WO2015093093A1 - Ultraviolet ray-curable resin composition, and laminate - Google Patents

Ultraviolet ray-curable resin composition, and laminate Download PDF

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Publication number
WO2015093093A1
WO2015093093A1 PCT/JP2014/071302 JP2014071302W WO2015093093A1 WO 2015093093 A1 WO2015093093 A1 WO 2015093093A1 JP 2014071302 W JP2014071302 W JP 2014071302W WO 2015093093 A1 WO2015093093 A1 WO 2015093093A1
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compound
group
resin composition
curable resin
laminate
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PCT/JP2014/071302
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French (fr)
Japanese (ja)
Inventor
裕一 松木
丈章 齋木
山本　正樹
成之 青野
依慶 米山
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横浜ゴム株式会社
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Priority to CN201480065593.8A priority Critical patent/CN105793362A/en
Priority to KR1020167009793A priority patent/KR20160100908A/en
Priority to JP2014540255A priority patent/JP6026550B2/en
Publication of WO2015093093A1 publication Critical patent/WO2015093093A1/en

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    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/045—Aromatic polycarbonates containing aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives thereof
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/02—Lenses; Lens systems ; Methods of designing lenses
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/303—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one or more carboxylic moieties in the chain

Definitions

  • the present invention relates to an ultraviolet curable resin composition and a laminate having a cured film formed using the same.
  • a light source for example, an LED backlight included in an electronic image display device that has become widespread in recent years emits light having a wavelength in the vicinity of 385 to 495 nm, that is, blue light. It has been pointed out that this blue light has adverse effects such as eye strain and dry eye symptoms; decreased retina function; and the secretion of melatonin that promotes sleep. is there.
  • Patent Document 1 describes “an optical article characterized by containing fullerenes as an absorption component of blue light” as an optical filter capable of cutting at least part of visible light of 380 to 500 nm. ([Claim 1] [0009]).
  • A nematic liquid crystal compound having a polymerizable functional group
  • B chiral agent
  • C photopolymerization initiator
  • R 1 represents a hydrocarbon group which may have a hydrogen atom or a hetero atom
  • R 2 represents a hydrogen atom or an organic group
  • a plurality of R 2 are the same. May be different.
  • the nematic liquid crystalline compound (A) is a compound represented by the following formula (2a)
  • the chiral agent (B) is a compound represented by the following formula (3a): [1] to [ 3]
  • the ultraviolet curable resin composition according to any one of [3].
  • n represents an integer of 2 to 5
  • m represents an integer of 2 to 5
  • the content of the chiral agent (B) is 1.0 to 30.0% by mass based on the total mass of the nematic liquid crystalline compound (A) and the chiral agent (B).
  • a resin layer is further provided between the substrate and the cured film, The laminate according to [7], wherein the resin layer is an acrylic resin layer having a surface tension of 32 mN / m or more.
  • the ultraviolet curable resin composition which can form the cured film excellent in a blue light cut function can be provided. Moreover, since the laminated body of this invention has a cured film formed using the ultraviolet curable resin composition of this invention, it is excellent in a blue light cut function.
  • FIG. 1 is a cross-sectional view schematically showing an example of the laminate of the present invention.
  • FIG. 2 is a graph showing the UV-visible light absorption spectrum of the laminate.
  • the ultraviolet curable resin composition of the present invention includes a nematic liquid crystalline compound (A) having a polymerizable functional group, a chiral agent (B), and a photopolymerization initiator.
  • the film has a blue light cut function.
  • a specific concavo-convex pattern is formed on the surface of the cured film due to a predetermined orientation (twisted) state of the nematic liquid crystalline compound resulting from the addition of the chiral agent, and the blue light region (385 nm This is probably because at least part of the light in the wavelength range of ⁇ 495 nm was reflected.
  • the nematic liquid crystalline compound (A) contained in the composition of the present invention is a nematic liquid crystalline compound having a polymerizable functional group, and a compound that exhibits a blue light cut function in combination with a chiral agent (B) described later. If it is, it will not specifically limit.
  • the polymerizable functional group include ethylenic double bonds such as a (meth) acryloyloxy group, a vinyl group, and an allyl group, and among them, a (meth) acryloyloxy group is preferable.
  • the “(meth) acryloyloxy group” means an acryloyloxy group (CH 2 ⁇ CHCOO—) or a methacryloyloxy group (CH 2 ⁇ C (CH 3 ) COO—).
  • nematic liquid crystalline compound for example, a rod-like liquid crystalline compound having two or more polymerizable functional groups in one molecule is preferable.
  • the nematic liquid crystalline compound is represented by the following formula (I).
  • Formula (I) (In the formula, R 3 and R 4 are polymerizable functional groups, each independently (meth) acrylic group, (thio) epoxy group, oxetane group, thietanyl group, aziridinyl group, pyrrole group, vinyl group, allyl group.
  • D 3 and D 4 represent a group selected from the group consisting of a fumarate group, a cinnamoyl group, an oxazoline group, a mercapto group, an iso (thio) cyanate group, an amino group, a hydroxyl group, a carboxyl group, and an alkoxysilyl group.
  • a group selected from the group consisting of a single bond, a linear or branched alkyl group having 1 to 20 carbon atoms, and a linear or branched alkylene oxide group having 1 to 20 carbon atoms C 3 to C 6 are a single bond, —O—, —S—, —S—S—, —CO—, —CS—, —OCO—, —CH 2 —, —OCH 2 —, —C.
  • .M represents a group selected from the group consisting of -CH 2 OCO- represents a mesogenic group, specifically, having a substituted or unsubstituted group Azomethines, azoxys, phenyls, biphenyls, terphenyls, naphthalenes, anthracenes, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, 2 to 4 skeletons selected from the group of alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolanes, alkenylcyclohexylbenzonitriles are represented by —O—, —S—, —SS—,
  • nematic liquid crystalline compound represented by the above formula (I) it is easy to adjust the alignment (twisted) state by a chiral agent (B) described later, and polymerization using a photopolymerization initiator (C) described later is possible.
  • a compound represented by the following formula (2a) is preferable because it easily proceeds.
  • n represents an integer of 2 to 5
  • nematic liquid crystal compound (A) other than the compound represented by the above formula (2a) include the following compounds.
  • the chiral agent (B) contained in the composition of the present invention is a chiral agent and is not particularly limited as long as it is a compound that exhibits a blue light cut function in combination with the above-described nematic liquid crystal compound (A).
  • the chiral agent (B) has a polymerizable functional group because it has excellent paintability and leveling properties (including compatibility with other components) and optical properties (total light transmittance / haze). It is preferable.
  • a polymeric functional group the thing similar to what was demonstrated in the nematic liquid crystalline compound (A) mentioned above is mentioned.
  • the polymerizable functional group that the chiral agent (B) may have preferably has the same polymerizable functional group as the polymerizable functional group that the nematic liquid crystalline compound (A) has, It is more preferable that both the liquid crystal compound (A) and the chiral agent (B) are (meth) acryloyloxy groups.
  • a compound having an isosorbide skeleton structure is preferable, and specifically, a compound represented by the following formula (II) is preferable.
  • P 1 and P 2 each independently represents a hydrocarbon group having 10 to 20 carbon atoms including one 1,4-cyclohexylene group, and the group has an etheric oxygen atom or ester. It may have a bond, and a hydrogen atom in the group may be substituted with a fluorine atom, provided that one of P 1 and P 2 further contains a polymerizable functional group.
  • the blue light cut function of the cured film cured together with the liquid crystalline compound represented by the above formula (2a) becomes better, so that the following formula (3a) It is preferable that it is a compound represented by these.
  • m represents an integer of 2 to 5.
  • chiral agent (B) other than the compound represented by the above formula (3a) include the following compounds.
  • chiral agent (B) other than the compound represented by the above formula (3a) specifically, for example, a compound represented by the following formula (3b), a compound represented by the following formula (3c) are preferable.
  • Examples of the chiral agent (B) other than the compounds represented by the above formulas (3a) to (3c) include, for example, JP-A-2005-289881, JP-A-2004-115414, JP-A-2003-66214, Published in JP2003-313187, JP2003-342219, JP2000-290315, JP6-072962, U.S. Pat. No. 6,468,444, WO98 / 00428, etc.
  • Commercially available products such as BASF's Palio Color LC756, ADEKA Kiracol's CNL617R, and CNL-686L can also be used as appropriate.
  • the content of the chiral agent (B) is the total mass of the nematic liquid crystalline compound (A) and the chiral agent (B).
  • the content is preferably 1.0 to 30.0% by mass.
  • the chiral agent (B) is preferably 4.0 to 6.5% by mass with respect to the total mass of the nematic liquid crystal compound (A) and the chiral agent (B).
  • the photopolymerization initiator (C) contained in the composition of the present invention is not particularly limited as long as it can polymerize the nematic liquid crystalline compound (A) and the chiral agent (B) with light.
  • Examples of the photopolymerization initiator (C) include acetophenone compounds, benzoin ether compounds, benzophenone compounds, sulfur compounds, azo compounds, peroxide compounds, phosphine oxide compounds, and the like.
  • benzoin benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, ⁇ , ⁇ -dimethoxy- ⁇ -phenylacetophenone Methylphenylglyoxylate, ethylphenylglyoxylate, 4,4′-bis (dimethylaminobenzophenone), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1, Carbonyl compounds such as 2-diphenylethane-1-one and 1-hydroxycyclohexyl phenyl ketone; Sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; Azobis Azo compounds such as sobutyronitrile and azobis
  • 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl are preferred from the viewpoints of light stability, high efficiency of photocleavage, surface curability, compatibility, low volatility, low odor and the like.
  • 2-hydroxy-2-methyl-1-phenyl are preferred from the viewpoints of light stability, high efficiency of photocleavage, surface curability, compatibility, low volatility, low odor and the like.
  • -Propan-1-one 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one is preferred.
  • the content of the photopolymerization initiator (C) is 0.5 to 20 parts by mass with respect to a total of 100 parts by mass of the nematic liquid crystalline compound (A) and the chiral agent (B). It is preferably 3 to 9 parts by mass.
  • the composition of the present invention can absorb a short wavelength region (385 to 420 nm) in the blue light region, and the blue light cut function as a whole is better, so that the nano formula represented by the following formula (1) is used.
  • the compound (D) having a phthalimide skeleton is preferably contained.
  • R 1 represents a hydrogen atom or a hetero atom substituted hydrocarbon group which may have a
  • R 2 represents a hydrogen atom or an organic group, plural R 2 may be the same May be different.
  • Examples of the hydrocarbon group optionally having a hetero atom represented by R 1 in the above formula (1) include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and these Combinations may be mentioned and may have an unsaturated bond.
  • Examples of the organic group represented by R 2 include functional groups such as amino groups and hydroxyl groups; hydrocarbon groups such as aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups; And hydrocarbon groups.
  • the hydrocarbon group may have a hetero atom or a double bond.
  • the hydrocarbon group represented by R 1 is preferably a linear or branched alkyl group, and preferably has 1 to 12 carbon atoms.
  • the hydrocarbon group is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.
  • the content is 0.05 to 10 parts by mass with respect to 100 parts by mass in total of the nematic liquid crystalline compound (A) and the chiral agent (B).
  • the amount is preferably 1.0 to 3.0 parts by mass.
  • composition of the present invention can absorb the short wavelength side region (385 to 430 nm) in the blue light region, and the blue light cut function as a whole becomes better. Therefore, the compound (E1) having a benzotriazole skeleton and It is preferable to contain a compound (E2) having a hydroxyphenyltriazine skeleton.
  • R 3 represents a hydrogen atom or a hydrocarbon group which may have a hetero atom.
  • Examples of the hydrocarbon group optionally having a hetero atom represented by R 3 in the above formula (4) include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and the like. Combinations may be mentioned and may have an unsaturated bond.
  • Examples of commercially available compounds having such a benzotriazole skeleton include Tinuvin Carbo protect (BASF) and Tinuvin 384-2 (BASF).
  • the content of the compound (E1) having a benzotriazole skeleton is 0.05 to 10 parts by mass with respect to 100 parts by mass in total of the nematic liquid crystalline compound (A) and the chiral agent (B).
  • the amount is preferably 1.0 to 3.0 parts by mass.
  • examples of the compound (E2) having a hydroxyphenyltriazine skeleton include compounds represented by the following formula (5).
  • R 4 represents a hydrocarbon group which may have a hetero atom.
  • R 5 represents a hydrogen atom or an organic group, and a plurality of R 5 are the same.
  • R 6 represents a hydrogen atom or an organic group, and a plurality of R 6 may be the same or different.
  • Examples of the hydrocarbon group optionally having a heteroatom represented by R 4 in the above formula (5) include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, these Combinations may be mentioned and may have an unsaturated bond. Of these, an aliphatic hydrocarbon group which may have a hetero atom or a hydroxy group is preferable.
  • Examples of the organic group represented by R 5 in the above formula (5) include functional groups such as amino groups and hydroxyl groups; hydrocarbons such as aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. Group; a hydrocarbon group obtained by combining these groups.
  • an aliphatic hydrocarbon group (particularly an alkyl group) is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group or an ethyl group is still more preferable.
  • the organic group represented by R 6 in the above formula (5) include functional groups such as amino groups and hydroxyl groups; hydrocarbons such as aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. Group; a hydrocarbon group obtained by combining these groups. In addition, the hydrocarbon group may have a hetero atom or a double bond.
  • an aliphatic hydrocarbon group (particularly an alkyl group or an alkoxy group) or an aromatic hydrocarbon group (particularly a phenyl group) is preferable.
  • Examples of commercially available compounds (E2) having such a hydroxyphenyltriazine skeleton include Tinuvin 400 (manufactured by BASF), Tinuvin 405 (manufactured by BASF), Tinuvin 460 (manufactured by BASF), Tinuvin ⁇ 477 (BASF). Manufactured), Tinuvin 479 (manufactured by BASF) and the like.
  • the content is 0.05 to 10 parts by mass with respect to 100 parts by mass in total of the nematic liquid crystalline compound (A) and the chiral agent (B). It is preferably 1.0 to 3.0 parts by mass.
