JP7054753B1 - Hardcourt resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plant-derived hard coat resin composition having good adhesion to a biomass plastic base material without primer treatment, excellent curability, high hardness of a cured film, and abrasion resistance. offer. SOLUTION: The coating agent to be applied to a biomass plastic substrate contains a polyfunctional glycerin (meth) acrylate and a photopolymerization initiator, and the acrylate is a biomass acrylate and / or a biomass acrylate having an OH group. It is a hard coat resin composition characterized by being an induced urethane (meth) acrylate. [Selection diagram] None

Description

The present invention relates to a hardcourt resin composition to be applied to a biomass plastic substrate.

In recent years, due to concerns about the depletion of petroleum resources, global warming, and the problem of an increase in carbon dioxide in the air that causes global warming, carbon neutrals that do not depend on petroleum resources for raw materials and do not increase carbon dioxide even when burned have become available. Biomass resources that can be established have attracted a great deal of attention, and in the field of polymers as well, biomass plastics produced from biomass resources such as plant-derived monomers have been developed.

For example, polycarbonate (hereinafter referred to as PC) resin, which is widely known as engineering plastics, is generally produced from bisphenol A and phosgen as raw materials, and takes advantage of its advantages such as transparency, heat resistance, and mechanical strength, and is electrically and electronic. It is used in a wide range of fields such as parts, automobile parts, building structures, films, and lenses. On the other hand, an aliphatic biomass PC having a skeleton obtained by using isosorbide as a plant-derived monomer and copolymerizing 1,4-cyclohexanedimethanol, which is an alicyclic dihydroxy compound, with respect to such a conventional product derived from petroleum raw materials. Has been proposed (Patent Document 1).

However, some of these biomass plastics have difficulty in adhesion to a hard coating agent (hereinafter referred to as HC agent) that protects the surface, and in particular, the PC resin itself does not have good adhesion to the HC resin. Therefore, a primer treatment may be required (Patent Document 2), and the biomass PC, which is a biomass product thereof, tends to have further inferior adhesion. Therefore, there has been a demand for a plant-derived HC agent having good adhesion even without primer treatment, excellent curability, high hardness of the cured film, and wear resistance.

Japanese Patent No. 5532531 Japanese Patent No. 6020670

The present invention provides a plant-derived HC resin composition having good adhesion to a biomass plastic substrate without primer treatment, excellent curability, high hardness of a cured film, and abrasion resistance. To provide.

In order to achieve the above object, the invention according to claim 1 is a coating agent to be applied to a biomass polycarbonate substrate, which comprises a biomass glycerin diacrylate and / and a glycerin triacrylate (a1) and a photopolymerization initiator (B). And a composition containing an acrylic polymer (C) or a bifunctional or higher alicyclic monomer , or a urethane (meth) acrylate (a2) derived from (a1) having an OH group, and photopolymerization initiation. A composition comprising the agent (B) and
In the case of (C), the blending amount of the (C) or the bifunctional or higher alicyclic monomer is 5 to 30 parts by weight with respect to 100 parts by weight of (a1), and the bifunctional or higher functional alicyclic monomer is used. In the case of (a1), a hard coat resin composition characterized by 30 parts by weight or less with respect to 100 parts by weight is provided.

Further, in the invention according to claim 2, the above (a2) is a urethane (meth) acrylate obtained by reacting a polyisocyanate with a polyol in advance and reacting a prepolymer having an isocyanate group at the end with (a1) having an OH group. The invention according to claim 3 is (a22) , wherein the (a2) is a urethane (meth) acrylate (a21) obtained by reacting (a1) having an OH group with a polyisocyanate. Item 1. The hard coat resin composition according to Item 1 is provided.

The invention according to claim 4 provides the hardcourt resin composition according to claim 1, wherein the weight average molecular weight of the above (C) is 20,000 to 50,000 .

