JP2016114919A - Optical film, manufacturing method therefor, information display device, and vehicle-mounted information display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical film which offers a level of weather resistance that is sufficient to prevent pealing and cracking of a reflection reduction layer and hard coat layer even when exposed to a high temperature/high humidity environment or direct sunlight environment for an extended period of time and a level of hardness that is sufficient to prevent temporal scratches and the like.SOLUTION: The present invention relates to an optical film having a resin layer (X) at least on one surface of a base material, the resin layer (X) containing an inorganic microparticle complex (M) consisting of; a composite resin (A), comprising a polysiloxane segment (a1) having a structural unit represented by a general formula (1) and/or general formula (2) and a silanol group and/or hydrolyzable silyl group, and a vinyl polymer segment (a2) bonded in a structure represented by a general formula (4); and inorganic microparticles (m), which are bonded together via a siloxane bond with the polysiloxane segment (a1).SELECTED DRAWING: Figure 1

Description

  The present invention relates to an optical film such as an antireflection film.

  As an information display device such as a liquid crystal display, a plasma display, an organic EL display, and a display to which a touch panel function is added, it prevents a decrease in visibility due to reflection of sunlight or the like even outdoors. And what is provided with the antireflection property is known.

  As the information display device having the antireflection property, for example, an information display device in which an antireflection film, an antiglare film, or the like is installed on the surface of the information display unit is known.

  As the antireflection film, for example, a surface of a transparent film provided with a low refractive index layer by a dry process method such as a vapor deposition method or a sputtering method (see, for example, Patent Document 1), a wet process is performed on the surface of the transparent film. A method in which a low refractive index layer is provided by a method (for example, see Patent Document 2) is known.

  Moreover, as the said anti-glare film, what provided the anti-glare layer which contains microparticles | fine-particles by the wet process method on the surface of a transparent film is known, for example (refer patent document 3).

  By the way, the information display device is being used in a wide range of applications including, for example, smartphones and car navigation systems, as image quality and functionality are enhanced. In particular, car navigation systems are generally often exposed to high temperatures and high humidity for a long period of time or to direct sunlight for a long period of time. Therefore, an information display device mounted on an automobile or the like is required to be able to maintain excellent optical characteristics such as antireflection properties for a long period even when exposed to such an environment.

  However, conventional optical films such as antireflection films may deteriorate due to the influence of direct sunlight or the influence of high temperature and high humidity, which may cause peeling or cracking of the reflection reducing layer or the hard coat layer. It was. Further, when the optical film is provided on the surface of the information display device on which the touch panel device is mounted, a finger or a touch pen repeatedly comes into contact with the operation. Therefore, the optical film has been required to have the above-described excellent weather resistance and the like, and to have a level of hardness that does not cause scratches over time.

JP 2003-149407 A Japanese Patent Laid-Open No. 2003-177209 JP 2003-248110 A

  The problem to be solved by the present invention is to cause peeling or cracking of a reflection reducing layer, a hard coat layer, etc. even when it is placed in a high temperature, high humidity environment or an environment exposed to direct sunlight for a long period of time. It is an object of the present invention to provide an optical film having a weather resistance level that does not occur and a hardness level that can prevent scratches over time.

  When the present inventors have studied to solve the above-mentioned problems, for example, a resin layer obtained by using a specific composite resin is provided between a base material such as triacetyl cellulose or polyethylene terephthalate and a reflection reducing layer. It has been found that the above problems can be solved.

  That is, the present invention is an optical film having a resin layer (X) on at least one side of a substrate, and having a reflection reducing layer (Y) on the surface of the resin layer (X), wherein the resin layer (X ) Has a structural unit represented by the general formula (1) and / or the general formula (2), a silanol group and / or a hydrolyzable silyl group, and a vinyl polymer segment ( a2) is bonded with the composite resin (A) bonded with the structure represented by the general formula (4) and the inorganic fine particles (m) via the siloxane bond in the polysiloxane segment (a1). The present invention relates to an optical film characterized by being a layer containing the inorganic fine particle composite (M).

  Since the optical film of the present invention is excellent in weather resistance, for example, even when exposed to a high temperature of about 100 ° C. and a high humidity environment of about 95%, or an environment exposed to direct sunlight, the reflection reducing layer. No peeling or cracking of the hard coat layer or the like. Moreover, even when the present invention is provided on the surface of an information display device on which a touch panel device is mounted, it is difficult to generate scratches or the like due to an operation with a finger, a touch pen, or the like.

It is a conceptual diagram which shows an example of the embodiment of the optical film of this invention. It is a conceptual diagram which shows an example of the embodiment of the optical film of this invention.

  The optical film of the present invention is an optical film having a resin layer (X) on at least one side of a substrate, and having a reflection reducing layer (Y) on the surface of the resin layer (X), wherein the resin layer ( A polysiloxane segment (a1) in which X) has a structural unit represented by the general formula (1) and / or the general formula (2), a silanol group and / or a hydrolyzable silyl group, and a vinyl polymer segment The composite resin (A) in which (a2) is bonded in the structure represented by the general formula (4) and the inorganic fine particles (m) are bonded through the siloxane bond in the polysiloxane segment (a1). It is a layer containing the inorganic fine particle composite (M), and can be suitably used particularly as an antireflection film.

  The optical film of the present invention has a specific resin layer (X) between the base material and the reflection reducing layer (Y). By providing the resin layer (X), even when exposed to a high temperature and high humidity environment or an environment exposed to direct sunlight, the reflection reducing layer or the like is not peeled or cracked. An optical film having weather resistance and a level of hardness that can prevent damage with time can be obtained.

  The resin layer (X) is provided on one side or both sides of the base material directly or via another layer, and is preferably provided directly on one side of the base material. The reflection reduction layer (Y) is provided directly on the surface of the resin layer (X) or via another layer, and is provided directly on the surface of the resin layer (X). Is preferred.

  First, the resin layer (X) will be described.

  The resin layer (X) is a layer provided between the base material and the reflection reduction layer (Y) for the purpose of preventing the reflection reduction layer (Y) from peeling off over time.

  The resin layer (X) has suitable adhesion to both the base material and the reflection reducing layer (Y).

  In addition, as the resin layer (X), for example, in the case where the optical film of the present invention is provided on the surface of an information display device having a touch panel function, the surface of the information display unit that can be generated by repeated operations with a touch pen or the like. In order to prevent scratches and the like, it is preferable to have a hardness of “H” or higher in the pencil hardness test specified in JIS 5600-5-4: 1999. That is, the resin layer (X) preferably serves as a so-called hard coat layer.

  The resin layer (X) has a thickness of 0.1 μm to 50 μm in order to achieve both excellent adhesion and high hardness to the base material (A) and the reflection reducing layer (Y). It is preferable to use one having a thickness of 0.5 μm to 50 μm, more preferably one having a thickness of 1 μm to 20 μm, and particularly preferably one having a thickness of 1 μm to 20 μm.

  In addition, as the resin layer (X), in order to obtain an optical film having further excellent antireflection properties, it is preferable to use one having a refractive index in the range of 1.45 to 1.55. It is more preferable to use one having a refractive index in the range of 1.47 to 1.53.

  The resin layer (X) may have a smooth surface or a fine uneven shape on the surface.

  The resin layer (X) may be composed of a single layer or may have a multilayer structure of two or more layers obtained using the same or different materials. For example, when the resin layer (X) is used as an antiglare layer, as the resin layer (X), for example, a lower layer having an uneven shape and the uneven shape can be finely adjusted to a desired uneven shape. What has a multilayer structure which consists of an upper layer can be used.

  The resin layer (X) comprises a polysiloxane segment (a1) having a structural unit represented by the general formula (1) and / or the general formula (2), a silanol group and / or a hydrolyzable silyl group, vinyl The composite resin (A) in which the polymer segment (a2) is bonded with the structure represented by the general formula (4), and the inorganic fine particles (m) have a siloxane bond in the polysiloxane segment (a1). It is a layer containing the inorganic fine particle composite body (M) bonded through the intermediate layer.

  The resin layer (X) can be formed, for example, by using the resin layer (X) forming composition. As the resin layer (X) forming composition, for example, a composition containing the inorganic fine particle composite body (M) is used.

  The inorganic fine particle composite (M) contained in the composition is one in which the polysiloxane segment (a1) constituting the composite resin (A) and the inorganic fine particles (m) are siloxane-bonded.

