacted at 60°C for 6 hours to obtain radical polymerizability Based polyurethane acrylate (A-1). Weight-average molecular weight = 12100, non-volatile matter = 30%, urethane bond equivalent = 170 g/mole

In addition, the polyurethane (meth)acrylate compound synthesized in the examples and comparative examples described below refers to the polyurethane (meth)acrylate compound and the aprotic as the reaction solvent Mixture of polar solvents. "Nonvolatile" means the substantial ratio of the polyurethane (meth)acrylate compound contained in the mixture obtained by the reaction. For example, in the above-mentioned polyurethane acrylate (A-1), "nonvolatile content = 30%" means that 30% of the polyurethane acrylate (A-1) and the reaction solvent are obtained A mixture of 70% N,N-dimethylformamide, which is used as component (A-1). The synthesis of the following polyurethane (meth)acrylate compounds will be described in the same way.

(1-2) Synthesis of Polyurethane (Meth)acrylate Compound (A-2) In a 300 mL eggplant-shaped flask, add 30.0 parts by weight of dicyclohexylmethane-4,4'-diisocyanate as (a1) component, 6.6 parts by weight of ethylene glycol as (a2) component, and (C) component 110.0 parts by weight of N,N-dimethylformamide and 0.024 parts by weight of dioctyltin dilaurate as a catalyst were reacted at 70°C for 6 hours while stirring. After completion of the reaction, 11.2 parts by weight of pentaerythritol triacrylate (manufactured by East Asia Synthesizing Co., Ltd., trade name: ARONIX M-306) as a component (a3) was added, and reacted at 60°C for 6 hours to obtain radically polymerizable Based polyurethane acrylate (A-2). Weight-average molecular weight = 5600, non-volatile matter = 30%, urethane bond equivalent = 179 g/mole

(1-3) Synthesis of Polyurethane (Meth)acrylate Compound (A-3) In a 300 mL eggplant-shaped flask, add 30.0 parts by weight of dicyclohexylmethane-4,4'-diisocyanate as (a1) component, 6.6 parts by weight of ethylene glycol as (a2) component, and (C) component 110.0 parts by weight of N,N-dimethylformamide and 0.024 parts by weight of dioctyltin dilaurate as a catalyst were reacted at 70°C for 6 hours while stirring. After completion of the reaction, 37.6 parts by weight of pentaerythritol triacrylate (manufactured by East Asia Synthetic Co., Ltd., trade name: ARONIX M-306) as a component (a3) was added, and reacted at 60°C for 6 hours to obtain radical polymerizability Based polyurethane acrylate (A-3). Weight average molecular weight = 5000, non-volatile matter = 40%, urethane bond equivalent = 181 g/mole

(1-4) Synthesis of Polyurethane (Meth)acrylate Compound (A-4) In a 300 mL eggplant flask, add 30.0 parts by weight of dicyclohexylmethane-4,4'-diisocyanate as (a1) component and 9.6 parts by weight of 1,4-butanediol as (a2) component as ( C) 118.6 parts by weight of N,N-dimethylformamide as a component and 0.024 parts by weight of dioctyltin dilaurate as a catalyst were reacted at 70°C for 6 hours while stirring. After completion of the reaction, 11.2 parts by weight of pentaerythritol triacrylate (manufactured by East Asia Synthesizing Co., Ltd., trade name: ARONIX M-306) as a component (a3) was added, and reacted at 60°C for 6 hours to obtain radically polymerizable Based polyurethane acrylate (A-4). Weight-average molecular weight = 5600, non-volatile matter = 30%, urethane bond equivalent = 194 g/mole

(1-5) Synthesis of Polyurethane (Meth)acrylate Compound (A-5) In a 300 mL eggplant-shaped flask, add 30.0 parts by weight of dicyclohexylmethane-4,4'-diisocyanate as (a1) component and 12.5 parts by weight of 1,6-hexanediol as (a2) component as ( C) 125.3 parts by weight of N,N-dimethylformamide and 0.024 parts by weight of dioctyltin dilaurate as a catalyst were reacted at 70°C for 6 hours while stirring. After completion of the reaction, 11.2 parts by weight of pentaerythritol triacrylate (manufactured by East Asia Synthetic Co., Ltd., trade name: ARONIX M-306) as a component (a3) was added, and reacted at 60°C for 6 hours to obtain polyaminocarboxylic acid Ester acrylate compound (A-5). Weight average molecular weight = 5600, non-volatile matter = 30%, urethane bond equivalent = 208 g/mole