  • the composition of the present invention preferably further contains a solvent from the viewpoint of good coatability.
  • a solvent will not be specifically limited if it can melt
  • ketones such as methyl ethyl ketone (MEK), methyl isobutyketone (MIBK), cyclohexanone; alcohols such as propylene glycol monomethyl ether (PGME) and isopropyl alcohol (IPA); cycloalkanes such as cyclohexane; toluene, xylene And aromatic hydrocarbon compounds such as benzyl alcohol.
  • PGME propylene glycol monomethyl ether
  • IPA isopropyl alcohol
  • cycloalkanes such as cyclohexane
  • toluene xylene
  • aromatic hydrocarbon compounds such as benzyl alcohol.
  • cyclohexanone and MIBK are preferred from the viewpoint of excellent solubility, drying properties, and paintability.
  • a solvent can be
  • the content of an arbitrary solvent is preferably 85 to 5% by mass in the total amount of the composition from the viewpoint of coating properties.
  • the composition of the present invention preferably further contains a leveling agent because the blue light cut function of the cured film becomes better.
  • a leveling agent examples include silicone leveling agents, acrylic leveling agents, vinyl leveling agents, and fluorine leveling agents. Among these, it is preferable to use an acrylic leveling agent because the uniformity of the cured film is improved and, as a result, the transparency of the cured film is improved.
  • the content of an arbitrary leveling agent is preferably 0.01 to 3% by mass in the total amount of the composition from the viewpoint of coatability.
  • composition of the present invention is, for example, an ultraviolet absorber, a filler, an anti-aging agent, an antistatic agent, a flame retardant, an adhesion-imparting agent, a dispersant, an antioxidant, Additives such as foaming agents, 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 the above-described nematic liquid crystal compound (A), chiral agent (B) and photopolymerization initiator (C), and any compound (D), compound (E1), It can be produced by uniformly mixing the compound (E2), a solvent, a leveling agent and an additive.
  • the laminate of the present invention is a laminate having a substrate and a cured film, and the cured film is formed using the above-described composition of the present invention. Since the laminated body of this invention has a cured film formed using the composition of this invention, it is excellent in a blue light cut function.
  • the laminated body 100 shown in FIG. 1 has the base material 102 and the cured film 104 formed using the composition of this invention.
  • the thickness of the substrate and the cured film is not particularly limited, but the thickness of the substrate is preferably about 50 to 300 ⁇ m, and the thickness of the cured film is preferably about 0.1 to 100 ⁇ m. .
  • the said base material is not specifically limited, As a constituent material, plastics, rubber
  • the plastic may be either a thermosetting resin or a thermoplastic resin. Specific examples thereof include polyethylene terephthalate (PET), cycloolefin polymer (homopolymer, copolymer, hydrogenated). For example, COP and COC), polymethyl methacrylate resin (PMMA resin), polycarbonate resin, polystyrene resin, acrylonitrile / styrene copolymer resin, polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, polyamide resin, etc. Is mentioned.
  • the base material may be subjected to a surface treatment such as a corona treatment.
  • the form of the substrate is not particularly limited, but is preferably a film.
  • COC is a copolymer (cycloolefin copolymer) of tetracyclododecene and an olefin such as ethylene.
  • COP is a polymer (cycloolefin polymer) obtained by ring-opening polymerization of norbornene and hydrogenation. Examples of COC and COP structures are shown below.
  • the orientation (twist) state of the liquid crystal compound constituting the cured film becomes good, and the adhesiveness with the base material is also good. Further, it is preferable to have a resin layer.
  • the resin layer is preferably an acrylic resin layer having a surface tension of 32 mN / m or more.
  • the surface tension is applied to the cured acrylic resin layer with a wet pen (8 sets of pen numbers 30, 32, 34, 36, 38, 40, 42 and 44 mN / m, manufactured by Alcotest).
  • a wet pen 8 sets of pen numbers 30, 32, 34, 36, 38, 40, 42 and 44 mN / m, manufactured by Alcotest.
  • an acrylic resin layer has a surface tension of 32 mN / m or more, it is abbreviated as, for example, an ultraviolet curable resin composition (hereinafter referred to as “hard coat resin composition”) used in a conventionally known hard coat. ) Is preferably an acrylic resin layer formed using The surface tension can be adjusted by adding a conventionally known leveling agent, surfactant, hydrophilicity or lipophilicity imparting agent.
  • the resin composition for hard coat for example, a composition containing a polyfunctional (meth) acrylate (a) and a photopolymerization initiator (b) described later can be used.
  • the polyfunctional (meth) acrylate (a) is not particularly limited as long as it is a compound having two or more (meth) acryloyloxy groups.
  • the (meth) acryloyloxy group can be bonded to an organic group.
  • the hydrocarbon group which may have hetero atoms, such as an oxygen atom, a nitrogen atom, and a sulfur atom, is mentioned, for example.
  • Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof.
  • the hydrocarbon group may include a straight chain and a branched chain, and may have an unsaturated bond.
  • the polyfunctional (meth) acrylate (a) has a high hardness of the resulting acrylic resin layer, and has better adhesion between the substrate and the cured film. It is preferable to have twelve.
  • polyfunctional (meth) acrylate (a) examples include polyhydric alcohol (meth) acrylic acid esters and urethane (meth) acrylates.
  • polyhydric alcohol (meth) acrylic acid esters include trifunctional groups such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol tri (meth) acrylate; pentaerythritol tetra Tetrafunctional system such as (meth) acrylate, dipentaerythritol tetra (meth) acrylate, tripentaerythritol tetra (meth) acrylate; dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol Penta (meth) acrylate, tripentaerythritol he
  • urethane (meth) acrylates examples include (meth) acrylic acid esters of polyhydric alcohols (in this case, (meth) acrylic acid esters of polyhydric alcohols include those having at least one hydroxy group). ) And a polyisocyanate compound.
  • (meth) acrylic acid ester of polyhydric alcohol used when producing urethane (meth) acrylate examples include the same as those described above.
  • polyisocyanate compounds used in the production of urethane (meth) acrylate include tolylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and tolidine diisocyanate.
  • Aromatic polyisocyanates such as 1,5-naphthalene diisocyanate and triphenylmethane triisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, bis (Isocyanate methyl) Cyclohexane, (including linear and / or cycloaliphatic systems.) Aliphatic polyisocyanates such as dicyclohexylmethane diisocyanate; these isocyanurate, biuret body, an adduct; and the urethane prepolymer.
  • the photopolymerization initiator (b) is not particularly limited as long as it can polymerize the polyfunctional (meth) acrylate (a) by light, and the photopolymerization contained in the composition of the present invention.
  • a thing similar to an initiator (C) can be selected suitably, and can be used.
  • the hard coat resin composition is, for example, an ultraviolet absorber, a filler, an anti-aging agent, an antistatic agent, a flame retardant, an adhesion-imparting agent, a dispersant, and an antioxidant as long as the object of the present invention is not impaired. Further, additives such as an antifoaming agent, a leveling agent, a matting agent, a light stabilizer, a dye and a pigment can be further contained. Examples of the leveling agent include silicone leveling agents, acrylic leveling agents, vinyl leveling agents, and fluorine leveling agents.
  • the thickness of the resin layer is preferably about 0.1 to 100 ⁇ m, more preferably 1 to 5 ⁇ m, because the adhesion between the substrate and the cured film becomes better. .
  • the laminate of the present invention may have a hard coat layer on the surface of the cured film opposite to the substrate.
  • the hard coat layer is preferably an acrylic resin layer formed using the hard coat resin composition described in the resin layer described above, and the formation method thereof is the same as the resin layer formation method described above. A similar method can be mentioned.
  • the thickness is not particularly limited, but is preferably about 0.01 to 50 ⁇ m, more preferably 1 to 5 ⁇ m.
  • the method for producing a laminate of the present invention includes, for example, a step of coating the composition of the present invention on a film-like substrate (or the above resin layer if the resin layer is provided), drying, and irradiating ultraviolet rays The method which has this is mentioned.
  • the method of coating the composition of the present invention on the substrate is not particularly limited, and for example, a known coating method such as brush coating, flow coating, dip coating, spray coating, spin coating or the like can be employed.
  • the temperature for drying after coating is preferably 20 to 110 ° C.
  • the ultraviolet irradiation after drying is 50 to 3,000 mJ / cm 2 from the viewpoint of fast curability and workability as the irradiation amount (integrated light amount) of the ultraviolet rays used when the composition of the present invention is cured.
  • the apparatus used for irradiating ultraviolet rays is not particularly limited. For example, a conventionally well-known thing is mentioned. Heating may be used in combination for curing.
  • the formation method of the said resin layer is a method similar to the composition of this invention, It can form by the process of apply
  • the laminate of the present invention can be used for, for example, an electronic image display device, a spectacle lens, a protective cover for lighting (particularly LED lighting), a solar cell module member, and the like.
  • the electronic image display device include display-use electronic device components such as a personal computer, a television, a touch panel, and a wearable terminal (for example, a computer terminal that can be worn on the body such as a glasses type or a wrist watch type).
  • the laminated body of the present invention can be incorporated in an electronic image display device or the like, or can be retrofitted (for example, attached from the outside).
  • the laminate of the present invention When the laminate of the present invention is built in an electronic image display device or the like, it can be applied to a portion other than the reflector, for example. Specifically, for example, it can be applied to a lens sheet, a diffusion sheet, and a light guide plate.
  • the composition of the present invention can be directly applied to an electronic image display device to form a cured film.
  • Examples 1 to 18 and Comparative Examples 1 and 2 ⁇ Preparation of composition> Each component of the following Table 1 was mixed with the composition (parts by mass) shown in Table 1 using a stirrer to prepare a composition.
  • Table 1 ⁇ Manufacture of laminates>
  • Each composition obtained as described above has a film thickness after drying with a bar coater on a polyethylene terephthalate film (PET fabric: trade name U46, manufactured by Toray Industries, Inc., thickness 125 ⁇ m) to be 1.5 ⁇ m. After applying at a clearance setting and drying it at 80 ° C. for 1 minute, this was irradiated with ultraviolet rays (UV) using a GSUV SYSTEM manufactured by Kawaguchi Spring Mfg. Co., Ltd.
  • UV ultraviolet rays
  • UV irradiation condition illuminance: 300 mW / cm 2.
  • the accumulated light quantity was 300 mJ / cm 2
  • the UV irradiation device was a high-pressure mercury lamp
  • the composition was cured to produce a laminate.
  • Nematic liquid crystalline compound A-2 Compound represented by the above formula (2b)
  • Non-liquid crystalline compound X-1 Hydroxy (meth) acrylate containing dipentaerythritol hexaacrylate (DPHA) as a main component [trade name: NX103-161, solid content 85%: manufactured by Asia Kogyo Co., Ltd.] and hexamethylene diisocyanate at a mass ratio (81/19).
  • DPHA dipentaerythritol hexaacrylate
  • Chiral agent B-2 Compound represented by the above formula (3b)
  • Chiral agent B-3 Compound represented by the above formula (3c)
  • Photopolymerization initiator C-1 Irgacure 184 (manufactured by BASF)
  • Compound D-1 Compound having a naphthalimide skeleton (R 1 in the above formula (1) is —CH 2 CH (CH 2 CH 2 CH 3 ) 2 , and R 2 is —O—CH 3 .
  • Compound E1-1 Compound having a benzotriazole skeleton (Tinuvin Carbo protect, manufactured by BASF)
  • Compound E1-2 Compound having a benzotriazole skeleton (Tinuvin 384-2, manufactured by BASF)
  • Compound E2-1 Compound having a hydroxyphenyltriazine skeleton (Tinuvin 477, manufactured by BASF)
  • Compound E2-2 Compound having a hydroxyphenyltriazine skeleton (Tinuvin 479, manufactured by BASF) -Methyl ethyl ketone: Solvent-Cyclohexanone: Solvent-Leveling agent: Acrylic leveling agent (BYK361N, manufactured by Big Chemie Japan)
  • Comparative Example 1 prepared by blending the non-liquid crystalline compound without blending the nematic liquid crystalline compound (A) having a polymerizable functional group is blue light. It was found that the cutting function was inferior (Comparative Example 1). Moreover, it turned out that the composition of the comparative example 2 prepared without mix
  • the composition prepared by blending the nematic liquid crystalline compound (A) having a polymerizable functional group, the chiral agent (B) and the photopolymerization initiator (C) is a cured product having a blue light cut function. It was found that a film could be formed, and all b * values were 2.0 or less, and it was found that the yellowness was very low despite having a blue light cut function (Example 1 to 18). It can be seen that a commercially available blue light cut film has a remarkable effect even when compared with the b * value generally in the range of 7 to 25.
  • FIG. 2 is a graph showing the UV-visible light absorption spectrum of the laminate.
  • base material only means the polyethylene terephthalate film alone used in the production of the laminate in the examples.
  • Examples 1, 4 and 10 do not transmit blue light compared to the base material alone or Comparative Example 1.
  • Example 19 to 34 Using each composition prepared in Examples 1 to 3 and Example 8, laminate A and laminate B were prepared by the following method, and the adhesion of the cured film was evaluated by the following method.
  • PET film ⁇ Manufacture of laminate A-base material (PET film)> After drying a polyethylene terephthalate film (PET fabric: trade name U46, manufactured by Toray Industries, Inc., thickness 125 ⁇ m) with an acrylic resin composition having the product numbers shown in Table 2 below (both manufactured by Yokohama Rubber Co., Ltd.) using a bar coater. The film was applied with a clearance setting such that the film thickness was 1.5 ⁇ m, and this was dried at 80 ° C. for 1 minute, and then UV (UV) was applied thereto using GSUV SYSTEM manufactured by Kawaguchi Spring Manufacturing Co., Ltd.
  • PTT fabric trade name U46, manufactured by Toray Industries, Inc., thickness 125 ⁇ m
  • acrylic resin composition having the product numbers shown in Table 2 below (both manufactured by Yokohama Rubber Co., Ltd.) using a bar coater.