(Composite resin (A))
The composite resin (A) used in the present invention is a polysiloxane segment having the structural unit represented by the general formula (1) and / or the general formula (2) and a silanol group and / or a hydrolyzable silyl group. (A1) (hereinafter simply referred to as “polysiloxane segment (a1)”) and a vinyl polymer segment (a2) are combined to form a structure represented by the general formula (4). It is (A).

(Polysiloxane segment (a1))
The composite resin (A) has a polysiloxane segment (a1). The polysiloxane segment (a1) is a segment obtained by condensing a silane compound having a silanol group and / or a hydrolyzable silyl group, and is represented by the general formula (1) and / or the general formula (2). And a silanol group and / or a hydrolyzable silyl group.

  The content of the polysiloxane segment (a1) is 10% by mass to 90% by mass with respect to the total solid content of the composite resin (A), which facilitates bonding with inorganic fine particles (m) described later. As a result, an optical film having both excellent weather resistance and high hardness can be obtained, which is preferable.

  The polysiloxane segment (a1) has a structural unit represented by the following general formulas (1) and (2) and a silanol group and / or a hydrolyzable silyl group.

In the general formulas (1) and (2), R ¹ , R ² and R ³ are each independently —R ⁴ —CH═CH ₂ , —R ⁴ —C (CH ₃ ) ═CH ₂ , —R ⁴ —O—CO—C (CH ₃ ) ═CH ₂ and —R ⁴ —O—CO—CH═CH ₂ , or a polymerizable double group selected from the group consisting of groups represented by the following formula (3) A group having a bond (wherein R ⁴ represents a single bond or an alkylene group having 1 to 6 carbon atoms), an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, aryl Group, an aralkyl group having 7 to 12 carbon atoms, and an epoxy group.

(In general formula (3), n is an integer represented by 1 to 5, and the structure Q represents either —CH═CH ₂ or —C (CH ₃ ) ═CH _2. )

  The structural unit represented by the general formula (1) and / or the general formula (2) is a three-dimensional network polysiloxane structural unit in which two or three of the silicon bonds are involved in crosslinking. Since a three-dimensional network structure is formed but a dense network structure is not formed, gelation or the like is not caused and storage stability is also improved.

Examples of the alkylene group having 1 to 6 carbon atoms constituting R ⁴ include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a sec-butylene group, and a tert-butylene group. , Pentylene group, isopentylene group, neopentylene group, tert-pentylene group, 1-methylbutylene group, 2-methylbutylene group, 1,2-dimethylpropylene group, 1-ethylpropylene group, hexylene group, isohesylene group, 1-methyl Pentylene group, 2-methylpentylene group, 3-methylpentylene group, 1,1-dimethylbutylene group, 1,2-dimethylbutylene group, 2,2-dimethylbutylene group, 1-ethylbutylene group, 1, 1,2-trimethylpropylene group, 1,2,2-trimethylpropylene group, 1-ethyl-2- Chill propylene group, a 1-ethyl-1-methylpropylene group. Among these, R ⁴ is preferably a single bond or an alkylene group having 2 to 4 carbon atoms because of easy availability of raw materials.

  Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and isopentyl. Group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl Group, 3-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2 , 2-trimethylpropyl group, 1-ethyl-2-methylpropyl group, 1-ethyl-1-methylpropyl group, and the like.

  Examples of the cycloalkyl group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

  Examples of the aryl group include a phenyl group, a naphthyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-vinylphenyl group, and a 3-isopropylphenyl group.

  Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.

In addition, when at least one of R ¹ , R ² and R ³ is a group having the polymerizable double bond, it can be cured by active energy rays or the like, active energy rays, silanol groups and / or The two curing mechanisms of the hydrolyzable silyl group condensation reaction are preferred because the resulting cured product has a higher crosslink density and a hard coat film having even better weather resistance can be obtained.

  Two or more groups having a polymerizable double bond are preferably present in the polysiloxane segment (a1), more preferably 3 to 200, and even more preferably 3 to 50.

  Specifically, if the content of the polymerizable double bond in the polysiloxane segment (a1) is 3% by mass to 35% by mass, a hard coat that achieves both excellent weather resistance and high hardness. A film can be obtained. The term “polymerizable double bond” as used herein is a general term for groups capable of performing a growth reaction with free radicals among vinyl groups, vinylidene groups, and vinylene groups. Moreover, the content rate of a polymerizable double bond shows the mass ratio with respect to the said polysiloxane segment (a1) of the said vinyl group, vinylidene group, and vinylene group.

As the group having a polymerizable double bond, all known functional groups containing a vinyl group, a vinylidene group, or a vinylene group can be used, and among them, —R ⁴ —C (CH ₃ ) ═CH ₂ and the (meth) acryloyl group represented by —R ⁴ —O—CO—C (CH ₃ ) ═CH ₂ are rich in reactivity at the time of ultraviolet curing, and a vinyl polymer segment (a2 described later) It is preferable to use it because of its good compatibility with (A).

  When the group having a polymerizable double bond is a group represented by the general formula (3), the structure Q in the formula indicates that a plurality of vinyl groups may be bonded to the aromatic ring. Yes. For example, when two Qs are bonded to the aromatic ring, it means that the following structures are also included.

Since the structure represented by the styryl group represented by the general formula (5) does not contain an oxygen atom, oxidative decomposition based on the oxygen atom is unlikely to occur. Moreover, since the said structure is excellent in thermal decomposition resistance, it is suitable for the use for which heat resistance is requested | required. This is considered to be because the reaction oxidized by the bulky structure is inhibited. In order to improve heat resistance, it is preferable to have a group having a polymerizable double bond selected from the group consisting of —R ⁴ —CH═CH ₂ and —R ⁴ —C (CH ₃ ) ═CH ₂ .

  In the present invention, the silanol group is a silicon-containing group having a hydroxyl group directly bonded to a silicon atom. Specifically, the silanol group is a silanol group formed by combining an oxygen atom having a bond with a hydrogen atom in the structural unit represented by the general formula (1) and / or the general formula (2). Preferably there is.

In the polysiloxane segment (a1), when at least one of R ¹ , R ² and R ³ is an epoxy group, it can be cured by thermal curing or active energy ray curing, Due to the two curing mechanisms of the condensation reaction of silanol groups and / or hydrolyzable silyl groups, the resulting cured product has a higher crosslinking density, and a hard coat having even better weather resistance and high hardness is obtained. be able to.

  In the present invention, the hydrolyzable silyl group is a silicon-containing group having a hydrolyzable group directly bonded to a silicon atom, and specifically includes, for example, a group represented by the general formula (6). .

(In the general formula (6), R ⁵ is a monovalent organic group such as an alkyl group, an aryl group or an aralkyl group, R ⁶ is a halogen atom, an alkoxy group, an acyloxy group, a phenoxy group, an aryloxy group, a mercapto group, (It is a hydrolyzable group selected from the group consisting of an amino group, an amide group, an aminooxy group, an iminooxy group and an alkenyloxy group, and b is an integer of 0 to 2.)

Examples of the alkyl group in R ⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a tert group. -Pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl Group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group 1-ethyl-2-methylpropyl group, 1-ethyl-1-methylpropyl group and the like.

  Examples of the aryl group include a phenyl group, a naphthyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-vinylphenyl group, and a 3-isopropylphenyl group.

  Examples of the aralkyl group include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.

In R ⁶ , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a second butoxy group, and a third butoxy group.
Examples of the acyloxy group include formyloxy, acetoxy, propanoyloxy, butanoyloxy, pivaloyloxy, pentanoyloxy, phenylacetoxy, acetoacetoxy, benzoyloxy, naphthoyloxy and the like.
Examples of the aryloxy group include phenyloxy and naphthyloxy.

  Examples of the alkenyloxy group include a vinyloxy group, allyloxy group, 1-propenyloxy group, isopropenyloxy group, 2-butenyloxy group, 3-butenyloxy group, 2-petenyloxy group, 3-methyl-3-butenyloxy group, 2 -A hexenyloxy group etc. are mentioned.

By hydrolyzing the hydrolyzable group represented by R ⁶ , the hydrolyzable silyl group represented by the general formula (6) becomes a silanol group. Among these, a methoxy group and an ethoxy group are preferable because of excellent hydrolyzability.

  The hydrolyzable silyl group specifically includes an oxygen atom having a bond in the structural unit represented by the general formula (1) and / or the general formula (2) bonded to the hydrolyzable group. Or it is preferable that it is the hydrolyzable silyl group substituted.