The invention according to claim 5 is any one of claims 1 to 4, wherein the biomass polycarbonate base material is one selected from the group consisting of a biomass polycarbonate film, a biomass polycarbonate sheet, and a biomass polycarbonate molded body. The hard coat resin composition described above is provided.

The invention according to claim 6 provides a laminate having a cured layer of the hard coat resin composition according to any one of claims 1 to 4 on a biomass polycarbonate film or a biomass polycarbonate sheet.

The invention according to claim 7 is a resin molded product using the laminate according to claim 6, and the invention according to claim 8 is a resin molded product.
Provided is a resin molded product having a cured layer of the hard coat resin composition according to any one of claims 1 to 4 on a biomass polycarbonate resin molded product.

The invention according to claim 9 provides an optical display device using the laminate according to claim 5 or the resin molded body according to any one of claims 7 or 8.

The resin composition of the present invention has good adhesion to a biomass plastic base material without primer treatment, has excellent curability, and has a hardened film having high hardness and abrasion resistance. Therefore, it is biomass. It is useful as a plant-derived HC agent for plastic substrates.

Hereinafter, the present invention will be described in detail.

The composition of the present invention comprises a polyfunctional glycerin (meth) acrylate (A) and a photopolymerization initiator (B). In addition, in this specification, (meth) acrylate includes both acrylate and methacrylate. Further, (poly) includes both cases with and without poly, and for example, (poly) ethylene glycol means polyethylene ethylene glycol and / and ethylene glycol.

The polyfunctional glycerin (meth) acrylate (A) used in the present invention is a urethane (meth) acrylate (a2) derived from the biomass (meth) acrylate (a1) and / and (a1) having an OH group. Yes, (a1) can be mentioned, for example, an ester compound of (poly) glycerin derived from a plant and (meth) acrylic acid. Compared to petroleum-derived polyfunctional glycerin (meth) acrylate, which is not biomass, it is highly sensitive and reactive, the cured film has high hardness, and it is scratch resistant such as steel wool resistance (hereinafter referred to as SW resistance). It also tends to be excellent in sex. It may be modified with (poly) alkylene oxide such as (poly) ethylene oxide or (poly) propylene oxide.

Examples of the (a1) include glycerin (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, diglycerin tri (meth) acrylate, diglycerin tetra (meth) acrylate, and their (poly). Examples thereof include ethylene oxide modified products and (poly) propylene oxide modified products, which can be used alone or in combination of two or more. Among these, glycerin diacrylate and glycerin triacrylate are preferable because they have high reactivity, the cured film has high hardness, and the scratch resistance is good.

Further, the (a2) includes a reaction compound of (a1) having an OH group and a polyisocyanate, for example, urethane (meth) acrylate (a21) obtained by reacting (a1) having an OH group with a polyisocyanate, or poly. Examples thereof include urethane (meth) acrylate (a22) obtained by reacting isocyanate and a polyol in advance with a prepolymer having an isocyanate group at the end and (a1) having an OH group.

Examples of the polyisocyanate include pentamethylene diisocyanate (hereinafter referred to as PDI), hexamethylene diisocyanate (hereinafter referred to as HDI), isophorone diisocyanate (hereinafter referred to as IPDI), diphenylmethane diisocyanate, tolylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, and the like. Examples thereof include hydrogenated xylylene diisocyanate, methylcyclohexylene diisocyanate, HDI isocyanurate form, IPDI isocyanurate form, etc., and they may be used alone or in combination of two or more. Among these, aliphatic and alicyclic diisocyanates having high weather resistance and resistance to yellowing are preferable, and among them, PDI and HDI having high stretchability and IPDI having high rigidity and relatively good reactivity are particularly preferable.

Examples of the urethane (meth) acrylate (a21) include compounds obtained by reacting glycerin diacrylate (hereinafter referred to as GDA) having an OH group (a1) with polyisocyanates such as PDI, HDI, and IPDI. Can be done.