  • the film was applied with a clearance setting such that the film thickness was 1.5 ⁇ m, and this was dried at 80 ° C. for
  • Irradiation UV irradiation conditions: illuminance: 300 mW / cm 2 , integrated light quantity: 300 mJ / cm 2 , UV irradiation apparatus: high-pressure mercury lamp
  • UV irradiation apparatus high-pressure mercury lamp
  • a wet pen 8 sets of pen numbers 30, 32, 34, 36, 38, 40, 42, and 44 mN / m, manufactured by Alcotest
  • the time passed the state of the pen streaks was visually confirmed, the largest pen number that did not repel ink was selected, and the surface tension was determined.
  • each composition prepared in Examples 1 to 3 and Example 8 was applied to the acrylic resin layer using a bar coater with a clearance setting such that the film thickness after drying was 1.5 ⁇ m. After drying at 80 ° C. for 1 minute, this was irradiated with ultraviolet rays (UV) using a GSUV SYSTEM manufactured by Kawaguchi Spring Manufacturing Co., Ltd. (UV irradiation conditions: illuminance 300 mW / cm 2 , integrated light quantity 300 mJ / cm 2 , The composition was cured by using a high-pressure mercury lamp (UV irradiation device) to prepare a laminate.
  • UV rays UV
  • Laminate B was prepared in the same manner as Laminate A, except that a cycloolefin film (COP fabric: trade name ZF16-100, manufactured by Nippon Zeon Co., Ltd., thickness 100 ⁇ ) subjected to corona treatment was used as the substrate.
  • COP fabric trade name ZF16-100, manufactured by Nippon Zeon Co., Ltd., thickness 100 ⁇
  • ⁇ Adhesion> The produced laminates A and B were subjected to a cross-cut peel test based on JIS K5400 to evaluate the adhesion. Specifically, using a cutter, cut only 1mm pitch in the cured film part and resin layer part of each laminate to make 100 bases (10x10), and cellophane adhesive on the bases A tape (18 mm in width) was completely attached, and immediately pulled off while keeping one end of the tape at a right angle to the substrate, and the number of remaining bases without being completely peeled was examined. When the number of remaining bases was 75 or more, it was evaluated as “ ⁇ ” as being excellent in adhesion, and when it was less than 75, it was evaluated as “x” as being slightly inferior in adhesion. The results are shown in Table 2 below.

Abstract

The purpose of the present invention is to provide an ultraviolet ray-curable resin composition from which a cured coating film having an excellent blue light-cutting function can be formed. The ultraviolet ray-curable resin composition according to the present invention comprises (A) a nematic liquid crystalline compound having a polymerizable functional group, (B) a chiral agent and (C) a photopolymerization initiator, and can be used for forming a cured coating film which is reduced in the transmittance to at least a portion of light having a wavelength ranging from 385 to 495 nm.

Description

紫外線硬化型樹脂組成物および積層体Ultraviolet curable resin composition and laminate
　本発明は、紫外線硬化型樹脂組成物およびこれを用いて形成される硬化皮膜を有する積層体に関する。 The present invention relates to an ultraviolet curable resin composition and a laminate having a cured film formed using the same.
　近年普及している電子画像表示装置が有する光源（例えば、ＬＥＤバックライト）は、３８５～４９５ｎｍ付近の波長を有する光、いわゆるブルーライトを発する。このブルーライトは、人に、眼精疲労やドライアイのような症状；網膜の機能低下；睡眠を促すメラトニンの分泌を抑制するため、体内時計がずれるというような悪影響を与えているという指摘がある。
　例えば、特許文献１には、３８０～５００ｎｍの可視光線の少なくとも一部をカットできる光学フィルターとして、「青色光の吸収成分としてフラーレン類を含有することを特徴とする光学物品。」が記載されている（［請求項１］［０００９］）。 A light source (for example, an LED backlight) included in an electronic image display device that has become widespread in recent years emits light having a wavelength in the vicinity of 385 to 495 nm, that is, blue light. It has been pointed out that this blue light has adverse effects such as eye strain and dry eye symptoms; decreased retina function; and the secretion of melatonin that promotes sleep. is there.
For example, Patent Document 1 describes “an optical article characterized by containing fullerenes as an absorption component of blue light” as an optical filter capable of cutting at least part of visible light of 380 to 500 nm. ([Claim 1] [0009]).
特開２００７－０９３９２７号公報JP 2007-093927 A
　本発明者らは、特許文献１に記載されたフラーレン類について検討したところ、ブルーライトカット機能が十分ではないことを明らかとした。
　そこで、本発明は、ブルーライトカット機能に優れる硬化皮膜を形成することができる紫外線硬化型樹脂組成物を提供することを課題とする。 The present inventors have examined the fullerenes described in Patent Document 1, and have found that the blue light cut function is not sufficient.
Then, this invention makes it a subject to provide the ultraviolet curable resin composition which can form the cured film excellent in a blue light cut function.
　本発明者らは、上記課題を解決するため鋭意検討した結果、重合性官能基を有するネマチック液晶性化合物（Ａ）、カイラル剤（Ｂ）および光重合開始剤（Ｃ）を含有する紫外線硬化型樹脂組成物を用いて形成される硬化皮膜が、ブルーライトカット機能に優れることを見出し、本発明を完成させた。
　すなわち、本発明者らは、以下の構成により上記課題が解決できることを見出した。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an ultraviolet curable type containing a nematic liquid crystal compound (A) having a polymerizable functional group, a chiral agent (B) and a photopolymerization initiator (C). The present inventors have found that a cured film formed using a resin composition has an excellent blue light cut function and completed the present invention.
That is, the present inventors have found that the above problem can be solved by the following configuration.
　［１］　重合性官能基を有するネマチック液晶性化合物（Ａ）、カイラル剤（Ｂ）および光重合開始剤（Ｃ）を含有し、３８５ｎｍ～４９５ｎｍの波長領域の少なくとも一部の光の透過率を低減する硬化皮膜を形成するための紫外線硬化型樹脂組成物。
　［２］　上記ネマチック液晶性化合物（Ａ）が有する重合性官能基が、（メタ）アクリロイルオキシ基である、［１］に記載の紫外線硬化型樹脂組成物。
　［３］　更に、下記式（１）で表されるナフタルイミド骨格を有する化合物（Ｄ）を含有する、［１］または［２］に記載の紫外線硬化型樹脂組成物。
Figure JPOXMLDOC01-appb-C000003
 　（式（１）中、Ｒ1は、水素原子またはヘテロ原子を有していてもよい炭化水素基を表し、Ｒ2は、水素原子または有機基を表し、複数のＲ2は同一であっても異なっていてもよい。）
　［４］　上記ネマチック液晶性化合物（Ａ）が下記式（２ａ）で表される化合物であり、上記カイラル剤（Ｂ）が下記式（３ａ）で表される化合物である、［１］～［３］のいずれかに記載の紫外線硬化型樹脂組成物。
Figure JPOXMLDOC01-appb-C000004
 　（式（２ａ）中、ｎは２～５の整数を表し、式（３ａ）中、ｍは２～５の整数を表す。）
　［５］　上記カイラル剤（Ｂ）の含有量が、上記ネマチック液晶性化合物（Ａ）および上記カイラル剤（Ｂ）の合計質量に対して１．０～３０．０質量％である、［１］～［４］のいずれかに記載の紫外線硬化型樹脂組成物。
　［６］　更に、ベンゾトリアゾール骨格を有する化合物（Ｅ１）および／またはヒドロキシフェニルトリアジン骨格を有する化合物（Ｅ２）を含有する、［１］～［５］のいずれかに記載の紫外線硬化型樹脂組成物。
　［７］　基材と、硬化皮膜とを有する積層体であって、
　上記硬化皮膜が、［１］～［６］のいずれかに記載の紫外線硬化型樹脂組成物を用いて形成される、積層体。
　［８］　上記基材と上記硬化皮膜との間に、更に樹脂層を有し、
　上記樹脂層が、表面張力が３２ｍＮ／ｍ以上のアクリル系樹脂層である、［７］に記載の積層体。
　［９］　電子画像表示装置または眼鏡レンズに使用される［７］または［８］に記載の積層体。 [1] A nematic liquid crystal compound (A) having a polymerizable functional group (A), a chiral agent (B), and a photopolymerization initiator (C), and having a light transmittance of at least part of a wavelength range of 385 nm to 495 nm. An ultraviolet curable resin composition for forming a reduced cured film.
[2] The ultraviolet curable resin composition according to [1], wherein the polymerizable functional group of the nematic liquid crystalline compound (A) is a (meth) acryloyloxy group.
[3] The ultraviolet curable resin composition according to [1] or [2], further comprising a compound (D) having a naphthalimide skeleton represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000003
 (In the formula (1), R 1 represents a hydrocarbon group which may have a hydrogen atom or a hetero atom, R 2 represents a hydrogen atom or an organic group, and a plurality of R 2 are the same. May be different.)
[4] The nematic liquid crystalline compound (A) is a compound represented by the following formula (2a), and the chiral agent (B) is a compound represented by the following formula (3a): [1] to [ 3] The ultraviolet curable resin composition according to any one of [3].
Figure JPOXMLDOC01-appb-C000004
 (In formula (2a), n represents an integer of 2 to 5, and in formula (3a), m represents an integer of 2 to 5)
[5] The content of the chiral agent (B) is 1.0 to 30.0% by mass based on the total mass of the nematic liquid crystalline compound (A) and the chiral agent (B). [1] The ultraviolet curable resin composition according to any one of to [4].
[6] The ultraviolet curable resin composition according to any one of [1] to [5], further comprising a compound (E1) having a benzotriazole skeleton and / or a compound (E2) having a hydroxyphenyltriazine skeleton. .
[7] A laminate having a substrate and a cured film,
A laminate in which the cured film is formed using the ultraviolet curable resin composition according to any one of [1] to [6].
[8] A resin layer is further provided between the substrate and the cured film,
The laminate according to [7], wherein the resin layer is an acrylic resin layer having a surface tension of 32 mN / m or more.
[9] The laminate according to [7] or [8], which is used for an electronic image display device or a spectacle lens.
　本発明によれば、ブルーライトカット機能に優れる硬化皮膜を形成することができる紫外線硬化型樹脂組成物を提供することができる。
　また、本発明の積層体は、本発明の紫外線硬化型樹脂組成物を用いて形成される硬化皮膜を有するため、ブルーライトカット機能に優れる。 ADVANTAGE OF THE INVENTION According to this invention, the ultraviolet curable resin composition which can form the cured film excellent in a blue light cut function can be provided.
Moreover, since the laminated body of this invention has a cured film formed using the ultraviolet curable resin composition of this invention, it is excellent in a blue light cut function.
図１は、本発明の積層体の一例を模式的に示す断面図である。FIG. 1 is a cross-sectional view schematically showing an example of the laminate of the present invention. 図２は、積層体のＵＶ－可視光吸収スペクトルを示すグラフである。FIG. 2 is a graph showing the UV-visible light absorption spectrum of the laminate.
 〔紫外線硬化型樹脂組成物〕
　本発明の紫外線硬化型樹脂組成物（以下、単に「本発明の組成物」ともいう。）は、重合性官能基を有するネマチック液晶性化合物（Ａ）、カイラル剤（Ｂ）および光重合開始剤（Ｃ）を含有し、３８５ｎｍ～４９５ｎｍの波長領域の少なくとも一部の光の透過率を低減する硬化皮膜を形成するための紫外線硬化型樹脂組成物である。 [Ultraviolet curable resin composition]
The ultraviolet curable resin composition of the present invention (hereinafter also simply referred to as “the composition of the present invention”) includes a nematic liquid crystalline compound (A) having a polymerizable functional group, a chiral agent (B), and a photopolymerization initiator. An ultraviolet curable resin composition for forming a cured film containing (C) and reducing the transmittance of at least part of light in the wavelength region of 385 nm to 495 nm.
　本発明においては、上述した通り、重合性官能基を有するネマチック液晶性化合物（Ａ）、カイラル剤（Ｂ）および光重合開始剤（Ｃ）を含有する組成物を用いることにより、形成される硬化皮膜がブルーライトカット機能を有する。
　これは、詳細には明らかではないが、カイラル剤の添加に起因したネマチック液晶性化合物の所定の配向（ねじれ）状態により、硬化皮膜の表面に特定の凹凸パターンが形成され、ブルーライト領域（３８５ｎｍ～４９５ｎｍの波長領域）の光の少なくとも一部が反射したためと考えられる。また、このような反射によって、ブルーライトカット機能を有するにも関わらず、自然光における青色光の反射により、硬化皮膜の黄色味の強くなるという問題を軽減することも可能になったと考えられる。
　なお、上述したメカニズムは本発明者らの推測であるため、実際のメカニズムと異なっていても、本発明の発明特定事項をすべて有する場合は、本発明の技術的範囲に属することは当然である。
　以下に、重合性官能基を有するネマチック液晶性化合物（Ａ）、カイラル剤（Ｂ）および光重合開始剤（Ｃ）ならびに他の任意成分について詳述する。 In the present invention, as described above, curing formed by using a composition containing a nematic liquid crystalline compound (A) having a polymerizable functional group, a chiral agent (B), and a photopolymerization initiator (C). The film has a blue light cut function.
Although this is not clear in detail, a specific concavo-convex pattern is formed on the surface of the cured film due to a predetermined orientation (twisted) state of the nematic liquid crystalline compound resulting from the addition of the chiral agent, and the blue light region (385 nm This is probably because at least part of the light in the wavelength range of ˜495 nm was reflected. In addition, it is considered that such a reflection can reduce the problem that the yellowishness of the cured film becomes strong due to the reflection of blue light in natural light in spite of having a blue light cut function.
In addition, since the mechanism mentioned above is a guess of the present inventors, even if it differs from an actual mechanism, when it has all the invention specific matters of this invention, it is natural that it belongs to the technical scope of this invention. .
Hereinafter, the nematic liquid crystal compound (A) having a polymerizable functional group, the chiral agent (B), the photopolymerization initiator (C), and other optional components will be described in detail.
