JP2016022684A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate excellent in scratch resistance, transparency, heat coloring resistance, heat resistance, bending resistance, flex resistance, and interference fringe resistance.SOLUTION: A laminate 1 comprises a transparent substrate layer 2, and a coat layer 3 placed on at least one side of the substrate layer 2. The substrate layer 2 is formed from a resin composition comprising an aromatic polyether, and the coat layer 3 is formed from a curable composition comprising organic particles, inorganic particles or a combination of them.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminate.

  In recent years, in order to prevent scratches and contamination of transparent base material layers such as films, laminates such as hard coat films in which a coating layer is provided on the surface of the base material layer by applying a curable resin composition are widely used. It is used. Such laminates include display devices such as touch panels, surface materials such as membrane switches and keypads, electrode substrates for liquid crystal cells constituting liquid crystal display elements, retardation films, optical filters, lenses, and films with transparent electrodes for touch panels. It is used as a coating material for electronic devices such as optical films for lighting such as LEDs and organic EL, solar cells, and transistors.

  The laminate is required to have various performances such as scratch resistance, transparency, heat resistance, heat resistance, bending resistance, bending resistance, interference fringe resistance, and the like. Among these performances, if the bending resistance is low, the product value may be impaired by bending or cracking during handling. In order to avoid the occurrence of bending and cracking, it has also been proposed to bond another protective film, but in this case, there is a disadvantage that the production cost increases.

  Under such circumstances, as a technique for enhancing various performances required for a laminate such as a hard coat film, a curable composition containing metal oxide particles having a refractive index of 1.50 or more and a specific urethane (meth) acrylate compound And a hard coat film (see Japanese Patent No. 2974576) containing an ultraviolet curable resin and particles of a high molecular weight polyester resin (see Japanese Patent Application Laid-Open No. 2006-182826). However, a laminate using any of the above-mentioned techniques does not sufficiently satisfy the above-described performance.

JP 2006-182826 A Japanese Patent No. 2974576

  The present invention has been made based on the circumstances as described above, and is a laminate excellent in scratch resistance, transparency, heat resistance, heat resistance, bending resistance, bending resistance, and interference fringe. For the purpose of provision.

（式（０）中、Ａｒ^１、Ａｒ^２、Ａｒ^３及びＡｒ^４は、それぞれ独立して、２価の芳香族炭化水素基又は２価のヘテロ芳香族基である。但し、上記芳香族炭化水素基及びヘテロ芳香族基が有する水素原子の一部又は全部は、置換されていてもよい。Ｒ^０は、単結合又は炭素数１〜２０の２価の炭化水素基である。但し、上記炭素数１〜２０の２価の炭化水素基が有する水素原子の一部又は全部は、置換されていてもよい。上記炭素数１〜２０の２価の炭化水素基は、エステル基、エーテル基又はカルボニル基を構造中に有していてもよい。Ｙは、カルボニル基又はスルホニル基である。ｍは、０又は１である。ｎは、０又は１である。） The present invention made to solve the above problems
A laminate comprising a transparent substrate layer and a coat layer laminated on at least one surface of the substrate layer, wherein the substrate layer has a structural unit represented by the following formula (0) It is formed with the resin composition containing aromatic polyether, The said coating layer is formed with the curable composition containing an organic particle, an inorganic particle, or these combination, It is characterized by the above-mentioned.

(In the formula (0), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently a divalent aromatic hydrocarbon group or a divalent heteroaromatic group, provided that the above aromatic carbonization is performed. Some or all of the hydrogen atoms of the hydrogen group and heteroaromatic group may be substituted, and R ⁰ is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, provided that the above Some or all of the hydrogen atoms of the divalent hydrocarbon group having 1 to 20 carbon atoms may be substituted, and the divalent hydrocarbon group having 1 to 20 carbon atoms may be an ester group or an ether group. Or a carbonyl group may be present in the structure, Y is a carbonyl group or a sulfonyl group, m is 0 or 1, and n is 0 or 1.)

  As described above, the laminate of the present invention is excellent in scratch resistance, transparency, heat resistance, heat resistance, bending resistance, bending resistance, and interference fringe resistance. Therefore, the laminate of the present invention can be suitably used as a material for touch panels and the like.

Typical sectional drawing which shows the laminated body which concerns on one Embodiment of this invention.

  Hereinafter, embodiments of the laminate and the curable composition of the present invention will be described in detail with reference to the drawings as appropriate.

[Laminate]
A laminate 1 in FIG. 1 includes a transparent substrate layer 2 and a coat layer 3 that is laminated on at least one surface (surface side) of the substrate layer 2.

(Flexibility)
The laminate 1 has a mandrel diameter of 2 mm or less in which a crack is generated in a bending resistance test by a cylindrical mandrel method. The laminate 1 has such a high bending resistance.

  Here, the “flexibility test by the cylindrical mandrel method” means JIS-K5600-5-1: 1999 paint general test method-Part 5: Mechanical properties of coating film-Section 1: Flex resistance ( According to the cylindrical mandrel method), a value measured using a type 1 test apparatus. Further, the crack is caused by peeling of the coating layer itself, peeling of the interface between the coating layer / base material layer, and the like, and is a white line visually recognized. In addition, when a crack is not generated using a mandrel having a diameter of 2 mm, it can be said that the diameter of the mandrel in which the crack is generated is 2 mm or less.

  Thus, as a means to make the diameter of the mandrel which a crack occurs in the laminated body 1 to 2 mm or less, the method of preparing the thickness of the base material layer 2 and the coating layer 3 which are mentioned later, and the material to be used is mentioned.

  The laminate 1 has high bending resistance because no cracks are generated in the bending resistance test.

(hardness)
The pencil hardness of the surface of the coat layer 3 of the laminate 1 is preferably 3B or more, and more preferably 2B or B. By setting it as pencil hardness of such a range, high hardness can be provided, maintaining the above-mentioned high bending resistance.

  Here, “pencil hardness” refers to a value measured in accordance with the scratch hardness (pencil method) of JIS-K5600-5-4.

(transparency)
The total light transmittance of the laminate 1 is preferably 85% or more, and more preferably 86% or more. In addition, the haze value of the laminate 1 is preferably 1% or less, and more preferably 0.01% or more and 0.5% or less. By setting the total light transmittance and the haze value within the above ranges, the transparency and the like can be improved and the touch panel can be suitably used.

  Here, “total light transmittance” and “haze value” refer to values measured in accordance with JIS-K7105.

  Further, the difference between the total light transmittance of the laminate 1 and the total light transmittance of only the base material layer 2 is within 1%, and the haze value of the laminate 1 and only the base material layer 2 The difference from the haze value is preferably within 1%. In such a case, since the coat layer 3 has particularly high transparency, it can be more suitably used for a touch panel or the like.

(Adhesion)
In the adhesion test by the cross-cut method based on JIS-K5600-5-6: 1999, the adhesion between the base material layer 2 and the coat layer 3 is preferably classification 0 or 1. By setting it as the adhesiveness of such a range, the mechanical strength of the said laminated body 1 can be improved.

  The difference in refractive index between the substrate layer 2 and the coat layer 3 at a wavelength of 589.3 nm is preferably 0.05 or less. By making the difference in refractive index between the base material layer 2 and the coat layer 3 small in this way, generation of interference fringes in the laminate 1 can be further suppressed.

JIS-Z8729: in the CIELAB of ^L * ^a * ^{b *} color system are measured in accordance with 2004 ^{b *} is 1.5 or less and 200 ° C., the amount of change in ^{b *} after heating 30 minutes Δb ^* is preferably 0.5 or less. By setting b ^* in the L ^* a ^* b ^* color system of CIELAB of the laminate 1 to be in the above specific range, the heat resistance and transparency of the laminate 1 can be further improved.

(Base material layer 2)
The base material layer 2 is transparent and is preferably colorless and transparent. The base material layer 2 is formed of a resin composition containing an aromatic polyether having a structural unit represented by the following formula (0) (hereinafter also referred to as “structural unit (0)”). By using such a resin composition, high heat resistance, transparency, heat coloring resistance, bending resistance, and bending resistance can be exhibited.

In the above formula (0), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently a divalent aromatic hydrocarbon group or a divalent heteroaromatic group. However, part or all of the hydrogen atoms of the aromatic hydrocarbon group and heteroaromatic group may be substituted. R ⁰ is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. However, one part or all part of the hydrogen atom which the said C1-C20 bivalent hydrocarbon group has may be substituted. The divalent hydrocarbon group having 1 to 20 carbon atoms may have an ester group, an ether group or a carbonyl group in the structure. Y is a carbonyl group or a sulfonyl group. m is 0 or 1. n is 0 or 1.

The divalent aromatic hydrocarbon group represented by Ar ¹ , Ar ² , Ar ³ and Ar ⁴ is preferably a C 6-20 divalent aromatic hydrocarbon group, such as a phenylene group or naphthylene. Group, anthranylene group and the like.