  Since the silanol group and the hydrolyzable silyl group undergo a hydrolytic condensation reaction between the hydrolyzable group in the silanol group and the hydrolyzable silyl group, the crosslinking density of the polysiloxane structure is increased. A cured product having excellent weather resistance can be formed.

  Further, the polysiloxane segment (a1) containing the silanol group or the hydrolyzable silyl group is bonded to the vinyl polymer segment (a2) described later via the structure represented by the general formula (4). Use when.

The polysiloxane segment (a1) is not particularly limited except that it has a structural unit represented by the general formula (1) and / or the general formula (2), and a silanol group and / or a hydrolyzable silyl group. And other groups may be included. For example,
Polysiloxanes R ¹ in the general formula (1) is a structural unit is a group having a polymerizable double bond, R ¹ in the general formula (1) coexist and the structural unit is an alkyl group such as methyl It may be segment (a1)
A structural unit R ¹ is an alkyl group such as a methyl group and structural units R ¹ is a group having a polymerizable double bond in the formula (1), the formula in (1), the general formula It may be a polysiloxane segment (a1) in which R ² and R ³ in (2) coexist with a structural unit that is an alkyl group such as a methyl group,
A structural unit in which R ¹ in the general formula (1) is a group having a polymerizable double bond, and a structural unit in which R ² and R ³ in the general formula (2) are alkyl groups such as a methyl group, The polysiloxane segment (a1) which coexists may be used, and there is no particular limitation.

  The polysiloxane segment (a1) is contained in an amount of 10 to 65% by mass with respect to the total solid content of the composition used for the formation of the resin layer (X). It is preferable when obtaining a hard coat film excellent in interlayer adhesion with the layer (Y).

(Vinyl polymer segment (a2))
The vinyl polymer segment (a2) is a polymer segment obtained by polymerizing a vinyl group or (meth) acryl group-containing monomer, and includes a vinyl polymer segment, an acrylic polymer segment, and a vinyl / acrylic copolymer. Examples include a coalesced segment and the like, which are appropriately selected depending on the application. Since the inorganic fine particle composite (M) has the vinyl polymer segment (a2), it is excellent in film forming properties even when the inorganic fine particles (m) are used.

  For example, the acrylic polymer segment is obtained by polymerizing or copolymerizing a general-purpose (meth) acrylic monomer. The (meth) acrylic monomer is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert- Alkyl (meth) acrylates having an alkyl group having 1 to 22 carbon atoms, such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate; benzyl (meth) acrylate, 2-phenylethyl Aralkyl (meth) acrylates such as (meth) acrylate; Cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 4-methoxybutyl Ω-alkoxyalkyl (meth) acrylates such as (meth) acrylate; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, etc .; alkyl crotonic acid, such as methyl crotonate and ethyl crotonate Esters: Dialkyl esters of unsaturated dibasic acids such as dimethyl malate, di-n-butyl maleate, dimethyl fumarate, dimethyl itaconate, and the like.

  In particular, when cyclohexyl (meth) acrylate is used as the (meth) acrylic monomer, it is preferable to further improve the adhesion of the resin layer (X) to the substrate, particularly a plastic substrate, preferably a polycarbonate substrate. . Cyclohexyl (meth) acrylate is preferably used in an amount of 20 to 75% by mass, more preferably 50 to 75% by mass, based on the total amount of vinyl group-containing monomers constituting the vinyl polymer segment (a2).

  Specific examples of the vinyl polymer segment (a2) include aromatic vinyl polymer segments, polyolefin polymers, fluoroolefin polymers, and the like, and copolymers thereof may be used. In order to obtain these vinyl polymers, a vinyl group-containing monomer may be polymerized. Specifically, α-olefins such as ethylene, propylene, 1,3-butadiene and cyclopentylethylene; styrene, 1-ethynyl- 4-methylbenzene, divinylbenzene, 1-ethynyl-4-methylethylbenzene, benzonitrile, acrylonitrile, p-tert-butylstyrene, 4-vinylbiphenyl, 4-ethynylbenzyl alcohol, 2-ethynylnaphthalene, phenanthrene-9-ethynyl And vinyl compounds having an aromatic ring such as fluorinated olefins such as vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene and chlorotrifluoroethylene. More preferred are styrene and p-tert-butylstyrene which are vinyl compounds having an aromatic ring.

  The vinyl polymer segment (a2) may be a vinyl / acrylic copolymer segment obtained by copolymerizing a (meth) acrylic monomer and a vinyl group-containing monomer.

  There are no particular limitations on the polymerization method, solvent, or polymerization initiator for copolymerizing the monomers, and the vinyl polymer segment (a2) can be obtained by a known method. For example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-) can be obtained by various polymerization methods such as bulk radical polymerization, solution radical polymerization, and non-aqueous dispersion radical polymerization. Dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), tert-butylperoxypivalate, tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, di- The vinyl polymer segment (a2) can be obtained by using a polymerization initiator such as tert-butyl peroxide, cumene hydroperoxide, diisopropyl peroxycarbonate or the like.

  The number average molecular weight of the vinyl polymer segment (a2) is preferably in the range of 500 to 200,000 in terms of number average molecular weight (hereinafter abbreviated as Mn), and the composite resin (A) is produced. It is possible to prevent thickening and gelation during the process and to have excellent durability. Mn is more preferably in the range of 700 to 100,000, and the range of 1,000 to 50,000 is preferable because the coating suitability and adhesion to the substrate described later can be further improved.

  Further, the hydroxyl value (OHv) of the vinyl polymer segment (a2) is preferably 65 mgKOH / g or less because of excellent water resistance and heat resistance, and more preferably 45 mgKOH / g or less. Similarly, a hydroxyl value of 65 mgKOH / g or less is preferable because of excellent adhesion to a plastic substrate after heat resistance test, preferably polycarbonate, and more preferably 45 mgKOH / g or less.

  Moreover, in order to make the said vinyl polymer segment (a2) into the composite resin (A) couple | bonded by the structure represented by the said polysiloxane segment (a1) and General formula (4), a vinyl polymer segment ( In a2), it has a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon atom. Since these silanol groups and / or hydrolyzable silyl groups are consumed in the composite resin (A) to form the structure represented by the general formula (4), the vinyl group in the composite resin (A) Almost no polymer segment (a2) is present. However, there is no problem even if silanol groups and / or hydrolyzable silyl groups remain in the vinyl polymer segment (a2). When the inorganic fine particle composite (M) is cured, hydroxyl groups in the silanol groups and Since the hydrolysis condensation reaction proceeds between the hydrolyzable groups in the hydrolyzable silyl group, the crosslink density of the polysiloxane structure of the resulting cured product is increased, so that both excellent weather resistance and high hardness are achieved. A hard coat film can be obtained.

  In order to introduce a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon atom into the vinyl polymer segment (a2), specifically, when the vinyl polymer segment (a2) is polymerized, A vinyl group-containing monomer containing a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon bond may be used in combination with the vinyl group polymerization monomer and the (meth) acryl monomer.

  Examples of vinyl group-containing monomers containing a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon atom include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, and vinyltri (2-methoxyethoxy). Silane, vinyltriacetoxysilane, vinyltrichlorosilane, 2-trimethoxysilylethyl vinyl ether, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxy Examples thereof include propylmethyldimethoxysilane and 3- (meth) acryloyloxypropyltrichlorosilane. Among these, vinyltrimethoxysilane and 3- (meth) acryloyloxypropyltrimethoxysilane are preferable because the hydrolysis reaction can easily proceed and by-products after the reaction can be easily removed.

  The vinyl polymer segment (a2) may have various functional groups. For example, a group having a polymerizable double bond, an epoxy group, an alcoholic hydroxyl group, and the like. For introduction, a vinyl group-containing monomer having a corresponding functional group may be added during polymerization.

  Examples of the vinyl group-containing monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, vinylcyclohexene oxide, glycidyl vinyl ether, methyl glycidyl vinyl ether or allyl. A glycidyl ether etc. are mentioned.

  Examples of the vinyl group-containing monomer having an alcohol hydroxyl group include (2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl monobutyl fumarate , Polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, “Placcel FM or Plaxel FA” [caprolactone addition monomer manufactured by Daicel Chemical Industries, Ltd.] Examples thereof include hydroxyalkyl esters of a tyrenic unsaturated carboxylic acid, or an adduct of these with ε-caprolactone.