(1-6) Synthesis of Polyurethane (Meth) Acrylate Compound (A'-1) Synthesize a polyurethane (meth)acrylate compound with a large value of urethane bond equivalent. In a 500 mL eggplant-shaped flask, 30.0 parts by weight of isophorone diisocyanate, polycarbonate diol (manufactured by Asahi Kasei Corporation, trade name: DURANOL T4691), 57.2 parts by weight, and 1,4-butanediol 4.3 parts by weight Parts, 150.0 parts by weight of methyl ethyl ketone (MEK) as a reaction solvent, and 0.005 parts by weight of dioctyl tin dilaurate as a catalyst, and reacted at 80° C. for 9 hours while stirring. After the reaction, after cooling to 60°C, 0.03 parts by weight of dioctyltin dilaurate, 0.05 parts by weight of methylhydroquinone, and 10.6 parts by weight of methyl ethyl ketone were added, and 2-hydroxyethyl methacrylate was added dropwise 8.1 parts by weight of the ester was reacted at 70°C for 10 hours to obtain a polyurethane methacrylate compound (A'-1). Weight-average molecular weight = 4250, non-volatile matter = 40%, urethane bond equivalent = 371 g/mole

(1-7) Synthesis of Polyurethane (Meth)acrylate Compound (A'-2) Synthesize a polyurethane (meth)acrylate compound with a large value of urethane bond equivalent. In a 500 mL eggplant-shaped flask, 77.7 parts by weight of dicyclohexylmethane-4,4'-diisocyanate and 45.1 parts by weight of glycerol monomethacrylate (manufactured by NOF Corporation, trade name: Blemmer GLM) were added as 204.8 parts by weight of ethyl acetate (EA) as the reaction solvent and 0.004 parts by weight of dioctyltin dilaurate as the catalyst were reacted at 60°C for 6 hours with stirring. After the reaction was completed, 14.6 parts by weight of pentaerythritol triacrylate (manufactured by East Asia Synthetic Co., Ltd., trade name: ARONIX M-306) was added, and reacted at 60°C for 6 hours to obtain a polyurethane acrylate compound (A '-2). Weight average molecular weight = 9200, non-volatile matter = 40%, urethane bond equivalent = 222 g/mole

The above (A-1) to (A-5) and (A'-1) and (A'-2), Irgacure907 (BASF) as the polymerization initiator (B), as the ethylenic unsaturation as the case may be Pentaerythritol triacrylate (ARONIX M-306 manufactured by East Asia Synthetic Chemical Co., Ltd.) of compound (D), and propylene glycol monomethyl ether (PGM) or methyl ethyl ketone (MEK) as solvents are listed in Table 1. The weight ratio is adjusted to produce the curable resin compositions of Examples 1 to 6 of the present invention and the curable resin compositions of Comparative Examples 1 to 4. Furthermore, as described above, the above-mentioned (A-1) to (A-5) and (A'-1) and (A'-2)-based polyurethane (meth)acrylate compounds react as A mixture of solvent aprotic polar solvents (C). The values of (A-1) to (A-5) and (A'-1) and (A'-2) in Table 1 and Table 2 are the whole of these components (that is, including the aprotic polar solvent (C) The weight ratio. Moreover, the value in parentheses is the weight ratio of only non-volatile matter (ie, polyurethane (meth)acrylate).

(2) Preparation of cured film of curable resin composition As the base material for forming the cured film of the curable resin composition, a polycarbonate film whose outermost layer is covered with acrylic resin is used. The above curable resin compositions were applied to the substrate by a bar coating method so that the film thickness after curing became 4 μm. Then, the substrate coated with the curable resin composition was dried in an oven at 100° C. for 1 minute, and then the curable resin composition was cured by irradiating ultraviolet rays as active energy rays. By this, a formed film having a cured film is obtained.

(3) Performance evaluation of formed film (3-1) Appearance evaluation For the formed film of each example, the haze value was measured using the haze meter specified in JIS K 7136. A larger haze value means more opaque, and a smaller value means more transparent.

(3-2) Evaluation of adhesion According to JIS K 5600-5-6, evaluation was performed as follows by visually inspecting the cured film for peeling of the cured film. Pass: No peeling is seen Unqualified: part or all stripped

(3-3) Evaluation of adhesion after heating Furthermore, each molded film was immersed in boiling water for 30 minutes, and evaluated according to JIS K 5600-5-6 by visually inspecting the molded film for peeling of the cured film, and evaluated as follows. Pass: No peeling is seen Unqualified: part or all stripped

(3-4) Evaluation of scratch resistance For each formed film obtained, a load of 250 g/cm ² was applied to steel wool #0000 and reciprocated 10 times, and the haze value was measured using a haze meter. The difference between the haze values before and after the scratch resistance test was determined. The smaller the value, the higher the scratch resistance.