The divalent heteroaromatic group represented by Ar ¹ , Ar ² , Ar ³ and Ar ⁴ is preferably a divalent heteroaromatic group having 3 to 20 carbon atoms, such as furan, pyrrole, thiophene, Examples include groups obtained by removing two hydrogen atoms from a heteroaromatic compound such as phosphole, pyrazole, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, indole, quinoline and acridine.

  Examples of the substituent that may be substituted with the divalent aromatic hydrocarbon group and the divalent heteroaromatic group include, for example, a halogen atom, a hydroxy group, a cyano group, a nitro group, a formyl group, or a monovalent organic group. Etc.

  As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.

Examples of the monovalent organic group include a group consisting of —CO—, —COO—, —OCO—, —O—, —NR—, —CS—, —S—, —SO— and —SO ₂ —. A monovalent group in which at least one group selected from the above and a monovalent aromatic group having 3 to 20 carbon atoms are combined, a monovalent aromatic group having 3 to 20 carbon atoms, and the like. The thing which the hydrogen atom which group has is substituted by the substituent is mentioned. R is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. Examples of the substituent include a hydroxy group, a cyano group, a carboxy group, and an ethynyl group.

  The monovalent aromatic group having 3 to 20 carbon atoms is preferably a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms or a monovalent heteroaromatic group having 3 to 20 carbon atoms. Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, and an anthranyl group. Examples of the monovalent heteroaromatic group having 3 to 20 carbon atoms include furan, pyrrole, thiophene, phosphole, pyrazole, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, indole, and quinoline. And groups obtained by removing one hydrogen atom from a heteroaromatic compound such as acridine.

The -CO -, - COO -, - OCO -, - O -, - NR -, - CS -, - S -, - SO- and -SO ₂ - at least one group and a carbon selected from the group consisting of Examples of the monovalent group in combination with the monovalent aromatic group of 3 to 20 include a phenoxy group, a naphthyloxy group, an anthranyloxy group, and an anilino group.

  As the structural unit represented by the above formula (0), the aromatic polyether is a structural unit represented by the following formula (1) (hereinafter also referred to as “structural unit (1)”), the following formula (2): It is preferable to have a structural unit represented by (hereinafter also referred to as “structural unit (2)”) or a combination thereof (hereinafter also referred to as “structural unit (i)”). By using such a resin composition containing an aromatic polyether, higher heat resistance, transparency, heat resistance, color resistance, bending resistance and bending resistance can be exhibited.

In the above formula (1), R ^{1 to} R ⁴ are each independently a monovalent organic group having 1 to 12 carbon atoms. a1 to d1 are each independently an integer of 0 to 4.

In the above formula ^{(2), R 1 '~R} 4' are each independently a monovalent organic group having 1 to 12 carbon atoms. a2 to d2 are each independently an integer of 0 to 4. Y ¹ is a single bond, —SO ₂ — or —CO—. R ⁷ and R ⁸ are each independently a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group. g1 and h1 are each independently an integer of 0 to 4. m1 is 0 or 1. However, when m1 is 0, R ⁷ is not a cyano group.

The monovalent organic group having 1 to 12 carbon atoms represented by R ^{1 to} R ⁴ is, for example, at least selected from the group consisting of a monovalent hydrocarbon group having 1 to 12 carbon atoms, an oxygen atom, and a nitrogen atom. Examples thereof include a monovalent organic group having 1 to 12 carbon atoms containing one kind of atom.

  Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include a linear or branched hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and 6 carbon atoms. -12 aromatic hydrocarbon groups and the like.

  The linear or branched hydrocarbon group having 1 to 12 carbon atoms is preferably a linear or branched hydrocarbon group having 1 to 8 carbon atoms, and is linear or branched having 1 to 5 carbon atoms. The hydrocarbon group is more preferable.

  Examples of the linear or branched hydrocarbon group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n -Pentyl group, n-hexyl group and n-heptyl group are preferred.

  As said C3-C12 alicyclic hydrocarbon group, a C3-C8 alicyclic hydrocarbon group is preferable, and a C3-C4 alicyclic hydrocarbon group is more preferable.

  Examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; a cyclobutenyl group such as a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group. An alkenyl group is mentioned. The bonding site of the alicyclic hydrocarbon group may be any carbon on the alicyclic ring.

  Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group, and a naphthyl group. The bonding site of the aromatic hydrocarbon group may be any carbon on the aromatic ring.

  As said C1-C12 organic group containing an oxygen atom, the organic group etc. which consist of a hydrogen atom, a carbon atom, and an oxygen atom etc. are mentioned, for example. Among these, an organic group having 1 to 12 carbon atoms in total consisting of an ether bond, a carbonyl group or an ester bond and a hydrocarbon group is preferable.

  Examples of the organic group having 1 to 12 carbon atoms having an ether bond include an alkoxy group having 1 to 12 carbon atoms, an alkenyloxy group having 2 to 12 carbon atoms, an alkynyloxy group having 2 to 12 carbon atoms, and 6 carbon atoms. -12 aryloxy group, C2-C12 alkoxyalkyl group, etc., specifically, methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group, phenoxy group, propenyloxy group, cyclohexyl An oxy group, a methoxymethyl group, an alkyl-substituted phenoxy group (the carbon number of the alkyl group is 1 to 4 and the number of the alkyl group is 1 to 5), a phenyl-substituted phenoxy group (the number of phenyl groups is 1 or 2) And the like.

  Examples of the organic group having 1 to 12 carbon atoms having a carbonyl group include an acyl group having 2 to 12 carbon atoms, and specifically, an acetyl group, a propionyl group, an isopropionyl group, a benzoyl group, and the like. Can be mentioned.

  Examples of the organic group having 1 to 12 carbon atoms having an ester bond include an acyloxy group having 2 to 12 carbon atoms, and specifically include an acetyloxy group, a propionyloxy group, an isopropionyloxy group, and benzoyl. An oxy group etc. are mentioned.

  As said C1-C12 organic group containing a nitrogen atom, the organic group which consists of a hydrogen atom, a carbon atom, and a nitrogen atom etc. is mentioned, for example, Specifically, a cyano group, an imidazole group, a triazole group, a benzimidazole is mentioned. Group, benztriazole group and the like.

  As said C1-C12 organic group containing an oxygen atom and a nitrogen atom, the organic group which consists of a hydrogen atom, a carbon atom, an oxygen atom, and a nitrogen atom is mentioned, for example, Specifically, an oxazole group, an oxadiazole Group, benzoxazole group, benzoxadiazole group and the like.

As R < ¹ > -R < ⁴ > in said Formula (1), a C1-C12 monovalent hydrocarbon group is preferable, a C6-C12 aromatic hydrocarbon group is more preferable, and a phenyl group is further more preferable.

In the above formula (1), when a1 and / or b1 is 1, the bonding position of R ¹ or R ^{2 to} the benzene ring is a main chain bond (ether bond) benzene ring bonded to each benzene ring. The ortho position with respect to the bonding position to is preferable in that a polymer having the structural unit (1) can be easily obtained. In this case, R ¹ and R ² are preferably sterically bulky groups such as a methyl group and a phenyl group. In the following, examples of R ^{1 ′ to} R ^{4 ′} and a2 to d2 in Formula (2), preferred groups, preferred numerical values, and bonding positions are the same as R ^{1 to} R ⁴ and a1 to d1 in Formula (1), respectively. It is. For example, preferred bonding positions and groups for R ¹ and R ² are the same for R ^{1 ′} and R ^{2 ′} of the structural unit (2).

  As m1, 0 is preferable.

In the above formula (2), when g1 and / or h1 is 1, the bonding position of R ⁷ or R ^{8 to} the benzene ring is the bonding position of the main chain bond bonded to each benzene ring to the benzene ring. On the other hand, the ortho-position is preferable in that a polymer having the structural unit (2) can be easily obtained. When m1 is 1 and g1 is 1, the bonding position of R ^{7 to} the benzene ring is preferably ortho to the bonding position of the ether bond to the benzene ring. In this case, R ⁷ and R ⁸ are preferably sterically bulky groups such as a methyl group and a phenyl group. Examples, preferred groups, and bonding sites of R ^{7 ′} , R ^{8 ′} , g2 and h2 in the formula (4) described later are the same as R ⁷ , R ⁸ , g1 and h1 in the formula (2), respectively.

Y ¹ is preferably a single bond.

Examples of the halogen atom represented by R ⁷ and R ⁸ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine source. Among these, a chlorine atom and a fluorine atom are preferable.

The monovalent organic group having 1 to 12 carbon atoms represented by R ⁷ and R ⁸ is, for example, a monovalent organic group having 1 to 12 carbon atoms exemplified as R ^{1 to} R ⁴ in the above formula (1). And the like groups. Among these, a monovalent hydrocarbon group having 1 to 12 carbon atoms is preferable, an aromatic hydrocarbon group having 6 to 12 carbon atoms is more preferable, and a phenyl group is further preferable.

