WO2014208323A1 - Resin compositions for forming hard coating layer - Google Patents

Resin compositions for forming hard coating layer Download PDF

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Publication number
WO2014208323A1
WO2014208323A1 PCT/JP2014/065239 JP2014065239W WO2014208323A1 WO 2014208323 A1 WO2014208323 A1 WO 2014208323A1 JP 2014065239 W JP2014065239 W JP 2014065239W WO 2014208323 A1 WO2014208323 A1 WO 2014208323A1
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Prior art keywords
meth
acrylate
hard coat
coat layer
acrylic polymer
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PCT/JP2014/065239
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French (fr)
Japanese (ja)
Inventor
美沙樹 松村
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横浜ゴム株式会社
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Priority to CN201480033519.8A priority Critical patent/CN105324687A/en
Priority to JP2015523958A priority patent/JPWO2014208323A1/en
Priority to KR1020157034836A priority patent/KR20160025505A/en
Publication of WO2014208323A1 publication Critical patent/WO2014208323A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • G02B1/105—
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/584—Scratch resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment

Definitions

  • the present invention relates to a resin composition for forming a hard coat layer.
  • a touch panel is attached to a flat panel display such as a personal computer, a mobile phone, a portable game device, and an ATM have begun to be commercialized. It is known that such a touch panel is provided with a hard coat layer on the surface for the purpose of imparting antifouling property, slipperiness, scratch resistance and the like.
  • Patent Document 1 includes a “hard coat film including a base sheet and a hard coat layer formed on at least one surface of the base sheet,
  • the hard coat layer includes a fluorine-based compound having a (meth) acryloyl group at a terminal, a polysiloxane compound having a (meth) acryloyl group at a terminal, a polyfunctional (meth) acryl monomer, and a photopolymerization initiator.
  • an object of the present invention is to provide a resin composition for forming a hard coat layer, which can form a hard coat layer having excellent antifouling properties and slipperiness and excellent scratch resistance.
  • the present inventor uses a resin composition containing a polyfunctional urethane (meth) acrylate and a silicone graft acrylic polymer exhibiting a predetermined fluorine compound and a specific glass transition temperature.
  • a hard coat layer having excellent antifouling properties and slipperiness and excellent scratch resistance can be formed, and the present invention has been completed. That is, it has been found that the above problem can be solved by the following configuration.
  • the content of the fluorine compound (B) is 0.3 to 3 parts by mass with respect to 100 parts by mass of the (meth) acrylate monomer (A), as described in (1) or (2) above Hard coat layer forming resin composition.
  • a resin composition for forming a hard coat layer capable of forming a hard coat layer having good antifouling properties and slipperiness and excellent scratch resistance.
  • FIG. 1 is a cross-sectional view schematically showing an example of the laminate of the present invention.
  • the resin composition for forming a hard coat layer of the present invention (hereinafter also simply referred to as “the composition of the present invention”) is a polyfunctional urethane (meth) acrylate having 3 or more (meth) acryloyloxy groups in the molecule.
  • the antifouling property and slipping property are improved, and a hard coat layer having excellent scratch resistance can be formed.
  • This is not clear in detail, but is estimated to be as follows. That is, by containing the fluorine compound (B), it is considered that fluorine is arranged (bleeded) on the outermost surface of the hard coat layer after curing, and exhibits excellent antifouling properties and scratch resistance.
  • the (meth) acrylate monomer (A) contained in the composition of the present invention has a urethane bond and has 3 or more, preferably 4 or more, more preferably 6 to 10
  • the monomer component is not particularly limited as long as it is a monomer component containing at least a polyfunctional urethane (meth) acrylate (A1) having a (meth) acryloyloxy group.
  • (meth) acryloyloxy group means an acryloyloxy group (CH 2 ⁇ CHCOO—) or a methacryloyloxy group (CH 2 ⁇ C (CH 3 ) COO—), and “(meth) “Acrylate” shall mean acrylate or methacrylate.
  • polyfunctional urethane (meth) acrylate (A1) examples include those having a urethane bond in the main chain and having three or more (meth) acryloyloxy groups bonded to the terminal or side chain of the main chain. It is done.
  • the polyfunctional urethane (meth) acrylate (A1) includes a polyol compound (a1) having two or more hydroxyl groups in one molecule, a polyisocyanate compound (a2), and a hydroxyl group in one molecule.
  • the reactive product of the polyol compound (a1), the polyisocyanate compound (a2), and the hydroxy (meth) acrylate (a3) is reacted with the polyol compound (a1) and the polyisocyanate compound (a2) to form an isocyanate group.
  • This is a product obtained by reacting hydroxy (meth) acrylate (b3) after producing a so-called urethane prepolymer having s.
  • the reactive product of the polyisocyanate compound (a2) and the hydroxy (meth) acrylate (a3) reacts the isocyanate group of the polyisocyanate compound (a2) with the hydroxyl group of the hydroxy (meth) acrylate (a3).
  • the resulting product reacts the isocyanate group of the polyisocyanate compound (a2) with the hydroxyl group of the hydroxy (meth) acrylate (a3).
  • the polyol compound (a1) is not particularly limited as long as it has two or more hydroxyl groups.
  • the polyol compound include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 3,3′-diene.
  • examples include methylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol (PTMG), polycarbonate diol, and lactone diol. These may be used alone or in combination of two or more. May be.
  • the polyisocyanate compound (a2) is not particularly limited as long as it has two or more isocyanate groups in the molecule.
  • Specific examples of the polyisocyanate compound include TDI (for example, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI)), MDI ( For example, 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI)), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diene Aromatic polyisocyanates such as isocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), trip
  • aliphatic polyisocyanates and alicyclic polyisocyanates are preferable, and HDI, IPDI, hydrogenated XDI, and hydrogenated MDI are more preferable.
  • the hydroxy (meth) acrylate (a3) is not particularly limited as long as it is a hydroxy (meth) acrylate having a hydroxyl group and a (meth) acryloyloxy group.
  • Specific examples of the compound whose skeleton is mono- or polypentaerythritol include pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth). ) Acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
  • HSA 2-hydroxyethyl acrylate
  • HEMA 2-hydroxyethyl methacrylate
  • 2-hydroxypropyl acrylate 2-hydroxybutyl acrylate
  • penta from the viewpoint of availability, reactivity, compatibility, and the like
  • Erythritol triacrylate, dipentaerythritol hexaacrylate and the like can be suitably used.
  • (meth) acrylate monomers for example, a compound having 3 or more (meth) acryloyloxy groups in one molecule (however, multifunctional And the like (excluding those corresponding to urethane (meth) acrylate (A1)).
  • the compound having three (meth) acryloyloxy groups in one molecule include, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol tri (meth).
  • An acrylate etc. are mentioned.
  • Specific examples of the compound having four (meth) acryloyloxy groups in one molecule include pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and tripentaerythritol tetra (meth).
  • An acrylate etc. are mentioned.
  • Specific examples of the compound having 5 or more (meth) acryloyloxy groups in one molecule include, for example, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol penta ( (Meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, etc. are mentioned.
  • the content of the polyfunctional urethane (meth) acrylate (A1) in the (meth) acrylate monomer (A) is based on the total mass of the (meth) acrylate monomer (A).
  • the content is preferably 10 to 100% by mass, and more preferably 20 to 80% by mass.
  • 100 mass% means using only the said polyfunctional urethane (meth) acrylate (A1) as said (meth) acrylate monomer (A).
  • the fluorine compound (B) contained in the composition of the present invention is not particularly limited as long as it is a fluorine compound having a (meth) acryloyloxy group.
  • the fluorine atom content of the fluorine compound (B) is excellent in optical characteristics, excellent in initial adhesion and wear resistance, and high in hardness, so that 10 in one molecule of the fluorine compound (B). It is preferably ⁇ 50 mass%, more preferably 30 ⁇ 50 mass%.
  • the number of (meth) acryloyloxy groups possessed by the fluorine compound (B) is preferably 1 to 3 because of excellent optical properties, excellent initial adhesion and wear resistance, and high hardness.
  • the fluorine compound (B) is not particularly limited in the structure other than the fluorine atom and the (meth) acryloyloxy group.
  • a hydrocarbon group that can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom Specific examples thereof include hydrocarbon polymers and polymers such as polyethers. Among these, those having a siloxane bond in the molecule are preferable because the slipping property of the hard coat layer formed using the composition of the present invention is better.
  • fluorine compound (B) examples include, for example, SUA1900L series (manufactured by Shin-Nakamura Kagaku Co., Ltd.), UT-3971 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), Megafax RS series, and Defensor TF3000 series (DIC).
  • Light pro-coat AFC3000 (manufactured by Kyoeisha Chemical Co., Ltd.), OPTOOL DAC-HP (manufactured by Daikin Industries), KSN5300 (manufactured by Shin-Etsu Chemical Co., Ltd.), KY-1203 (manufactured by Shin-Etsu Chemical Co., Ltd.), UVHC series (GE Toshiba) Commercial products such as those manufactured by Silicone Co., Ltd. can be used. Of these, KY-1203 (manufactured by Shin-Etsu Chemical Co., Ltd.) having a siloxane bond in the molecule is preferably used.
  • the content of the fluorine compound (B) is preferably 0.3 to 3 parts by mass with respect to 100 parts by mass of the (meth) acrylate monomer (A). More preferably, it is 2 parts by mass.
  • the silicone graft acrylic polymer (C) contained in the composition of the present invention is a silicone graft acrylic polymer having a glass transition temperature of 0 ° C. or less and having a (meth) acryloyloxy group.
  • the glass transition temperature refers to the glass transition temperature (Tmg) determined according to JIS K7121 (1987) using a differential scanning calorimeter (DSC).
  • the “silicone graft acrylic polymer” refers to a polymer obtained by grafting a silicone skeleton to a polymer chain of an acrylic polymer.
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is a divalent aliphatic group having 1 to 6 carbon atoms which may contain an ether group
  • R 3 is a fatty acid having 1 to 30 carbon atoms.
  • a group, an aromatic group, or a hydroxyl group, h represents a number of 0, 1 or 2, and j represents a number of 0 to 500.
  • the silicone graft acrylic polymer (C) is not particularly limited as long as it is a silicone graft acrylic polymer having a (meth) acryloyloxy group, but the skeleton is synthesized by copolymerization of a silicone macromonomer and a (meth) acrylic monomer.
  • the comb-shaped graft polymer is preferably a comb-shaped graft composed of a silicone macromonomer in which the trunk portion is a (meth) acrylic polymer and the branch portion occupies 30 to 40% by mass of the whole. More preferably it is a polymer.