The synthesis method of (a21) is not particularly limited, and a known method can be used. The reaction ratio (molar ratio) between GDA and polyisocyanate (a1) is preferably GDA hydroxyl group: isocyanate group = 1: 0.7 to 1: 1, preferably 1: 0.8 to 1: 1. Is more preferable. It is preferable to use a catalyst for the above reaction, and examples thereof include tin-based materials such as dibutyltin dilaurate and metal alkoxide-based materials such as cobalt naphthenate. The reaction may be carried out in the absence of a solvent, but an organic solvent having no functional group that reacts with an isocyanate group, for example, esters such as ethyl acetate and butyl acetate, and ketones such as methyl ethyl ketone and isobutyl ketone can be used. The reaction temperature can be appropriately set, but is preferably 40 to 110 ° C, more preferably 50 to 90 ° C.

The urethane (meth) acrylate (a22) is formed by reacting an alkylene glycol having a short carbon chain with a polyisocyanate in a molecule in that a main skeleton having a highly rigid linear structure having excellent chemical resistance can be formed. It is preferable to have a skeleton having a high urethane concentration. For example, a compound obtained by reacting GDA with a prepolymer having an isocyanate group at the end obtained by reacting ethylene glycol (hereinafter referred to as EG) with IPDI can be mentioned.

Mw. Of the above (a22). Is preferably 1,500 to 30,000, more preferably 2,000 to 15,000, and particularly preferably 3,000 to 10,000. Within this range, it becomes easy to adjust the viscosity to have good workability, and sufficient flexibility and steel wool property can be ensured. The Mw of (a22) can be adjusted by the molar ratio of ethylene glycol to be reacted and IPDI, and when the molar ratio of IPDI to ethylene glycol is brought closer, Mw tends to increase. Mw was measured and calculated by gel permeation chromatography using a tetrahydrofuran eluent on a column using a filler based on styrenedivinylbenzene to measure and calculate the molecular weight in terms of standard polystyrene.

The synthesis method of (a22) is not particularly limited, and a known method can be used. The reaction may be carried out in the absence of a solvent, but as the molecular weight of (A) increases, stirring may become difficult. Therefore, an organic solvent having no functional group that reacts with an isocyanate group, for example, an ester such as ethyl acetate or butyl acetate. Classes, ketones such as methyl ethyl ketone and isobutyl ketone may be used. Further, it is preferable to use a catalyst for the reaction between the hydroxyl group of ethylene glycol and (a1) and the isocyanate group. Examples of such cases include tin-based materials such as dibutyltin dilaurate and metal alkoxide-based materials such as cobalt naphthenate. The reaction temperature can be appropriately set, but is preferably 40 to 110 ° C, more preferably 50 to 90 ° C.

The blending amount of (A) is preferably 65 to 99% by weight, more preferably 70 to 98% by weight, and particularly preferably 75 to 97% by weight, based on the total solid content of the composition. When the content is 65% by weight or more, sufficient adhesion to the substrate can be ensured, and when the content is 99% by weight or less, sufficient curability can be ensured.

The photopolymerization initiator (B) used in the present invention generates radicals by irradiation with ultraviolet rays, electron beams, etc., and the radicals trigger a polymerization reaction. A general-purpose photopolymerization initiator can be used. By arbitrarily selecting the light absorption wavelength of the polymerization initiator, curability can be imparted over a wide wavelength range from the ultraviolet region to the visible light region. Specifically, 2.2-dimethoxy-1.2-diphenylethan-1-one as a benzyl ketal system, 1-hydroxy-cyclohexyl-phenyl-ketone and 1- [4- (2- (2-) as an α-hydroxyacetophenone system. Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one is a 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 as an α-aminoacetophenone system. -On is an acylphosphine oxide system such as 2.4.6-trimethylbenzoyl-diphenyl-phosphinoxide and bis (2.4.6-trimethylbenzoyl) -phenylphosphinoxide, which may be used alone or in combination of two or more. Can be used in combination. Among these, it is preferable to blend an α-hydroxyphenone system that does not easily turn yellow.