[Inorganic fine particles (m)]
The inorganic fine particles (m) are not particularly limited as long as the effects of the present invention are not impaired, but have a functional group capable of forming a siloxane bond because they are bonded to the polysiloxane segment (a1) via a siloxane bond.

  The functional group that can form a siloxane bond may be any functional group that can form a siloxane bond, such as a hydroxyl group, a silanol group, or an alkoxysilyl group. The inorganic fine particles (m) themselves that can form siloxane bonds may be included, or functional groups may be introduced by modifying the inorganic fine particles (m).

  As a method for modifying the inorganic fine particles (m), a publicly known and commonly used method may be used, and there are methods such as silane coupling agent treatment and coating with a resin having a functional group capable of forming a siloxane bond.

As the inorganic fine particles (m), for example, those having excellent heat resistance include alumina, magnesia, titania, zirconia, silica (quartz, fumed silica, precipitated silica, anhydrous silicic acid, fused silica, crystalline silica, super Amorphous silica, etc.), etc .; those having excellent thermal conductivity, such as boron nitride, aluminum nitride, alumina, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, etc .; those having excellent conductivity, simple metals or alloys Metal fillers and / or metal-coated fillers using (for example, iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.); , Minerals such as talc, zeolite, wollastonite, smectite, potassium titanate, magnesium sulfate Um, Sepiolite, Zonolite, Aluminum borate, Calcium carbonate, Titanium oxide, Barium sulfate, Zinc oxide, Magnesium hydroxide; High refractive index: Barium titanate, Zirconia, Titanium oxide, etc .; Photocatalytic properties Is a photocatalytic metal such as titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, nickel, iron, cobalt, silver, molybdenum, strontium, chromium, barium, lead, a composite of the above metals, Those oxides, etc .; those having excellent wear resistance, such as silica, alumina, zirconia, magnesium, etc., and their composites and oxides; those having excellent electrical conductivity, such as metals such as silver, copper, etc. , Tin oxide, indium oxide, etc .; those with excellent insulation, silica, etc .; As what is, titanium oxide, zinc oxide and the like.
These inorganic fine particles (m) may be appropriately selected depending on the use, and may be used alone or in combination. Further, the inorganic fine particles (m) have various characteristics other than the characteristics mentioned in the examples, and therefore may be selected according to the timely use.

For example, when silica is used as the inorganic fine particles (m), known silica fine particles such as powdered silica and colloidal silica can be used without any particular limitation. Examples of commercially available powdered silica fine particles include Aerosil 50 and 200 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, and H122 manufactured by Asahi Glass Co., Ltd., and E220A manufactured by Nippon Silica Industry Co., Ltd. E220, SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.
Examples of commercially available colloidal silica include methanol silica sol manufactured by Nissan Chemical Industries, Ltd., IPA-ST, PGM-ST, 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.

  Surface-modified silica fine particles may be used. For example, the silica fine particles may be surface-treated with a reactive silane coupling agent having a hydrophobic group or those modified with a compound having a (meth) acryloyl group. can give. As commercially available silica powder modified with a compound having a (meth) acryloyl group, as commercially available colloidal silica modified with a compound having a (meth) acryloyl group, such as Aerosil RM50, R7200, R711 manufactured by Nippon Aerosil Co., Ltd. Is a colloidal silica surface-treated with a reactive silane coupling agent having a hydrophobic group, such as MIBK-SD, MEK-SD, manufactured by Nissan Chemical Industries, Ltd., MIBK-ST, manufactured by Nissan Chemical Industries, Ltd., MEK-ST etc. are mentioned.

  The shape of the silica fine particles is not particularly limited, and those having a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, or an indefinite shape can be used. For example, as a commercially available hollow silica fine particle, Sirinax (registered trademark) manufactured by Nittetsu Mining Co., Ltd. can be used.

  As the titanium oxide fine particles, not only extender pigments but also ultraviolet light responsive photocatalysts can be used. For example, anatase type titanium oxide, rutile type titanium oxide, brookite type titanium oxide and the like can be used. Furthermore, particles designed to respond to visible light by doping a different element in the crystal structure of titanium oxide can also be used. As an element to be doped in titanium oxide, anionic elements such as nitrogen, sulfur, carbon, fluorine and phosphorus, and cationic elements such as chromium, iron, cobalt and manganese are preferably used. Moreover, as a form, a sol or slurry dispersed in powder, an organic solvent or water can be used. Examples of commercially available powdered titanium oxide fine particles include Aerosil P-25 manufactured by Nippon Aerosil Co., Ltd., ATM-100 manufactured by Teika Co., Ltd., and the like. Moreover, as a commercially available slurry-like titanium oxide microparticles | fine-particles, for example, Teika Co., Ltd. TKD-701 etc. are mentioned.

  The primary particle diameter of the inorganic fine particles (m) is preferably in the range of 5 to 200 nm. When it is 5 nm or more, the inorganic fine particles (m) in the dispersion have good dispersion, and when the diameter is within 200 nm, the strength of the cured product becomes good. More preferably, it is 10 nm to 100 nm. The “particle diameter” here is measured using a scanning electron microscope (TEM) or the like.

  The inorganic fine particles (m) can be blended at a ratio of 5 to 90% by mass with respect to the total solid content of the inorganic fine particle composite body (M), and the blending amount may be changed as appropriate according to the application.

  For example, in order to achieve both wear resistance and interlayer adhesion, the inorganic fine particles (m) are preferably used in the range of 5 to 90% by mass, and in order to further improve the wear resistance, 5 to 60 are used. It is particularly preferable to use in the range of mass%.

  In addition, alumina, magnesia, titania, zirconia, silica, or the like may be added separately as inorganic fine particles that are not bonded to the composite resin (A).

[Method for producing inorganic fine particle composite (M)]
The inorganic fine particle composite (M) comprises a step 1 of synthesizing a vinyl polymer segment (a2) having a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon atom, an alkoxysilane and an inorganic fine particle (m ) And a step 3 of condensation reaction of alkoxysilane. At this time, each step may be performed separately or at the same time. For example, it can be manufactured by the following method.

<Method 1> Vinyl-based polymer segment (a2) having a silanol group and / or a hydrolyzable silyl group directly bonded to the carbon atom obtained in step 1, and a silanol group and / or hydrolyzable silyl group-containing silane compound And the inorganic fine particles (m) are mixed in Step 2, and this mixture is condensed in Step 3 with a silanol group and / or hydrolyzable silyl group-containing silane compound to form a polysiloxane segment (a1) and vinyl A method of forming a bond between the polymer segment (a2) and the inorganic fine particles (m).

<Method 2> Silanol group and / or hydrolyzable silyl group-containing silane compound and inorganic fine particles (m) are mixed in step 2, and in step 3, silanol group and / or hydrolyzable silyl group-containing silane compound is condensed. And after forming the polysiloxane segment (a1) and the inorganic fine particle bond, the vinyl polymer segment (a2) having a silanol group and / or hydrolyzable silyl group obtained in step 1 and the polysiloxane segment ( a1) A method of forming a bond by hydrolyzing and condensing inorganic fine particles (m) again in Step 3.

  Next, step 1, step 2, and step 3 will be specifically described.

Step 1 is a step of synthesizing a vinyl polymer segment (a2) having a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon atom. In order to introduce a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon atom into the vinyl polymer segment (a2), specifically, when the vinyl polymer segment (a2) is polymerized, What is necessary is just to use together the vinyl-type monomer containing the silanol group and / or hydrolyzable silyl group which were directly couple | bonded with the carbon bond with respect to a vinyl group polymerization monomer and a (meth) acryl monomer.
Thereafter, the vinyl polymer segment (a2) is hydrolyzed and condensed with a silane compound containing a silanol group and / or a hydrolyzable silyl group, so that the silanol group directly bonded to the carbon atom and / or the hydrolysis can be obtained. A polysiloxane segment precursor may be bonded to the functional silyl group.