  The aromatic polyether includes a structural unit represented by the following formula (3) (hereinafter also referred to as “structural unit (3)”) and a structural unit represented by the following formula (4) (hereinafter referred to as “structural unit ( It is preferable that the resin further has at least one selected from the group consisting of “4)” (hereinafter also referred to as “structural unit (ii)”). When the aromatic polyether further has the structural unit (ii), the mechanical properties of the obtained base material layer can be improved.

In the above formula (3), ^{R 5} and ^{R 6} are independently a monovalent organic group having 1 to 12 carbon atoms. Z ¹ is a single bond, —O—, —S—, —SO ₂ —, —CO—, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms. e1 and f1 are each independently an integer of 0 to 4. n1 is 0 or 1.

In the above formula (4), R ^{5 ′} and R ^{6 ′} are each independently a monovalent organic group having 1 to 12 carbon atoms. Z ² is a single bond, —O—, —S—, —SO ₂ —, —CO—, —CONH—, —COO—, or a divalent organic group having 1 to 12 carbon atoms. e2 and f2 are each independently an integer of 0 to 4. n2 is 0 or 1. R ^{7 ′} and R ^{8 ′} each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms, or a nitro group. Y ² is a single bond, —SO ₂ — or —CO—. m2 is 0 or 1. However, when m2 is 0, R ^{7 ′} is not a cyano group. g2 and h2 are each independently an integer of 0 to 4.

Examples of the monovalent organic group having 1 to 12 carbon atoms represented by R ⁵ and R ⁶ include the same groups as the monovalent organic group having 1 to 12 carbon atoms in (1) above.

Examples of the divalent organic group having 1 to 12 carbon atoms represented by Z ¹ include a divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms, A C1-C12 divalent organic group containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom, and a carbon containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom Examples thereof include divalent halogenated organic groups of 1 to 12.

  Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms include a linear or branched divalent hydrocarbon group having 1 to 12 carbon atoms and a divalent alicyclic carbon group having 3 to 12 carbon atoms. A hydrogen group, a C6-C12 bivalent aromatic hydrocarbon group, etc. are mentioned.

  Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms include a methylene group, an ethylene group, a trimethylene group, an isopropylidene group, a pentamethylene group, a hexamethylene group, and a heptamethylene group.

Examples of the divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms include a cycloalkylene group such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group; a cyclobutenylene group and a cyclopentenylene group. And cycloalkenylene groups such as a cyclohexenylene group. The bonding site of the alicyclic hydrocarbon group may be any carbon on the alicyclic ring.

Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenylene group, a naphthylene group, and a biphenylene group. The bonding site of the aromatic hydrocarbon group may be any carbon on the aromatic ring.

  Examples of the divalent halogenated hydrocarbon group having 1 to 12 carbon atoms include a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms and a divalent halogenated alicyclic hydrocarbon group having 3 to 12 carbon atoms. Group, a bivalent halogenated aromatic hydrocarbon group having 6 to 12 carbon atoms, and the like.

  Examples of the linear or branched divalent halogenated hydrocarbon group having 1 to 12 carbon atoms include difluoromethylene group, dichloromethylene group, tetrafluoroethylene group, tetrachloroethylene group, hexafluorotrimethylene group, hexachloro A trimethylene group, a hexafluoroisopropylidene group, a hexachloroisopropylidene group, etc. are mentioned.

  Examples of the divalent halogenated alicyclic hydrocarbon group having 3 to 12 carbon atoms include, for example, at least a part of hydrogen atoms of the groups exemplified in the divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms. And a group substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

  Examples of the divalent halogenated aromatic hydrocarbon group having 6 to 12 carbon atoms include a fluorine atom in which at least a part of the hydrogen atoms exemplified in the above divalent aromatic hydrocarbon group having 6 to 12 carbon atoms is a fluorine atom. , A group substituted with a chlorine atom, a bromine atom or an iodine atom.

  Examples of the organic group having 1 to 12 carbon atoms containing at least one atom selected from the group consisting of the oxygen atom and the nitrogen atom include an organic group consisting of a hydrogen atom and a carbon atom, and an oxygen atom and / or a nitrogen atom. And a divalent organic group having 1 to 12 carbon atoms having an ether bond, a carbonyl group, an ester bond or an amide bond and a hydrocarbon group.

Specifically, the divalent halogenated organic group having 1 to 12 carbon atoms containing at least one atom selected from the group consisting of the oxygen atom and nitrogen atom is specifically selected from the group consisting of an oxygen atom and a nitrogen atom. And a group in which at least a part of the hydrogen atoms exemplified in the divalent organic group having 1 to 12 carbon atoms containing at least one kind of atom is substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, etc. It is done.

In the above formula (3), when e1 and / or f1 is 1, the bonding position of R ⁵ or R ^{6 to} the benzene ring is the bonding position of the ether bond bonded to each benzene ring to the benzene ring. On the other hand, the ortho-position is preferable because a polymer having the structural unit (3) can be easily obtained. In this case, R ⁵ and R ⁶ are preferably sterically bulky groups such as a methyl group and a phenyl group.

Z ¹ in the above formula (3) is preferably a single bond, —O—, —SO ₂ —, —CO— or a divalent organic group having 1 to 12 carbon atoms, and a divalent organic group having 1 to 12 carbon atoms. A hydrocarbon group and a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms are more preferred.

Exemplary R ^{5 'and} R ^6' in the formula (4), preferred groups are respectively same as ^{R 5} and ^{R 6} in the formula (3).

  Preferred numerical values of e2 and f2 in the above formula (4) are the same as e1 and f1 in the above formula (3).

Examples and preferred groups of Z ² in the above formula (4) are the same as Z ¹ in the above formula (3).

  As said n2, 1 is preferable.

Exemplary R ^{7 'and} R ^8' in the formula (4), preferred groups are respectively same as ^{R 7} and ^{R 8} in the formula (2).

Examples and preferred groups of Y ² in the above formula (4) are the same as those of Y ¹ in the above formula (2).

  As m2 in the above formula (4), 0 is preferable.

  The preferable ranges of g2 and h2 in the above formula (4) are the same as g1 and h1 in the above formula (2), respectively.

  Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms include a linear or branched divalent hydrocarbon group having 1 to 12 carbon atoms and a divalent alicyclic carbon group having 3 to 12 carbon atoms. A hydrogen group is preferred.

  The aromatic polyether has a molar ratio of the structural unit (i) to the structural unit (ii) (however, the sum of the structural unit (i) and the structural unit (ii) is 100). From the viewpoint of optical properties, heat resistance and mechanical properties, the structural unit (i): structural unit (ii) is preferably 50:50 to 100: 0, and the structural unit (i): structural unit (ii) = 70:30 to 100: 0 is more preferable, and structural unit (i): structural unit (ii) is more preferably 80:20 to 100: 0. The aromatic polyether may further copolymerize a structure represented by the following formula (8-1) or the following formula (8-2) in the main chain. With such a structure, a low birefringence can be obtained.

  In the above formula (8-1) and the above formula (8-2), s is an integer of 1 to 4.

  The aromatic polyether preferably contains 70 mol% or more of the structural unit (i) and the structural unit (ii) in the total structural units from the viewpoint of optical properties, heat resistance and mechanical properties. More preferably, it contains 95 mol% or more.

  The resin composition may contain, for example, an ultraviolet absorber, a plasticizer, a stabilizer, etc. as other additives.

  Although it does not specifically limit as average thickness of the said base material layer 2, 10 micrometers or more and 500 micrometers or less are preferable, and 20 micrometers or more and 200 micrometers or less are more preferable. By setting the base material layer 2 to an average thickness in the above range, the bending resistance, strength, and the like can be improved in a balanced manner.

  Although it does not specifically limit as a manufacturing method of the said base material layer 2, It can manufacture by forming into a film the material which has the said resin etc. as a main component. The film forming method is not particularly limited, and examples thereof include known film forming methods such as a solvent casting method, a melt extrusion method, and a calender method. In addition, after the film formation, the base material layer 2 may be subjected to a stretching process.

(Coat layer 3)
The coat layer 3 is usually formed by applying a curable composition. The preferred composition of this curable composition will be described in detail later.

  The average thickness of the coat layer 3 is preferably 0.05 μm or more and 10 μm or less, and more preferably 0.1 μm or more and 5 μm or less. By setting the average thickness of the coat layer 3 within the above range, the transparency and the like can be improved while maintaining the bending resistance and the blocking resistance.

(Curable composition)
The curable composition contains organic particles, inorganic particles, or a combination thereof. It is preferable that the said curable composition contains a urethane (meth) acrylate compound (B) further, and can contain another (meth) acrylate compound (C) etc. in addition. The curable composition may contain a silane coupling agent, a dispersant for various inorganic particles, and the like.