The blending amount of (B) is preferably 0.5 to 10 parts by weight, more preferably 2 to 8 parts by weight, based on 100 parts by weight of the radically polymerizable component. When the content is 0.5 parts by weight or more, sufficient curability is exhibited, and when the content is 10 parts by weight or less, yellowing of the coating film and deterioration of storage stability can be prevented without excessive addition. Examples of commercially available products include Omnirad 184 and 2959 (trade name: manufactured by IGM Resins).

In the present invention, the acrylic polymer (C) may be further blended. By blending (C), even when applied with a thick film (for example, 10 μm or more), the curing shrinkage can be alleviated and the adhesion to the substrate can be stabilized. In particular, when the biomass plastic base material is a molded product, it is preferable to mix it. Examples of the monomer constituting (C) include (meth) acrylate, (meth) acrylic acid, vinyl compounds and the like, and they can be used alone or in combination of two or more. Among these, a copolymer composed of (meth) acrylate and (meth) acrylic acid is preferable in terms of adhesion to a bioplastic substrate and compatibility with (A), and C1 to 8 ( A copolymer composed of meth) acrylate and methacrylic acid is more preferable, and a copolymer composed of C1 to 8 methacrylate and methacrylic acid is particularly preferable in that the glass transition point can be increased.

The weight average molecular weight (hereinafter referred to as Mw) of (C) is preferably 10,000 to 50,000, more preferably 20,000 to 40,000, and particularly preferably 25,000 to 35,000. When it is 10,000 or more, the hardness of the cured film can be sufficiently increased, and when it is 50,000 or less, it becomes easy to adjust the viscosity to be suitable for workability. Mw was measured and calculated by gel permeation chromatography using a tetrahydrofuran eluent on a column using a filler based on styrenedivinylbenzene to measure and calculate the molecular weight in terms of standard polystyrene.

The blending amount of (C) is preferably 30 parts by weight or less with respect to 100 parts by weight of (A), and more preferably 5 to 25 parts by weight when applied to a molded product. When the amount is 5 parts by weight or more, sufficient adhesion to the base material can be ensured even if a thick film is formed, and when the amount is 30 parts by weight or less, sufficient steel wool resistance can be ensured. As a commercially available product, there is Z-700BA-2 (trade name: manufactured by Aica Kogyo Co., Ltd., a copolymer of C1 to 8 methacrylate and methacrylic acid, Mw31,000).

In the present invention, the (meth) acrylate monomer (D) may be further blended. (D) is preferably bifunctional or higher in terms of reactivity, and is preferably hexafunctional or lower in terms of reducing curing shrinkage. For example, examples of the chain alkyl monomer include (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa. The (meth) acrylate is dimethylol tricyclodecane diacrylate as the alicyclic monomer, hydrogenated bisphenol A di (meth) acrylate, and pentaerythritol tri (meth) acrylate and dipentaerythritol tetra (meth) as the monomer having a hydroxyl group. Meta) acrylate can be mentioned, and can be used alone or in combination of two or more. Among these, alicyclic monomers having good adhesion to a biomass plastic substrate and high rigidity are preferable, and dimethyloltricyclodecanediacrylate is particularly preferable.

The blending amount of (D) is preferably 30 parts by weight or less, more preferably 25 parts by weight or less, based on 100 parts by weight of (A). When the content is 30 parts by weight or less, sufficient adhesion to the base material can be ensured, and the degree of biomass can be maintained high. In particular, when dimethylol tricyclodecane acrylate is used, the curing shrinkage can be reduced without lowering the comparative hardness and SW resistance, and the adhesion to the substrate can be stabilized.