Step 2 is a step of mixing the silanol group and / or hydrolyzable silyl group-containing silane compound and the inorganic fine particles (m). As the silane compound, a general-purpose silanol group and / or hydrolyzable silyl group-containing silane compound described later can be used. At this time, when there is a group to be introduced into the polysiloxane segment, a silane compound having the group to be introduced is used in combination. For example, when an aryl group is introduced, a silane compound having both an aryl group and a silanol group and / or a hydrolyzable silyl group may be appropriately used in combination. When a group having a polymerizable double bond is introduced, a silane compound having both a group having a polymerizable double bond and a silanol group and / or a hydrolyzable silyl group may be used in combination.
A known dispersion method can be used for mixing. Examples of the mechanical means include a disperser, a disperser having a stirring blade such as a turbine blade, a paint shaker, a roll mill, a ball mill, an attritor, a sand mill, a bead mill, and the like, and glass beads and zirconia beads for uniform mixing. It is preferable to disperse by a bead mill using a dispersion medium such as

  Examples of the bead mill include: Star mill manufactured by Ashizawa Finetech Co., Ltd .; MSC-MILL, SC-MILL, Attritor MA01SC manufactured by Mitsui Mining Co., Ltd .; Nano Glen Mill, Pico Glen Mill, Pure Glen Mill manufactured by Asada Tekko Co., Ltd. Megacapper Glen Mill, Cera Power Glen Mill, Dual Glen Mill, AD Mill, Twin AD Mill, Basket Mill, Twin Basket Mill: Apex Mill, Ultra Apex Mill, Super Apex Mill manufactured by Kotobuki Industries Co., Ltd.

  Step 3 is a step of subjecting a silanol group and / or hydrolyzable silyl group-containing silane compound to a condensation reaction. By this step 3, the silanol group and / or hydrolyzable silyl group-containing silane compound is condensed to form a siloxane bond.

  The silanol group and / or hydrolyzable silyl group of the polysiloxane segment (a1) and the silanol group and / or hydrolyzable silyl group of the vinyl polymer segment (a2) are subjected to a dehydration condensation reaction. In this case, the bond represented by the general formula (4) is generated. Accordingly, in the general formula (4), carbon atoms constitute a part of the vinyl polymer segment (a2), and silicon atoms bonded only to oxygen atoms constitute a part of the polysiloxane segment (a1). And

  Further, the silanol group and / or hydrolyzable silyl group-containing silane compound and the inorganic fine particles (m) are condensed in a mixed state, whereby the silanol group and / or hydrolyzable silyl group-containing silane compound and the inorganic fine particles (m). A siloxane bond is formed between the polysiloxane segment (a1) and the inorganic fine particles (m).

  In the composite resin (A), the bonding position of the polysiloxane segment (a1) and the vinyl polymer segment (a2) is arbitrary. For example, the polysiloxane segment (a1) is on the polymer segment (a2) side. Examples include composite resins having a graft structure chemically bonded as a chain, and composite resins having a block structure in which the polymer segment (a2) and the polysiloxane segment (a1) are chemically bonded.

  Specific examples of the silane compound having both a silanol group and / or a hydrolyzable silyl group and a polymerizable double bond used in Steps 1 to 3 include vinyltrimethoxysilane and vinyltriethoxysilane. , Vinylmethyldimethoxysilane, vinyltri (2-methoxyethoxy) silane, vinyltriacetoxysilane, vinyltrichlorosilane, 2-trimethoxysilylethyl vinyl ether, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyl Examples include oxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, and 3- (meth) acryloyloxypropyltrichlorosilane. Among these, vinyltrimethoxysilane and 3- (meth) acryloyloxypropyltrimethoxysilane are preferable because the hydrolysis reaction can easily proceed and by-products after the reaction can be easily removed.

  Examples of the general-purpose silane compound used in Steps 1 to 3 include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, Various organotrialkoxysilanes such as iso-butyltrimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane Various diorganodialkoxysilanes such as diphenyldimethoxysilane, methylcyclohexyldimethoxysilane, and methylphenyldimethoxysilane; methyltrichlorosilane, ethylto Chlorosilane, phenyl trichlorosilane, vinyl trichlorosilane, dimethyl dichlorosilane, chlorosilane such as diethyl dichlorosilane or diphenyl dichlorosilane and the like. Of these, organotrialkoxysilanes and diorganodialkoxysilanes that can easily undergo a hydrolysis reaction and easily remove by-products after the reaction are preferable.

  In addition, a tetrafunctional alkoxysilane compound such as tetramethoxysilane, tetraethoxysilane or tetra n-propoxysilane or a partial hydrolysis condensate of the tetrafunctional alkoxysilane compound may be used in combination as long as the effects of the present invention are not impaired. it can. When the tetrafunctional alkoxysilane compound or a partially hydrolyzed condensate thereof is used in combination, the silicon atoms of the tetrafunctional alkoxysilane compound are 20 with respect to the total silicon atoms constituting the polysiloxane segment (a1). It is preferable to use together so that it may become the range which does not exceed mol%.

  In addition, a metal alkoxide compound other than a silicon atom such as boron, titanium, zirconium or aluminum can be used in combination with the silane compound as long as the effects of the present invention are not impaired. For example, it is preferable to use the metal alkoxide compound in combination in a range not exceeding 25 mol% with respect to all silicon atoms constituting the polysiloxane segment (a1).

  In order to introduce the group represented by the formula (3) into the polysiloxane segment (a1), a silane compound having a group represented by the formula (3) may be used. Specific examples of the silane compound having a group represented by the formula (3) include p-styryltrimethoxysilane and p-styryltriethoxysilane.

In step 2, some or all of the silanol group and / or hydrolyzable silyl group-containing silane compound to be mixed with the inorganic fine particles (m) may be hydrolyzed and condensed.
Furthermore, a dispersion medium may be used for the purpose of adjusting the solid content and viscosity. The dispersion medium may be a liquid medium that does not impair the effects of the present invention, and includes various organic solvents, water, liquid organic polymers, and monomers.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK), cyclic ethers such as tetrahydrofuran (THF) and dioxolane, and esters such as methyl acetate, ethyl acetate, and butyl acetate. Aromatics such as toluene and xylene, and alcohols such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether, and normal propyl alcohol, which can be used alone or in combination.

  In the hydrolysis condensation reaction in the steps 2 and 3, a part of the hydrolyzable group is hydrolyzed under the influence of water or the like to form a hydroxyl group, and then the hydroxyl groups or between the hydroxyl group and the hydrolyzable group. It refers to a condensing reaction that progresses between. The hydrolysis-condensation reaction can be performed by a known method, but a method in which the reaction is advanced by supplying water and a catalyst in the production process is simple and preferable.

  Examples of the catalyst used include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate and acetic acid; inorganic bases such as sodium hydroxide and potassium hydroxide; tetraisopropyl titanate , Titanates such as tetrabutyl titanate; 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), 1 Compounds containing various basic nitrogen atoms, such as 1,4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine, dimethylbenzylamine, monoethanolamine, imidazole, 1-methylimidazole; Tetramethylammonium salt, tetrabutylammonium salt, dilauryldimethylammonium Quaternary ammonium salts such as chloride, bromide, carboxylate or hydroxide as counter anions; dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetylacetate Examples thereof include tin carboxylates such as narate, tin octylate and tin stearate. A catalyst may be used independently and may be used together 2 or more types.

  The amount of the catalyst added is not particularly limited, but in general, it is preferably used in the range of 0.0001 to 10% by mass with respect to the total amount of each compound having the silanol group or hydrolyzable silyl group. , More preferably in the range of 0.0005 to 3% by mass, and particularly preferably in the range of 0.001 to 1% by mass.

The amount of water to be supplied is preferably 0.05 mol or more with respect to 1 mol of the silanol group or hydrolyzable silyl group of each compound having the silanol group or hydrolyzable silyl group, The above is more preferable, and particularly preferably 0.5 mol or more.
These catalyst and water may be supplied collectively or sequentially, or may be supplied by previously mixing the catalyst and water.

  The reaction temperature at the time of performing the hydrolysis-condensation reaction in Step 2 and Step 3 is suitably in the range of 0 ° C to 150 ° C, and preferably in the range of 20 ° C to 100 ° C. The reaction can be carried out under any conditions of normal pressure, increased pressure, or reduced pressure. Moreover, you may remove the alcohol and water which are the by-products which can be produced | generated in the said hydrolysis-condensation reaction by methods, such as distillation, as needed.