(Organic particles)
As the organic particles, solid particles such as acrylic fine particles are preferably used. Examples of the acrylic fine particles include a methyl methacrylate polymer, a copolymer of methacrylic acid and an alkyl compound, and the like. Examples of commercially available organic particles include Zefiac F-320, F-301, F-340, F-325, F-351 (manufactured by Ganz Kasei Co., Ltd.), and acrylic fine particles MP-300 (manufactured by Soken Chemical Co., Ltd.). Etc.

(Inorganic particles (A1))
As the inorganic particles (A1), potassium, calcium, strontium, barium, hafnium, gallium, niobium, lanthanum, silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony, cerium oxide particles, sulfide Product particles, carbide particles, nitride particles, or a combination thereof is preferable, and oxide particles of titanium, zirconium, potassium, tin, and silicon are more preferable. Since such inorganic particles (A1) are highly refractive particles, a coating layer having a relatively high refractive index can be obtained, and as a result, the difference in refractive index from the base material layer can be reduced. The interference fringe resistance can be improved.

  Examples of the oxide particles include particles of silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, cerium oxide, and the like. Can do. Among these, silica, alumina, zirconia, titanium oxide, and antimony oxide particles are preferable from the viewpoint of high hardness. These can be used alone or in combination of two or more.

  The oxide particles are preferably used in the form of powder or dispersed sol. When used as a dispersion sol, the dispersion medium is preferably an organic dispersion medium from the viewpoint of dispersibility with other components. Examples of such an organic dispersion medium include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, and γ- Esters such as butyrolactone, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide and dimethylacetamide And amides such as N-methylpyrrolidone. Among these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, and xylene are preferable.

  In order to improve the dispersibility of the particles, various coupling agents, surfactants, and dispersants may be used. Examples of coupling agents include silane coupling agents and titanium coupling agents. For example, KBE-1003, KBM-1003, KBM-303, KBM-403, KBM-402, KBE-403 from Shin-Etsu Chemical Co., Ltd. Silane coupling agents such as KBE-402, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-9659, Matsumoto Fine Chemical Co., Ltd., Olgax TC-100, TC401 TC-710, TC-1040, TC-201, TC-750, and the like. Examples of the surfactant and dispersant include DisperBYK111, 171, 180, 2022, and 2152, BYK4510, BK1000, Cray Valley SMA1000P, SMA EF-30, Toagosei Co., Ltd., Alfon UC. -3900, US-6110, and the like.

  Commercially available products as silicon oxide particles (for example, silica particles) include, for example, colloidal silica, methanol silica sol, IPA-ST-S, IPA-ST-ZL, IPA-ST- from Nissan Chemical Industries, Ltd. L, IPA-ST-UP, MEK-ST, MEK-ST-L, MEK-ST-UP, MEK-ST-ZL, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc. can be mentioned. Examples of the powder silica include Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Silex H31, H32, H51, H52, H121, H122 from Asahi Glass Co., E220A from Nippon Silica Industry, E220, Fuji Silysia's SYLYSIA470, Nippon Sheet Glass's SG flakes, and the like.

  As an aqueous dispersion of alumina particles, alumina sol-100, -200, -520 of Nissan Chemical Industries, Ltd. As an isopropanol dispersion of alumina particles, AS-150I of Sumitomo Osaka Cement Co., Ltd. As a toluene dispersion of alumina particles, AS-150T from Sumitomo Osaka Cement Co., Ltd. As a toluene dispersion of zirconia particles, HXU-110JC from Sumitomo Osaka Cement Co., Ltd. As an aqueous dispersion of zinc antimonate powder, Cellnax from Nissan Chemical Industries, Ltd .; alumina, oxidation As powders and solvent dispersions of titanium, tin oxide, indium oxide, zinc oxide and the like, nanotech of CI Kasei Co., Ltd .; as an aqueous dispersion sol of antimony-doped tin oxide, SN-100D of Ishihara Sangyo Co., Ltd .; Mitsubishi Materials' product; as a cerium oxide aqueous dispersion, Takika Mention may be made of the company Nidoraru the like of.

  Examples of the propylene glycol monomethyl ether dispersion of titanium oxide particles include “SRD-PGME” manufactured by Sakai Chemical Industry Co., Ltd. and “OPTOLAKE-2120Z” manufactured by JGC Catalysts & Chemicals.

  As commercial products of zirconia particles, trade names of Daiichi Rare Chemicals Co., Ltd .: EP, UEP, RC, trade names of Nippon Electric Works: N-PC, PCS, TZ-3Y-E, TZ-4YS of Tosoh Corporation TZ-6YS, TZ-8YS, TZ-10YS, TZ-0, and the like. Examples of the methyl ethyl ketone dispersion of zirconium oxide-based particles include “SZR-K” manufactured by Sakai Chemical Industry Co., Ltd. and “Nanouse OZ-S30K” manufactured by Nissan Chemical Industries, Ltd.

  The shape of the oxide particles is not particularly limited, and may be spherical, hollow, porous, annular, rod-like, plate-like, fiber-like, chain-like, indefinite or the like, but spherical is preferred. . The average particle size of the oxide particles is preferably 0.1 μm or less, more preferably 0.05 μm or less, and further preferably 0.03 μm or less.

  The average particle size is obtained by automatically calculating the particle size distribution according to the Mie theory from scattered light data measured by a batch measurement method using a laser diffraction / scattering particle size distribution measuring apparatus (for example, HORIBA LB-550). Mean median diameter. The median diameter is a particle diameter corresponding to a cumulative frequency distribution of 50%.

(Reactive particles)
The reactive particles can be obtained by bonding inorganic particles (A1) and an organic compound (A2) having a specific reactive group.

(Organic compound (A2))
The organic compound (A2) is an organic compound having a polymerizable unsaturated group and a hydrolyzable silyl group as a reactive group.

  The polymerizable unsaturated group is not particularly limited, and examples thereof include acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, maleate group, and acrylamide group. Can be mentioned. This polymerizable unsaturated group is a group that undergoes addition polymerization with active radical species.

  The hydrolyzable silyl group is a silanol group or a group that generates a silanol group by hydrolysis. Examples of the group that forms a silanol group include a group in which an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen atom, or the like is bonded to a silicon atom, but an alkoxy group or an aryloxy group is bonded to a silicon atom. An organic compound containing a selected group, that is, an alkoxysilyl group or an aryloxysilyl group is preferred. Here, the alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and the aryloxy group is preferably an aryloxy group having 6 to 18 carbon atoms. This hydrolyzable silyl group (a silanol group or a group that generates a silanol group) is a group that binds to the inorganic particles (A1) by a condensation reaction or a condensation reaction that occurs following hydrolysis.

  Examples of the organic compound (A2) include 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 2-methacryloyloxyethyltrimethoxysilane, 2-acryloyloxyethyltrimethoxysilane, and 3-methacryloyloxy. Propyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltriethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, Examples thereof include at least one silane compound selected from vinyltrimethoxysilane and vinyltriethoxysilane.

  Among these, from 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane At least one silane compound selected is preferable from the viewpoint of excellent reactivity with the inorganic particles (A1).

  The organic compound (A2) preferably further has a group represented by the following formula (5) in addition to the polymerizable unsaturated group and the hydrolyzable silyl group.

  In Formula (5), X is NH, O, or S. Y is O or S.

  Specific examples of the group represented by the above formula (5) include [—O—C (═O) —NH—], [—O—C (═S) —NH—], [—S—C. (= O) -NH-], [-NH-C (= O) -NH-], -NH-C (= S) -NH-], and [-S-C (= S) -NH-]. There are six types. These groups may be used alone or in combination of two or more. Among these, from the viewpoint of thermal stability, in addition to [—O—C (═O) —NH—] group, [—O—C (═S) —NH—] group and [—S—C ( ═O) —NH—] group is preferred. The group represented by the above formula (5) generates an appropriate cohesive force due to hydrogen bonding between molecules, and when made into a cured product, has excellent mechanical strength, adhesion to the base material layer, heat resistance, and flexibility. Properties such as properties can be imparted.

  As the organic compound (A2), a compound represented by the following formula (6) is preferable.

In the above formula (6), at least one of R ¹ , R ² and R ³ is a hydroxy group, an alkoxy group or an aryloxy group, and the remainder is a hydrogen atom, an alkyl group or an aryl group. R ⁴ is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms. R ⁵ is a divalent organic group. R ⁶ is a (q + 1) valent organic group. Z is a monovalent organic group having a polymerizable unsaturated group that undergoes an intermolecular crosslinking reaction in the presence of an active radical species. q is an integer of 1-20.

In the above formula (6), the alkoxy group and the alkyl group represented by R ^1, R ² and R ³ include those having 1 to 8 carbon atoms, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, octyl An oxy group, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group and the like are preferable. Moreover, as an aryloxy group and an aryl group, a C6-C18 thing is mentioned, A phenoxy group, a xylyloxy group, a phenyl group, a xylyl group etc. are preferable. Examples of the group represented by R ¹ (R ² ) (R ³ ) Si— (hydrolyzable silyl group) include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and dimethyl. A methoxysilyl group etc. can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.