In the present invention, an oligomer having a photopolymerizable functional group may be further blended. For example, urethane (meth) acrylate (excluding (a2)), epoxy (meth) acrylate, polyester (meth) acrylate, acrylic (meth) acrylate and the like can be mentioned, and can be used alone or in combination of two or more. ..

In addition, if necessary, the composition includes surface conditioners, light stabilizers, polymerization inhibitors, wetting agents, antioxidants, curing aids, silane coupling agents, plasticizers, and more. Additives such as sensitizers, antifoaming agents, flame retardants, inorganic fillers, organic fine particles, colorants such as pigments, dyes and pigments, antibacterial agents, and antiviral agents can be used in combination.

The surface adjusting agent is blended for the purpose of improving the leveling property after coating and imparting antifouling property (fingerprint resistance) and water repellency. Fluorine having a reactive functional group that polymerizes with (A) and (D) in that the effect can be maintained for a long period of time without being removed from the cured film over time. It is preferably a system, a silicone system, or a fluorosilicone system.

The blending amount of the surface conditioner with respect to 100 parts by weight of the photocurable component is preferably 0.01 to 3.0 parts by weight, more preferably 0.05 to 1.0 part by weight. By blending in this range, it is possible to sufficiently adjust the surface without excessive addition. Commercially available products include X-71-1203M (trade name: Shin-Etsu Chemical Co., Ltd., solid content 20%), Megafuck RS-851, RS-852 (trade name: all manufactured by DIC) for fluorosilicone compounds. , Opstar TU2225 (trade name: manufactured by JSR Corporation), and examples of the commercially available fluorocompound product include KY-1216 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd., solid content 20%).

Examples of the biomass plastic base material to which the HC resin composition of the present invention is applied include biomass PC resin and biomass polyester resin. Among these, the present HC resin composition adheres to the biomass PC base material. Especially excellent in sex. Examples of the biomass PC base material include a biomass polycarbonate film or sheet, as well as molded products manufactured by extrusion molding, injection molding, vacuum forming, blow molding, or the like.

When coating the HC resin composition of the present invention, it may be diluted with a solvent in order to improve the coating characteristics. Examples of the diluting solvent include alcohol solvents such as ethanol, n-propyl alcohol, isopropyl alcohol (hereinafter IPA), n-butyl alcohol, isobutyl alcohol and diacetone alcohol, acetone, methyl ethyl ketone (hereinafter MEK), methyl isobutyl ketone and cyclohexanone. Examples thereof include a ketone solvent such as, an ester solvent such as ethyl acetate and butyl acetate, and an ether solvent such as PGM, diethyl ether and diisopropyl ether, which can be used alone or in combination of two or more. The solid content at the time of dilution is exemplified as 5 to 95%, but it is not particularly specified and can be appropriately set so as to have a viscosity that is easy to apply.

The method for applying the HC resin composition of the present invention is not particularly limited, and for flat surfaces such as films and sheets, known spray coats, roll coats, die coats, air knife coats, blade coats, and spin coats are used. , Reverse coat, gravure coat, wire bar, etc. or gravure printing, screen printing, offset printing, inkjet printing, etc. can be used, and spray coating is applied to those with uneven surfaces instead of flat shapes such as molded products. The method is useful. Further, this method is excellent as a method capable of applying a large area even to a planar shape without making a large capital investment.

The coating film thickness of the HC resin composition may be, but is not limited to, 0.5 μm to 50 μm when dried. However, when the film is coated, it is preferably 1 to 10 μm for the purpose of preventing warpage due to curing shrinkage.