  • silicone macromonomer examples include monomers having a vinyl group at one end of the siloxane skeleton of polydimethylsiloxane, and specific examples thereof include compounds represented by the following formula.
  • (meth) acrylic monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and t-butyl (meth).
  • the method of copolymerizing the silicone macromonomer and the (meth) acrylic monomer described above is not particularly limited.
  • the skeleton of the silicone graft acrylic polymer (C) is formed by radical polymerization using a photopolymerization initiator. Can be synthesized.
  • silicone graft acrylic polymer (C) for example, as shown in Examples described later, commercially available products such as a hydroxyl group-containing silicone graft acrylic polymer (Symac (registered trademark) US-270, manufactured by Toagosei Co., Ltd.) are used. It can also be prepared by introducing an acryloyloxy group by reacting the hydroxyl group with an isocyanate group such as 2-isocyanatoethyl acrylate.
  • the content of the silicone graft acrylic polymer (C) is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylate monomer (A). More preferably, it is 1 to 3 parts by mass.
  • the photopolymerization initiator (D) contained in the composition of the present invention is not particularly limited as long as it can polymerize the above-described (meth) acrylate monomer (A) by light.
  • the photopolymerization initiator (D) include alkylphenone photopolymerization initiators, acetophenones, benzophenones, Michler benzoylbenzoate, ⁇ -amyloxime ester, tetramethylchuram monosulfide, benzoins, and benzoinmethyl.
  • Examples include ethers, thioxanthones, propiophenones, benzyls, and acylphosphine oxides. These may be used alone or in combination of two or more.
  • alkylphenone photopolymerization initiators are preferred from the viewpoints of light stability, high efficiency of photocleavage, surface curability, compatibility, low volatility, and low odor.
  • Specific examples of the alkylphenone photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one and the like.
  • the content of the photopolymerization initiator (D) is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylate monomer (A), and 5 to 10 parts by mass. More preferably, it is part.
  • Organic solvent (E) contained in the composition of the present invention is not particularly limited, and specific examples thereof include alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, decalin; benzene, toluene, xylene, mesitylene, dodecyl.
  • Aromatic hydrocarbons such as benzene and methylnaphthalene; Halides such as methylene chloride, chloroform, ethylene chloride and chlorobenzene; Ethers such as THF, dibutyl ether, dipentyl ether, dihexyl ether, diheptyl ether and dioctyl ether; Ethyl acetate , Esters such as butyl acetate, butyl acrylate, methyl methacrylate, hexamethylene diacrylate, trimethylolpropane triacrylate; methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone Any of the ketones; glycol ethers such as propylene glycol monomethyl ether, methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve; and the like. These may be used alone or in combination of two or more. You may use together.
  • composition of the present invention is within the range not impairing the object of the present invention, for example, a filler, an antioxidant, an antistatic agent, a flame retardant, an adhesion imparting agent, a dispersant, an antioxidant, an antifoaming agent, and a leveling.
  • Additives such as additives, matting agents, light stabilizers, dyes, pigments can be further contained.
  • the production method of the composition of the present invention is not particularly limited, and examples thereof include a method in which the above-described essential components and optional components are placed in a reaction vessel and sufficiently mixed using a stirrer such as a mixing mixer under reduced pressure. .
  • the laminate of the present invention is a laminate having a base material and a hard coat layer provided on the base material, and the hard coat layer is a laminate formed using the composition of the present invention. is there.
  • the said base material is not specifically limited, As a material, a plastics, rubber
  • the plastic may be either a thermosetting resin or a thermoplastic resin. Specific examples thereof include polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, acrylonitrile / styrene copolymer resin, polyvinyl chloride resin, and acetate. Resin, ABS resin, polyester resin, and hard-to-adhesive resin such as polyamide resin are exemplified.
  • FIG. 1 is a cross-sectional view schematically showing a cross section of an example of the laminate of the present invention.
  • the laminate 100 includes a hard coat layer 102 and a base material 104.
  • the thickness of the hard coat layer 102 is not particularly limited, but is preferably 1 to 20 ⁇ m, and more preferably 1 to 10 ⁇ m.
  • the method for producing the laminate of the present invention is not particularly limited.
  • the laminate of the present invention can be produced by applying the composition of the present invention described above on the substrate and curing it after drying.
  • the application method is not particularly limited, and for example, known application methods such as brush coating, flow coating, dip coating, spray coating, and spin coating can be employed.
  • the drying method is not particularly limited, and when a plastic substrate is used as the substrate, for example, the drying conditions are 70 ° C. ⁇ 3 minutes for a polycarbonate substrate and 70 ° C. ⁇ 10 minutes for a PMMA substrate. Is preferred.
  • the curing method is not particularly limited, and examples thereof include a curing method using ultraviolet rays.
  • the irradiation amount of the ultraviolet light used for curing the composition of the present invention is 500 to 3,000 mJ / cm 2 from the viewpoint of fast curability and workability. Is preferred.
  • ⁇ Silicone graft acrylic polymer synthetic product (1)> Hydroxyl group-containing silicone-grafted acrylic polymer (Symac US270, manufactured by Toagosei Co., Ltd.) 100 g, 2-isocyanate ethyl acrylate (Karenz AOI, Showa Denko Co., Ltd.) 3.3 g, methyl ethyl ketone 3.7 g, and a tin catalyst were added at 50 ° C. The reaction was performed for 6 hours.
  • ⁇ Silicone graft acrylic polymer synthetic product (2)> Hydroxyl group-containing silicone-grafted acrylic polymer (Reseta GS1015, manufactured by Toagosei Co., Ltd.) 100 g, 2-isocyanate ethyl acrylate (Karenz AOI, Showa Denko Co., Ltd.) 13.6 g, methyl ethyl ketone 81.7 g, tin catalyst were added, and 50 ° C. for 6 hours. Reacted.
  • Fluorine compound OPTOOL DAC-HP ((meth) acryloyloxy group: present, siloxane bond: none, manufactured by Daikin) Fluorine compound: KY-1203 ((meth) acryloyloxy group: yes, siloxane bond: yes, manufactured by Shin-Etsu) Fluorine compound: Megafac F-555 ((meth) acryloyloxy group: none, siloxane bond: none, manufactured by DIC)
  • Silicone graft acrylic monomer Synthetic product (1) -Silicone graft acrylic monomer: Cymac US270 ((meth) acryloyloxy group: none, manufactured by Toagosei Co., Ltd.) Silicone graft acrylic monomer: Synthetic product (2)
  • Silicone compound Silaplane FM-0711 (one-end methacryloyl group, manufactured by Chisso Corporation) Silicone compound: X-22-1602 (both terminal acryloyl groups, manufactured by Shin-Etsu Chemical Co., Ltd.)
  • Photopolymerization initiator 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals)
  • Organic solvent methyl isobutyl ketone
  • Comparative Example 1 prepared without blending the fluorine compound (B) was inferior in antifouling property and inferior in scratch resistance. Moreover, it turned out that the comparative example 2 prepared without mix
  • the comparative example 5 prepared without mix
  • the comparative example 6 which mix
  • blended the silicone compound are inferior in an optical characteristic (haze) and scratch resistance.
  • the silicone graft acrylic polymer (C) having a (meth) acryloyloxy group was blended with a (meth) acryloyloxy group, the antifouling property and slipping property were all good, and the scratch resistance was excellent. It was found that a coat layer could be formed.
  • Examples 2 to 6 using the fluorine compound (B) having a siloxane bond in the molecule had better slipperiness than Example 1. Further, from the comparison between Example 2 and Example 6, the content of the silicone graft acrylic polymer (C) having a (meth) acryloyloxy group is 100 parts by mass of the (meth) acrylate monomer (A). It was found that the antifouling property and scratch resistance were better when the content was 1 to 5 parts by mass.

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Abstract

　The purpose of the present invention is to provide resin compositions for forming a hard coating layer, with which a hard coating layer of good soiling resistance and slip properties, as well as exceptional scratch resistance, can be formed. These resin compositions for forming a hard coating layer are resin compositions for forming a hard coating layer, containing: (A) a (meth)acrylate monomer including a urethane (meth)acrylate (A1) having in each single molecule three or more (meth)acryloyloxy groups; (B) a fluorine compound having a (meth)acryloyloxy group; (C) a silicone graft acrylic polymer of a glass transition temperature of O℃ or below, having a (meth)acryloyloxy group; (D) a photopolymerization initiator; and (E) an organic solvent.

Description

ハードコート層形成用樹脂組成物Hard coat layer forming resin composition
　本発明は、ハードコート層形成用樹脂組成物に関する。 The present invention relates to a resin composition for forming a hard coat layer.
　近年、パーソナルコンピューター、携帯電話、携帯ゲーム機器、ＡＴＭ等のフラットパネルディスプレイにタッチパネルが付与された製品が数多く商品化され始めている。
　このようなタッチパネルには、防汚性、滑り性、耐傷性などを付与することを目的としたハードコート層を表面に設けることが知られている。 In recent years, many products in which a touch panel is attached to a flat panel display such as a personal computer, a mobile phone, a portable game device, and an ATM have begun to be commercialized.
It is known that such a touch panel is provided with a hard coat layer on the surface for the purpose of imparting antifouling property, slipperiness, scratch resistance and the like.
　例えば、特許文献１には、「基材シートと、前記基材シートの少なくとも一方の面に形成されたハードコート層とを備えたハードコートフィルムであって、
　前記ハードコート層が、末端に（メタ）アクリロイル基を有するフッ素系化合物、末端に（メタ）アクリロイル基を有するポリシロキサン系化合物、多官能（メタ）アクリルモノマー、光重合開始剤を含むハードコート層形成用組成物を活性エネルギー線で硬化した硬化物であって、
　前記ハードコートフィルムを蛍光X線（XRF）解析して得られたフッ素原子およびケイ素原子のKα線のピーク強度をそれぞれaおよびbとしたとき、
　０．０１≦ａ／ｂ≦０．５・・・・・・・・・・・・・・・式（１）
　を満たすハードコートフィルム。」が記載されている。 For example, Patent Document 1 includes a “hard coat film including a base sheet and a hard coat layer formed on at least one surface of the base sheet,
The hard coat layer includes a fluorine-based compound having a (meth) acryloyl group at a terminal, a polysiloxane compound having a (meth) acryloyl group at a terminal, a polyfunctional (meth) acryl monomer, and a photopolymerization initiator. A cured product obtained by curing the forming composition with active energy rays,
When the peak intensity of the Kα ray of fluorine atoms and silicon atoms obtained by fluorescent X-ray (XRF) analysis of the hard coat film is a and b, respectively.