　＜ネマチック液晶性化合物（Ａ）＞
　本発明の組成物が含有するネマチック液晶性化合物（Ａ）は、重合性官能基を有するネマチック液晶性化合物であり、後述するカイラル剤（Ｂ）との組み合わせにおいて、ブルーライトカット機能を発現する化合物であれば特に限定されない。
　ここで、重合性官能基としては、例えば、（メタ）アクリロイルオキシ基、ビニル基、アリル基等のエチレン性二重結合が挙げられ、中でも、（メタ）アクリロイルオキシ基であるのが好ましい。なお、「（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－）を意味するものとする。 <Nematic liquid crystalline compound (A)>
The nematic liquid crystalline compound (A) contained in the composition of the present invention is a nematic liquid crystalline compound having a polymerizable functional group, and a compound that exhibits a blue light cut function in combination with a chiral agent (B) described later. If it is, it will not specifically limit.
Here, examples of the polymerizable functional group include ethylenic double bonds such as a (meth) acryloyloxy group, a vinyl group, and an allyl group, and among them, a (meth) acryloyloxy group is preferable. The “(meth) acryloyloxy group” means an acryloyloxy group (CH 2 ═CHCOO—) or a methacryloyloxy group (CH 2 ═C (CH 3 ) COO—).
　このようなネマチック液晶性化合物としては、例えば、１分子中に２つ以上の重合性官能基を有する棒状液晶性化合物であるのが好ましく、具体的には、下記式（Ｉ）で表される化合物であるのが好ましい。
　Ｒ3－Ｃ3－Ｄ3－Ｃ5－Ｍ－Ｃ6－Ｄ4－Ｃ4－Ｒ4　・・・式（Ｉ）
（式中、Ｒ3及びＲ4は重合性官能基であり、それぞれ独立して（メタ）アクリル基、（チオ）エポキシ基、オキセタン基、チエタニル基、アジリジニル基、ピロール基、ビニル基、アリル基、フマレート基、シンナモイル基、オキサゾリン基、メルカプト基、イソ（チオ）シアネート基、アミノ基、ヒドロキシル基、カルボキシル基、及びアルコキシシリル基からなる群より選択される基を表す。Ｄ3及びＤ4は単結合、炭素原子数１～２０個の直鎖状又は分岐鎖状のアルキル基、及び炭素原子数１～２０個の直鎖状又は分岐鎖状のアルキレンオキサイド基からなる群より選択される基を表す。Ｃ3～Ｃ6は単結合、－Ｏ－、－Ｓ－、－Ｓ－Ｓ－、－ＣＯ－、－ＣＳ－、－ＯＣＯ－、－ＣＨ2－、－ＯＣＨ2－、－Ｃ＝Ｎ－Ｎ＝Ｃ－、－ＮＨＣＯ－、－ＯＣＯＯ－、－ＣＨ2ＣＯＯ－、及び－ＣＨ2ＯＣＯ－からなる群より選択される基を表す。Ｍはメソゲン基を表し、具体的には、非置換又は置換基を有していてもよい、アゾメチン類、アゾキシ類、フェニル類、ビフェニル類、ターフェニル類、ナフタレン類、アントラセン類、安息香酸エステル類、シクロヘキサンカルボン酸フェニルエステル類、シアノフェニルシクロヘキサン類、シアノ置換フェニルピリミジン類、アルコキシ置換フェニルピリミジン類、フェニルジオキサン類、トラン類、アルケニルシクロヘキシルベンゾニトリル類の群から選択された２～４個の骨格を、－Ｏ－、－Ｓ－、－Ｓ－Ｓ－、－ＣＯ－、－ＣＳ－、－ＯＣＯ－、－ＣＨ2－、－ＯＣＨ2－、－Ｃ＝Ｎ－Ｎ＝Ｃ－、－ＮＨＣＯ－、－ＯＣＯＯ－、－ＣＨ2ＣＯＯ－、及び－ＣＨ2ＯＣＯ－等の結合基によって結合されて形成される。） As such a nematic liquid crystalline compound, for example, a rod-like liquid crystalline compound having two or more polymerizable functional groups in one molecule is preferable. Specifically, the nematic liquid crystalline compound is represented by the following formula (I). Preferably it is a compound.
R 3 -C 3 -D 3 -C 5 -MC 6 -D 4 -C 4 -R 4 ... Formula (I)
(In the formula, R 3 and R 4 are polymerizable functional groups, each independently (meth) acrylic group, (thio) epoxy group, oxetane group, thietanyl group, aziridinyl group, pyrrole group, vinyl group, allyl group. D 3 and D 4 represent a group selected from the group consisting of a fumarate group, a cinnamoyl group, an oxazoline group, a mercapto group, an iso (thio) cyanate group, an amino group, a hydroxyl group, a carboxyl group, and an alkoxysilyl group. A group selected from the group consisting of a single bond, a linear or branched alkyl group having 1 to 20 carbon atoms, and a linear or branched alkylene oxide group having 1 to 20 carbon atoms C 3 to C 6 are a single bond, —O—, —S—, —S—S—, —CO—, —CS—, —OCO—, —CH 2 —, —OCH 2 —, —C. = NN-C-, -NHC O -, - OCOO -, - CH 2 COO-, and .M represents a group selected from the group consisting of -CH 2 OCO- represents a mesogenic group, specifically, having a substituted or unsubstituted group Azomethines, azoxys, phenyls, biphenyls, terphenyls, naphthalenes, anthracenes, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, 2 to 4 skeletons selected from the group of alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolanes, alkenylcyclohexylbenzonitriles are represented by —O—, —S—, —SS—, —CO—, -CS -, - OCO -, - CH 2 -, - OCH 2 -, - C = N-N = C -, - NHCO -, - OCOO-, CH 2 COO-, and is formed are joined by a linking group of -CH 2 OCO-, and the like.)
　上記式（Ｉ）で表されるネマチック液晶性化合物としては、後述するカイラル剤（Ｂ）により配向（ねじれ）状態を調整しやすく、また、後述する光重合開始剤（Ｃ）を用いた重合が進行し易い理由から、下記式（２ａ）で表される化合物であるのが好ましい。
Figure JPOXMLDOC01-appb-C000005
 　（式（２ａ）中、ｎは２～５の整数を表す。） As the nematic liquid crystalline compound represented by the above formula (I), it is easy to adjust the alignment (twisted) state by a chiral agent (B) described later, and polymerization using a photopolymerization initiator (C) described later is possible. A compound represented by the following formula (2a) is preferable because it easily proceeds.
Figure JPOXMLDOC01-appb-C000005
 (In the formula (2a), n represents an integer of 2 to 5)
　上記式（２ａ）で表される化合物以外のネマチック液晶性化合物（Ａ）としては、具体的には、例えば、以下に示す化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-I000007
Figure JPOXMLDOC01-appb-I000008
Figure JPOXMLDOC01-appb-I000009
Figure JPOXMLDOC01-appb-I000010
Figure JPOXMLDOC01-appb-I000011
Figure JPOXMLDOC01-appb-I000012
Figure JPOXMLDOC01-appb-I000013
Figure JPOXMLDOC01-appb-I000014
Figure JPOXMLDOC01-appb-I000015
Specific examples of the nematic liquid crystal compound (A) other than the compound represented by the above formula (2a) include the following compounds.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-I000007
Figure JPOXMLDOC01-appb-I000008
Figure JPOXMLDOC01-appb-I000009
Figure JPOXMLDOC01-appb-I000010
Figure JPOXMLDOC01-appb-I000011
Figure JPOXMLDOC01-appb-I000012
Figure JPOXMLDOC01-appb-I000013
Figure JPOXMLDOC01-appb-I000014
Figure JPOXMLDOC01-appb-I000015
　これらのうち、下記式（２ｂ）で表される化合物、下記式（２ｃ）で表される化合物であるのが好ましい。
Figure JPOXMLDOC01-appb-C000016
 Among these, a compound represented by the following formula (2b) and a compound represented by the following formula (2c) are preferable.
Figure JPOXMLDOC01-appb-C000016
　＜カイラル剤（Ｂ）＞
　本発明の組成物が含有するカイラル剤（Ｂ）は、カイラル剤であり、上述したネマチック液晶性化合物（Ａ）との組み合わせにおいて、ブルーライトカット機能を発現する化合物であれば特に限定されない。 <Chiral agent (B)>
The chiral agent (B) contained in the composition of the present invention is a chiral agent and is not particularly limited as long as it is a compound that exhibits a blue light cut function in combination with the above-described nematic liquid crystal compound (A).
　本発明においては、塗装性やレベリング性（他成分との相溶性を含む）、更には光学特性（全光線透過率／ヘイズ）に優れる理由から、カイラル剤（Ｂ）が重合性官能基を有しているのが好ましい。
　ここで、重合性官能基としては、上述したネマチック液晶性化合物（Ａ）において説明したものと同様のものが挙げられる。
　カイラル剤（Ｂ）が有していてもよい重合性官能基は、ネマチック液晶性化合物（Ａ）が有している重合性官能基と同じ重合性官能基を有していることが好ましく、ネマチック液晶性化合物（Ａ）およびカイラル剤（Ｂ）がいずれも（メタ）アクリロイルオキシ基であるのことがより好ましい。 In the present invention, the chiral agent (B) has a polymerizable functional group because it has excellent paintability and leveling properties (including compatibility with other components) and optical properties (total light transmittance / haze). It is preferable.
Here, as a polymeric functional group, the thing similar to what was demonstrated in the nematic liquid crystalline compound (A) mentioned above is mentioned.
The polymerizable functional group that the chiral agent (B) may have preferably has the same polymerizable functional group as the polymerizable functional group that the nematic liquid crystalline compound (A) has, It is more preferable that both the liquid crystal compound (A) and the chiral agent (B) are (meth) acryloyloxy groups.
　このようなカイラル剤としては、例えば、イソソルビド骨格構造を有する化合物であるのが好ましく、具体的には、下記式（ＩＩ）で表される化合物であるのが好ましい。
Figure JPOXMLDOC01-appb-C000017
 （式中、Ｐ1及びＰ2は、それぞれ独立に、１，４－シクロヘキシレン基を１個含む炭素数が１０～２０の炭化水素基を表し、基中にエーテル結合性の酸素原子またはエステル結合を有していてもよく、基中の水素原子がフッ素原子に置換されていてもよい。但し、Ｐ1及びＰ2はＰ１及びＰ２の一方は、さらに重合性官能基を含む。） As such a chiral agent, for example, a compound having an isosorbide skeleton structure is preferable, and specifically, a compound represented by the following formula (II) is preferable.
Figure JPOXMLDOC01-appb-C000017
 (In the formula, P 1 and P 2 each independently represents a hydrocarbon group having 10 to 20 carbon atoms including one 1,4-cyclohexylene group, and the group has an etheric oxygen atom or ester. It may have a bond, and a hydrogen atom in the group may be substituted with a fluorine atom, provided that one of P 1 and P 2 further contains a polymerizable functional group.
　上記式（ＩＩ）で表されるカイラル剤としては、上記式（２ａ）で表される液晶性化合物とともに硬化させた硬化皮膜のブルーライトカット機能がより良好となる理由から、下記式（３ａ）で表される化合物であるのが好ましい。
Figure JPOXMLDOC01-appb-C000018
 　（式（３ａ）中、ｍは２～５の整数を表す。） As the chiral agent represented by the above formula (II), the blue light cut function of the cured film cured together with the liquid crystalline compound represented by the above formula (2a) becomes better, so that the following formula (3a) It is preferable that it is a compound represented by these.
Figure JPOXMLDOC01-appb-C000018
 (In the formula (3a), m represents an integer of 2 to 5.)
　上記式（３ａ）で表される化合物以外のカイラル剤（Ｂ）としては、具体的には、例えば、以下に示す化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-I000020
Figure JPOXMLDOC01-appb-I000021
Specific examples of the chiral agent (B) other than the compound represented by the above formula (3a) include the following compounds.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-I000020
Figure JPOXMLDOC01-appb-I000021
　上記式（３ａ）で表される化合物以外の他のカイラル剤（Ｂ）としては、具体的には、例えば、下記式（３ｂ）で表される化合物、下記式（３ｃ）で表される化合物が好適に挙げられる。
Figure JPOXMLDOC01-appb-C000022
 As other chiral agent (B) other than the compound represented by the above formula (3a), specifically, for example, a compound represented by the following formula (3b), a compound represented by the following formula (3c) Are preferable.
Figure JPOXMLDOC01-appb-C000022
　上記式（３ａ）～（３ｃ）で表される化合物以外のカイラル剤（Ｂ）としては、例えば、特開２００５－２８９８８１号公報、特開２００４－１１５４１４号公報、特開２００３-６６２１４号公報、特開２００３-３１３１８７号公報、特開２００３－３４２２１９号公報、特開２０００－２９０３１５号公報、特開平６－０７２９６２号公報、米国特許第６４６８４４４号公報、ＷＯ９８／００４２８号公報等に掲載されるものを適宜使用することができ、また、ＢＡＳＦ社パリオカラーのＬＣ７５６、ＡＤＥＫＡ社キラコールのＣＮＬ６１７Ｒ、ＣＮＬ－６８６Ｌなどの市販品も適宜使用することができる。 Examples of the chiral agent (B) other than the compounds represented by the above formulas (3a) to (3c) include, for example, JP-A-2005-289881, JP-A-2004-115414, JP-A-2003-66214, Published in JP2003-313187, JP2003-342219, JP2000-290315, JP6-072962, U.S. Pat. No. 6,468,444, WO98 / 00428, etc. Commercially available products such as BASF's Palio Color LC756, ADEKA Kiracol's CNL617R, and CNL-686L can also be used as appropriate.