After applying the HC resin composition of the present invention, it is cured using an ultraviolet irradiator. Examples of the light source for irradiating ultraviolet rays include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, carbon arc lamps, xenon lamps, metal halide lamps, electrodeless ultraviolet lamps, LED lamps, and the like. An irradiation intensity of 500 mW / cm ² to 3000 mW / cm ² and an integrated light amount of 50 to 2,000 mJ / cm ² are exemplified. The atmosphere to be irradiated may be air or an inert gas such as nitrogen or argon, but curing in the inert gas is preferable in order to prevent the curing inhibition by oxygen. If it is difficult to set the environment of the inert gas atmosphere, a release film may be attached immediately after application and the film may be cured in a state where contact between the coating film surface and air is blocked.

The flexibility of the cured film obtained by curing the HC resin composition of the present invention is preferably 10 mm or less, more preferably 8 mm or less, and particularly preferably 6 mm or less. Flexibility correlates with the adhesion to the substrate when the film is thickened, and when the variation in coating film thickness is relatively large as in the spray coating method, if the flexibility is good, strain due to curing shrinkage Is relaxed, and the adhesion to the base material is also improved.

A laminate having a cured layer obtained by applying the HC resin composition of the present invention to a biomass plastic film or sheet and curing it by irradiation with ultraviolet rays can be used for a hard coat film or the like of a liquid crystal screen constituting an optical display device. .. Further, a decorative layer can be further added and used for a resin molded body such as insert molding.

Hereinafter, the present invention will be described in detail based on Examples and Comparative Examples, but only specific examples thereof are shown and the present invention is not particularly limited thereto. The blending amount indicates a part by weight, and if not indicated, the measurement was carried out under the condition of room temperature of 25 ° C. and relative humidity of 65%.

Preparation of Urethane Acrylate 1 (hereinafter referred to as "Ureaku 1") 237 parts by weight of IPDI and a catalyst are charged in a 4-neck flask equipped with a thermometer, agitator, a water-cooled condenser, and a nitrogen gas inlet, and the temperature is 60 ° C or lower. 496 parts of M-920 (trade name: manufactured by Toagosei Co., Ltd., hydroxyl value 240 mgKOH / g, biomass glyceringe / triacrylate) was removed in about 1 hour, and then reacted at 60 ° C. for about 8 hours to absorb infrared rays. After confirming that the peak of the residual isocyanate group had disappeared by analysis, the reaction was terminated to obtain ureac 1 (GDA-IPDI-GDA).

Preparation of Urethane Acrylate 2 178 parts by weight of PDI and a catalyst are charged in a four-necked flask equipped with a thermometer, agitator, a water-cooled condenser, and a nitrogen gas inlet, and M-920 (commodity) at 60 ° C or lower. Name: Toagosei Co., Ltd., hydroxyl value 240 mgKOH / g, biomass glycerinji / triacrylate) 496 parts were removed in about 1 hour, then reacted at 60 ° C. for about 8 hours, and the residual isocyanate group was analyzed by infrared absorption analysis. After confirming that the peak had disappeared, the reaction was terminated to obtain ureac 2 (GDA-PDI-GDA).

Preparation of Urethane Acrylate 3 163 parts by weight of HDI and a catalyst are charged in a 4-necked flask equipped with a thermometer, agitator, a water-cooled condenser, and a nitrogen gas inlet, and M-920 (commodity) at 60 ° C or lower. Name: Toagosei Co., Ltd., hydroxyl value 240 mgKOH / g, biomass glycerinji / triacrylate) 496 parts were removed in about 1 hour, then reacted at 60 ° C. for about 8 hours, and the residual isocyanate group was analyzed by infrared absorption analysis. After confirming that the peak had disappeared, the reaction was terminated to obtain ureac 3 (GDA-HDI-GDA).