  As the composition for forming the resin layer (X) containing the inorganic fine particle composite (M), when the inorganic fine particle composite (M) is cured by being irradiated with active energy rays, It is preferable to use a polymerization initiator. Known photopolymerization initiators may be used, and for example, one or more selected from the group consisting of acetophenones, benzyl ketals, and benzophenones can be preferably used. Examples of the acetophenones include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4 -(2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone and the like. Examples of the benzyl ketals include 1-hydroxycyclohexyl-phenyl ketone and benzyl dimethyl ketal. Examples of the benzophenones include benzophenone and methyl o-benzoylbenzoate. Examples of the benzoins include benzoin, benzoin methyl ether, and benzoin isopropyl ether. A photoinitiator (B) may be used independently and may use 2 or more types together.

  1-15 mass% is preferable with respect to 100 mass parts of said inorganic fine particle composite bodies (M), and, as for the usage-amount of the said photoinitiator (B), 2-10 mass% is more preferable.

  The composition for forming the resin layer (X) preferably contains an ultraviolet absorber. Thereby, yellow discoloration which may occur when a plastic substrate is used as the substrate can be suppressed. Moreover, the adhesiveness of the said base material and resin layer (X) can be improved further, and the hard coat film provided with the further outstanding weather resistance can be obtained.

  As the ultraviolet absorber, various commonly used inorganic and organic ultraviolet absorbers can be used, for example. Examples of the UV absorber include compound derivatives such as hydroxybenzophenone-based, benzotriazole-based, cyanoacrylate-based, and triazine-based main skeletons, and polymers such as vinyl polymers containing these UV absorbers in the side chains. Specifically, 2,4′-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-n-benzyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy Benzophenone, 2,2′-dihydroxy-4,4′-diethoxybenzophenone, 2,2′-dihydroxy-4,4′-dipropoxybenzophenone, 2,2′-dihydroxy-4,4′-dibutoxybenzophenone, 2,2'-dihydroxy-4-methoxy-4'-propoxybenzofe 2,2,2'-dihydroxy-4-methoxy-4'-butoxybenzophenone, 2,3,4-trihydroxybenzophenone, 2- (2-hydroxy-5-t-methylphenyl) benzotriazole, 2- (2 -Hydroxy-5-t-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyltriazine, 4- (2-acryloxyethoxy) -2-hydroxybenzophenone polymer 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-ben Polymers like triazole is exemplified. Among these, 2,2 ', 4,4'-tetrahydroxybenzophenone is preferably used from the viewpoint of volatility. Two or more of these organic ultraviolet absorbers may be used in combination.

  Moreover, it is preferable to contain an active energy ray hardening monomer as needed, especially polyfunctional (meth) acrylate. The polyfunctional (meth) acrylate is not particularly limited, and known ones can be used. For example, 1,2-ethanediol diacrylate, 1,2-propanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, Tripropylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, tris (2-acryloyloxy) isocyanurate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, di (trimethylolpropane) tetraacrylate, di (penta Erythritol) pentaacrylate, di (pentaerythritol) hexaacrylate, etc. have two or more polymerizable double bonds in one molecule That polyfunctional (meth) acrylate. Moreover, urethane acrylate, polyester acrylate, epoxy acrylate, etc. can be illustrated as polyfunctional acrylate. These may be used alone or in combination of two or more. For example, when the above-described polyisocyanate is used in combination, an acrylate having a hydroxyl group such as pentaerythritol triacrylate or dipentaerythritol pentaacrylate is preferable. In order to further increase the crosslinking density, it is also effective to use a (meth) acrylate having a particularly high functional group number such as di (pentaerythritol) pentaacrylate or di (pentaerythritol) hexaacrylate.

  In addition, a monofunctional (meth) acrylate can be used in combination with the polyfunctional (meth) acrylate. For example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate (for example, “Plexel” manufactured by Daicel Chemical Industries), phthalic acid and propylene Mono (meth) acrylate of polyester diol obtained from glycol, mono (meth) acrylate of polyester diol obtained from succinic acid and propylene glycol, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, pentaerythritol Tri (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, (meth) acrylate of various epoxy esters Hydroxyl group-containing (meth) acrylic acid esters such as phosphoric acid adducts; carboxyl group-containing vinyl monomers such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid; vinyl sulfonic acid, styrene sulfone Sulfonic acid group-containing vinyl monomers such as acid and sulfoethyl (meth) acrylate; 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxypropyl acid phosphate, 2- (meth) acryloyloxy-3- Examples thereof include acidic phosphate ester vinyl monomers such as chloro-propyl acid phosphate and 2-methacryloyloxyethylphenyl phosphoric acid; vinyl monomers having a methylol group such as N-methylol (meth) acrylamide. These can use 1 type (s) or 2 or more types.

  As the usage-amount in the case of using the said polyfunctional acrylate, 1-85 mass% is preferable with respect to the total solid content of the said inorganic fine particle composite body (M), and 5-80 mass% is more preferable. By using the polyfunctional acrylate within the above range, physical properties such as hardness of the resulting layer can be improved.

  When the composite resin (A) contains an epoxy group, a known curing agent for epoxy resin can be used. For example, phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclo Pentadiene phenol addition resin, phenol aralkyl resin (Xylok resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl Modified phenolic resin (polyhydric phenol compound in which phenol nucleus is linked by bismethylene group), biphenyl modified naphthol resin (polyvalent naphtholation in which phenol nucleus is linked by bismethylene group) Product), aminotriazine-modified phenolic resins (polyhydric phenol compounds in which phenol nuclei are linked by melamine, benzoguanamine, etc.) and alkoxy group-containing aromatic ring-modified novolak resins (polyphenols in which phenol nuclei and alkoxy group-containing aromatic rings are linked by formaldehyde) Phenolic compounds), such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methyl Acid anhydride compounds such as hexahydrophthalic anhydride; Amide compounds such as polyamide resin synthesized from dimer of dicyandiamide and linolenic acid and ethylenediamine; Diaminodiphenylmethane, diethylenetriamine, trie Rentetoramin, diaminodiphenyl sulfone, isophoronediamine, imidazo - Le, BF3-amine complex, amine compounds such as guanidine derivatives.

  In addition to the reactive compound, a curing accelerator can be used in combination as appropriate. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. Particularly, in terms of excellent curability, heat resistance, electrical characteristics, moisture resistance reliability, etc., 2-ethyl-4-methylimidazole is used for imidazole compounds, triphenylphosphine is used for phosphorus compounds, and 1,8-diazabicyclo is used for tertiary amines. -[5.4.0] -undecene (DBU) is preferred.

  On the other hand, when using both active energy ray curing and thermosetting, each catalyst is selected in consideration of the polymerizable double bond reaction in the composition, the reaction temperature of the thermosetting reactive group, the reaction time, etc. It is preferable to do. Moreover, it is also possible to use a thermosetting resin together. Examples of the thermosetting resin include vinyl resins, unsaturated polyester resins, polyurethane resins, epoxy resins, epoxy ester resins, acrylic resins, phenol resins, petroleum resins, ketone resins, silicon resins, and modified resins thereof.

  In addition to the inorganic fine particle composite body (M), the resin layer (X) -forming composition may contain an organic solvent for the purpose of adjusting the viscosity.

  Examples of the organic solvent include aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, n-octane, cyclohexane and cyclopentane; aromatic hydrocarbons such as toluene, xylene and ethylbenzene. Alcohols such as methanol, ethanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; ethyl acetate, butyl acetate, n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl Esters such as ether acetate; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone and cyclohexanone; diethylene glycol dimethyl ether, diethylene glycol dibuty Polyalkylene glycol dialkyl ethers such as ethers; ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane; N-methylpyrrolidone, dimethylformamide, dimethylacetamide or ethylene carbonate used alone or in combination of two or more Can be used.

  The resin layer (X) forming composition may be an inorganic pigment, organic pigment, extender pigment, clay mineral, wax, surfactant, stabilizer, flow regulator, dye, leveling agent, rheology control agent, if necessary. Various additives such as an antifoaming agent, an antioxidant, or a plasticizer can also be used.

  The leveling agent is a liquid organic polymer that does not directly contribute to the curing reaction, for example, a carboxyl group-containing polymer modified product (Floren G-900, NC-500: Kyoeisha), an acrylic polymer (Floren WK-20: Kyoeisha), Examples include amine salts of specially modified phosphate esters (HIPLAAD ED-251: Enomoto Kasei), modified acrylic block copolymers (DISPERBYK2000; Big Chemie), and the like.

  Next, the reflection reducing layer (Y) constituting the optical film of the present invention will be described.

  The optical film of the present invention has a reflection reducing layer (Y) in order to prevent a decrease in the visibility of an image or the like due to reflection of sunlight or the like on the surface of the information display unit of the information display device.