　本発明においては、硬化皮膜のブルーライトカット機能がより良好となる理由から、上記カイラル剤（Ｂ）の含有量が、上記ネマチック液晶性化合物（Ａ）および上記カイラル剤（Ｂ）の合計質量に対して１．０～３０．０質量％であるのが好ましい。
　特に、上記ネマチック液晶性化合物（Ａ）として上記式（２ａ）で表される化合物を用い、上記カイラル剤（Ｂ）として上記式（３ａ）で表される化合物を用いた場合には、上記カイラル剤（Ｂ）の含有量が、上記ネマチック液晶性化合物（Ａ）および上記カイラル剤（Ｂ）の合計質量に対して４．０～６．５質量％であるのが好ましい。 In the present invention, because the blue light cut function of the cured film becomes better, the content of the chiral agent (B) is the total mass of the nematic liquid crystalline compound (A) and the chiral agent (B). The content is preferably 1.0 to 30.0% by mass.
In particular, when the compound represented by the formula (2a) is used as the nematic liquid crystalline compound (A) and the compound represented by the formula (3a) is used as the chiral agent (B), the chiral The content of the agent (B) is preferably 4.0 to 6.5% by mass with respect to the total mass of the nematic liquid crystal compound (A) and the chiral agent (B).
　＜光重合開始剤（Ｃ）＞
　本発明の組成物が含有する光重合開始剤（Ｃ）は、光によって上記ネマチック液晶性化合物（Ａ）および上記カイラル剤（Ｂ）を重合することができるものであれば特に限定されない。
　光重合開始剤（Ｃ）としては、例えば、アセトフェノン系化合物、ベンゾインエーテル系化合物、ベンゾフェノン系化合物、硫黄化合物、アゾ化合物、パーオキサイド化合物、ホスフィンオキサイド系化合物等が挙げられる。
　具体的には、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、アセトイン、ブチロイン、トルオイン、ベンジル、ベンゾフェノン、ｐ－メトキシベンゾフェノン、ジエトキシアセトフェノン、α，α－ジメトキシ－α－フェニルアセトフェノン、メチルフェニルグリオキシレート、エチルフェニルグリオキシレート、４，４′－ビス（ジメチルアミノベンゾフェノン）、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトンなどのカルボニル化合物；テトラメチルチウラムモノスルフィド、テトラメチルチウラムジスルフィドなどの硫黄化合物；アゾビスイソブチロニトリル、アゾビス－２，４－ジメチルバレロなどのアゾ化合物；ベンゾイルパーオキサイド、ジ－ｔ－ブチルパーオキサイドなどのパーオキサイド化合物；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。 <Photopolymerization initiator (C)>
The photopolymerization initiator (C) contained in the composition of the present invention is not particularly limited as long as it can polymerize the nematic liquid crystalline compound (A) and the chiral agent (B) with light.
Examples of the photopolymerization initiator (C) include acetophenone compounds, benzoin ether compounds, benzophenone compounds, sulfur compounds, azo compounds, peroxide compounds, phosphine oxide compounds, and the like.
Specifically, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone Methylphenylglyoxylate, ethylphenylglyoxylate, 4,4′-bis (dimethylaminobenzophenone), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1, Carbonyl compounds such as 2-diphenylethane-1-one and 1-hydroxycyclohexyl phenyl ketone; Sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; Azobis Azo compounds such as sobutyronitrile and azobis-2,4-dimethylvalero; peroxide compounds such as benzoyl peroxide and di-t-butyl peroxide; and the like. These may be used alone or in combination. You may use the above together.
　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、低臭気などの観点から、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－オンが好ましい。 Of these, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl are preferred from the viewpoints of light stability, high efficiency of photocleavage, surface curability, compatibility, low volatility, low odor and the like. -Propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one is preferred.
　本発明においては、上記光重合開始剤（Ｃ）の含有量は、上記ネマチック液晶性化合物（Ａ）および上記カイラル剤（Ｂ）の合計１００質量部に対して、０．５～２０質量部であるのが好ましく、３～９質量部であるのがより好ましい。 In the present invention, the content of the photopolymerization initiator (C) is 0.5 to 20 parts by mass with respect to a total of 100 parts by mass of the nematic liquid crystalline compound (A) and the chiral agent (B). It is preferably 3 to 9 parts by mass.
　＜ナフタルイミド骨格を有する化合物（Ｄ）＞
　本発明の組成物は、ブルーライト領域の中でも短波長側の領域（３８５～４２０ｎｍ）を吸収でき、ブルーライトカット機能が全体としてより良好となる理由から、下記式（１）で表されるナフタルイミド骨格を有する化合物（Ｄ）を含有するのが好ましい。
Figure JPOXMLDOC01-appb-C000023
 　（式（１）中、Ｒ1は、水素原子またはヘテロ原子を有していてもよい炭化水素基を表し、Ｒ2は、水素原子または有機基を表し、複数のＲ2は同一であっても異なっていてもよい。） <Compound (D) having naphthalimide skeleton>
The composition of the present invention can absorb a short wavelength region (385 to 420 nm) in the blue light region, and the blue light cut function as a whole is better, so that the nano formula represented by the following formula (1) is used. The compound (D) having a phthalimide skeleton is preferably contained.
Figure JPOXMLDOC01-appb-C000023
 (In the formula (1), R 1 represents a hydrogen atom or a hetero atom substituted hydrocarbon group which may have a, R 2 represents a hydrogen atom or an organic group, plural R 2 may be the same May be different.)
　上記式（１）中のＲ1で示されるヘテロ原子を有していてもよい炭化水素基としては、例えば、脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基、これらの組み合わせが挙げられ、不飽和結合を有してもよい。
　また、Ｒ2で示される有機基としては、例えば、アミノ基、水酸基などの官能基；脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基などの炭化水素基；これらを組み合わせた炭化水素基；が挙げられる。なお、炭化水素基は、ヘテロ原子や二重結合を有していてもよい。
　また、Ｒ1で示される炭化水素基は、直鎖状または分岐状のアルキル基であるのが好ましく、炭素数は１～１２であるのが好ましい。
　また、Ｒ2で示される有機基のうち、炭化水素基としては、アルコキシ基であるのが好ましく、メトキシ基またはエトキシ基であるのがより好ましい。 Examples of the hydrocarbon group optionally having a hetero atom represented by R 1 in the above formula (1) include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and these Combinations may be mentioned and may have an unsaturated bond.
Examples of the organic group represented by R 2 include functional groups such as amino groups and hydroxyl groups; hydrocarbon groups such as aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups; And hydrocarbon groups. In addition, the hydrocarbon group may have a hetero atom or a double bond.
Further, the hydrocarbon group represented by R 1 is preferably a linear or branched alkyl group, and preferably has 1 to 12 carbon atoms.
Of the organic groups represented by R 2 , the hydrocarbon group is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.
　ナフタルイミド骨格を有する化合物（Ｄ）を含有する場合の含有量は、上記ネマチック液晶性化合物（Ａ）および上記カイラル剤（Ｂ）の合計１００質量部に対して、０．０５～１０質量部であるのが好ましく、１．０～３．０質量部であるのがより好ましい。 When the compound (D) having a naphthalimide skeleton is contained, the content is 0.05 to 10 parts by mass with respect to 100 parts by mass in total of the nematic liquid crystalline compound (A) and the chiral agent (B). The amount is preferably 1.0 to 3.0 parts by mass.
　＜化合物（Ｅ１）／化合物（Ｅ２）＞
　本発明の組成物は、ブルーライト領域の中でも短波長側の領域（３８５～４３０ｎｍ）を吸収でき、ブルーライトカット機能が全体としてより良好となる理由から、ベンゾトリアゾール骨格を有する化合物（Ｅ１）および／またはヒドロキシフェニルトリアジン骨格を有する化合物（Ｅ２）を含有するのが好ましい。 <Compound (E1) / Compound (E2)>
The composition of the present invention can absorb the short wavelength side region (385 to 430 nm) in the blue light region, and the blue light cut function as a whole becomes better. Therefore, the compound (E1) having a benzotriazole skeleton and It is preferable to contain a compound (E2) having a hydroxyphenyltriazine skeleton.
　ベンゾトリアゾール骨格を有する化合物（Ｅ１）としては、例えば、下記式（４）で表される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000024
 　（式（４）中、Ｒ3は、水素原子またはヘテロ原子を有していてもよい炭化水素基を表す。） As a compound (E1) which has a benzotriazole skeleton, the compound represented by following formula (4) is mentioned, for example.
Figure JPOXMLDOC01-appb-C000024
 (In formula (4), R 3 represents a hydrogen atom or a hydrocarbon group which may have a hetero atom.)
　上記式（４）中のＲ3で示されるヘテロ原子を有していてもよい炭化水素基としては、例えば、脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基、これらの組み合わせが挙げられ、不飽和結合を有してもよい。 Examples of the hydrocarbon group optionally having a hetero atom represented by R 3 in the above formula (4) include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and the like. Combinations may be mentioned and may have an unsaturated bond.
　このようなベンゾトリアゾール骨格を有する化合物（Ｅ１）の市販品としては、例えば、チヌビンＣａｒｂｏ ｐｒｏｔｅｃｔ（ＢＡＳＦ社製）、チヌビン３８４－２（ＢＡＳＦ社製）等が挙げられる。 Examples of commercially available compounds having such a benzotriazole skeleton (E1) include Tinuvin Carbo protect (BASF) and Tinuvin 384-2 (BASF).
　ベンゾトリアゾール骨格を有する化合物（Ｅ１）を含有する場合の含有量は、上記ネマチック液晶性化合物（Ａ）および上記カイラル剤（Ｂ）の合計１００質量部に対して、０．０５～１０質量部であるのが好ましく、１．０～３．０質量部であるのがより好ましい。 The content of the compound (E1) having a benzotriazole skeleton is 0.05 to 10 parts by mass with respect to 100 parts by mass in total of the nematic liquid crystalline compound (A) and the chiral agent (B). The amount is preferably 1.0 to 3.0 parts by mass.
　一方、ヒドロキシフェニルトリアジン骨格を有する化合物（Ｅ２）としては、例えば、下記式（５）で表される化合物等が挙げられる。
Figure JPOXMLDOC01-appb-C000025
 　（式（５）中、Ｒ4は、ヘテロ原子を有していてもよい炭化水素基を表す。Ｒ5は、水素原子または有機基を表し、複数のＲ5は、いずれも同一であっても異なっていてもよい。Ｒ6は、水素原子または有機基を表し、複数のＲ6は、いずれも同一であっても異なっていてもよい。） On the other hand, examples of the compound (E2) having a hydroxyphenyltriazine skeleton include compounds represented by the following formula (5).
Figure JPOXMLDOC01-appb-C000025
 (In the formula (5), R 4 represents a hydrocarbon group which may have a hetero atom. R 5 represents a hydrogen atom or an organic group, and a plurality of R 5 are the same. R 6 represents a hydrogen atom or an organic group, and a plurality of R 6 may be the same or different.)
　上記式（５）中のＲ4で示されるヘテロ原子を有していてもよい炭化水素基としては、例えば、脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基、これらの組み合わせが挙げられ、不飽和結合を有してもよい。なかでも、ヘテロ原子やヒドロキシ基を有していてもよい脂肪族炭化水素基であるのが好ましい。
　上記式（５）中のＲ5で示される有機基としては、例えば、アミノ基、水酸基などの官能基；脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基などの炭化水素基；これらを組み合わせた炭化水素基；が挙げられる。なかでも、脂肪族炭化水素基（特にアルキル基）であるのが好ましく、炭素数１～４のアルキル基であるのがより好ましく、メチル基またはエチル基であるのが更に好ましい。
　上記式（５）中のＲ6で示される有機基としては、例えば、アミノ基、水酸基などの官能基；脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基などの炭化水素基；これらを組み合わせた炭化水素基；が挙げられる。なお、炭化水素基は、ヘテロ原子や二重結合を有していてもよい。なかでも、脂肪族炭化水素基（特に、アルキル基、アルコキシ基）、芳香族炭化水素基（特にフェニル基）であるのが好ましい。 Examples of the hydrocarbon group optionally having a heteroatom represented by R 4 in the above formula (5) include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, these Combinations may be mentioned and may have an unsaturated bond. Of these, an aliphatic hydrocarbon group which may have a hetero atom or a hydroxy group is preferable.
Examples of the organic group represented by R 5 in the above formula (5) include functional groups such as amino groups and hydroxyl groups; hydrocarbons such as aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. Group; a hydrocarbon group obtained by combining these groups. Of these, an aliphatic hydrocarbon group (particularly an alkyl group) is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group or an ethyl group is still more preferable.
Examples of the organic group represented by R 6 in the above formula (5) include functional groups such as amino groups and hydroxyl groups; hydrocarbons such as aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. Group; a hydrocarbon group obtained by combining these groups. In addition, the hydrocarbon group may have a hetero atom or a double bond. Of these, an aliphatic hydrocarbon group (particularly an alkyl group or an alkoxy group) or an aromatic hydrocarbon group (particularly a phenyl group) is preferable.
　このようなヒドロキシフェニルトリアジン骨格を有する化合物（Ｅ２）の市販品としては、例えば、チヌビン４００（ＢＡＳＦ社製）、チヌビン ４０５（ＢＡＳＦ社製）、チヌビン４６０（ＢＡＳＦ社製）、チヌビン ４７７（ＢＡＳＦ社製）、チヌビン４７９（ＢＡＳＦ社製）等が挙げられる。 Examples of commercially available compounds (E2) having such a hydroxyphenyltriazine skeleton include Tinuvin 400 (manufactured by BASF), Tinuvin 405 (manufactured by BASF), Tinuvin 460 (manufactured by BASF), Tinuvin 社 477 (BASF). Manufactured), Tinuvin 479 (manufactured by BASF) and the like.
　ヒドロキシフェニルトリアジン骨格を有する化合物（Ｅ２）を含有する場合の含有量は、上記ネマチック液晶性化合物（Ａ）および上記カイラル剤（Ｂ）の合計１００質量部に対して、０．０５～１０質量部であるのが好ましく、１．０～３．０質量部であるのがより好ましい。 When the compound (E2) having a hydroxyphenyltriazine skeleton is contained, the content is 0.05 to 10 parts by mass with respect to 100 parts by mass in total of the nematic liquid crystalline compound (A) and the chiral agent (B). It is preferably 1.0 to 3.0 parts by mass.