Preparation of Urethane Acrylate 4 Add 200 parts by weight of ethylene glycol (hereinafter referred to as EG) and 786 parts by weight of IPDI (NCO group 37.5%) in MEK solvent (solid content 50%) together with a catalyst at 90 ° C. The mixture was stirred and reacted for 120 minutes, and the reaction was terminated when the peak of the isocyanate group reached a predetermined amount in the infrared absorption analysis. Next, as (a1), 136 parts by weight of M-920 (trade name: manufactured by Toagosei Co., Ltd., hydroxyl value 240 mgKOH / g, biomass glycerin di / triacrylate) was added dropwise at 70 ° C. or lower in 60 minutes, and the mixture was stirred and reacted. After that, the mixture was stirred and reacted at 80 ° C. for 300 minutes, and it was confirmed by infrared absorption analysis that the isocyanate group had disappeared. After cooling, the solid content was adjusted to 50% by MEK, and Mw. 4,000 Ureaku 4 (GDA- (IPDI-EG) n-IPDI-GDA) was obtained.

Example 1
M-920 (trade name: Toagosei Co., Ltd., plant-derived biomass glyceringe / triacrylate) is used as (A), and Omnirad2959 (trade name: IGM Resins Co., Ltd., α-hydroxyphenone type) is used as (B). The HC resin composition of Example 1 was prepared by further blending MEK as a diluting solvent so that the solid content was 90%, and stirring until the mixture was uniformly dissolved in the formulation shown in Table 1.

Examples 2 to 11
In addition to the materials used in Example 1, M-930 (trade name: manufactured by Toa Synthetic Co., Ltd., plant-derived biomass glycerin triacrylate) and ureac 1-4 as (A), and Z-700BA-2 as (C). (Product name: Aika Kogyo Co., Ltd., C1-8 methacrylate and methacrylic acid copolymer, Mw31,000) is used as (D) as DPHA (trade name: Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate). And DCP-A (trade name: manufactured by Kyoeisha Chemical Co., Ltd., dimethyloltricyclodecandyacrylate) as a surface conditioner, X-71-1203M (trade name: manufactured by Shinetsu Chemical Industry Co., Ltd., solid content 20%, polymerizable functionality). A fluorosilicone compound having a group) was used, and MEK was used as a diluting solvent. Examples 1 to 7 had a solid content of 90%, and Examples 8 to 11 had a solid content of 30%. , The HC resin compositions of Examples 2 to 11 were prepared by stirring until they were uniformly dissolved with the formulations shown in Table 1.

Comparative Examples 1 to 7
In addition to the materials used in the examples, petroleum-derived glycerin diacrylate NK ester 701A (trade name: manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) was used, and MEK was further added as a diluting solvent so that the solid content was 90%. The HC resin compositions of Comparative Examples 1 to 7 were prepared by stirring until they were uniformly dissolved with the formulations shown in Table 2.

Table 1

Table 2

The evaluation method was as follows.

Preparation of HC film for evaluation <br /> Using the HC resin composition prepared above, DKW # 200KK (trade name: biomass PC film with a thickness of 200 μm made from Durabio manufactured by Ewa Co., Ltd. and Mitsubishi Chemical Co., Ltd.) The film is coated so that the dry film thickness is 6 μm, dried in a constant temperature bath at 30 ° C for 1 minute, and then irradiated with ultraviolet rays so that the output is 1300 mW / cm2 and the integrated light amount is 300 mJ with a high-pressure mercury lamp. Prepared.

Total light transmittance: The HC film for evaluation after UV curing was measured using a haze meter Haze-GARD2 manufactured by Toyo Seiki Seisakusho in accordance with JIS K7361-1.

Haze: The above-mentioned evaluation HC film after UV curing was measured using Haze-GARD2 manufactured by Toyo Seiki Seisakusho Co., Ltd. in accordance with JIS K7361-1.

Adhesion: According to the old JIS K5400, 10 × 10 squares were prepared in 1 mm square and a grid test was performed, and the peeled state of the coating film was confirmed with cellophane tape (specified in JIS Z1522). When the cellophane tape attached to the coating film side was peeled off, the case where the peeled mass was 0 was evaluated as ◯, and the case where even 1 cell was peeled off was evaluated as x. Two types of substrate, biomass PC and PET, were used, and U403 (trade name: Toray Industries, Inc., polyester film, thickness 100 μm) was used as the PET substrate, and the film thickness and curing conditions were the same as those of the biomass PC.