R ⁴ may contain a chain, branched or cyclic structure in its structure. Examples of such a structure include an aliphatic group having 1 to 12 carbon atoms such as a methylene group, an ethylene group, a propylene group, a methylethylene group, a butylene group, a methylpropylene group, an octamethylene group, and a dodecamethylene group; a cyclohexylene group and the like And an alicyclic group having 3 to 12 carbon atoms; an aromatic group having 6 to 12 carbon atoms such as a phenylene group, a 2-methylphenylene group, a 3-methylphenylene group, and a biphenylene group. Among these, preferred examples include a methylene group, a propylene group, a cyclohexylene group, and a phenylene group.

R ⁵ is preferably a divalent organic group having a molecular weight (total atomic weight of atoms constituting the group) of 14 to 10,000, particularly a molecular weight of 76 to 500. Examples of these organic groups include divalent organic groups having an aliphatic or aromatic structure, and the structure may include a chain, branched or cyclic structure. Examples of such a structural unit include a chain such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, a hexamethylene group, a 2,2,4-trimethylhexamethylene group, and a 1- (methylcarboxyl) -pentamethylene group. A divalent organic group having a structure skeleton; a divalent organic group having an alicyclic structure skeleton such as isophorone, cyclohexylmethane, methylenebis (4-cyclohexane), hydrogenated dienylmethane, hydrogenated xylene, hydrogenated toluene; And a divalent organic group having a skeleton of an aromatic ring structure such as benzene, toluene, xylene, paraphenylene, diphenylmethane, diphenylpropane, and naphthalene.

Examples of R ⁶ include a (q + 1) -valent linear or branched saturated hydrocarbon group or unsaturated hydrocarbon group. More specifically, in addition to the divalent organic group of R ⁵ described above, a trivalent organic group such as 2-ethyl-2-methylenepropylene, a trivalent organic group having an isocyanuric skeleton, 2,2-di- Examples include tetravalent organic groups such as substituted alkylene such as methylenepropylene, and hexavalent organic groups such as alkylene derived from dipentaerythritol. Of these, ethylene, 2-ethyl-2-methylenepropylene, trivalent organic groups having an isocyanuric skeleton, substituted alkylene such as 2,2-dimethylenepropylene, and alkylene derived from dipentaerythritol are preferable.

  Examples of Z include acryloxy group, methacryloxy group, vinyl group, propenyl group, butanedienyl group, styryl group, ethynyl group, cinnamoyl group, maleate group, acrylamide group and the like. Of these, an acryloxy group, a methacryloxy group, and a vinyl group are more preferable.

  Although q is an integer of 1-20, the integer of 1-10 is preferable and the integer of 1-5 is more preferable.

  These organic compounds (A2) can be produced, for example, by the method described in JP-A-9-100111.

The method for bonding the inorganic particles (A1) and the organic compound (A2) is not particularly limited,
A method in which the inorganic particles (A1) and the organic compound (A2) are mixed in an organic solvent containing water, and a hydrolysis / condensation reaction is performed at once;
A method in which the organic compound (A2) is hydrolyzed in the presence of an organic solvent containing water in advance and then subjected to a condensation reaction with the inorganic particles (A1).
The inorganic particles (A1) and the organic compound (A2) are mixed with water, an organic solvent, and other components such as a compound having two or more polymerizable unsaturated groups in the molecule, a radical polymerization initiator, and the like. Examples include a method in which a decomposition / condensation reaction is performed at once.

  By these methods, at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium on the surface of the inorganic particles (A1) and the organic compound (A2) in the molecule Reactive particles in which the inorganic particles (A1) and the organic compound (A2) are chemically bonded are obtained by bonding silicon atoms through oxygen atoms.

  In addition, when the inorganic particles (A1) are silica particles and the organic compound (A2) is an organic compound (A2) having a silanol group or a group that generates a silanol group, these are water or an organic containing water. After mixing with a solvent, water or an organic solvent is distilled off under reduced pressure or normal pressure to produce polymerization reactive silica particles in which silica particles and an organic compound (A2) are bonded via a silyloxy group. it can. This reaction can be performed, for example, based on the description in JP-A-9-100111.

  When using a plurality of inorganic particles (A1), each inorganic particle (A1) may be separately subjected to a hydrolysis / condensation reaction with the organic compound (A2), or the plurality of inorganic particles (A1) may be preliminarily used. After mixing, the organic compound (A2) may be subjected to a hydrolysis / condensation reaction. In addition, since the hardened | cured material excellent in blocking resistance is obtained by making a spherical and chain | strand-shaped inorganic particle (A1) react with an organic compound (A2) simultaneously, it is used preferably.

  The binding amount of the organic compound (A2) is preferably 0.1% by mass or more, more preferably 1% by mass based on 100% by mass of the reactive particles (the total of the inorganic particles (A1) and the organic compound (A2)). % Or more, particularly preferably 3 mass% or more and 40 mass parts or less. When the bound amount of the bound organic compound (A2) is less than 0.01% by mass, the dispersibility of the reactive particles in the composition is not sufficient, and the resulting cured product has sufficient transparency, blocking resistance, and the like. It may disappear.

  The content of reactive particles in the curable composition is preferably 30% by mass to 85% by mass, and more preferably 35% by mass to 80% by mass in the total solid content. If it is less than 30% by mass, sufficient hardness may not be obtained when a cured product is obtained. On the other hand, when it exceeds 90% by mass, the film formability is insufficient, and the adhesion to the base material layer is lowered. The content of the reactive particles means a solid content, and when the reactive particles are used in the form of a dispersion medium-dispersed sol, the content does not include the amount of the dispersion medium.

(Urethane (meth) acrylate compound (B))
The said urethane (meth) acrylate compound (B) has a function which improves the bending resistance etc. of the hardened | cured material obtained.

  The urethane (meth) acrylate compound (B) preferably has 2 or more (meth) acryloyl groups, more preferably 2 or more and 15 or less (meth) acryloyl groups.

  As said urethane (meth) acrylate compound (B), the urethane (meth) acrylate whose polystyrene conversion number average molecular weight is 500-50000 in a gel permeation chromatography (GPC) is used suitably. The GPC pattern of the urethane (meth) acrylate compound (B) uses an HLC-8020 high performance liquid chromatograph (manufactured by Tosoh Corporation), a styrene / divinylbenzene copolymer resin as a GPC column, and tetrahydrofuran as an eluent. Use to measure. As a urethane (meth) acrylate compound (B), it is preferable that the value obtained by dividing the molecular weight by the number of (meth) acryloyl groups exceeds 1,000.

  The urethane (meth) acrylate compound (B) is not particularly limited as long as it is a compound having a (meth) acryloyl group and a urethane bond. Examples of commercially available products thereof include H-7 and UN-5500. Art Resin UN-333, KY-111, UN-2600, UN-2700, H-34, UN-3320HA, UN-3320HS, UN-904M, UN-905 (above, Negami Industrial Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8807, EBECRYL9260, EBECRYL9270 (above, Daicel Ornex), U-4HA, U-6HA, U-6LPA, UA-1100H, UA-200PA, UA-4200, UA-122P, UA-53H, NK ABE-300, A9300, A-LEN-10, NK ester AMP-10G, A-TMM-3LM-N, A-DPH, A-TMMT (above, Shin-Nakamura Chemical Co., Ltd.), KAYRAD-R604 (Nipponization) Pharmaceutical Co., Ltd.), Funkuru FA-BZA (Hitachi Chemical Industry Co., Ltd.) These can be used alone or in combination of two or more.

  Among these, as a urethane (meth) acrylate compound (B), what has cyclic structures, such as a benzene ring, a triazine ring, a cyclohexane ring, a cyclopentane ring, is preferable.

  Content of the said urethane (meth) acrylate compound (B) is 10 mass% or more and 60 mass% or less normally in a total solid, and 20 mass% or more and 60 mass% or less are preferable. By setting it as such a range, the bending resistance etc. of the laminated body obtained can be improved effectively.

  Moreover, 15 mass% or more and 85 mass% or less are preferable in all (meth) acrylate components other than the (A) component in the said composition, and, as for content of the said urethane (meth) acrylate compound (B), 20 mass%. More preferably, it is 80 mass% or less. By setting it as such content, while a favorable softness | flexibility is effectively provided to a coating layer, the higher balance with surface hardness can be aimed at. Here, all (meth) acrylate components other than (A) component are (meth) acrylate components (having (meth) acryloyl groups) contained in all soluble components except (A) component which is insoluble particles. Compound). Specifically, it means the total amount of the component (B) and the component (C) described in detail later.