　＜溶剤＞
　本発明の組成物は、塗工性が良好となる観点から、更に、溶剤を含むのが好ましい。
　溶剤は、上述した各成分を溶解することができるものであれば特に限定されない。例えば、メチルエチルケトン（ＭＥＫ）、メチルイソブチケトン（ＭＩＢＫ）、シクロヘキサノンのようなケトン類；プロピレングリコールモノメチルエーテル（ＰＧＭＥ）、イソプロピルアルコール（ＩＰＡ）のようなアルコール；シクロヘキサンのようなシクロアルカン；トルエン、キシレン、ベンジルアルコールのような芳香族炭化水素化合物が挙げられる。なかでも、溶解性、乾燥性や塗装性に優れるという観点から、シクロヘキサノン、ＭＩＢＫが好ましい。
　溶剤は、それぞれ単独でまたは２種以上を組み合わせて使用することができる。 <Solvent>
The composition of the present invention preferably further contains a solvent from the viewpoint of good coatability.
A solvent will not be specifically limited if it can melt | dissolve each component mentioned above. For example, ketones such as methyl ethyl ketone (MEK), methyl isobutyketone (MIBK), cyclohexanone; alcohols such as propylene glycol monomethyl ether (PGME) and isopropyl alcohol (IPA); cycloalkanes such as cyclohexane; toluene, xylene And aromatic hydrocarbon compounds such as benzyl alcohol. Of these, cyclohexanone and MIBK are preferred from the viewpoint of excellent solubility, drying properties, and paintability.
A solvent can be used individually or in combination of 2 types or more, respectively.
　本発明においては、任意の溶剤の含有量は、塗工性の観点から、組成物の全量中、８５～５質量％であるのが好ましい。 In the present invention, the content of an arbitrary solvent is preferably 85 to 5% by mass in the total amount of the composition from the viewpoint of coating properties.
　＜レベリング剤＞
　本発明の組成物は、硬化皮膜のブルーライトカット機能がより良好となる理由から、更に、レベリング剤を含むのが好ましい。
　レベリング剤としては、例えば、シリコーン系レベリング剤、アクリル系レベリング剤、ビニル系レベリング剤、フッ素系レベリング剤等が挙げられる。
　これらのうち、硬化皮膜の均一性を高め、結果として、硬化皮膜の透明性が良好となるという理由から、アクリル系レベリング剤を用いるのが好ましい。 <Leveling agent>
The composition of the present invention preferably further contains a leveling agent because the blue light cut function of the cured film becomes better.
Examples of the leveling agent include silicone leveling agents, acrylic leveling agents, vinyl leveling agents, and fluorine leveling agents.
Among these, it is preferable to use an acrylic leveling agent because the uniformity of the cured film is improved and, as a result, the transparency of the cured film is improved.
　本発明においては、任意のレベリング剤の含有量は、塗工性の観点から、組成物の全量中、０．０１～３質量％であるのが好ましい。 In the present invention, the content of an arbitrary leveling agent is preferably 0.01 to 3% by mass in the total amount of the composition from the viewpoint of coatability.
　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、紫外線吸収剤、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、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。 The composition of the present invention is, for example, an ultraviolet absorber, a filler, an anti-aging agent, an antistatic agent, a flame retardant, an adhesion-imparting agent, a dispersant, an antioxidant, Additives such as foaming agents, matting agents, light stabilizers, dyes, pigments can be further contained.
　本発明の組成物の製造方法は特に限定されず、上述したネマチック液晶性化合物（Ａ）、カイラル剤（Ｂ）および光重合開始剤（Ｃ）ならびに任意の化合物（Ｄ）、化合物（Ｅ１）、化合物（Ｅ２）、溶剤、レベリング剤および添加剤を均一に混合することによって製造することができる。 The production method of the composition of the present invention is not particularly limited, and the above-described nematic liquid crystal compound (A), chiral agent (B) and photopolymerization initiator (C), and any compound (D), compound (E1), It can be produced by uniformly mixing the compound (E2), a solvent, a leveling agent and an additive.
 〔積層体〕
　本発明の積層体は、基材と、硬化皮膜とを有する積層体であって、上記硬化皮膜が、上述した本発明の組成物を用いて形成される積層体である。
　本発明の積層体は、本発明の組成物を用いて形成される硬化皮膜を有するため、ブルーライトカット機能に優れる。 [Laminate]
The laminate of the present invention is a laminate having a substrate and a cured film, and the cured film is formed using the above-described composition of the present invention.
Since the laminated body of this invention has a cured film formed using the composition of this invention, it is excellent in a blue light cut function.
　次に、本発明の積層体の構成について、図１を用いて説明する。
　図１に示す積層体１００は、基材１０２と、本発明の組成物を用いて形成される硬化皮膜１０４とを有する。
　ここで、基材および硬化皮膜の厚さは特に制限されないが、基材の厚さは５０～３００μｍ程度であるのが好ましく、硬化皮膜の厚さは０．１～１００μｍ程度であるのが好ましい。 Next, the structure of the laminated body of this invention is demonstrated using FIG.
The laminated body 100 shown in FIG. 1 has the base material 102 and the cured film 104 formed using the composition of this invention.
Here, the thickness of the substrate and the cured film is not particularly limited, but the thickness of the substrate is preferably about 50 to 300 μm, and the thickness of the cured film is preferably about 0.1 to 100 μm. .
　＜基材＞
　上記基材は特に限定されず、その構成材料としては、例えば、プラスチック、ゴム、ガラス、金属、セラミック等が挙げられる。
　ここで、プラスチックは、熱硬化性樹脂および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、ポリエチレンテレフタレート（ＰＥＴ）、シクロオレフィン系重合体（単独重合体、共重合体、水素添加物を含む。例えば、ＣＯＰやＣＯＣ）、ポリメチルメタクリレート樹脂（ＰＭＭＡ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、ポリアミド樹脂等が挙げられる。
　また、上記基材は、例えば、コロナ処理のような表面処理がなされていてもよい。
　また、上記基材の形態は特に限定されないが、フィルム状であるのが好ましい。 <Base material>
The said base material is not specifically limited, As a constituent material, plastics, rubber | gum, glass, a metal, a ceramic etc. are mentioned, for example.
Here, the plastic may be either a thermosetting resin or a thermoplastic resin. Specific examples thereof include polyethylene terephthalate (PET), cycloolefin polymer (homopolymer, copolymer, hydrogenated). For example, COP and COC), polymethyl methacrylate resin (PMMA resin), polycarbonate resin, polystyrene resin, acrylonitrile / styrene copolymer resin, polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, polyamide resin, etc. Is mentioned.
The base material may be subjected to a surface treatment such as a corona treatment.
The form of the substrate is not particularly limited, but is preferably a film.
　ここで、ＣＯＣは、テトラシクロドデセンとエチレン等のオレフィンとの共重合体（シクロオレフィンコポリマー）である。また、ＣＯＰは、ノルボルネン類を開環重合し、水素添加して得られる重合体（シクロオレフィンポリマー）である。
　以下に、ＣＯＣおよびＣＯＰの構造の例を示す。 Here, COC is a copolymer (cycloolefin copolymer) of tetracyclododecene and an olefin such as ethylene. COP is a polymer (cycloolefin polymer) obtained by ring-opening polymerization of norbornene and hydrogenation.
Examples of COC and COP structures are shown below.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　＜樹脂層＞
　本発明の積層体は、上記硬化皮膜を構成する液晶性化合物の配向（ねじれ）状態が良好となり、上記基材との密着性も良好となる理由から、上記基材と上記硬化皮膜との間に、樹脂層を有しているのが好ましい。
　本発明においては、上記樹脂層を設ける場合、上記樹脂層は、表面張力が３２ｍＮ／ｍ以上のアクリル系樹脂層であるのが好ましい。
　ここで、表面張力は、硬化後のアクリル系樹脂層に、濡れペン（ペンナンバー３０、３２、３４、３６、３８、４０、４２および４４ｍＮ／ｍの８本セット、アルコテスト社製）を塗り、塗った後に２～５秒経過した際にペン筋の状態を目視により確認し、インクがはじかない最も大きなペンナンバーを選定して判定する。 <Resin layer>
In the laminate of the present invention, the orientation (twist) state of the liquid crystal compound constituting the cured film becomes good, and the adhesiveness with the base material is also good. Further, it is preferable to have a resin layer.
In the present invention, when the resin layer is provided, the resin layer is preferably an acrylic resin layer having a surface tension of 32 mN / m or more.
Here, the surface tension is applied to the cured acrylic resin layer with a wet pen (8 sets of pen numbers 30, 32, 34, 36, 38, 40, 42 and 44 mN / m, manufactured by Alcotest). When 2 to 5 seconds have elapsed after coating, the state of the pen streaks is visually confirmed, and the largest pen number that does not repel ink is selected and determined.
　このようなアクリル系樹脂層は、表面張力が３２ｍＮ／ｍ以上であれば、例えば、従来公知のハードコートに用いられる紫外線硬化型樹脂組成物（以下、「ハードコート用樹脂組成物」と略す。）を用いて形成されるアクリル系樹脂層であるのが好ましい。なお、表面張力の調整は、従来公知のレベリング剤、界面活性剤、親水性または親油性付与剤などを含有させることにより行うことができる。
　ここで、上記ハードコート用樹脂組成物としては、例えば、後述する多官能（メタ）アクリレート（ａ）および光重合開始剤（ｂ）等を含有する組成物を用いることができる。 If such an acrylic resin layer has a surface tension of 32 mN / m or more, it is abbreviated as, for example, an ultraviolet curable resin composition (hereinafter referred to as “hard coat resin composition”) used in a conventionally known hard coat. ) Is preferably an acrylic resin layer formed using The surface tension can be adjusted by adding a conventionally known leveling agent, surfactant, hydrophilicity or lipophilicity imparting agent.
Here, as the resin composition for hard coat, for example, a composition containing a polyfunctional (meth) acrylate (a) and a photopolymerization initiator (b) described later can be used.
　（多官能（メタ）アクリレート（ａ））
　上記多官能（メタ）アクリレート（ａ）は、（メタ）アクリロイルオキシ基を２個以上有する化合物であれば特に制限されない。
　（メタ）アクリロイルオキシ基は有機基に結合することができる。有機基としては、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してもよい炭化水素基が挙げられる。炭化水素基としては、例えば、脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基、これらの組み合わせが挙げられる。炭化水素基は直鎖状、分岐状を含むことができ、不飽和結合を有してもよい。
　多官能（メタ）アクリレート（ａ）は、得られるアクリル系樹脂層の硬度が高く、上記基材と上記硬化皮膜との密着性がより良好となる理由から、（メタ）アクリロイルオキシ基を４～１２個有するのが好ましい。 (Polyfunctional (meth) acrylate (a))
The polyfunctional (meth) acrylate (a) is not particularly limited as long as it is a compound having two or more (meth) acryloyloxy groups.
The (meth) acryloyloxy group can be bonded to an organic group. As an organic group, the hydrocarbon group which may have hetero atoms, such as an oxygen atom, a nitrogen atom, and a sulfur atom, is mentioned, for example. Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof. The hydrocarbon group may include a straight chain and a branched chain, and may have an unsaturated bond.
The polyfunctional (meth) acrylate (a) has a high hardness of the resulting acrylic resin layer, and has better adhesion between the substrate and the cured film. It is preferable to have twelve.
　多官能（メタ）アクリレート（ａ）としては、例えば、多価アルコールの（メタ）アクリル酸エステル、ウレタン（メタ）アクリレートが挙げられる。
　多価アルコールの（メタ）アクリル酸エステルとしては、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）アクリレートのような３官能系；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）アクリレートのような４官能系；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）アクリレートのような５官能以上の系が挙げられる。 Examples of the polyfunctional (meth) acrylate (a) include polyhydric alcohol (meth) acrylic acid esters and urethane (meth) acrylates.
Examples of polyhydric alcohol (meth) acrylic acid esters include trifunctional groups such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol tri (meth) acrylate; pentaerythritol tetra Tetrafunctional system such as (meth) acrylate, dipentaerythritol tetra (meth) acrylate, tripentaerythritol tetra (meth) acrylate; dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol Penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol o Data (meth) 5 or higher functional systems such as acrylate.
　ウレタン（メタ）アクリレートとしては、例えば、多価アルコールの（メタ）アクリル酸エステル（この場合、多価アルコールの（メタ）アクリル酸エステルとしては例えば、少なくとも１つのヒドロキシ基を有するものが挙げられる。）とポリイソシアネート化合物との反応物が挙げられる。
　ウレタン（メタ）アクリレートを製造する際に使用される多価アルコールの（メタ）アクリル酸エステルとしては、例えば、上記と同様のものが挙げられる。
　ウレタン（メタ）アクリレートを製造する際に使用される、ポリイソシアネート化合物としては、例えば、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、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、テトラメチルキシリレンジイソシアネート、トリジンジイソシアネート、１，５－ナフタレンジイソシアネート、トリフェニルメタントリイソシアネートのような芳香族系ポリイソシアネート；ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、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、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、ビス（イソシアネートメチル）シクロヘキサン、ジシクロヘキシルメタンジイソシアネートのような脂肪族系ポリイソシアネート（鎖状及び／又は脂環式系を含む。）；これらのイソシアヌレート体、ビューレット体、アダクト体；ウレタンプレポリマーが挙げられる。 Examples of urethane (meth) acrylates include (meth) acrylic acid esters of polyhydric alcohols (in this case, (meth) acrylic acid esters of polyhydric alcohols include those having at least one hydroxy group). ) And a polyisocyanate compound.
Examples of the (meth) acrylic acid ester of polyhydric alcohol used when producing urethane (meth) acrylate include the same as those described above.
Examples of polyisocyanate compounds used in the production of urethane (meth) acrylate include tolylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and tolidine diisocyanate. Aromatic polyisocyanates such as 1,5-naphthalene diisocyanate and triphenylmethane triisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, bis (Isocyanate methyl) Cyclohexane, (including linear and / or cycloaliphatic systems.) Aliphatic polyisocyanates such as dicyclohexylmethane diisocyanate; these isocyanurate, biuret body, an adduct; and the urethane prepolymer.