0.01 ≦ a / b ≦ 0.5 (1)
Meet hard coat film. Is described.
特開２０１２－２４０２６６号公報JP 2012-240266 A
　本発明者は、特許文献１に記載されたハードコート層（ハードコートフィルム）について検討したところ、防汚性および滑り性は良好であるが、耐傷性については改善の余地があることを明らかとした。 The inventor examined the hard coat layer (hard coat film) described in Patent Document 1 and found that the antifouling property and slipperiness were good, but there was room for improvement in terms of scratch resistance. did.
　そこで、本発明は、防汚性および滑り性が良好となり、耐傷性に優れるハードコート層を形成することができるハードコート層形成用樹脂組成物を提供することを課題とする。 Therefore, an object of the present invention is to provide a resin composition for forming a hard coat layer, which can form a hard coat layer having excellent antifouling properties and slipperiness and excellent scratch resistance.
　本発明者は、上記課題を解決するため鋭意検討した結果、多官能ウレタン（メタ）アクリレートとともに、所定のフッ素化合物および特定のガラス転移温度を示すシリコーングラフトアクリルポリマーを含有する樹脂組成物を用いることにより、防汚性および滑り性が良好となり、耐傷性に優れるハードコート層を形成できることを見出し、本発明を完成させた。
　すなわち、以下の構成により上記課題を解決できることを見出した。 As a result of intensive studies to solve the above problems, the present inventor uses a resin composition containing a polyfunctional urethane (meth) acrylate and a silicone graft acrylic polymer exhibiting a predetermined fluorine compound and a specific glass transition temperature. Thus, the present inventors have found that a hard coat layer having excellent antifouling properties and slipperiness and excellent scratch resistance can be formed, and the present invention has been completed.
That is, it has been found that the above problem can be solved by the following configuration.
　（１）１分子中に３個以上の（メタ）アクリロイルオキシ基を有する多官能ウレタン（メタ）アクリレート（Ａ１）を含む（メタ）アクリレート単量体（Ａ）と、
　（メタ）アクリロイルオキシ基を有するフッ素化合物（Ｂ）と、
　ガラス転移温度が０℃以下であり、（メタ）アクリロイルオキシ基を有するシリコーングラフトアクリルポリマー（Ｃ）と、
　光重合開始剤（Ｄ）と、
　有機溶媒（Ｅ）と、を含有するハードコート層形成用樹脂組成物。
　（２）上記フッ素化合物（Ｂ）が、分子内にシロキサン結合を有する上記（１）に記載のハードコート層形成用樹脂組成物。
　（３）上記フッ素化合物（Ｂ）の含有量が、上記（メタ）アクリレート単量体（Ａ）１００質量部に対して０．３～３質量部である上記（１）または（２）に記載のハードコート層形成用樹脂組成物。
　（４）上記シリコーングラフトアクリルポリマー（Ｃ）の含有量が、上記（メタ）アクリレート単量体（Ａ）１００質量部に対して１～５質量部である上記（１）～（３）のいずれかに記載のハードコート層形成用樹脂組成物。
　（５）基材と、上記基材上に設けられるハードコート層とを有する積層体であって、
　上記ハードコート層が、上記（１）～（４）のいずれかに記載のハードコート層形成用樹脂組成物を用いて形成された積層体。 (1) a (meth) acrylate monomer (A) containing a polyfunctional urethane (meth) acrylate (A1) having three or more (meth) acryloyloxy groups in one molecule;
A fluorine compound (B) having a (meth) acryloyloxy group;
Silicone graft acrylic polymer (C) having a glass transition temperature of 0 ° C. or lower and having a (meth) acryloyloxy group;
A photopolymerization initiator (D);
A resin composition for forming a hard coat layer, comprising an organic solvent (E).
(2) The resin composition for forming a hard coat layer according to (1), wherein the fluorine compound (B) has a siloxane bond in the molecule.
(3) The content of the fluorine compound (B) is 0.3 to 3 parts by mass with respect to 100 parts by mass of the (meth) acrylate monomer (A), as described in (1) or (2) above Hard coat layer forming resin composition.
(4) Any of (1) to (3) above, wherein the content of the silicone graft acrylic polymer (C) is 1 to 5 parts by mass with respect to 100 parts by mass of the (meth) acrylate monomer (A). A resin composition for forming a hard coat layer according to claim 1.
(5) A laminate having a base material and a hard coat layer provided on the base material,
A laminate in which the hard coat layer is formed using the resin composition for forming a hard coat layer according to any one of (1) to (4).
　本発明によれば、防汚性および滑り性が良好となり、耐傷性に優れるハードコート層を形成することができるハードコート層形成用樹脂組成物を提供することができる。 According to the present invention, it is possible to provide a resin composition for forming a hard coat layer capable of forming a hard coat layer having good antifouling properties and slipperiness and excellent scratch resistance.
図１は本発明の積層体の一例を模式的に表す断面図である。FIG. 1 is a cross-sectional view schematically showing an example of the laminate of the present invention.
［ハードコート層形成用樹脂組成物］
　本発明のハードコート層形成用樹脂組成物（以下、単に「本発明の組成物」ともいう。）は、分子中に３個以上の（メタ）アクリロイルオキシ基を有する多官能ウレタン（メタ）アクリレート（Ａ１）を含む（メタ）アクリレート単量体（Ａ）と、（メタ）アクリロイルオキシ基を有するフッ素化合物（Ｂ）と、ガラス転移温度が０℃以下であり、（メタ）アクリロイルオキシ基を有するシリコーングラフトアクリルポリマー（Ｃ）と、光重合開始剤（Ｄ）と、有機溶媒（Ｅ）と、を含有するハードコート層形成用の樹脂組成物である。 [Resin composition for forming hard coat layer]
The resin composition for forming a hard coat layer of the present invention (hereinafter also simply referred to as “the composition of the present invention”) is a polyfunctional urethane (meth) acrylate having 3 or more (meth) acryloyloxy groups in the molecule. A (meth) acrylate monomer (A) containing (A1), a fluorine compound (B) having a (meth) acryloyloxy group, a glass transition temperature of 0 ° C. or less, and having a (meth) acryloyloxy group It is the resin composition for hard-coat layer formation containing a silicone graft acrylic polymer (C), a photoinitiator (D), and an organic solvent (E).
　本発明においては、上記多官能ウレタン（メタ）アクリレート（Ａ１）を含む（メタ）アクリレート単量体（Ａ）とともに、上記フッ素化合物（Ｂ）および上記シリコーングラフトアクリルポリマー（Ｃ）を含有する樹脂組成物を用いるこことにより、防汚性および滑り性が良好となり、耐傷性に優れるハードコート層を形成することができる。
　これは、詳細には明らかではないが、およそ以下のとおりと推測される。
　すなわち、上記フッ素化合物（Ｂ）を含有することにより、硬化後にハードコート層の最表面にフッ素が配列（ブリード）し、優れた防汚性と耐傷性を発現すると考えられ、また、上記シリコーングラフトアクリルポリマー（Ｃ）を含有することにより、硬化後にハードコート層の表面近傍（表層）にシリコーンが偏在し、優れた滑り性を発現すると考えられる。
　また、この効果（特に耐傷性）は、後述する比較例、特に、ガラス転移温度が０℃より高いシリコーングラフトポリマーを用いた比較例６や、末端に（メタ）アクリロイル基を有するものの、グラフトポリマーに該当しないシリコーンを用いた比較例７および８では発現しない効果であるため、意外な効果であることが分かる。 In the present invention, a resin composition containing the fluorine compound (B) and the silicone graft acrylic polymer (C) together with the (meth) acrylate monomer (A) containing the polyfunctional urethane (meth) acrylate (A1). By using the product, the antifouling property and slipping property are improved, and a hard coat layer having excellent scratch resistance can be formed.
This is not clear in detail, but is estimated to be as follows.
That is, by containing the fluorine compound (B), it is considered that fluorine is arranged (bleeded) on the outermost surface of the hard coat layer after curing, and exhibits excellent antifouling properties and scratch resistance. By containing the acrylic polymer (C), it is considered that silicone is unevenly distributed in the vicinity of the surface (surface layer) of the hard coat layer after curing, and exhibits excellent slipperiness.
Moreover, this effect (especially scratch resistance) is a comparative example to be described later, in particular, comparative example 6 using a silicone graft polymer having a glass transition temperature higher than 0 ° C., and a graft polymer having a (meth) acryloyl group at the terminal. Since it is an effect which does not appear in comparative examples 7 and 8 using silicone which does not correspond to, it turns out that it is an unexpected effect.
　以下に、（メタ）アクリレート単量体（Ａ）、フッ素化合物（Ｂ）、シリコーングラフトアクリルポリマー（Ｃ）、光重合開始剤（Ｄ）および有機溶媒（Ｅ）について詳述する。 Hereinafter, the (meth) acrylate monomer (A), the fluorine compound (B), the silicone graft acrylic polymer (C), the photopolymerization initiator (D), and the organic solvent (E) will be described in detail.
 〔（メタ）アクリレート単量体（Ａ）〕
　本発明の組成物に含有される（メタ）アクリレート単量体（Ａ）は、ウレタン結合を有し、１分子中に３個以上、好ましくは４個以上、より好ましくは６～１０個の（メタ）アクリロイルオキシ基を有する多官能ウレタン（メタ）アクリレート（Ａ１）を少なくとも含む単量体成分であれば特に限定されない。
　ここで、「（メタ）アクリロイルオキシ基」とは、アクリロイルオキシ基（ＣＨ2＝ＣＨＣＯＯ－）またはメタクリロイルオキシ基（ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯ－）を意味するものとし、「（メタ）アクリレート」とは、アクリレートまたはメタクリレートを意味するものとする。 [(Meth) acrylate monomer (A)]
The (meth) acrylate monomer (A) contained in the composition of the present invention has a urethane bond and has 3 or more, preferably 4 or more, more preferably 6 to 10 ( The monomer component is not particularly limited as long as it is a monomer component containing at least a polyfunctional urethane (meth) acrylate (A1) having a (meth) acryloyloxy group.
Here, the “(meth) acryloyloxy group” means an acryloyloxy group (CH 2 ═CHCOO—) or a methacryloyloxy group (CH 2 ═C (CH 3 ) COO—), and “(meth) “Acrylate” shall mean acrylate or methacrylate.