(Other (meth) acrylate compounds (C))
The other (meth) acrylate compound (C) is suitably used for increasing the adhesion between the coating layer 3 and the base material layer 2 and adjusting the hardness. The (meth) acrylate compound (C) is a compound having one or more (meth) acryloyl groups in one molecule, and examples thereof include (meth) acrylic esters.

  (Meth) acrylic esters include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecane dimethanol diacrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyl acrylate, phenoxyethyl acrylate, glycerin tri (meth) acrylate, tris ( 2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1 3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) Hydroxyl-containing (meth) acrylates such as acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, and hydroxyl groups thereof Poly (meth) acrylates of adducts with ethylene oxide or propylene oxide, oligoesters (meth) acrylates having two or more (meth) acryloyl groups in the molecule, oligoethers (meth) acrylates, oligourethanes (meth) A Relate acids, and can be exemplified oligo epoxy (meth) acrylate, and the like.

  Among these, tricyclodecane dimethanol diacrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (Meth) acrylate is preferred.

  Examples of commercially available products of such (meth) acrylate compound (C) include, for example, Aronix M-400, M-408, M-450, M-305, M-309, M-310, M- 315, M-320, M-350, M-360, M-208, M-210, M-215, M-220, M-225, M-233, M-240, M-245, M-260, M-270, M-1100, M-1200, M-1210, M-1310, M-1600, M-221, M-203, TO-924, TO-1270, TO-1231, TO-595, TO- 756, TO-1343, TO-902, TO-904, TO-905, TO-1330, Nippon Kayaku's KAYARAD D-310, D-330, DPHA, DPCA-20, DPCA-30 DPCA-60, DPCA-120, DN-0075, DN-2475, SR-295, SR-355, SR-399E, SR-494, SR-9041, SR-368, SR-415, SR-444, SR- 454, SR-492, SR-499, SR-502, SR-9020, SR-9035, SR-111, SR-212, SR-213, SR-230, SR-259, SR-268, SR-272, SR-344, SR-349, SR-601, SR-602, SR-610, SR-9003, PET-30, T-1420, GPO-303, TC-120S, HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-551, R-712, R-167, R-526, R-551, R-712, R-604, R-684, TMPTA, THE-330, TPA-320, TPA-330, KS-HDDA, KS-TPGDA, KS-TMPTA, Kyoeisha Chemical Light Acrylate PE-4A, DPE- 6A, DTMP-4A, Hitachi Chemical Co., Ltd. FA-511AS, FA-512AS, Shin Nakamura Chemical Co., Ltd. NK ester A-TMM-3LM-N, and the like.

  The content of the other (meth) acrylate compound (C) is preferably 1% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 40% by mass or less in the total solid content. When the amount is less than 1% by mass, the function of the component (C) may not be sufficiently exhibited. When the amount exceeds 40% by mass, the bending resistance may be deteriorated.

(Radical polymerization initiator (D))
The curable composition may further contain a radical polymerization initiator (D). Examples of the radical polymerization initiator (D) include a compound that generates active radical species (radiation (light) polymerization initiator) by radiation (light) irradiation, and a compound that thermally generates active radical species (thermal polymerization initiation). Agent) and the like. If necessary, a radiation (light) polymerization initiator and a thermal polymerization initiator can be used in combination.

  The radiation (photo) polymerization initiator is not particularly limited as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2 , 2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy Roxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2 , 4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) and the like.

  Examples of commercially available radiation (photo) polymerization initiators include trade names of Ciba Specialty Chemicals: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG 24- 61, Darocur 1116, 1173, manufactured by BASF, Inc. Product name: Lucyrin TPO, UCB, Inc. Product name: Ubekril P36, Fratteri Lamberti, Inc. Product names: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B Etc.

  Examples of the thermal polymerization initiator include peroxides and azo compounds. Specific examples include benzoyl peroxide, t-butyl-peroxybenzoate, and azobisisobutyronitrile. .

  As content of the said radical polymerization initiator (D), 0.01 to 10 mass% is preferable in a total solid, and 0.1 to 5 mass% is more preferable. If it is less than 0.01% by mass, the hardness may be insufficient, and if it exceeds 10% by mass, it may not be sufficiently cured to the inside (base material layer 2 side).

(Other polymerizable compounds)
The curable composition may contain other polymerizable compounds. Examples of the polymerizable compound include vinyl compounds.

  Examples of the vinyl compounds include divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether.

(Other additives)
The curable composition may further contain other additives. Examples of the additive include an anti-blocking material, a leveling agent, an ultraviolet absorber, an antioxidant, a light stabilizer, a pigment, a dye, a filling agent, a dispersant, a plasticizer, a surfactant, a thixotropic agent, and a slip agent. Antifouling agents, antistatic agents, antibacterial agents, weathering agents, bluing agents and the like.

  The said curable composition can improve blocking resistance by containing an anti-blocking material. As the anti-blocking material added to the curable composition, particles having a particle size of preferably 9 or more and 12 or less with respect to the thickness 10 of the coat layer are preferable. The material of the particle may be an organic material or an inorganic material, and is not particularly limited, but is preferably an organic material, for example, Chemisno SX-130H, MX-150, MX-80H3WT from Soken Chemical Co., Ltd. , Sekisui Chemical Co., Ltd. Duomaster XS-10, XS-50, Nippon Shokubai Co., Ltd. Eposter S12, Sakai Chemical Industry Co., Ltd. MC-1N organic particles, Negami Kogyo Co., Ltd. Art Pearl MM-110SMA, MM An organic solvent dispersion of organic particles such as -110 SPA. The addition amount of the anti-blocking material is usually 0.01 parts by mass or more and preferably 0.005 parts by mass or more and less than 0.1 parts by mass with respect to 100 parts by mass of the curable composition.

  As the leveling agent, it is preferable to appropriately select and use a silicone-based or fluorine-based leveling agent. Examples of the silicone leveling agent include polydimethylsiloxane, polymethylalkylsiloxane, polyether-modified polydimethylsiloxane, polysiloxane having a (meth) acryl group, and the like.

  Examples of the ultraviolet absorber include benzotriazole-based, benzophenone-based, salicylic acid-based, and cyanoacrylate-based ultraviolet absorbers.

  Examples of the antioxidant include hindered phenol-based, sulfur-based, and phosphorus-based antioxidants.

  Examples of the light stabilizer include hindered amine light stabilizers.

  Each of these additives may be used alone or in combination of two or more. Moreover, as content of these other additives, 10 mass% or less is preferable in a total solid, and 3 mass parts or less are preferable.

(solvent)
The curable composition is usually used after being diluted with a solvent in order to adjust the viscosity (coating property) and the thickness of the coating film. As a viscosity of the said curable composition, it is 0.1-50,000 mPa * second / 25 degreeC normally, Preferably it is 0.5-10,000 mPa * second / 25 degreeC.

  Examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone cyclopentanone and cyclohexanone; esters such as ethyl acetate and butyl acetate; alcohols such as isopropyl alcohol and ethyl alcohol; benzene, toluene, xylene and methoxybenzene Aromatic hydrocarbons such as 1,2-dimethoxybenzene; phenols such as phenol and parachlorophenol; halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, tetrachloroethane, trichloroethylene, tetrachloroethylene, and chlorobenzene It is done. These solvents can be used alone or in combination of two or more.

  The content of the solution is preferably 70% by mass or less, more preferably 30% by mass to 60% by mass.

  The coating method of the curable composition is not particularly limited, and a known method can be used, and examples thereof include dipping coating, spray coating, flow coating, shower coating, roll coating, spin coating, brush coating, and the like. be able to.

  After application of the curable composition, preferably after drying the solvent (volatile component) at 0 to 200 ° C., the coating layer 3 can be formed by performing a curing treatment with heat and / or radiation.

  When using heat, as the heat source, for example, an electric heater, an infrared lamp, hot air, or the like can be used. The preferable curing conditions in the case of heat are 20 to 150 ° C., and are performed within a range of 10 seconds to 24 hours.

In the case of radiation (light), the radiation source is not particularly limited as long as the composition can be cured in a short time after application. For example, as an infrared radiation source, a lamp, a resistance heating plate, Commercially available lasers, etc., as visible ray sources, sunlight, lamps, fluorescent lamps, lasers, etc., ultraviolet ray sources, mercury lamps, halide lamps, lasers, etc., and electron beam sources Using thermionic electrons generated from tungsten filaments, cold cathode method for generating metal through high voltage pulse, and secondary electron method using secondary electrons generated by collision between ionized gaseous molecules and metal electrode Can be mentioned. Moreover, as a source of alpha rays, beta rays, and gamma rays, for example, a fission material such as Co ₆₀ can be used. For the gamma rays, a vacuum tube that collides accelerated electrons with the anode can be used. These radiations can be irradiated alone or in combination of two or more at a certain time.

As the radiation, ultraviolet rays or electron beams are preferably used. In such a case, the preferable irradiation amount of ultraviolet rays is 0.01 to 10 J / cm ² , more preferably 0.1 to ² J / cm ² . Moreover, preferable irradiation conditions of the electron beam are an acceleration voltage of 10 to 300 kV, an electron density of 0.02 to 0.30 mA / cm ² , and an electron beam irradiation amount of 1 to 10 Mrad.