　（光重合開始剤（ｂ））
　一方、上記光重合開始剤（ｂ）は、光によって上記多官能（メタ）アクリレート（ａ）を重合することができるものであれば特に限定されず、本発明の組成物が含有する上記光重合開始剤（Ｃ）と同様のものを適宜選択して用いることができる。 (Photopolymerization initiator (b))
On the other hand, the photopolymerization initiator (b) is not particularly limited as long as it can polymerize the polyfunctional (meth) acrylate (a) by light, and the photopolymerization contained in the composition of the present invention. A thing similar to an initiator (C) can be selected suitably, and can be used.
　上記ハードコート用樹脂組成物は、本発明の目的を損なわない範囲で、例えば、紫外線吸収剤、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。
　レベリング剤としては、例えば、シリコーン系レベリング剤、アクリル系レベリング剤、ビニル系レベリング剤、フッ素系レベリング剤等が挙げられる。 The hard coat resin composition is, for example, an ultraviolet absorber, a filler, an anti-aging agent, an antistatic agent, a flame retardant, an adhesion-imparting agent, a dispersant, and an antioxidant as long as the object of the present invention is not impaired. Further, additives such as an antifoaming agent, a leveling agent, a matting agent, a light stabilizer, a dye and a pigment can be further contained.
Examples of the leveling agent include silicone leveling agents, acrylic leveling agents, vinyl leveling agents, and fluorine leveling agents.
　また、上記樹脂層の厚さは、上記基材と上記硬化皮膜との密着性がより良好となる理由から、０．１～１００μｍ程度であるのが好ましく、１～５μｍであるのがより好ましい。 The thickness of the resin layer is preferably about 0.1 to 100 μm, more preferably 1 to 5 μm, because the adhesion between the substrate and the cured film becomes better. .
　＜ハードコート層＞
　本発明の積層体は、上記硬化皮膜の上記基材とは反対側の表面に、ハードコート層を有していてもよい。
　ここで、ハードコート層は、上述した樹脂層において説明したハードコート用樹脂組成物を用いて形成されるアクリル系樹脂層であるのが好ましく、その形成方法は、上述した樹脂層の形成方法と同様の方法が挙げられる。
　ハードコート層を有する場合、その厚さは特に限定されないが、０．０１～５０μｍ程度であるのが好ましく、１～５μｍであるのがより好ましい。 <Hard coat layer>
The laminate of the present invention may have a hard coat layer on the surface of the cured film opposite to the substrate.
Here, the hard coat layer is preferably an acrylic resin layer formed using the hard coat resin composition described in the resin layer described above, and the formation method thereof is the same as the resin layer formation method described above. A similar method can be mentioned.
In the case of having a hard coat layer, the thickness is not particularly limited, but is preferably about 0.01 to 50 μm, more preferably 1 to 5 μm.
　＜製造方法＞
　本発明の積層体の製造方法は、例えば、フィルム状の基材（上記樹脂層を有する場合は上記樹脂層）上に、本発明の組成物を塗工し、乾燥し、紫外線を照射する工程を有する方法が挙げられる。
　ここで、本発明の組成物を基材上に塗工する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、塗工後に乾燥させる温度は、２０～１１０℃であるのが好ましい。
　また、乾燥後の紫外線照射は、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（積算光量）として、速硬化性、作業性の観点から、５０～３，０００ｍＪ／ｃｍ2が好ましい。紫外線を照射するために使用する装置は特に制限されない。例えば、従来公知のものが挙げられる。硬化させるに際し加熱を併用してもよい。
　なお、上記樹脂層の形成方法は、本発明の組成物と同様の方法で、基材上に塗工し、乾燥し、紫外線を照射する工程により形成することができる。 <Manufacturing method>
The method for producing a laminate of the present invention includes, for example, a step of coating the composition of the present invention on a film-like substrate (or the above resin layer if the resin layer is provided), drying, and irradiating ultraviolet rays The method which has this is mentioned.
Here, the method of coating the composition of the present invention on the substrate is not particularly limited, and for example, a known coating method such as brush coating, flow coating, dip coating, spray coating, spin coating or the like can be employed.
The temperature for drying after coating is preferably 20 to 110 ° C.
Further, the ultraviolet irradiation after drying is 50 to 3,000 mJ / cm 2 from the viewpoint of fast curability and workability as the irradiation amount (integrated light amount) of the ultraviolet rays used when the composition of the present invention is cured. preferable. The apparatus used for irradiating ultraviolet rays is not particularly limited. For example, a conventionally well-known thing is mentioned. Heating may be used in combination for curing.
In addition, the formation method of the said resin layer is a method similar to the composition of this invention, It can form by the process of apply | coating on a base material, drying, and irradiating an ultraviolet-ray.
　本発明の積層体は、例えば、電子画像表示装置、眼鏡レンズ、照明（特に、ＬＥＤ照明）用の保護カバー、太陽電池モジュール部材等に使用することができる。
　電子画像表示装置としては、例えば、パソコン、テレビ、タッチパネル、ウェラブル端末（例えば、眼鏡型、腕時計型などの身体に身につけることが可能なコンピューター端末）などのディスプレイ用途電子デバイス部品が挙げられる。
　本発明の積層体を電子画像表示装置等に内蔵または後付け（例えば外部からの貼付等）することができる。本発明の積層体を電子画像表示装置等に内蔵する場合、例えば反射板以外の部分に適用することができる。具体的には例えば、レンズシート、拡散シート、導光板に適用することができる。
　本発明の組成物を電子画像表示装置に直接適用して硬化皮膜を形成することができる。 The laminate of the present invention can be used for, for example, an electronic image display device, a spectacle lens, a protective cover for lighting (particularly LED lighting), a solar cell module member, and the like.
Examples of the electronic image display device include display-use electronic device components such as a personal computer, a television, a touch panel, and a wearable terminal (for example, a computer terminal that can be worn on the body such as a glasses type or a wrist watch type).
The laminated body of the present invention can be incorporated in an electronic image display device or the like, or can be retrofitted (for example, attached from the outside). When the laminate of the present invention is built in an electronic image display device or the like, it can be applied to a portion other than the reflector, for example. Specifically, for example, it can be applied to a lens sheet, a diffusion sheet, and a light guide plate.
The composition of the present invention can be directly applied to an electronic image display device to form a cured film.
　以下に、実施例を示し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ない。 Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
 〔実施例１～１８および比較例１～２〕
　＜組成物の調製＞
　下記第１表の各成分を、第１表に示す組成（質量部）で、撹拌機を用いて混合し、組成物を調製した。
　＜積層体の製造＞
　上記のようにして得られた各組成物をポリエチレンテレフタレートフィルム（ＰＥＴ生地：商品名Ｕ４６、東レ社製、厚さ１２５μｍ）にバーコーターを用いて乾燥後の膜厚で１．５μｍとなるようなクリアランス設定で塗布し、これを８０℃の条件下で１分間乾燥させた後、これに川口スプリング製作所社製のＧＳＵＶ ＳＹＳＴＥＭを用いて紫外線（ＵＶ）を照射（ＵＶ照射条件：照度３００ｍＷ／ｃｍ2、積算光量３００ｍＪ／ｃｍ2、ＵＶ照射装置は高圧水銀灯）して組成物を硬化させ、積層体を作製した。 [Examples 1 to 18 and Comparative Examples 1 and 2]
<Preparation of composition>
Each component of the following Table 1 was mixed with the composition (parts by mass) shown in Table 1 using a stirrer to prepare a composition.
<Manufacture of laminates>
Each composition obtained as described above has a film thickness after drying with a bar coater on a polyethylene terephthalate film (PET fabric: trade name U46, manufactured by Toray Industries, Inc., thickness 125 μm) to be 1.5 μm. After applying at a clearance setting and drying it at 80 ° C. for 1 minute, this was irradiated with ultraviolet rays (UV) using a GSUV SYSTEM manufactured by Kawaguchi Spring Mfg. Co., Ltd. (UV irradiation condition: illuminance: 300 mW / cm 2). The accumulated light quantity was 300 mJ / cm 2 , the UV irradiation device was a high-pressure mercury lamp), and the composition was cured to produce a laminate.
 〔評価〕
　製造した積層体を用いて以下の評価を行った。結果を第１表に示す。 [Evaluation]
The following evaluation was performed using the manufactured laminated body. The results are shown in Table 1.
　＜硬化皮膜のブルーライトの平均カット率＞
　上述のとおり製造した積層体に、装置として日立分光光度計３９００Ｈを用いて８００～３００ｎｍ領域の光を照射し、その３８５ｎｍ～４９５ｎｍ領域における平均透過率（％）を測定した。測定結果を下記式に当てはめて積層体のブルーライトの平均カット率を算出した。
　硬化皮膜のブルーライトの平均カット率（％）＝１００－（３８５～４９５ｎｍ領域の平均透過率）
　ここで、基材（ＰＥＴフィルム）のみ、実施例１、４および１０ならびに比較例１の吸収スペクトルを図２のグラフに示す。 <Average cut rate of blue light of cured film>
The laminate manufactured as described above was irradiated with light in the 800 to 300 nm region using a Hitachi spectrophotometer 3900H as an apparatus, and the average transmittance (%) in the 385 to 495 nm region was measured. The measurement result was applied to the following formula to calculate the average blue light cut rate of the laminate.
Average cut rate of blue light of cured film (%) = 100− (average transmittance in the region of 385 to 495 nm)
Here, only the base material (PET film), the absorption spectra of Examples 1, 4 and 10 and Comparative Example 1 are shown in the graph of FIG.
　＜黄色味＞
　作製した積層体の色差（Ｌ＊ａ＊ｂ＊表色系）について、ハンディタイプの簡易型分光色差計ＣＭ－５００（コニカミノルタ社製）を用い、ＪＩＳ Ｚ８７３０：２００９で規定されている方法で測定した。ｂ＊値の測定結果を下記第１表に示す。 <Yellow taste>
About the color difference (L * a * b * color system) of the produced laminate, a handy type simple spectral color difference meter CM-500 (manufactured by Konica Minolta Co., Ltd.) was used and the method specified in JIS Z8730: 2009. It was measured. The measurement results of b * values are shown in Table 1 below.
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
　第１表に示される各成分の詳細は以下のとおりである。
　・ネマチック液晶性化合物Ａ－１：上記式（２ａ）で表される化合物（ｎ＝４）
　・ネマチック液晶性化合物Ａ－２：上記式（２ｂ）で表される化合物
　・非液晶性化合物Ｘ－１：ジペンタエリスリトールヘキサアクリレート（ＤＰＨＡ）を主成分として含むヒドロキシ（メタ）アクリレート〔商品名：ＮＸ１０３－１６１、固形分８５％：亜細亜工業社製〕と、ヘキサメチレンジイソシアネートとを、質量比（８１／１９）で反応させた反応物
　・カイラル剤Ｂ－１：上記式（３ａ）で表される化合物（ｍ＝４）
　・カイラル剤Ｂ－２：上記式（３ｂ）で表される化合物
　・カイラル剤Ｂ－３：上記式（３ｃ）で表される化合物
　・光重合開始剤Ｃ－１：イルガキュア１８４（ＢＡＳＦ社製）
　・化合物Ｄ－１：ナフタルイミド骨格を有する化合物（上記式（１）におけるＲ1が、－ＣＨ2ＣＨ（ＣＨ2ＣＨ2ＣＨ3）2であり、Ｒ2が、－Ｏ－ＣＨ3である化合物）
　・化合物Ｅ１－１：ベンゾトリアゾール骨格を有する化合物（チヌビンＣａｒｂｏ ｐｒｏｔｅｃｔ、ＢＡＳＦ社製）
　・化合物Ｅ１－２：ベンゾトリアゾール骨格を有する化合物（チヌビン３８４－２、ＢＡＳＦ社製）
　・化合物Ｅ２－１：ヒドロキシフェニルトリアジン骨格を有する化合物（チヌビン４７７、ＢＡＳＦ社製）
　・化合物Ｅ２－２：ヒドロキシフェニルトリアジン骨格を有する化合物（チヌビン４７９、ＢＡＳＦ社製）
　・メチルエチルケトン：溶媒
　・シクロヘキサノン：溶媒
　・レベリング剤：アクリル系レベリング剤（ＢＹＫ３６１Ｎ、ビックケミー・ジャパン社製） The details of each component shown in Table 1 are as follows.
Nematic liquid crystalline compound A-1: compound represented by the above formula (2a) (n = 4)
Nematic liquid crystalline compound A-2: Compound represented by the above formula (2b) Non-liquid crystalline compound X-1: Hydroxy (meth) acrylate containing dipentaerythritol hexaacrylate (DPHA) as a main component [trade name: NX103-161, solid content 85%: manufactured by Asia Kogyo Co., Ltd.] and hexamethylene diisocyanate at a mass ratio (81/19). Chiral agent B-1: represented by the above formula (3a) Compound (m = 4)
Chiral agent B-2: Compound represented by the above formula (3b) Chiral agent B-3: Compound represented by the above formula (3c) Photopolymerization initiator C-1: Irgacure 184 (manufactured by BASF)
Compound D-1: Compound having a naphthalimide skeleton (R 1 in the above formula (1) is —CH 2 CH (CH 2 CH 2 CH 3 ) 2 , and R 2 is —O—CH 3 . Compound)
Compound E1-1: Compound having a benzotriazole skeleton (Tinuvin Carbo protect, manufactured by BASF)
Compound E1-2: Compound having a benzotriazole skeleton (Tinuvin 384-2, manufactured by BASF)
Compound E2-1: Compound having a hydroxyphenyltriazine skeleton (Tinuvin 477, manufactured by BASF)
Compound E2-2: Compound having a hydroxyphenyltriazine skeleton (Tinuvin 479, manufactured by BASF)
-Methyl ethyl ketone: Solvent-Cyclohexanone: Solvent-Leveling agent: Acrylic leveling agent (BYK361N, manufactured by Big Chemie Japan)
　第１表に示す結果から明らかなように、重合性官能基を有するネマチック液晶性化合物（Ａ）を配合せず、非液晶性化合物を配合して調製した比較例１の組成物は、ブルーライトカット機能に劣ることが分かった（比較例１）。
　また、カイラル剤（Ｂ）を配合せずに調製した比較例２の組成物は、ブルーライトカット機能が不十分であることが分かった（比較例２）。 As is apparent from the results shown in Table 1, the composition of Comparative Example 1 prepared by blending the non-liquid crystalline compound without blending the nematic liquid crystalline compound (A) having a polymerizable functional group is blue light. It was found that the cutting function was inferior (Comparative Example 1).