  The reflection reducing layer (Y) may be constituted by a so-called low refractive index layer (b1) alone, and is a laminate of a high refractive index layer (b2) and a low refractive index layer (b1). Alternatively, the intermediate refractive index layer, the high refractive index layer (b2), and the low refractive index layer (b1) may be laminated.

  The low refractive index layer (b1) preferably has a refractive index in the range of 1.20 to 1.45, and more preferably has a refractive index of 1.23 to 1.42. .

  The high refractive index layer (b2) preferably has a refractive index of 1.55 to 2.00, and more preferably has a refractive index of 1.60 to 1.80.

  It is preferable to use a medium refractive index layer having an intermediate refractive index between the refractive index of the low refractive index layer (b1) and the refractive index of the high refractive index layer (b2).

  The said reflection reduction layer (Y) can be formed by apply | coating the composition for reflection reduction layer (Y) formation, and drying.

  As the composition for forming the reflection reducing layer (Y), for example, the composition for forming the low refractive index layer (b1), the composition for forming the high refractive index layer (b2), or the like can be used.

  As the composition for forming the low refractive index layer (b1), for example, a composition containing a filler and a binder can be used.

  As said filler, what contains the particle | grains which have a particle | grain which has a space | gap, a metal fluoride, etc., for example can be used.

  As the particles having voids, those having a porous structure containing gas inside can be used. Specifically, examples of the particles having voids include hollow silica particles and silica particles having a nanoporous structure.

  Further, as the particles made of the metal fluoride, particles made of magnesium fluoride, aluminum fluoride, calcium fluoride, lithium fluoride or the like can be used.

  Moreover, as said filler, what was modified with the organic compound etc. can also be used. Specifically, as the modified filler, one obtained by polymerizing a crosslinkable monomer or an oligomer thereof in the presence of the unmodified particles can be used. The said filler can be used combining 1 type (s) or 2 or more types. The filler may be crystalline, sol, or gel.

  As the filler, it is preferable to use hollow silica particles.

  The hollow silica particles may have a spherical shape, a chain shape, a needle shape, a plate shape, a scale shape, a rod shape, a fiber shape, or an indefinite shape. Among these, it is preferable to use spherical or acicular particles as the hollow silica particles.

  When the shape of the hollow silica particles is spherical, the average particle diameter is preferably 5 nm to 100 nm, more preferably 20 nm to 80 nm, and 40 nm to 70 nm is excellent in low refractive index and excellent It is more preferable because both transparency can be achieved.

  As the binder that can be used in the composition for forming the low refractive index layer (b1), for example, an active energy ray-curable compound such as a compound having a polymerizable unsaturated double bond can be used.

  Specific examples of the polymerizable unsaturated double bond include an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group, and an acryloyl group and a methacryloyl group are preferable.

  Examples of the active energy ray-curable compound include ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth). ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethylene oxide modified (EO modified) trimethylolpropane tri (Meth) acrylate, propylene oxide modified (PO modified) trimethylolpropane tri (meth) acrylate, EO modified phosphate Poly (poly) acrylates such as (meth) acrylate, tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, 1,3,5-cyclohexanetriol tri (meth) acrylate, acrylic ( Epoxy (meth) acrylates such as (meth) acrylate, di (meth) acrylate of bisphenol A diglycidyl ether, di (meth) acrylate of hexanediol diglycidyl ether, urethane (meth) acrylate, and some of them are polymerized The formed oligomer can be used.

  Among these, as the active energy ray-curable compound, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and urethane acrylate are used. It is preferable to use it for obtaining an optical film such as an antireflection film excellent in translucency and appearance quality.

  The active energy ray-curable compound is preferably included in the range of 5% by mass to 95% by mass with respect to the total solid content of the composition for forming the low refractive index layer (b1).

  Further, as the binder, a fluorine-based polymer, a silicon-based polymer, or the like can be used.

  As the fluorine-based polymer, for example, those obtained by polymerizing monomers such as vinylidene fluoride and hexafluoropropylene can be used.

  As the composition for forming the low refractive index layer (b1), a composition containing a known silicone antifouling agent, fluorine antifouling agent, slip agent, etc., as necessary, in addition to the above-described components is used. can do.

  The thickness of the low refractive index layer (b1) is preferably in the range of 50 nm to 300 nm, more preferably in the range of 50 nm to 150 nm, and in the range of 80 nm to 120 nm, the appearance quality is excellent. It is preferable for obtaining an optical film such as an antireflection film excellent in antireflection properties.

  The high refractive index layer (b2) can be formed by using a composition for forming a high refractive index layer (b2).

  As the composition for forming the high refractive index layer (b2), a composition containing a compound having a polymerizable unsaturated double bond and, if necessary, high refractive index inorganic particles can be used.

  As the compound having a polymerizable unsaturated double bond, the same active energy ray-curable compounds exemplified as those usable in the composition for forming the low refractive index layer (b1) can be used. .

  As the high refractive index inorganic particles, those having a refractive index of 1.65 to 2.00 are preferably used. For example, zinc oxide having a refractive index of 1.90, refractive index of 2.3 to 2. 7 titania, ceria having a refractive index of 1.95, tin-doped indium oxide having a refractive index of 1.95 to 2.00, antimony-doped tin oxide having a refractive index of 1.75 to 1.85, refractive index of 1 .87 yttria, zirconia having a refractive index of 2.10, or the like can be used alone or in combination of two or more.

  The thickness of the high refractive index layer (b2) is preferably in the range of 10 nm to 300 nm, and more preferably in the range of 30 nm to 200 nm.

  The thickness of the reflection reducing layer (Y) including the low refractive index layer (b1) and the high refractive index layer (b2) is preferably in the range of 80 nm to 400 nm, and in the range of 80 nm to 300 nm. Is more preferable.

  Next, the base material which comprises the optical film of this invention is demonstrated.

  As the substrate, a substrate having a level of transparency that can be used in optical applications can be used.

  Examples of the base material include polyester base materials such as polyethylene terephthalate base materials and polyethylene naphthalate base materials, cellulose base materials such as triacetyl cellulose, polyethylene base materials, polypropylene base materials, polystyrene base materials, and ethylene-vinyl acetate resins. (EVA) base materials, polyvinyl resin base materials such as polyvinyl chloride base materials, polyvinylidene chloride base materials, polysulfone base materials, polyether sulfone base materials, polycarbonate base materials, polyamide base materials, polyimide base materials, acrylic resins A plastic substrate such as a substrate, a glass plate, a ceramic plate, or the like can be used.

  Among these, it is preferable to use a polyethylene terephthalate base, a triacetyl cellulose base, or the like as the base.

  As described above, it is preferable to use a highly transparent substrate as described above, and specifically, a substrate having a total visible light transmittance of 70% or more is preferably used. In addition, as said base material, what was colored in the range which can maintain favorable transparency can also be used.

  As the base material, it is preferable to use a material having a thickness of 5 μm to 300 μm in order to achieve both excellent transparency and good handleability, and it is preferable to use a material having a thickness of 10 μm to 250 μm. It is more preferable to use a material having a thickness of 25 μm to 200 μm.

  In addition, as the substrate, a substrate composed of a single layer can be used, but a multilayer substrate composed of two or more layers composed of the same or different materials can also be used. The surface of the substrate is preferably a smooth surface.

  In addition, as the base material, one having one or both surfaces subjected to easy adhesion treatment can be used in order to further improve the adhesion with the resin layer (X). Examples of the easy adhesion treatment method include a method of providing a primer layer on one side or both sides of the substrate.

  Next, the manufacturing method of the optical film of this invention is demonstrated.

  For example, the optical film of the present invention is obtained by applying and drying the resin layer (X) forming composition on at least one surface of the substrate, and then irradiating and reacting with an active energy ray. After applying and drying the reflection reducing layer (Y) forming composition on the surface of the resin layer (X) or the resin layer (A ′), the step [1] of forming the cured resin layer (A ′) It can be manufactured by passing through the step [2] of forming the reflection reducing layer (Y) by reacting with irradiation with active energy rays.

  In the step [1], the resin layer (X) -forming composition is applied to at least one surface of the base material, and substantially all of the polymerizable unsaturated double bonds are polymerized to form a resin layer ( This is a step of forming a semi-cured resin layer (A ′) by forming X) or polymerizing a part thereof.