　＜多官能ウレタン（メタ）アクリレート（Ａ１）＞
　多官能ウレタン（メタ）アクリレート（Ａ１）としては、例えば、主鎖にウレタン結合を有し、３個以上の（メタ）アクリロイルオキシ基が主鎖の末端または側鎖に結合しているものが挙げられる。
　具体的には、上記多官能ウレタン（メタ）アクリレート（Ａ１）としては、１分子中に２個以上の水酸基を有するポリオール化合物（ａ１）、ポリイソシアネート化合物（ａ２）、および、１分子中に水酸基と（メタ）アクリロイルオキシ基とを有するヒドロキシ（メタ）アクリレート（ａ３）の反応性生物；ポリイソシアネート化合物（ａ２）、および、１分子中に水酸基と（メタ）アクリロイルオキシ基とを有するヒドロキシ（メタ）アクリレート（ａ３）の反応性生物；等が挙げられる。 <Polyfunctional urethane (meth) acrylate (A1)>
Examples of the polyfunctional urethane (meth) acrylate (A1) include those having a urethane bond in the main chain and having three or more (meth) acryloyloxy groups bonded to the terminal or side chain of the main chain. It is done.
Specifically, the polyfunctional urethane (meth) acrylate (A1) includes a polyol compound (a1) having two or more hydroxyl groups in one molecule, a polyisocyanate compound (a2), and a hydroxyl group in one molecule. And (meth) acryloyloxy group-containing hydroxy (meth) acrylate (a3) reactive product; polyisocyanate compound (a2), and hydroxyl (meth) acryloyloxy group-containing hydroxy (meth) ) Reactive organisms of acrylate (a3);
　ここで、ポリオール化合物（ａ１）、ポリイソシアネート化合物（ａ２）、および、ヒドロキシ（メタ）アクリレート（ａ３）の反応性生物は、ポリオール化合物（ａ１）およびポリイソシアネート化合物（ａ２）を反応させ、イソシアネート基を有するいわゆるウレタンプレポリマーを生成した後に、ヒドロキシ（メタ）アクリレート（ｂ３）を反応させて得られる生成物である。 Here, the reactive product of the polyol compound (a1), the polyisocyanate compound (a2), and the hydroxy (meth) acrylate (a3) is reacted with the polyol compound (a1) and the polyisocyanate compound (a2) to form an isocyanate group. This is a product obtained by reacting hydroxy (meth) acrylate (b3) after producing a so-called urethane prepolymer having s.
　一方、ポリイソシアネート化合物（ａ２）、および、ヒドロキシ（メタ）アクリレート（ａ３）の反応性生物は、ポリイソシアネート化合物（ａ２）のイソシアネート基とヒドロキシ（メタ）アクリレート（ａ３）の水酸基とを反応させて得られる生成物である。 On the other hand, the reactive product of the polyisocyanate compound (a2) and the hydroxy (meth) acrylate (a3) reacts the isocyanate group of the polyisocyanate compound (a2) with the hydroxyl group of the hydroxy (meth) acrylate (a3). The resulting product.
　（ポリオール化合物（ａ１））
　上記ポリオール化合物（ａ１）は、水酸基を２個以上有するものであれば特に限定されない。
　ポリオール化合物としては、例えば、エチレングリコール、プロピレングリコール、ジエチレングリコール、トリエチレングリコール、ブチレングリコール、ネオペンチルグリコール、１，６－ヘキサンジオール、３－メチル－１，５－ペンタンジオール、３，３′－ジメチロールヘプタン、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、ポリテトラメチレンエーテルグリコール（ＰＴＭＧ）、ポリカーボネートジオール、ラクトン系ジオール等が挙げられ、これらを１種単独で用いてもよく、２種以上を併用してもよい。 (Polyol compound (a1))
The polyol compound (a1) is not particularly limited as long as it has two or more hydroxyl groups.
Examples of the polyol compound include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 3,3′-diene. Examples include methylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol (PTMG), polycarbonate diol, and lactone diol. These may be used alone or in combination of two or more. May be.
　（ポリイソシアネート化合物（ａ２））
　上記ポリイソシアネート化合物（ａ２）は、分子内にイソシアネート基を２個以上有するものであれば特に限定されない。
　ポリイソシアネート化合物としては、具体的には、例えば、ＴＤＩ（例えば、２，４－トリレンジイソシアネート（２，４－ＴＤＩ）、２，６－トリレンジイソシアネート（２，６－ＴＤＩ））、ＭＤＩ（例えば、４，４′－ジフェニルメタンジイソシアネート（４，４′－ＭＤＩ）、２，４′－ジフェニルメタンジイソシアネート（２，４′－ＭＤＩ））、１，４－フェニレンジイソシアネート、ポリメチレンポリフェニレンポリイソシアネート、キシリレンジイソシアネート（ＸＤＩ）、テトラメチルキシリレンジイソシアネート（ＴＭＸＤＩ）、トリジンジイソシアネート（ＴＯＤＩ）、１，５－ナフタレンジイソシアネート（ＮＤＩ）、トリフェニルメタントリイソシアネートなどの芳香族ポリイソシアネート；ヘキサメチレンジイソシアネート（ＨＤＩ）、トリメチルヘキサメチレンジイソシアネート（ＴＭＨＤＩ）、リジンジイソシアネート、ノルボルナンジイソシアネート（ＮＢＤＩ）などの脂肪族ポリイソシアネート；トランスシクロヘキサン－１，４－ジイソシアネート、イソホロンジイソシアネート（ＩＰＤＩ）、ビス（イソシアネートメチル）シクロヘキサン（Ｈ6ＸＤＩ）、ジシクロヘキシルメタンジイソシアネート（Ｈ12ＭＤＩ）などの脂環式ポリイソシアネート；これらのカルボジイミド変性ポリイソシアネート；これらのイソシアヌレート変性ポリイソシアネート；等が挙げられ、これらを１種単独で用いてもよく、２種以上を併用してもよい。
　これらのうち、脂肪族ポリイソシアネート、脂環式ポリイソシアネートが好ましく、ＨＤＩ、ＩＰＤＩ、水添ＸＤＩ、水添ＭＤＩがより好ましい。 (Polyisocyanate compound (a2))
The polyisocyanate compound (a2) is not particularly limited as long as it has two or more isocyanate groups in the molecule.
Specific examples of the polyisocyanate compound include TDI (for example, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI)), MDI ( For example, 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI)), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diene Aromatic polyisocyanates such as isocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate; Aliphatic polyisocyanates such as cyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI); transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis (isocyanatomethyl) cyclohexane ( H 6 XDI), alicyclic polyisocyanates such as dicyclohexylmethane diisocyanate (H 12 MDI); these carbodiimide-modified polyisocyanates; these isocyanurate-modified polyisocyanates; and the like. In addition, two or more kinds may be used in combination.
Of these, aliphatic polyisocyanates and alicyclic polyisocyanates are preferable, and HDI, IPDI, hydrogenated XDI, and hydrogenated MDI are more preferable.
　（ヒドロキシ（メタ）アクリレート（ａ３））
　ヒドロキシ（メタ）アクリレート（ａ３）としては、水酸基および（メタ）アクリロイルオキシ基を有するヒドロキシ（メタ）アクリレートであれば特に限定されず、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、骨格がモノまたはポリペンタエリスリトールである化合物等が挙げられ、これらを１種単独で用いてもよく、２種以上を併用してもよい。
　なお、骨格がモノまたはポリペンタエリスリトールである化合物の具体例としては、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられる。
　これらのうち、入手の容易さ、反応性、相溶性等の観点から、２－ヒドロキシエチルアクリレート（ＨＥＡ）、２－ヒドロキシエチルメタクリレート（ＨＥＭＡ）、２－ヒドロキシプロピルアクリレート、２－ヒドロキシブチルアクリレート、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールヘキサアクリレート等を好適に用いることができる。 (Hydroxy (meth) acrylate (a3))
The hydroxy (meth) acrylate (a3) is not particularly limited as long as it is a hydroxy (meth) acrylate having a hydroxyl group and a (meth) acryloyloxy group. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Examples include meth) acrylate, 2-hydroxybutyl (meth) acrylate, compounds having a skeleton of mono- or polypentaerythritol, and these may be used alone or in combination of two or more.
Specific examples of the compound whose skeleton is mono- or polypentaerythritol include pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth). ) Acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
Of these, 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, penta from the viewpoint of availability, reactivity, compatibility, and the like Erythritol triacrylate, dipentaerythritol hexaacrylate and the like can be suitably used.
　＜その他の（メタ）アクリレート単量体＞
　上記多官能ウレタン（メタ）アクリレート（Ａ１）以外の（メタ）アクリレート単量体（Ａ）としては、例えば、１分子中に３個以上の（メタ）アクリロイルオキシ基を有する化合物（ただし、多官能ウレタン（メタ）アクリレート（Ａ１）に相当するものを除く。）等が挙げられる。 <Other (meth) acrylate monomers>
As the (meth) acrylate monomer (A) other than the polyfunctional urethane (meth) acrylate (A1), for example, a compound having 3 or more (meth) acryloyloxy groups in one molecule (however, multifunctional And the like (excluding those corresponding to urethane (meth) acrylate (A1)).
　１分子中に３個の（メタ）アクリロイルオキシ基を有する化合物としては、具体的には、例えば、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート等が挙げられる。 Specific examples of the compound having three (meth) acryloyloxy groups in one molecule include, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol tri (meth). An acrylate etc. are mentioned.
　１分子中に４個の（メタ）アクリロイルオキシ基を有する化合物としては、具体的には、例えば、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、トリペンタエリスリトールテトラ（メタ）アクリレート等が挙げられる。 Specific examples of the compound having four (meth) acryloyloxy groups in one molecule include pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and tripentaerythritol tetra (meth). An acrylate etc. are mentioned.
　１分子中に５個以上の（メタ）アクリロイルオキシ基を有する化合物としては、具体的には、例えば、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリペンタエリスリトールペンタ（メタ）アクリレート、トリペンタエリスリトールヘキサ（メタ）アクリレート、トリペンタエリスリトールヘプタ（メタ）アクリレート、トリペンタエリスリトールオクタ（メタ）アクリレート等が挙げられる。 Specific examples of the compound having 5 or more (meth) acryloyloxy groups in one molecule include, for example, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol penta ( (Meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, etc. are mentioned.