  As described above, the laminate 1 has high transparency, heat resistance, bending resistance, blocking resistance, and hardness, and is excellent in handling properties (workability during winding and unwinding into a roll shape, etc.). . Therefore, the laminate 1 is suitably used as a surface material for display devices such as touch panels, membrane switches, and keypads. When used in a touch panel or the like, a transparent electrode film (ITO or the like) is laminated on the surface side of the coat layer 3 of the laminate 1.

  By forming a coat layer with the curable composition, a laminate excellent in bending resistance and blocking resistance can be obtained. Since the curable composition is the same as that described above as the material for forming the coat layer, a detailed description thereof will be omitted.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

<Preparation of base material layer (I)>
[Production of Base Material Layer I-1]
(Polymer synthesis)
In a 3 L four-necked flask, component (A): 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile (hereinafter also referred to as “DFBN”), component (B): 9,9-bis (4 -Hydroxyphenyl) fluorene (hereinafter also referred to as “BPFL”) 70.08 g (0.200 mol), resorcinol (hereinafter also referred to as “RES”) 5.51 g (0.050 mol), 41.46 g of potassium carbonate ( 0.300 mol), 443 g of N, N-dimethylacetamide (hereinafter also referred to as “DMAc”) and 111 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-Stark tube and a cooling tube were attached to the four-necked flask.

Next, after the atmosphere in the flask was replaced with nitrogen, the obtained solution was reacted at 140 ° C. for 3 hours, and water produced was removed from the Dean-Stark tube as needed. When no more water was observed, the temperature was gradually raised to 160 ° C. and reacted at that temperature for 6 hours.
After cooling to room temperature (25 ° C.), the produced salt was removed with a filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum dried at 60 ° C. overnight to obtain a white powder (polymer) (yield 95.67 g, yield 95%).

Table 1 shows the physical properties of the obtained polymer. The obtained polymer was subjected to a structural analysis and a weight average molecular weight measurement. As a result, the characteristic absorption of the infrared absorption spectrum is 3035 (C—H stretching), 2229 cm ⁻¹ (CN), 1574 cm ⁻¹ , 1499 cm ⁻¹ (aromatic ring skeleton absorption), 1240 cm ⁻¹ (—O—). The weight average molecular weight was 130,000.

(Film production)
Next, the obtained polymer was redissolved in DMAc to obtain a composition having a polymer concentration of 20% by mass. The above composition was applied onto a substrate made of polyethylene terephthalate (PET) using a doctor blade, dried at 70 ° C. for 30 minutes, then dried at 100 ° C. for 30 minutes to form a film, and then a PET substrate. More peeled. Thereafter, the film was fixed to a metal frame and further dried at 230 ° C. for 2 hours to obtain an evaluation film having a thickness of 30 μm. The obtained film for evaluation (base material layer I-1) has haze = 0.1%, total light transmittance = 90.1%, b * = 0.9, and the refractive index of D-line wavelength is 1.66. Met.

[Production of Base Material Layer I-2]
It carried out similarly to preparation of the base material layer I-1 except having used 11.41 g (0.050 mol) of 2, 2-bis (4-hydroxyphenyl) propane instead of 5.51 g of RES. The obtained film (base material layer I-2) had haze = 0.2%, total light transmittance = 90.2%, b * = 0.8, and the refractive index of D-line wavelength was 1.66. It was.

[Base Material Layer I-3 (for Comparative Example)]
A polyester film “Lumirror, Grade: U34” manufactured by Toray Industries Inc. having a thickness of 50 μm was used. In the base material layer I-3, haze = 0.2%, total light transmittance = 93.0%, b * = 0.2, and the refractive index at the D-line wavelength was 1.65.

(Urethane (meth) acrylate compound (B))
The urethane (meth) acrylate compound (B) component used in Examples and Comparative Examples is shown below.
(B-1): Hitachi Chemical Co., Ltd. benzyl acrylate, product name “Funkle FA-BZA” molecular weight 162, functional group number 1
(B-2): Shin-Nakamura Chemical Co., Ltd. ethoxylated bisphenol A diacrylate, product name “NK ester ABE300”, molecular weight 466, functional group number 2
(B-3): ε-caprolactone-modified tris- (2-acryloyloxyethyl) isocyanurate manufactured by Shin-Nakamura Chemical Co., Ltd., product name “NK ester A9300”, molecular weight, functional group number 3
(B-4): Shin-Nakamura Chemical Co., Ltd. ethoxylated o-phenylphenol acrylate, product name “NK ester A-LEN-10”, molecular weight 268, number of functional groups 1
(B-5): Shin Nakamura Chemical Co., Ltd. phenoxyethylene glycol acrylate, product name “NK ester AMP-10G”, molecular weight 192, number of functional groups 1
(B-6): Nippon Kayaku Co., Ltd. dioxane glycol diacrylate, product name “Kayarad R604”, molecular weight 326, functional group number 2
(B-7): A urethane acrylate containing a triazine ring from Negami Kogyo Co., Ltd., product name “Art Resin H-7”, molecular weight 25729, functional group number 4
(B-8): Carbonate urethane acrylate from Negami Kogyo Co., Ltd., product name “Art Resin UN-5500”, molecular weight 50000, number of functional groups 2
(B-9): Shin-Nakamura Chemical Industry Tetramethylol Methanetri / Tetraacrylate, Product Name “NK Ester A-TMM-3LM-N”, Molecular Weight 298, Functional Group Number 3-4
(B-10): Shin-Nakamura Chemical Co., Ltd. dipentaerythritol hexaacrylate, product name “NK ester A-DPH”, molecular weight 578, number of functional groups 6
(B-11): urethane acrylate containing a triazine ring from Negami Kogyo Co., Ltd., product name “Art Resin H-34”, molecular weight 34100, functional group number 4
(B-12): Shin-Nakamura Chemical Co., Ltd. dipentaerythritol tetraacrylate, product name “NK Ester A-TMMT”, molecular weight 352, functional group number 4
(B-13): Dipentaerythritol hexaacrylate of Shin-Nakamura Chemical Co., Ltd., product name “NK Ester A-DPH”, molecular weight 578, number of functional groups 6
(B-14): Daicel Ornex's aliphatic urethane acrylate, product name “EBECRYL270”, molecular weight 1500, functional group number 2

(Inorganic particle component)
A1-1: Propylene glycol monomethyl ether dispersion of titanium oxide particles from Sakai Chemical Industry Co., Ltd., product name “SRD-PGME”, average particle size 20 nm, solid content 20% by mass
A1-2: Methyl ethyl ketone dispersion of zirconium oxide-based particles of Sakai Chemical Industry Co., Ltd., product name “SZR-K”, average particle size 6 nm, solid content 30% by mass
A1-3: Propylene glycol monomethyl ether dispersion of titanium oxide-based particles of JGC Catalysts & Chemicals, product name "OPTOLAKE-2120Z", average particle size 13 nm, solid content 20% by mass
A1-4: Methyl ethyl ketone dispersion of zirconium oxide-based particles of Nissan Chemical Industries, Ltd., product name “Nanouse OZ-S30K”, average particle size 20 nm, solid content 30% by mass
A1-5: Methyl ethyl ketone dispersion of silica particles of Nissan Chemical Industries, Ltd., product name “MEK-ST”, average particle size 20 nm, solid content 30% by mass
A1-6: Methyl ethyl ketone dispersion of silica particles of Nissan Chemical Industries, Ltd., product name “MEK-ST-L”, average particle size 45 nm, solid content 30% by mass

  The compositions of B-1 to B-14 and inorganic particle components A1-1 to A1-6 of the urethane (meth) acrylate compound (B) used above are shown in Table 1 below. In addition, the ratio of the amount of a compound in Table 1 shows mass ratio.

(Preparation of curable composition)
The curable composition is a 30 mL light-shielding screw tube bottle, in which the curable resin composition component, the inorganic particle component, and the photopolymerization initiator are sequentially added at the solid content blending ratio described in the coating layer II in Table 2 and Table 3. Then, it was mixed with methyl ethyl ketone, and then stirred for 1 hour with a mix rotor under the condition of a rotation speed of 40 rpm. Thereby, 20 g of a methyl ethyl ketone diluted solution of a curable composition having a solid content of 20% by mass was prepared.

[Example 1]
(Production of laminate)
Installed A4 size base film on Yasuda Seiki Seisakusho's auto applicator (Yasuda Seiki Seisakusho No. 542-AB-H), and used a 1/2 inch diameter, count 2 bar coater, methyl ethyl ketone as curable composition 2 mL of the diluted solution was weighed and applied on the base film at a speed of 50 mm / second. Subsequently, the solvent was dried at 100 ° C. for 3 minutes using an air-cooled constant temperature dryer (Yamato Scientific Co., Ltd., model: DKS402), and an exposure machine (conveyor type ultraviolet exposure machine US2 from I Graphics Co., Ltd.) under nitrogen. The cured resin composition was cured with a mercury lamp under a condition of a UV integrated light quantity of 600 mJ / cm ² with a mercury lamp to obtain a laminate.