Pencil hardness: Based on JISK5600-5-4 (1999 version), measured with a pencil scratch coating film hardness tester (type P) manufactured by Toyo Seiki Seisakusho with a load of 750 g, and H or more is 〇, less than H. Was set to x.

SW resistance: A load of 1000 g / cm2 is placed on steel wool # 0000 and reciprocated 10 times. The thing was set as x.

Curability: DKW # 200KK (trade name: Biomass PC film with a thickness of 200 μm made from Durabio manufactured by Ewa Co., Ltd. and Mitsubishi Chemical Corporation) is coated so that the dry film thickness is 6 μm, and 30 in a constant temperature bath. After drying at ° C for 1 minute, irradiate with a high-pressure mercury lamp at an output of 1300 mW / cm2, 300 mJ or 1000 mJ, check the touch tack on the surface of the coating film, and if it is cured without tack, it is marked with ○ and not cured. The thing was set as x.

Flexibility: Measured using a cylindrical mandrel bending tester according to JIS K5600-5-1 using an HC film for evaluation. The mandrel was changed to a smaller one until cracking or peeling of the coating film occurred, and the diameter of the mandrel where cracking or peeling occurred for the first time was recorded.

Evaluation results <br /> Table 3

Table 4

Each formulation of the example was good in all aspects of total light transmittance, haze, adhesion, pencil hardness, SW resistance, curability and flexibility.

On the other hand, Comparative Examples 1 to 4 using petroleum-derived polyfunctional glycerin (meth) acrylate have poor curability, poor SW resistance and pencil hardness, and petroleum-derived (meth) acrylate monomer not containing (A). In Comparative Examples 5 to 7 using the above, the adhesion to the substrate and the flexibility were insufficient, and none of the formulations was suitable for the present invention.

Claims (9)

A coating agent applied to a biomass polycarbonate base material,
A composition comprising glycerin diacrylate and / or glycerin triacrylate (a1) of biomass, a photopolymerization initiator (B), an acrylic polymer (C) or a bifunctional or higher alicyclic monomer .
Or,
A composition comprising a urethane (meth) acrylate (a2) derived from (a1) having an OH group and a photopolymerization initiator (B).
The blending amount of the (C) or bifunctional or higher alicyclic monomer is
In the case of (C), it is 5 to 30 parts by weight with respect to 100 parts by weight of (a1) .
In the case of a bifunctional or higher alicyclic monomer, (a1) 30 parts by weight or less with respect to 100 parts by weight.
A hard-coated resin composition characterized by being. The above (a2) is characterized by being a urethane (meth) acrylate (a22) obtained by reacting a polyisocyanate with a polyol in advance and reacting a prepolymer having an isocyanate group at the end with (a1) having an OH group. The hard coat resin composition according to claim 1. The hardcourt resin composition according to claim 1, wherein the (a2) is a urethane (meth) acrylate (a21) obtained by reacting (a1) having an OH group with a polyisocyanate. The hardcourt resin composition according to claim 1, wherein the weight average molecular weight of (C) is 20,000 to 50,000 . The hard coat resin composition according to any one of claims 1 to 4, wherein the biomass polycarbonate base material is one selected from the group consisting of a biomass polycarbonate film, a biomass polycarbonate sheet, and a biomass polycarbonate molded body. A laminate having a cured layer of the hardcourt resin composition according to any one of claims 1 to 4 on a biomass polycarbonate film or a biomass polycarbonate sheet. A resin molded product using the laminate according to claim 6. A resin molded product having a cured layer of the hard coat resin composition according to any one of claims 1 to 4 on a biomass polycarbonate resin molded product. An optical display device using the laminated body according to claim 6 or the resin molded body according to any one of claims 7 or 8.