　本発明においては、上記（メタ）アクリレート単量体（Ａ）における上記多官能ウレタン（メタ）アクリレート（Ａ１）の含有量は、上記（メタ）アクリレート単量体（Ａ）の総質量に対して１０～１００質量％であるのが好ましく、２０～８０質量％であるのがより好ましい。
　なお、１００質量％とは、上記（メタ）アクリレート単量体（Ａ）として、上記多官能ウレタン（メタ）アクリレート（Ａ１）のみを用いることを意味する。 In the present invention, the content of the polyfunctional urethane (meth) acrylate (A1) in the (meth) acrylate monomer (A) is based on the total mass of the (meth) acrylate monomer (A). The content is preferably 10 to 100% by mass, and more preferably 20 to 80% by mass.
In addition, 100 mass% means using only the said polyfunctional urethane (meth) acrylate (A1) as said (meth) acrylate monomer (A).
 〔フッ素化合物（Ｂ）〕
　本発明の組成物に含有されるフッ素化合物（Ｂ）は、（メタ）アクリロイルオキシ基を有するフッ素化合物であれば特に限定されない。
　ここで、上記フッ素化合物（Ｂ）が有するフッ素原子の含有量は、光学特性により優れ、初期密着性、耐摩耗性に優れ、硬度が高いという理由から、フッ素化合物（Ｂ）１分子中の１０～５０質量％であるのが好ましく、３０～５０質量％であるのがより好ましい。
　また、上記フッ素化合物（Ｂ）が有する（メタ）アクリロイルオキシ基は、光学特性により優れ、初期密着性、耐摩耗性に優れ、硬度が高いという理由から、１～３個であるのが好ましい。 [Fluorine compound (B)]
The fluorine compound (B) contained in the composition of the present invention is not particularly limited as long as it is a fluorine compound having a (meth) acryloyloxy group.
Here, the fluorine atom content of the fluorine compound (B) is excellent in optical characteristics, excellent in initial adhesion and wear resistance, and high in hardness, so that 10 in one molecule of the fluorine compound (B). It is preferably ˜50 mass%, more preferably 30˜50 mass%.
In addition, the number of (meth) acryloyloxy groups possessed by the fluorine compound (B) is preferably 1 to 3 because of excellent optical properties, excellent initial adhesion and wear resistance, and high hardness.
　上記フッ素化合物（Ｂ）は、フッ素原子および（メタ）アクリロイルオキシ基以外の構造は特に限定されず、例えば、酸素原子、窒素原子、硫黄原子のようなヘテロ原子を有することができる炭化水素基が挙げられ、具体的には、炭化水素ポリマー、ポリエーテルのようなポリマーが挙げられる。
　これらに相当するもののうち、本発明の組成物を用いて形成されるハードコート層の滑り性がより良好となる理由から、分子内にシロキサン結合を有するものが好ましい。 The fluorine compound (B) is not particularly limited in the structure other than the fluorine atom and the (meth) acryloyloxy group. For example, a hydrocarbon group that can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom Specific examples thereof include hydrocarbon polymers and polymers such as polyethers.
Among these, those having a siloxane bond in the molecule are preferable because the slipping property of the hard coat layer formed using the composition of the present invention is better.
　このようなフッ素化合物（Ｂ）としては、具体的には、例えば、ＳＵＡ１９００Ｌシリーズ（新中村科学社製）、ＵＴ－３９７１（日本合成化学工業社製）、メガファックＲＳシリーズおよびディフェンサＴＦ３０００シリーズ（ＤＩＣ社製）、ライトプロコートＡＦＣ３０００（共栄社化学社製）、オプツールＤＡＣ－ＨＰ（ダイキン工業社製）、ＫＳＮ５３００（信越化学社製）、ＫＹ－１２０３（信越化学工業社製）、ＵＶＨＣシリーズ（ＧＥ東芝シリコーン社製）等の市販品を用いることができる。
　これらのうち、分子内にシロキサン結合を有するＫＹ－１２０３（信越化学工業社製）を用いるのが好ましい。 Specific examples of such a fluorine compound (B) include, for example, SUA1900L series (manufactured by Shin-Nakamura Kagaku Co., Ltd.), UT-3971 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), Megafax RS series, and Defensor TF3000 series (DIC). Light pro-coat AFC3000 (manufactured by Kyoeisha Chemical Co., Ltd.), OPTOOL DAC-HP (manufactured by Daikin Industries), KSN5300 (manufactured by Shin-Etsu Chemical Co., Ltd.), KY-1203 (manufactured by Shin-Etsu Chemical Co., Ltd.), UVHC series (GE Toshiba) Commercial products such as those manufactured by Silicone Co., Ltd. can be used.
Of these, KY-1203 (manufactured by Shin-Etsu Chemical Co., Ltd.) having a siloxane bond in the molecule is preferably used.
　本発明においては、上記フッ素化合物（Ｂ）の含有量は、上記（メタ）アクリレート単量体（Ａ）１００質量部に対して０．３～３質量部であるのが好ましく、０．５～２質量部であるのがより好ましい。 In the present invention, the content of the fluorine compound (B) is preferably 0.3 to 3 parts by mass with respect to 100 parts by mass of the (meth) acrylate monomer (A). More preferably, it is 2 parts by mass.
 〔シリコーングラフトアクリルポリマー（Ｃ）〕
　本発明の組成物に含有されるシリコーングラフトアクリルポリマー（Ｃ）は、ガラス転移温度が０℃以下であり、（メタ）アクリロイルオキシ基を有するシリコーングラフトアクリルポリマーである。
　ここで、ガラス転移温度とは、示差走査熱量計（ＤＳＣ）を用いて、ＪＩＳ Ｋ７１２１（１９８７）に従い求めたガラス転移温度（Ｔｍｇ）をいう。
　また、「シリコーングラフトアクリルポリマー」とは、アクリル系ポリマーの高分子鎖にシリコーン骨格をグラフト化させたものをいう。なお、特開２００３－３４７８４号公報に記載された下記式（１）で表されるシリコーンマクロマー（Ａ）は、アクリルポリマーに該当しないため、後述する比較例、すなわち、サイラプレーンＦＭ－０７１１（下記式（１）中、Ｒ1＝メチル基、Ｒ2＝プロピレン鎖、ｈ＝２、ｊ＝１１、Ｒ3＝ブチル基で表される化合物）を用いた比較例７に示すように、ハードコート層の光学特性（ヘイズ）が劣り、耐傷性にも劣る結果となる。 [Silicone graft acrylic polymer (C)]
The silicone graft acrylic polymer (C) contained in the composition of the present invention is a silicone graft acrylic polymer having a glass transition temperature of 0 ° C. or less and having a (meth) acryloyloxy group.
Here, the glass transition temperature refers to the glass transition temperature (Tmg) determined according to JIS K7121 (1987) using a differential scanning calorimeter (DSC).
The “silicone graft acrylic polymer” refers to a polymer obtained by grafting a silicone skeleton to a polymer chain of an acrylic polymer. Since the silicone macromer (A) represented by the following formula (1) described in JP-A-2003-34784 does not correspond to an acrylic polymer, a comparative example described later, that is, Silaplane FM-0711 (described below) As shown in Comparative Example 7 using the formula (1), R 1 = methyl group, R 2 = propylene chain, h = 2, j = 11, and R 3 = butyl group) This results in poor optical properties (haze) of the layer and poor scratch resistance.
Figure JPOXMLDOC01-appb-C000001
（式中、式中でＲ1は水素原子又はメチル基、Ｒ2はエーテル基を含有しても良い炭素数１～６の２価脂肪族基、Ｒ3は炭素原子数１～３０の脂肪族基、芳香族基、又はヒドロキシル基を示し、ｈは０、１又は２の数字を示し、ｊは０～５００の数字を示す。）
Figure JPOXMLDOC01-appb-C000001
Wherein R 1 is a hydrogen atom or a methyl group, R 2 is a divalent aliphatic group having 1 to 6 carbon atoms which may contain an ether group, and R 3 is a fatty acid having 1 to 30 carbon atoms. A group, an aromatic group, or a hydroxyl group, h represents a number of 0, 1 or 2, and j represents a number of 0 to 500.)
　上記シリコーングラフトアクリルポリマー（Ｃ）は、（メタ）アクリロイルオキシ基を有するシリコーングラフトアクリルポリマーであれば特に限定されないが、その骨格は、シリコーンマクロモノマーと（メタ）アクリル系モノマーとの共重合により合成された櫛型グラフトポリマーであるのが好ましく、具体的には、幹部分が（メタ）アクリル系ポリマーであり、枝部分が全体の３０～４０質量％を占めるシリコーンマクロモノマーで構成された櫛形グラフトポリマーであるのがより好ましい。 The silicone graft acrylic polymer (C) is not particularly limited as long as it is a silicone graft acrylic polymer having a (meth) acryloyloxy group, but the skeleton is synthesized by copolymerization of a silicone macromonomer and a (meth) acrylic monomer. The comb-shaped graft polymer is preferably a comb-shaped graft composed of a silicone macromonomer in which the trunk portion is a (meth) acrylic polymer and the branch portion occupies 30 to 40% by mass of the whole. More preferably it is a polymer.
　上記シリコーンマクロモノマーは、例えば、ポリジメチルシロキサンのシロキサン骨格の片末端にビニル基を有する単量体が挙げられ、具体的には、下記式で表される化合物が好適に挙げられる。 Examples of the silicone macromonomer include monomers having a vinyl group at one end of the siloxane skeleton of polydimethylsiloxane, and specific examples thereof include compounds represented by the following formula.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　一方、（メタ）アクリル系モノマーとしては、具体的には、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソアミルアクリレート、イソオクチル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ｎ－ノニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、ベンジル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、２－ジシクロペンテノキシエチル（メタ）アクリレート、トリシクロデカニル（メタ）アクリレート、その水素添加物、イソボニル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、エトキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、メトキシエトキシエチル（メタ）アクリレート、エトキシエトキシエチルアクリレート、フェノキシエチル（メタ）アクリレート、フェノキシプロピル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、（メタ）アクリロイルモルホリン等の１官能性の（メタ）アクリレートモノマーが挙げられる。 On the other hand, specific examples of (meth) acrylic monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and t-butyl (meth). Acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isoamyl acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, n-nonyl (meth) acrylate, cyclohexyl (meth) acrylate , Lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-dicyclopentenoxy Ethyl (meth) acrylate, tricyclodecanyl (meth) acrylate, its hydrogenated product, isobonyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxyethoxyethyl (Meth) acrylate, ethoxyethoxyethyl acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, And monofunctional (meth) acrylate monomers such as 4-hydroxybutyl (meth) acrylate and (meth) acryloylmorpholine.