[Evaluation]
Each evaluation below was performed with respect to each obtained base material layer (I), each coating layer (II), and each laminated body. The evaluation results are shown in Tables 2 and 3.

(1) Refractive index The refractive index of wavelength 589nm was measured using the reflective spectral film thickness meter FE-3000 of Otsuka Electronics. When the difference in refractive index between the base material layer and the coating layer was 0.05 or less, A was used.

(2) Total light transmittance The total light transmittance was measured using a haze / transmittance meter HM-150 manufactured by Murakami Color Research Laboratory Co., Ltd. according to JIS-K7105 “Testing method for optical properties of plastics”. The case where the total light transmittance was 85% or more was designated as A, and the case where the total light transmittance was less than 85% was designated as B.

(3) Haze (%)
Using a haze / transmittance meter HM-150 manufactured by Murakami Color Research Laboratory Co., Ltd., the measurement was performed in accordance with JIS-K7105 “Testing methods for optical properties of plastics”. The case where the haze was 1% or less was designated as A, and the case where the haze exceeded 1% was designated as B.

(4) b *
Using a spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation, measurement is performed in the wavelength range of 380 to 780 nm, and JIS-Z8729 “Color display method: L * a * b * color system and L * u * v * B * was calculated based on “color system”. The evaluation was A when b * was 1.5 or less and B when b * exceeded 1.5.

(5) Δb *
Using a Yamato Scientific air blowing constant temperature dryer DKS402, b * after heating at 200 ° C. for 30 minutes was measured, and the difference from b * before heating was calculated to be Δb *. The evaluation was A when Δb * was 0.5 or less, and B when Δb * exceeded 0.5.

(6) Adhesion Measurement and evaluation are performed in accordance with JIS-K5600-5-6 “General test method for coating materials—Part 5: Mechanical properties of coating film—Section 6: Adhesiveness (cross-cut method)” It was. Evaluation was classified as A in JIS-K5600-5-6 Table 1, that is, when there was no peeling of the coating layer, and when it was other than the above classification 0, that is, when there was peeling of the coating layer.

(7) Bending resistance After the laminate was bent 180 degrees, the laminate was returned to a smooth state and cracks were confirmed. The evaluation was performed at any 10 locations of the laminate, and A was given when there were no cracks at 10 locations, and B was given when there were 1 or more cracks among 10 locations.

(8) Bending resistance It measured based on JIS-K5600-5-1 using the mandrel 2mm in diameter using the TQC cylindrical mandrel bending tester of a Cortec company. The evaluation was A when no crack occurred and B when crack occurred.

(9) Pencil hardness JIS-K5600-5-4 “Paint general test method-No. 1” under the conditions of 750 g load and speed 1.0 mm / sec using a pencil scratch coating film hardness tester manufactured by Toyo Seiki Seisakusho. 5 parts: Mechanical properties of coating film-Section 4: Scratch hardness (pencil method) " In the evaluation, the case of 3B or more was A, and the case of less than 3B was B.

(10) Scratch resistance Using a tribostation TYPE32 from Shinto Kagaku Co., Ltd. After 0000 steel wool was brought into contact with the evaluation sample, the load was 100 g / cm 2, the speed was 6 m / min, the stroke was 10 cm, and the number of sliding operations was 10 times. The evaluation was A when no scratch was generated, and B when scratch was generated.

(11) Anti-interference fringes Using a Panasonic Hf fluorescent lamp, product number FHF32EXNH as a light source, light was applied to the laminate, and the presence or absence of interference fringes was determined visually at an angle of 45 degrees. The evaluation was A when no interference fringes were generated, and B when interference fringes were generated.

  The laminate of the present invention is excellent in scratch resistance, transparency, heat coloring resistance, heat resistance, bending resistance, bending resistance, and interference fringe resistance. Therefore, the laminate of the present invention can be suitably used as a material for touch panels and the like.

1 Laminated body 2 Base material layer 3 Coat layer

Claims (12)

A laminate comprising a transparent substrate layer and a coat layer laminated on at least one surface of the substrate layer,
The base material layer is formed of a resin composition containing an aromatic polyether having a structural unit represented by the following formula (0),
The said coating layer is formed with the curable composition containing an organic particle, an inorganic particle, or these combination, The laminated body characterized by the above-mentioned.

(In the formula (0), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently a divalent aromatic hydrocarbon group or a divalent heteroaromatic group, provided that the above aromatic carbonization is performed. Some or all of the hydrogen atoms of the hydrogen group and heteroaromatic group may be substituted, and R ⁰ is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, provided that the above Some or all of the hydrogen atoms of the divalent hydrocarbon group having 1 to 20 carbon atoms may be substituted, and the divalent hydrocarbon group having 1 to 20 carbon atoms may be an ester group or an ether group. Or a carbonyl group may be present in the structure, Y is a carbonyl group or a sulfonyl group, m is 0 or 1, and n is 0 or 1.) The aromatic polyether has a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), or a combination thereof as the structural unit represented by the above formula (0). Item 2. The laminate according to Item 1.

(In formula (1), R ^{1 to} R ⁴ are each independently a monovalent organic group having 1 to 12 carbon atoms. A 1 to d 1 are each independently an integer of 0 to 4)

(In formula (2), R ^{1 ′ to} R ^{4 ′} are each independently a monovalent organic group having 1 to 12 carbon atoms. A2 to d2 are each independently an integer of 0 to 4. Y ¹ is a single bond, —SO ₂ — or —CO—, and R ⁷ and R ⁸ are each independently a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group. G1 and h1 are each independently an integer of 0 to 4. m1 is 0 or 1. However, when m1 is 0, R ⁷ is not a cyano group. The laminate according to claim 1 or 2, wherein the aromatic polyether further comprises a structural unit represented by the following formula (3), a structural unit represented by the following formula (4), or a combination thereof.

(In Formula (3), R ⁵ and R ⁶ are each independently a monovalent organic group having 1 to 12 carbon atoms. Z ¹ is a single bond, —O—, —S—, —SO _2. -, -CO-, -CONH-, -COO-, or a divalent organic group having 1 to 12 carbon atoms, e1 and f1 are each independently an integer of 0 to 4. n1 is 0 or 1)

(In Formula (4), R ^{5 ′} and R ^{6 ′} are each independently a monovalent organic group having 1 to 12 carbon atoms. Z ² is a single bond, —O—, —S—, — SO _2- , -CO-, -CONH-, -COO- or a divalent organic group having 1 to 12 carbon atoms, e2 and f2 are each independently an integer of 0 to 4. n2 is Each of R ^{7 ′} and R ^{8 ′} is independently a halogen atom, a monovalent organic group having 1 to 12 carbon atoms, or a nitro group, Y ² is a single bond, —SO ₂ —; Or —CO—, m2 is 0 or 1. However, when m2 is 0, R ^{7 ′} is not a cyano group, and g2 and h2 are each independently an integer of 0 to 4. )   The laminate according to claim 1, wherein the average thickness of the coat layer is 0.05 μm or more and 10 μm or less.   The inorganic particles are potassium, calcium, strontium, barium, hafnium, gallium, niobium, lanthanum, silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony, cerium oxide particles, sulfide particles, carbides The laminate according to any one of claims 1 to 4, comprising particles, nitride particles, or a combination thereof.   The laminate according to any one of claims 1 to 5, wherein the curable composition is an ultraviolet curable composition.   The adhesion between the base material layer and the coating layer is classified as 0 or 1 in the adhesion test by the cross-cut method according to JIS-K5600-5-6: 1999. The laminated body of any one of Claims.   The lamination according to any one of claims 1 to 7, wherein in a bending resistance test by a cylindrical mandrel method according to JIS-K5600-5-1: 1999, a diameter of a mandrel in which a crack occurs is 2 mm or less. body.   The laminate according to any one of claims 1 to 8, wherein a pencil hardness of the surface of the coat layer measured in accordance with JIS-K5600-5-4: 1999 is 3B or more.   The laminate according to any one of claims 1 to 9, wherein a difference in refractive index between the base material layer and the coat layer at a wavelength of 589.3 nm is 0.05 or less.   The laminate according to any one of claims 1 to 10, wherein the total light transmittance measured in accordance with JIS-K7105 is 85% or more and the haze value is 1% or less. JIS-Z8729: in the CIELAB of ^L * ^a * ^{b *} color system are measured in accordance with 2004 ^{b *} is 1.5 or less and 200 ° C., the amount of change in ^{b *} after heating 30 minutes The laminate according to any one of claims 1 to 11, wherein Δb ^* is 0.5 or less.

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