Moreover, it turned out that the composition of the comparative example 2 prepared without mix | blending a chiral agent (B) has inadequate blue light cut function (comparative example 2).
　これに対し、重合性官能基を有するネマチック液晶性化合物（Ａ）、カイラル剤（Ｂ）および光重合開始剤（Ｃ）を配合して調製した組成物は、いずれもブルーライトカット機能を有する硬化皮膜を形成できることが分かり、また、いずれのｂ＊値も２．０以下となり、ブルーライトカット機能を有しているにも関わらず、黄色味が非常に低いことが分かった（実施例１～１８）。なお、市販のブルーライトカットフィルムにおいては、一般的にｂ＊値が７～２５の範囲にあることと対比しても、顕著な効果であることが分かる。
　特に、ネマチック液晶性化合物（Ａ）およびカイラル剤（Ｂ）とともに、ナフタルイミド骨格を有する化合物（Ｄ）、ベンゾトリアゾール骨格を有する化合物（Ｅ１）、または、ヒドロキシフェニルトリアジン骨格を有する化合物（Ｅ２）を併用した実施例２～８、１１～１２、１４および１６～１８の組成物は、ブルーライトカット機能がより向上することが分かった。 On the other hand, the composition prepared by blending the nematic liquid crystalline compound (A) having a polymerizable functional group, the chiral agent (B) and the photopolymerization initiator (C) is a cured product having a blue light cut function. It was found that a film could be formed, and all b * values were 2.0 or less, and it was found that the yellowness was very low despite having a blue light cut function (Example 1 to 18). It can be seen that a commercially available blue light cut film has a remarkable effect even when compared with the b * value generally in the range of 7 to 25.
In particular, together with the nematic liquid crystalline compound (A) and the chiral agent (B), a compound (D) having a naphthalimide skeleton, a compound (E1) having a benzotriazole skeleton, or a compound (E2) having a hydroxyphenyltriazine skeleton It was found that the compositions of Examples 2 to 8, 11 to 12, 14 and 16 to 18 used in combination improved the blue light cut function.
　図２は、積層体のＵＶ－可視光吸収スペクトルを示すグラフである。図２において「基材のみ」は実施例において積層体の製造に使用されたポリエチレンテレフタレートフィルム単独を意味する。図２に示す結果から明らかなように、実施例１、４および１０は、基材のみまたは比較例１より、ブルーライトを透過しないことが分かる。 FIG. 2 is a graph showing the UV-visible light absorption spectrum of the laminate. In FIG. 2, “base material only” means the polyethylene terephthalate film alone used in the production of the laminate in the examples. As is clear from the results shown in FIG. 2, it can be seen that Examples 1, 4 and 10 do not transmit blue light compared to the base material alone or Comparative Example 1.
 〔実施例１９～３４〕
　実施例１～３および実施例８で調製した各組成物を用いて、以下に示す方法で積層体Ａおよび積層体Ｂを作製し、以下に示す方法で硬化皮膜の密着性を評価した。 [Examples 19 to 34]
Using each composition prepared in Examples 1 to 3 and Example 8, laminate A and laminate B were prepared by the following method, and the adhesion of the cured film was evaluated by the following method.
　＜積層体Ａの製造－基材（ＰＥＴフィルム）＞
　ポリエチレンテレフタレートフィルム（ＰＥＴ生地：商品名Ｕ４６、東レ社製、厚さ１２５μｍ）に、下記第２表に示す品番のアクリル系樹脂組成物（いずれも横浜ゴム社製）をバーコーターを用いて乾燥後の膜厚で１．５μｍとなるようなクリアランス設定で塗布し、これを８０℃の条件下で１分間乾燥させた後、これに川口スプリング製作所社製のＧＳＵＶ ＳＹＳＴＥＭを用いて紫外線（ＵＶ）を照射（ＵＶ照射条件：照度３００ｍＷ／ｃｍ2、積算光量３００ｍＪ／ｃｍ2、ＵＶ照射装置は高圧水銀灯）して硬化させ、ＰＥＴ基材上にアクリル系樹脂層を形成した。形成したアクリル系樹脂層に、濡れペン（ペンナンバー３０、３２、３４、３６、３８、４０、４２および４４ｍＮ／ｍの８本セット、アルコテスト社製）を塗り、塗った後に２～５秒経過した際にペン筋の状態を目視により確認し、インクがはじかない最も大きなペンナンバーを選定し、表面張力を決定した。
　次いで、実施例１～３および実施例８で調製した各組成物を上記アクリル系樹脂層にバーコーターを用いて乾燥後の膜厚で１．５μｍとなるようなクリアランス設定で塗布し、これを８０℃の条件下で１分間乾燥させた後、これに川口スプリング製作所社製のＧＳＵＶ ＳＹＳＴＥＭを用いて紫外線（ＵＶ）を照射（ＵＶ照射条件：照度３００ｍＷ／ｃｍ2、積算光量３００ｍＪ／ｃｍ2、ＵＶ照射装置は高圧水銀灯）して組成物を硬化させ、積層体を作製した。 <Manufacture of laminate A-base material (PET film)>
After drying a polyethylene terephthalate film (PET fabric: trade name U46, manufactured by Toray Industries, Inc., thickness 125 μm) with an acrylic resin composition having the product numbers shown in Table 2 below (both manufactured by Yokohama Rubber Co., Ltd.) using a bar coater. The film was applied with a clearance setting such that the film thickness was 1.5 μm, and this was dried at 80 ° C. for 1 minute, and then UV (UV) was applied thereto using GSUV SYSTEM manufactured by Kawaguchi Spring Manufacturing Co., Ltd. Irradiation (UV irradiation conditions: illuminance: 300 mW / cm 2 , integrated light quantity: 300 mJ / cm 2 , UV irradiation apparatus: high-pressure mercury lamp) was cured by curing to form an acrylic resin layer on the PET substrate. Apply a wet pen (8 sets of pen numbers 30, 32, 34, 36, 38, 40, 42, and 44 mN / m, manufactured by Alcotest) to the formed acrylic resin layer, and apply for 2 to 5 seconds. When the time passed, the state of the pen streaks was visually confirmed, the largest pen number that did not repel ink was selected, and the surface tension was determined.
Next, each composition prepared in Examples 1 to 3 and Example 8 was applied to the acrylic resin layer using a bar coater with a clearance setting such that the film thickness after drying was 1.5 μm. After drying at 80 ° C. for 1 minute, this was irradiated with ultraviolet rays (UV) using a GSUV SYSTEM manufactured by Kawaguchi Spring Manufacturing Co., Ltd. (UV irradiation conditions: illuminance 300 mW / cm 2 , integrated light quantity 300 mJ / cm 2 , The composition was cured by using a high-pressure mercury lamp (UV irradiation device) to prepare a laminate.
　＜積層体Ｂの製造－基材（シクロオレフィン）＞
　基材として、コロナ処理が施されたシクロオレフィンフィルム（ＣＯＰ生地：商品名ＺＦ１６－１００、日本ゼオン社製、厚さ１００μ）を用いた以外は、積層体Ａと同様の方法により、積層体Ｂを作製した。 <Production of Laminate B-Base Material (Cycloolefin)>
Laminate B was prepared in the same manner as Laminate A, except that a cycloolefin film (COP fabric: trade name ZF16-100, manufactured by Nippon Zeon Co., Ltd., thickness 100 μ) subjected to corona treatment was used as the substrate. Was made.
　＜密着性＞
　作製した積層体ＡおよびＢについて、ＪＩＳ Ｋ５４００に基づいた碁盤目剥離試験を行い、密着性を評価した。
　具体的には、カッターを用いて各積層体の硬化皮膜の部分と樹脂層の部分のみに１ｍｍピッチで切れ込みを入れ、基盤目を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。残った基盤目の数が７５個以上の場合は密着性に優れるものとして「○」と評価し、７５個未満の場合は密着性にやや劣るものとして「×」と評価した。結果を下記第２表に示す。 <Adhesion>
The produced laminates A and B were subjected to a cross-cut peel test based on JIS K5400 to evaluate the adhesion.
Specifically, using a cutter, cut only 1mm pitch in the cured film part and resin layer part of each laminate to make 100 bases (10x10), and cellophane adhesive on the bases A tape (18 mm in width) was completely attached, and immediately pulled off while keeping one end of the tape at a right angle to the substrate, and the number of remaining bases without being completely peeled was examined. When the number of remaining bases was 75 or more, it was evaluated as “◯” as being excellent in adhesion, and when it was less than 75, it was evaluated as “x” as being slightly inferior in adhesion. The results are shown in Table 2 below.
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000028
　第２表に示す結果から、積層体として、基材と硬化皮膜との間に樹脂層を設ける場合、樹脂層を構成するアクリル系ポリマーの表面張力が３２ｍＮ／ｍ以上であると、基材と硬化皮膜との密着性が良好となることが分かった。 From the results shown in Table 2, when a resin layer is provided between the substrate and the cured film as a laminate, the surface tension of the acrylic polymer constituting the resin layer is 32 mN / m or more. It was found that the adhesion with the cured film was good.
　１００　積層体
　１０２　基材
　１０４　硬化皮膜 100 Laminated body 102 Base material 104 Cured film

Claims (9)

  1. 　重合性官能基を有するネマチック液晶性化合物（Ａ）、カイラル剤（Ｂ）および光重合開始剤（Ｃ）を含有し、３８５ｎｍ～４９５ｎｍの波長領域の少なくとも一部の光の透過率を低減する硬化皮膜を形成するための紫外線硬化型樹脂組成物。 Curing containing a nematic liquid crystal compound (A) having a polymerizable functional group, a chiral agent (B) and a photopolymerization initiator (C) and reducing the transmittance of at least part of light in the wavelength region of 385 nm to 495 nm An ultraviolet curable resin composition for forming a film.
  2. 　前記ネマチック液晶性化合物（Ａ）が有する重合性官能基が、（メタ）アクリロイルオキシ基である、請求項１に記載の紫外線硬化型樹脂組成物。 The ultraviolet curable resin composition according to claim 1, wherein the polymerizable functional group of the nematic liquid crystalline compound (A) is a (meth) acryloyloxy group.
  3. 　更に、下記式（１）で表されるナフタルイミド骨格を有する化合物（Ｄ）を含有する、請求項１または２に記載の紫外線硬化型樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     　（式（１）中、Ｒ1は、水素原子またはヘテロ原子を有していてもよい炭化水素基を表し、Ｒ2は、水素原子または有機基を表し、複数のＲ2は同一であっても異なっていてもよい。）     Furthermore, the ultraviolet curable resin composition of Claim 1 or 2 containing the compound (D) which has a naphthalimide skeleton represented by following formula (1).
    Figure JPOXMLDOC01-appb-C000001
     (In the formula (1), R 1 represents a hydrocarbon group which may have a hydrogen atom or a hetero atom, R 2 represents a hydrogen atom or an organic group, and a plurality of R 2 are the same. May be different.)
  4. 　前記ネマチック液晶性化合物（Ａ）が下記式（２ａ）で表される化合物であり、前記カイラル剤（Ｂ）が下記式（３ａ）で表される化合物である、請求項１～３のいずれかに記載の紫外線硬化型樹脂組成物。
    Figure JPOXMLDOC01-appb-C000002
     　（式（２ａ）中、ｎは２～５の整数を表し、式（３ａ）中、ｍは２～５の整数を表す。）     The nematic liquid crystal compound (A) is a compound represented by the following formula (2a), and the chiral agent (B) is a compound represented by the following formula (3a). The ultraviolet curable resin composition described in 1.
    Figure JPOXMLDOC01-appb-C000002
     (In formula (2a), n represents an integer of 2 to 5, and in formula (3a), m represents an integer of 2 to 5)
  5. 　前記カイラル剤（Ｂ）の含有量が、前記ネマチック液晶性化合物（Ａ）および前記カイラル剤（Ｂ）の合計質量に対して１．０～３０．０質量％である、請求項１～４のいずれかに記載の紫外線硬化型樹脂組成物。 The content of the chiral agent (B) is 1.0 to 30.0 mass% with respect to the total mass of the nematic liquid crystal compound (A) and the chiral agent (B). The ultraviolet curable resin composition in any one.
  6. 　更に、ベンゾトリアゾール骨格を有する化合物（Ｅ１）および／またはヒドロキシフェニルトリアジン骨格を有する化合物（Ｅ２）を含有する、請求項１～５のいずれかに記載の紫外線硬化型樹脂組成物。 The ultraviolet curable resin composition according to claim 1, further comprising a compound (E1) having a benzotriazole skeleton and / or a compound (E2) having a hydroxyphenyltriazine skeleton.
  7. 　基材と、硬化皮膜とを有する積層体であって、
    　前記硬化皮膜が、請求項１～６のいずれかに記載の紫外線硬化型樹脂組成物を用いて形成される、積層体。     A laminate having a substrate and a cured film,
    A laminate in which the cured film is formed using the ultraviolet curable resin composition according to any one of claims 1 to 6.
  8. 　前記基材と前記硬化皮膜との間に、更に樹脂層を有し、
    　前記樹脂層が、表面張力が３２ｍＮ／ｍ以上のアクリル系樹脂層である、請求項７に記載の積層体。     Between the base material and the cured film, further having a resin layer,
    The laminate according to claim 7, wherein the resin layer is an acrylic resin layer having a surface tension of 32 mN / m or more.
  9. 　電子画像表示装置または眼鏡レンズに使用される請求項７または８に記載の積層体。 The laminate according to claim 7 or 8, which is used for an electronic image display device or a spectacle lens.
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