　上述したシリコーンマクロモノマーと（メタ）アクリル系モノマーとを共重合させる方法は特に限定されず、例えば、光重合開始剤を用いてラジカル重合させることにより、上記シリコーングラフトアクリルポリマー（Ｃ）の骨格を合成することができる。 The method of copolymerizing the silicone macromonomer and the (meth) acrylic monomer described above is not particularly limited. For example, the skeleton of the silicone graft acrylic polymer (C) is formed by radical polymerization using a photopolymerization initiator. Can be synthesized.
　一方、上記シリコーングラフトアクリルポリマー（Ｃ）は、例えば、後述する実施例でも示す通り、水酸基含有のシリコーングラフトアクリルポリマー（サイマック（登録商標）ＵＳ－２７０、東亜合成社製）などの市販品を用い、その水酸基と、２－イソシアネートエチルアクリレートなどのイソシアネート基とを反応させることにより、アクリロイルオキシ基を導入することにより、調製することもできる。 On the other hand, as the silicone graft acrylic polymer (C), for example, as shown in Examples described later, commercially available products such as a hydroxyl group-containing silicone graft acrylic polymer (Symac (registered trademark) US-270, manufactured by Toagosei Co., Ltd.) are used. It can also be prepared by introducing an acryloyloxy group by reacting the hydroxyl group with an isocyanate group such as 2-isocyanatoethyl acrylate.
　本発明においては、上記シリコーングラフトアクリルポリマー（Ｃ）の含有量は、上記（メタ）アクリレート単量体（Ａ）１００質量部に対して１～１０質量部であるのが好ましく、１～５質量部であるのがより好ましく、１～３質量部であるのが更に好ましい。 In the present invention, the content of the silicone graft acrylic polymer (C) is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylate monomer (A). More preferably, it is 1 to 3 parts by mass.
 〔光重合開始剤（Ｄ）〕
　本発明の組成物に含有される光重合開始剤（Ｄ）は、上述した（メタ）アクリレート単量体（Ａ）等を光によって重合させ得るものであれば特に限定されない。
　上記光重合開始剤（Ｄ）としては、例えば、アルキルフェノン系光重合開始剤、アセトフェノン類、ベンゾフェノン類、ミヒラーベンゾイルベンゾエート、α－アミロキシムエステル、テトラメチルチュウラムモノサルファイド、ベンゾイン類、ベンゾインメチルエーテル、チオキサントン類、プロピオフェノン類、ベンジル類、アシルホスフィンオキシド類が挙げられ、これらを１種単独で用いてもよく、２種以上を併用してもよい。 [Photopolymerization initiator (D)]
The photopolymerization initiator (D) contained in the composition of the present invention is not particularly limited as long as it can polymerize the above-described (meth) acrylate monomer (A) by light.
Examples of the photopolymerization initiator (D) include alkylphenone photopolymerization initiators, acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, tetramethylchuram monosulfide, benzoins, and benzoinmethyl. Examples include ethers, thioxanthones, propiophenones, benzyls, and acylphosphine oxides. These may be used alone or in combination of two or more.
　これらのうち、光安定性、光開裂の高効率性、表面硬化性、相溶性、低揮発、低臭気という観点から、アルキルフェノン系光重合開始剤であるのが好ましい。
　アルキルフェノン系光重合開始剤としては、具体的には、例えば、１－ヒドロキシ－シクロヘキシル－フェニル－ケトン、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン等が挙げられる。 Of these, alkylphenone photopolymerization initiators are preferred from the viewpoints of light stability, high efficiency of photocleavage, surface curability, compatibility, low volatility, and low odor.
Specific examples of the alkylphenone photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one and the like.
　本発明においては、上記光重合開始剤（Ｄ）の含有量は、上記（メタ）アクリレート単量体（Ａ）１００質量部に対して１～２０質量部であるのが好ましく、５～１０質量部であるのがより好ましい。 In the present invention, the content of the photopolymerization initiator (D) is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylate monomer (A), and 5 to 10 parts by mass. More preferably, it is part.
 〔有機溶剤（Ｅ）〕
　本発明の組成物に含有される有機溶剤（Ｅ）は特に限定されず、その具体例としては、シクロヘキサン、メチルシクロヘキサン、デカリンなどの脂環式炭化水素類；ベンゼン、トルエン、キシレン、メシチレン、ドデシルベンゼン、メチルナフタレンなどの芳香族炭化水素類；メチレンクロライド、クロロホルム、エチレンクロライド、クロロベンゼンなどのハロゲン化物；ＴＨＦ、ジブチルエーテル、ジペンチルエーテル、ジヘキシルエーテル、ジヘプチルエーテル、ジオクチルエーテルなどのエーテル類；酢酸エチル、酢酸ブチル、アクリル酸ブチル、メタクリル酸メチル、ヘキサメチレンジアクリレート、トリメチロールプロパントリアクリレートなどのエステル類；メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン類；プロピレングリコールモノメチルエーテル、メチルセルソルブ、エチルセルソルブ、プロピルセルソルブ、ブチルセルソルブなどのグリコールエーテル類；等が挙げられ、これらを１種単独で用いてもよく、２種以上を併用してもよい。 [Organic solvent (E)]
The organic solvent (E) contained in the composition of the present invention is not particularly limited, and specific examples thereof include alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, decalin; benzene, toluene, xylene, mesitylene, dodecyl. Aromatic hydrocarbons such as benzene and methylnaphthalene; Halides such as methylene chloride, chloroform, ethylene chloride and chlorobenzene; Ethers such as THF, dibutyl ether, dipentyl ether, dihexyl ether, diheptyl ether and dioctyl ether; Ethyl acetate , Esters such as butyl acetate, butyl acrylate, methyl methacrylate, hexamethylene diacrylate, trimethylolpropane triacrylate; methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone Any of the ketones; glycol ethers such as propylene glycol monomethyl ether, methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve; and the like. These may be used alone or in combination of two or more. You may use together.
 〔その他の添加剤〕
　本発明の組成物は、本発明の目的を損なわない範囲で、例えば、充填剤、老化防止剤、帯電防止剤、難燃剤、接着性付与剤、分散剤、酸化防止剤、消泡剤、レベリング剤、艶消し剤、光安定剤、染料、顔料のような添加剤を更に含有することができる。 [Other additives]
The composition of the present invention is within the range not impairing the object of the present invention, for example, a filler, an antioxidant, an antistatic agent, a flame retardant, an adhesion imparting agent, a dispersant, an antioxidant, an antifoaming agent, and a leveling. Additives such as additives, matting agents, light stabilizers, dyes, pigments can be further contained.
 〔製造方法〕
　本発明の組成物の製造方法は、特に限定されず、例えば、反応容器に上述した必須成分および任意成分を入れ、減圧下で混合ミキサー等のかくはん機を用いて十分に混合する方法が挙げられる。 〔Production method〕
The production method of the composition of the present invention is not particularly limited, and examples thereof include a method in which the above-described essential components and optional components are placed in a reaction vessel and sufficiently mixed using a stirrer such as a mixing mixer under reduced pressure. .
[積層体]
　本発明の積層体は、基材と、上記基材上に設けられるハードコート層とを有する積層体であって、上記ハードコート層が、本発明の組成物を用いて形成された積層体である。
　ここで、上記基材は特に限定されず、その材料としては、例えば、プラスチック、ゴム、ガラス、金属、セラミック等を用いることができ、中でも、プラスチックを用いるのが好ましい。
　上記プラスチックは、熱硬化性樹脂、熱可塑性樹脂のいずれであってもよく、その具体例としては、ポリメチルメタクリレート樹脂、ポリカーボネート樹脂、ポリスチレン樹脂、アクリロニトリル・スチレン共重合樹脂、ポリ塩化ビニル樹脂、アセテート樹脂、ＡＢＳ樹脂、ポリエステル樹脂、ポリアミド樹脂のような難接着性樹脂が挙げられる。 [Laminate]
The laminate of the present invention is a laminate having a base material and a hard coat layer provided on the base material, and the hard coat layer is a laminate formed using the composition of the present invention. is there.
Here, the said base material is not specifically limited, As a material, a plastics, rubber | gum, glass, a metal, a ceramic etc. can be used, for example, It is preferable to use a plastic especially.
The plastic may be either a thermosetting resin or a thermoplastic resin. Specific examples thereof include polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, acrylonitrile / styrene copolymer resin, polyvinyl chloride resin, and acetate. Resin, ABS resin, polyester resin, and hard-to-adhesive resin such as polyamide resin are exemplified.
　次に、本発明の積層体について添付の図面を用いて説明する。
　図１は、本発明の積層体の一例の断面を模式的に示す断面図である。
　図１において、積層体１００は、ハードコート層１０２と基材１０４とを有する。
　ここで、ハードコート層１０２の厚さは特に限定されないが、１～２０μｍであるのが好ましく、１～１０μｍであるのがより好ましい。 Next, the laminated body of this invention is demonstrated using attached drawing.
FIG. 1 is a cross-sectional view schematically showing a cross section of an example of the laminate of the present invention.
In FIG. 1, the laminate 100 includes a hard coat layer 102 and a base material 104.
Here, the thickness of the hard coat layer 102 is not particularly limited, but is preferably 1 to 20 μm, and more preferably 1 to 10 μm.
　本発明の積層体を作製する方法は特に限定されず、例えば、上記基材上に上述した本発明の組成物を塗布し、乾燥後に硬化させることにより作製することができる。
　ここで、上記塗布の方法は特に限定されず、例えば、はけ塗り、流し塗り、浸漬塗り、スプレー塗り、スピンコート等の公知の塗布方法を採用できる。
　また、上記乾燥の方法は特に限定されず、上記基材としてプラスチック基材を使用する場合、例えば、ポリカーボネート基材で７０℃×３分、ＰＭＭＡ基材で７０℃×１０分の乾燥条件であるのが好ましい。
　更に、上記硬化の方法は特に限定されず、例えば、紫外線による硬化方法が挙げられる。本発明の組成物を紫外線照射によって硬化させる場合、本発明の組成物を硬化させる際に使用する紫外線の照射量としては、速硬化性、作業性の観点から、５００～３，０００ｍＪ／ｃｍ2が好ましい。 The method for producing the laminate of the present invention is not particularly limited. For example, the laminate of the present invention can be produced by applying the composition of the present invention described above on the substrate and curing it after drying.
Here, the application method is not particularly limited, and for example, known application methods such as brush coating, flow coating, dip coating, spray coating, and spin coating can be employed.
The drying method is not particularly limited, and when a plastic substrate is used as the substrate, for example, the drying conditions are 70 ° C. × 3 minutes for a polycarbonate substrate and 70 ° C. × 10 minutes for a PMMA substrate. Is preferred.