(3-5) Evaluation of chemical resistance For each formed film obtained, 0.2 g of a commercially available sunscreen (Ultra Sheer Dry-Touch Sunscreen SPF45, manufactured by Neutrogena) was applied to an area of 1 cm ² . Let stand at 80°C for 1 hour. Afterwards, the applied sunscreen was washed with a large amount of water, and the change of the appearance of the hardened film was observed by visual observation. High: No changes are seen in the appearance: Part of the appearance sees changes such as whitening Low: Changes in the appearance sees changes such as whitening

(3-6) Evaluation of extensibility For each formed film obtained, a tensile test was carried out at a high temperature (150°C) (sample size: 200 mm×10 mm, distance between chucks: 110 mm, and tensile speed: 50 mm/min). The time at which the cured film cracked was defined as the elongation at break point, and the stretchability of the formed film was evaluated from the results.

[Table 1]

[Table 2]

In addition, the value in parentheses in Table 1 is the amount of non-volatile components. For example, the value "46.1" in the column A-1 of Example 1 of Table 1 means that the polyurethane acrylate of A-1 and DMF as the reaction solvent (ie, aprotic polar solvent (C)) The total amount is 46.1 parts by weight, and the amount of polyurethane acrylate A-1 is 13.8 parts by weight. For convenience of manufacturing, the polyurethane (meth)acrylate as the component (A) is used in the form of a mixture of the polyurethane (meth)acrylate and the aprotic polar solvent (C) Therefore, it is described in the table as described above. The curable resin composition of Example 1 is composed of 46.1 parts by weight of A-1 dissolved in an aprotic polar solvent (C), 0.9 parts by weight of a polymerization initiator (B), and 7.7 ethylenically unsaturated monomers (D) 45.3 parts by weight of the diluent and the diluent are mixed to prepare the obtained product. Similarly, the values in parentheses in Table 2 are the non-volatile content. For example, the value "53.9" described in column A'-1 of Comparative Example 1 in Table 2 means that the polyurethane acrylate of A'-1 is used as a reaction solvent (that is, an aprotic polar solvent (C)) The total amount of MEK is 53.9 parts by weight, and the amount of polyurethane methacrylate A'-1 is 21.6 parts by weight. The curable resin composition of Comparative Example 1 was prepared by mixing 53.9 parts by weight of A′-1 dissolved in an aprotic polar solvent (C), 1.2 parts by weight of a polymerization initiator (B), and 44.9 parts by weight of MEK. Producer.

Furthermore, the meaning of the abbreviations in the table is as follows: Irgacure907: 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one (BASF) M-306: Pentaerythritol triacrylate (East Asia Synthesis) PGM: propylene glycol monomethyl ether MEK: methyl ethyl ketone DMF: N,N-dimethylformamide EA: ethyl acetate

The cured films of the embodiments of the present invention are excellent in adhesion, and maintain the adhesion even after heating. The curable resin composition of the embodiment of the present invention can form a cured coating film excellent in scratch resistance and chemical resistance. The formed film using the curable resin composition of the embodiment of the present invention has a high elongation at break point, that is, extensibility, suggesting a sufficient elongation that can withstand the insert molding method and the like. On the other hand, the formed film using the curable resin composition of the comparative example is insufficient in any of the properties of adhesion, scratch resistance, chemical resistance, and elongation, and is used in the curable resin composition of the comparative example. The equivalent of the urethane bond of the polyurethane (meth)acrylate (A) does not satisfy the requirements of the present invention.

Claims (7)

A curable resin composition comprising a polyurethane (meth)acrylate compound (A) having a urethane bond equivalent weight of 210 g/mol or less, a polymerization initiator (B), and Aprotic polar solvent (C). The curable resin composition according to claim 1, wherein the polyurethane (meth)acrylate compound (A) is a polyisocyanate compound (a1) and a polyol compound having 1 to 6 carbon atoms (a2) A compound formed by reacting with (meth)acrylic acid hydroxyalkyl ester compound (a3). The curable resin composition according to claim 1 or 2, which further contains an ethylenically unsaturated compound (D) having one or more radical polymerizable groups in the molecule. The curable resin composition according to claim 1 or 2, which further contains a protic polar solvent. The curable resin composition according to claim 3, which further contains a protic polar solvent. A formed film having a cured film obtained by curing the curable resin composition according to any one of claims 1 to 5 and a base material. A molded product having a hardened film obtained by hardening the curable resin composition according to any one of claims 1 to 5 on the surface.