Furthermore, the curing method is not particularly limited, and examples thereof include a curing method using ultraviolet rays. When the composition of the present invention is cured by ultraviolet irradiation, the irradiation amount of the ultraviolet light used for curing the composition of the present invention is 500 to 3,000 mJ / cm 2 from the viewpoint of fast curability and workability. Is preferred.
　以下に、実施例を挙げて本発明を具体的に説明する。ただし、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
　＜シリコーングラフトアクリルポリマー：合成品（１）＞
　水酸基含有シリコーングラフトアクリルポリマー（サイマックＵＳ２７０、東亞合成社製）１００ｇ、２－イソシアネートエチルアクリレート（カレンズＡＯＩ、昭和電工社製）３．３ｇ、メチルエチルケトン３．７ｇ、および、スズ触媒を添加し、５０℃６時間反応させた。
　フーリエ変換型赤外分光（ＦＴ－ＩＲ）にて、２－イソシアネートエチルアクリレート由来のＮＣＯのピークが消失したことを確認し、固形分３０％のアクリロイルオキシ基を有するシリコーングラフトアクリルポリマー（１）を得た。
　なお、得られたシリコーングラフトアクリルポリマー（１）のガラス転移温度（Ｔｇ）は、－５０℃であった。 <Silicone graft acrylic polymer: synthetic product (1)>
Hydroxyl group-containing silicone-grafted acrylic polymer (Symac US270, manufactured by Toagosei Co., Ltd.) 100 g, 2-isocyanate ethyl acrylate (Karenz AOI, Showa Denko Co., Ltd.) 3.3 g, methyl ethyl ketone 3.7 g, and a tin catalyst were added at 50 ° C. The reaction was performed for 6 hours.
It was confirmed by Fourier transform infrared spectroscopy (FT-IR) that the NCO peak derived from 2-isocyanatoethyl acrylate disappeared, and a silicone graft acrylic polymer (1) having an acryloyloxy group with a solid content of 30% was obtained. Obtained.
The resulting silicone graft acrylic polymer (1) had a glass transition temperature (Tg) of −50 ° C.
　＜シリコーングラフトアクリルポリマー：合成品（２）＞
　水酸基含有シリコーングラフトアクリルポリマー（レゼタＧＳ１０１５、東亞合成社製）１００ｇ、２－イソシアネートエチルアクリレート（カレンズＡＯＩ、昭和電工社製）１３．６ｇ、メチルエチルケトン８１．７ｇ、スズ触媒を添加し、５０℃６時間反応させた。
　フーリエ変換型赤外分光（ＦＴ－ＩＲ）にて、２－イソシアネートエチルアクリレート由来のＮＣＯのピークが消失したことを確認し、固形分３０％のアクリロイルオキシ基を有するシリコーングラフトアクリルポリマー（２）を得た。
　なお、得られたシリコーングラフトアクリルポリマー（２）のガラス転移温度（Ｔｇ）は、１３℃であった。 <Silicone graft acrylic polymer: synthetic product (2)>
Hydroxyl group-containing silicone-grafted acrylic polymer (Reseta GS1015, manufactured by Toagosei Co., Ltd.) 100 g, 2-isocyanate ethyl acrylate (Karenz AOI, Showa Denko Co., Ltd.) 13.6 g, methyl ethyl ketone 81.7 g, tin catalyst were added, and 50 ° C. for 6 hours. Reacted.
It was confirmed by Fourier transform infrared spectroscopy (FT-IR) that the NCO peak derived from 2-isocyanatoethyl acrylate disappeared, and a silicone graft acrylic polymer (2) having an acryloyloxy group with a solid content of 30% was obtained. Obtained.
In addition, the glass transition temperature (Tg) of the obtained silicone graft acrylic polymer (2) was 13 ° C.
［実施例１～６、比較例１～８］
　下記第１表に示す各成分を、同表に示す配合量（単位：質量部）で、かくはん機を用いて混合し、各例の樹脂組成物（以下、単に「組成物」ともいう。）を得た。 [Examples 1 to 6, Comparative Examples 1 to 8]
Each component shown in Table 1 below is mixed in the blending amount (unit: parts by mass) shown in the same table using a stirrer, and the resin composition of each example (hereinafter also simply referred to as “composition”). Got.
 〔評価〕
　得られた各組成物（固形分：６０質量％）を、ＰＥＴフィルム（ルミラーＵ４６、東レ社製、厚さ：１２５μｍ）の片面上に、バーコーターＮｏ．５を用いて塗布した。
　次いで、８０℃で１分乾燥した後、日本電池社製のＧＳ ＵＶ ＳＹＳＴＥＭを用いて、ピーク強度が３００ｍＷ／ｃｍ2、積算光量が３００ｍＪ／ｃｍ2となるようにＵＶ照射を行ってハードコート層（厚さ：５μｍ）を形成し、評価用サンプルを作製した。
　この評価用サンプルを用いて、各特性を以下の方法により評価した。結果を下記第１表に示す。 [Evaluation]
Each composition obtained (solid content: 60% by mass) was placed on one side of a PET film (Lumirror U46, manufactured by Toray Industries, Inc., thickness: 125 μm) with a bar coater No. 5 was applied.
Next, after drying at 80 ° C. for 1 minute, using a GS UV SYSTEM manufactured by Nihon Battery Co., Ltd., UV irradiation is performed so that the peak intensity is 300 mW / cm 2 and the integrated light quantity is 300 mJ / cm 2 , thereby forming a hard coat layer. (Thickness: 5 μm) was formed to prepare a sample for evaluation.
Each characteristic was evaluated by the following method using this sample for evaluation. The results are shown in Table 1 below.
　＜初期密着性＞
　作製した評価用サンプルのハードコート層に、１ｍｍの基盤目１００個（１０×１０）を作り、基盤目上にセロハン粘着テープ（幅１８ｍｍ）を完全に付着させ、直ちにテープの一端を基板に対して直角に保ちながら瞬間的に引き離し、完全に剥がれないで残った基盤目の数を調べた。なお、下記第１表中、「１００／１００」は、全ての碁盤目が剥離しなかったことを表し、「０／１００」は、全ての碁盤目が剥離したことを表す。 <Initial adhesion>
On the hard coat layer of the prepared sample for evaluation, 100 1 mm bases (10 × 10) are made, and a cellophane adhesive tape (width 18 mm) is completely attached on the bases, and one end of the tape is immediately attached to the substrate. While keeping at a right angle, they were pulled apart instantaneously, and the number of bases that remained without being completely removed was examined. In Table 1 below, “100/100” represents that all grids were not peeled off, and “0/100” represents that all grids were peeled off.
　＜耐湿熱密着性＞
　作製した評価用サンプルを８５℃、８５％ＲＨの環境下に５００時間放置した後に、上述した初期密着性と同様の評価を行った。 <Moisture and heat resistant adhesion>
The prepared sample for evaluation was allowed to stand in an environment of 85 ° C. and 85% RH for 500 hours, and then the same evaluation as the above-described initial adhesion was performed.
　＜透明性（ヘイズ）＞
　ＪＩＳ Ｋ７３６１－１:1997に従い、作製した評価用サンプルを正方形（３０ｍｍ×３０ｍｍ）に切り出したものについて、ヘイズメーター（ＨＭ１５０、村上色彩技術研究所社製）を用いてヘイズ率を測定した。 <Transparency (Haze)>
In accordance with JIS K7361-1: 1997, a haze ratio was measured using a haze meter (HM150, manufactured by Murakami Color Research Laboratory Co., Ltd.) for a sample that was cut into a square (30 mm × 30 mm).
　＜滑り性＞
　作製した評価用サンプルのハードコート層の表面をベンコットンを用いて滑らせた。
　その結果、極めて良く滑るものを「Ａ」と評価し、良く滑るものを「Ｂ」と評価し、殆ど滑らないものを「Ｃ」と評価した。 <Slipperiness>
The surface of the hard coat layer of the produced sample for evaluation was slid using Ben cotton.
As a result, those that slipped very well were evaluated as “A”, those that slipped well were evaluated as “B”, and those that did not slip almost were evaluated as “C”.
　＜防汚性＞
　作製した評価用サンプルのハードコート層の表面に油性ペン（マッキー、ゼブラ社製）で線を描き、ベンコットンで拭取れるまでの拭取り回数を測定した。 <Anti-fouling>
A line was drawn on the surface of the hard coat layer of the prepared sample for evaluation with an oil-based pen (Mckey, manufactured by Zebra Co.), and the number of times of wiping until wiping with Ben cotton was measured.
　＜耐傷性＞
　（外観）
　作製した評価用サンプルのハードコート層を、ボンスター＃００００（日本スチールウール社製）のスチールウールを用い、荷重１ｋｇ／ｃｍ2、ストローク３ｃｍ、１０００回往復して擦り、ハードコート層における傷の発生有無を目視で確認した。
　（マジック拭取り）
　作製した評価用サンプルのハードコート層を、ボンスター＃００００（日本スチールウール社製）のスチールウールを用い、荷重１ｋｇ／ｃｍ2、ストローク３ｃｍ、１０００回往復して擦った。
　その後、ハードコート層の表面に油性ペン（マッキー、ゼブラ社製）で線を描き、ベンコットンで拭取れるまでの拭取り回数を測定した。なお、下記第１表中、何回拭いても全く拭取ることができない（薄くもならない）については、「×」と評価している。 <Scratch resistance>
(appearance)
The hard coat layer of the prepared sample for evaluation was rubbed with a steel wool of Bonstar # 0000 (manufactured by Nippon Steel Wool Co., Ltd.) with a load of 1 kg / cm 2 , a stroke of 3 cm, and reciprocated 1000 times to generate scratches in the hard coat layer. The presence or absence was confirmed visually.
(Magic wipe)
The hard coat layer of the produced sample for evaluation was rubbed by reciprocating 1000 times with a load of 1 kg / cm 2 and a stroke of 3 cm using steel wool of Bonstar # 0000 (manufactured by Nippon Steel Wool Co., Ltd.).
Thereafter, a line was drawn on the surface of the hard coat layer with an oil-based pen (Mckey, manufactured by Zebra Co.), and the number of times of wiping until wiping with Ben cotton was measured. In addition, in Table 1 below, a case where it cannot be wiped at all (it cannot be thinned) is evaluated as “x”.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　上記第１表に示す成分は、以下に示す通りである。
　・（メタ）アクリレート：ジペンタエリスリトールヘキサアクリレート（ミラマーＭ６００、Miwon社製）
　・（メタ）アクリレート：ＨＤＩ系多官能ウレタン（メタ）アクリレート（ＮＸ１０３－２１１、（メタ）アクリロイルオキシ基：１２個、亜細亜工業社製）
　・（メタ）アクリレート：ＩＰＤＩ系多官能ウレタン（メタ）アクリレート（ＫＲＭ８２００ＡＥ、（メタ）アクリロイルオキシ基：６個以上、ダイセルサイテック社製）
　・（メタ）アクリレート：Ｈ１２ＭＤＩ系多官能ウレタン（メタ）アクリレート（ＮＸ１０３－１１２ＶＥ、（メタ）アクリロイルオキシ基：６個、亜細亜工業社製） The components shown in Table 1 are as shown below.
・ (Meth) acrylate: Dipentaerythritol hexaacrylate (Miramar M600, manufactured by Miwon)
・ (Meth) acrylate: HDI-based polyfunctional urethane (meth) acrylate (NX103-211, (meth) acryloyloxy groups: 12, manufactured by Asia Industrial Co., Ltd.)
・ (Meth) acrylate: IPDI polyfunctional urethane (meth) acrylate (KRM8200AE, (meth) acryloyloxy group: 6 or more, manufactured by Daicel Cytec Co., Ltd.)
-(Meth) acrylate: H12MDI polyfunctional urethane (meth) acrylate (NX103-112VE, (Meth) acryloyloxy group: 6 pieces, manufactured by Asia Industrial Co., Ltd.)
　・フッ素化合物：オプツールＤＡＣ－ＨＰ（（メタ）アクリロイルオキシ基：あり、シロキサン結合：なし、ダイキン社製）
　・フッ素化合物：ＫＹ－１２０３（（メタ）アクリロイルオキシ基：あり、シロキサン結合：あり、信越社製）
　・フッ素化合物：メガファックＦ－５５５（（メタ）アクリロイルオキシ基：なし，シロキサン結合：なし、ＤＩＣ社製） Fluorine compound: OPTOOL DAC-HP ((meth) acryloyloxy group: present, siloxane bond: none, manufactured by Daikin)
Fluorine compound: KY-1203 ((meth) acryloyloxy group: yes, siloxane bond: yes, manufactured by Shin-Etsu)
Fluorine compound: Megafac F-555 ((meth) acryloyloxy group: none, siloxane bond: none, manufactured by DIC)
　・シリコーングラフトアクリルモノマー：合成品（１）
　・シリコーングラフトアクリルモノマー：サイマックＵＳ２７０（（メタ）アクリロイルオキシ基：なし，東亞合成社製）
　・シリコーングラフトアクリルモノマー：合成品（２） Silicone graft acrylic monomer: Synthetic product (1)
-Silicone graft acrylic monomer: Cymac US270 ((meth) acryloyloxy group: none, manufactured by Toagosei Co., Ltd.)
Silicone graft acrylic monomer: Synthetic product (2)
　・シリコーン化合物：サイラプレーンＦＭ－０７１１（片末端メタクリロイル基、チッソ社製）
　・シリコーン化合物：Ｘ－２２－１６０２（両末端アクリロイル基、信越化学社製） Silicone compound: Silaplane FM-0711 (one-end methacryloyl group, manufactured by Chisso Corporation)
Silicone compound: X-22-1602 (both terminal acryloyl groups, manufactured by Shin-Etsu Chemical Co., Ltd.)
　・光重合開始剤：１－ヒドロキシ－シクロヘキシル－フェニル－ケトン（イルガキュア１８４、チバスペシャルティケミカルズ社製）
　・有機溶剤：メチルイソブチルケトン Photopolymerization initiator: 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals)
Organic solvent: methyl isobutyl ketone
　上記第１表に示す結果から、フッ素化合物（Ｂ）を配合せずに調製した比較例１は、防汚性に劣り、耐傷性も劣ることが分かった。
　また、シリコーングラフトアクリルポリマー（Ｃ）を配合せずに調製した比較例２は、滑り性が劣ることが分かった。
　また、（メタ）アクリロイル基を有していないフッ素化合物や、（メタ）アクリロイル基を有していないシリコーングラフトアクリルポリマーを配合した比較例３および４は、いずれも耐傷性が劣ることが分かった。
　また、（メタ）アクリレート単量体（Ａ）として多官能ウレタン（メタ）アクリレート（Ａ１）を配合せずに調製した比較例５は、耐湿熱密着性が劣ることが分かった。
　また、Ｔｇが０℃より高いシリコーングラフトアクリルポリマーを配合した比較例６は、耐傷性に劣ることが分かった。
　また、シリコーングラフトアクリルポリマー（Ｃ）に代えて、シリコーン化合物を配合した比較例７および８は、いずれも光学特性（ヘイズ）や耐傷性が劣ることが分かった。 From the results shown in Table 1, it was found that Comparative Example 1 prepared without blending the fluorine compound (B) was inferior in antifouling property and inferior in scratch resistance.
Moreover, it turned out that the comparative example 2 prepared without mix | blending a silicone graft acrylic polymer (C) is inferior in slipperiness.
Moreover, it turned out that both the comparative examples 3 and 4 which mix | blended the fluorine compound which does not have a (meth) acryloyl group, and the silicone graft acrylic polymer which does not have a (meth) acryloyl group are inferior in scratch resistance. .
Moreover, it turned out that the comparative example 5 prepared without mix | blending polyfunctional urethane (meth) acrylate (A1) as a (meth) acrylate monomer (A) is inferior in heat-and-moisture resistant adhesiveness.
Moreover, it turned out that the comparative example 6 which mix | blended the silicone graft acrylic polymer whose Tg is higher than 0 degreeC is inferior to scratch resistance.
Moreover, it turned out that it replaces with a silicone graft | grafting acrylic polymer (C), and both the comparative examples 7 and 8 which mix | blended the silicone compound are inferior in an optical characteristic (haze) and scratch resistance.
　これに対し、１分子中に３個以上の（メタ）アクリロイルオキシ基を有する多官能ウレタン（メタ）アクリレート（Ａ１）と、（メタ）アクリロイルオキシ基を有するフッ素化合物（Ｂ）と、ガラス転移温度が０℃以下であり、（メタ）アクリロイルオキシ基を有するシリコーングラフトアクリルポリマー（Ｃ）とを配合した実施例１～６は、いずれも防汚性および滑り性が良好となり、耐傷性に優れるハードコート層を形成できることが分かった。
　特に、分子内にシロキサン結合を有するフッ素化合物（Ｂ）を用いた実施例２～６は、実施例１と比較して、滑り性がより良好となることが分かった。
　また、実施例２と実施例６との対比から、（メタ）アクリロイルオキシ基を有するシリコーングラフトアクリルポリマー（Ｃ）の含有量が、（メタ）アクリレート単量体（Ａ）１００質量部に対して１～５質量部であると、防汚性および耐傷性がより良好となることが分かった。 In contrast, a polyfunctional urethane (meth) acrylate (A1) having three or more (meth) acryloyloxy groups in one molecule, a fluorine compound (B) having a (meth) acryloyloxy group, and a glass transition temperature. In Examples 1 to 6, in which the silicone graft acrylic polymer (C) having a (meth) acryloyloxy group was blended with a (meth) acryloyloxy group, the antifouling property and slipping property were all good, and the scratch resistance was excellent. It was found that a coat layer could be formed.
In particular, it was found that Examples 2 to 6 using the fluorine compound (B) having a siloxane bond in the molecule had better slipperiness than Example 1.
Further, from the comparison between Example 2 and Example 6, the content of the silicone graft acrylic polymer (C) having a (meth) acryloyloxy group is 100 parts by mass of the (meth) acrylate monomer (A). It was found that the antifouling property and scratch resistance were better when the content was 1 to 5 parts by mass.
　１００　　積層体
　１０２　　ハードコート層
　１０４　　基材 100 Laminated body 102 Hard coat layer 104 Base material

Claims (5)

  1. 　１分子中に３個以上の（メタ）アクリロイルオキシ基を有する多官能ウレタン（メタ）アクリレート（Ａ１）を含む（メタ）アクリレート単量体（Ａ）と、
    　（メタ）アクリロイルオキシ基を有するフッ素化合物（Ｂ）と、
    　ガラス転移温度が０℃以下であり、（メタ）アクリロイルオキシ基を有するシリコーングラフトアクリルポリマー（Ｃ）と、
    　光重合開始剤（Ｄ）と、
    　有機溶媒（Ｅ）と、を含有するハードコート層形成用樹脂組成物。     (Meth) acrylate monomer (A) containing polyfunctional urethane (meth) acrylate (A1) having 3 or more (meth) acryloyloxy groups in one molecule;
    A fluorine compound (B) having a (meth) acryloyloxy group;
    Silicone graft acrylic polymer (C) having a glass transition temperature of 0 ° C. or lower and having a (meth) acryloyloxy group;
    A photopolymerization initiator (D);
    A resin composition for forming a hard coat layer, comprising an organic solvent (E).
  2. 　前記フッ素化合物（Ｂ）が、分子内にシロキサン結合を有する請求項１に記載のハードコート層形成用樹脂組成物。 The resin composition for forming a hard coat layer according to claim 1, wherein the fluorine compound (B) has a siloxane bond in the molecule.
  3. 　前記フッ素化合物（Ｂ）の含有量が、前記（メタ）アクリレート単量体（Ａ）１００質量部に対して０．３～３質量部である請求項１または２に記載のハードコート層形成用樹脂組成物。 The hard coat layer forming method according to claim 1 or 2, wherein the content of the fluorine compound (B) is 0.3 to 3 parts by mass with respect to 100 parts by mass of the (meth) acrylate monomer (A). Resin composition.
  4. 　前記シリコーングラフトアクリルポリマー（Ｃ）の含有量が、前記（メタ）アクリレート単量体（Ａ）１００質量部に対して１～５質量部である請求項１～３のいずれかに記載のハードコート層形成用樹脂組成物。 The hard coat according to any one of claims 1 to 3, wherein the content of the silicone graft acrylic polymer (C) is 1 to 5 parts by mass with respect to 100 parts by mass of the (meth) acrylate monomer (A). Layer forming resin composition.
  5. 　基材と、前記基材上に設けられるハードコート層とを有する積層体であって、
    　前記ハードコート層が、請求項１～４のいずれかに記載のハードコート層形成用樹脂組成物を用いて形成された積層体。     A laminate having a base material and a hard coat layer provided on the base material,
    A laminate in which the hard coat layer is formed using the resin composition for forming a hard coat layer according to any one of claims 1 to 4.
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