  Examples of the method for applying the resin layer (X) forming composition on one or both surfaces of the substrate include, for example, a die coater, a curtain flow coater, a roll coater, a reverse roll coater, a gravure coater, a micro gravure coater, and a knife coater. , A method using a bar coater, a spin coater and the like.

  Examples of a method for polymerizing a part or all of the polymerizable unsaturated double bonds contained in the layer formed by coating by the above method include ultraviolet rays, electron beams, α rays, β rays, and γ rays. And a method of irradiating various active energy rays.

  As an apparatus for irradiating the active energy ray, for example, in the case of ultraviolet rays, the generation source thereof is a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, an electrodeless lamp (fusion lamp), a chemical lamp, a black light. Lamps, mercury-xenon lamps, short arc lamps, helium / cadmium lasers, argon lasers, sunlight, LEDs and the like can be mentioned.

Irradiation intensity of the active energy ray ^is preferably ^{100mJ / cm 2 ~800mJ / cm 2} , more preferably ^{300mJ / cm 2 ~700mJ / cm 2} .

  The semi-cured resin layer (A ′) formed through the step [1] is a layer in which a part of the polymerizable unsaturated double bond remains. Most of the polymerizable unsaturated double bonds are radically polymerized and consumed in the step [2] described later.

  Moreover, when the composition containing the curing agent is used as the resin layer (X) forming composition, heating or the like is performed as necessary before, simultaneously with, or after irradiation with the active energy ray. Thus, the reaction between the curing agent and the composite resin (A1) can be advanced. The heating may be performed, for example, at about 80 ° C. for about 20 minutes to 4 hours after irradiation with active energy rays. When the reaction between the curing agent and the composite resin (A1) is a reaction between an isocyanate group that the curing agent may have and an alcoholic hydroxyl group that the composite resin (A1) may have, You may use a urethanization catalyst as needed. Moreover, the said reaction does not necessarily require a heating, For example, you may make it progress gradually by leaving to stand for a fixed period in room temperature environment.

  In the step [2], the reflection-reducing layer (Y) is formed on the surface of the resin layer (A ′) or the resin layer (X) provided on at least one side of the base material formed in the step [1]. This is a step of forming a reflection reducing layer (Y) by applying a forming composition and drying it, and then irradiating and reacting with an active energy ray.

  Examples of the method for applying the composition for forming the reflection reducing layer (Y) include a die coater, a curtain flow coater, a roll coater, a reverse roll coater, a gravure coater, a micro gravure coater, a knife coater, a bar coater, and a spin coater. A method using a die coater is preferable.

  As a method for further improving the adhesion between the resin layer (A ′) and the reflection reducing layer (Y), the surface of the resin layer (A ′) is preliminarily formed by a sandblasting method or a solvent treatment method. Examples of the method include a method of making the surface uneven, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone treatment, ultraviolet irradiation treatment, and oxidation treatment.

  In the step [2], as the method of irradiating the active energy ray, the same method as the line type and apparatus exemplified as those usable when forming the resin layer (X) is used. Can be done.

  Here, when the resin layer (X) is formed in the step [1], the coating layer of the composition for forming the reflection reducing layer (Y) is cured by irradiation with active energy rays in the step [2], and the reflection reducing layer. (Y) is formed. In addition, when the semi-cured resin layer (A ′) is formed in the step [1], the coating layer of the composition for forming the reflection reducing layer (Y) is cured by irradiation with active energy rays in the step [2]. Then, the reflection reducing layer (Y) is formed, and the polymerizable unsaturated double bond remaining in the resin layer (A ′) is also polymerized to form the resin layer (X). By adopting this method, the adhesion between the resin layer (X) and the reflection reducing layer (Y) can be remarkably improved.

Irradiation intensity of the active energy ^rays, 100 mJ / cm 2 is preferably _{^{~800mJ / cm 2, 300mJ / cm}} 2 ~700mJ / cm 2 and it is the resin layer (A ') remaining in the polymerizable unsaturated This is more preferable in that most or all of the double bonds undergo radical polymerization.

  Moreover, when manufacturing the optical film which has the structure by which the high refractive index layer (b2) and the low refractive index layer (b1) were laminated | stacked as said reflection reduction layer (Y), as said process [2], After applying and drying the composition for forming a high refractive index layer (b2) on the surface of the resin layer (X) or the resin layer (A ′) and irradiating active energy rays as necessary, the low refractive index The composition for forming the layer (b1) is applied and dried, and irradiated with active energy rays, whereby a high refractive index layer (b2) and a low refractive index layer (b1) are sequentially laminated on the surface of the resin layer (X). It is preferable to go through a step of forming the formed reflection reducing layer (Y).

  Examples of a method for applying the composition for forming the low refractive index layer (b1) on the surface of the high refractive index layer (b2) include a die coater, a curtain flow coater, a roll coater, a reverse roll coater, a gravure coater, Examples thereof include a method using a micro gravure coater, a knife coater, a bar coater, a spin coater and the like.

  The visibility reflectance of the optical film produced by the production method is preferably 2.0% or less, more preferably 1.5% or less, and further preferably 1.0% or less. .

  As a specific embodiment of the optical film of the present invention obtained by the above method, for example, as shown in FIG. 1, a reflection reducing layer comprising a substrate 12, a resin layer (X) 11 and a low refractive index layer 10 is provided. The laminated optical film 13 is mentioned. Further, as a specific embodiment of the optical film of the present invention, for example, as shown in FIG. 2, reflection reduction comprising a base material 12, a resin layer (X) 11, a high refractive index layer 14, and a low refractive index layer 10 is performed. The optical film 15 with which the layer was laminated | stacked is mentioned.

  The optical film manufactured by the above manufacturing method has various functional layers such as a decorative layer, an adhesive, an electromagnetic wave shielding layer, an infrared absorption layer, an ultraviolet absorption layer, and a color correction layer on one or both sides as necessary. You may have.

  The functional layer may be a single layer or a plurality of layers. For example, the functional layer may be a single layer and have a plurality of performances. For example, a single layer having antifouling performance and infrared absorption performance may be used.

  As described above, the optical film may have a decorative layer or a pressure-sensitive adhesive layer on part or all of one side or both sides thereof. The antireflection film provided with a part or all of the decorative layer can be used as a decorative film. Moreover, the antireflection film provided with a part or all of the pressure-sensitive adhesive layer can be used as a protective film.

  Examples of the decorative layer include those composed of letters, figures, symbols, and frame-like borders for concealment.

  The present invention will be described more specifically with reference to examples.

In the examples, the number average molecular weight is a value measured under the following conditions by GPC (gel permeation chromatography) method.
(a) Apparatus: Gel permeation chromatograph GCP-244 (manufactured by WATERS)
(b) Column: Two Shodex HFIP 80M (made by Showa Denko KK)
(c) Solvent: Dimethylformamide
(d) Flow rate: 0.5 ml / min
(e) Temperature: 23 ° C
(f) Sample concentration: 0.1% by mass Solubility: complete dissolution Filtration: Myshori disk W-13-5
(g) Injection amount: 0.300 ml
(h) Detector: R-401 type differential refractometer (WATERS)
(i) Molecular weight calibration: Polystyrene (standard product)

  In the examples, the hydroxyl value (OHv) of the vinyl polymer segment was measured in accordance with JIS-K0070. The obtained value was estimated in terms of solid content in consideration of the vinyl polymer concentration of the resin solution.

  In the examples, the abbreviations of the formulations used are as shown in Tables 1 to 3 below.

Synthesis of Polysiloxane Segment Precursor <Synthesis Example 1> Synthesis of Polysiloxane Segment Precursor (a1-1) In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, cooling pipe and nitrogen gas inlet, MTM
415 parts by mass of S and 756 parts by mass of MPTS were charged, and the temperature was raised to 60 ° C. while stirring under nitrogen gas aeration. Subsequently, a mixture consisting of 0.1 part by weight of Phoslex A-4 and 121 parts by weight of deionized water was added dropwise over 5 minutes. After completion of the dropwise addition, the reaction vessel was heated to 80 ° C. and stirred for 4 hours to carry out a hydrolysis condensation reaction, thereby obtaining a reaction product.

  By removing methanol and water contained in the obtained reaction product under conditions of 40 to 60 ° C. under reduced pressure of 1 to 30 kilopascals (kPa), a polysiloxane segment precursor having a number average molecular weight of 1000 is obtained. 1000 mass parts of bodies (a1-1) were obtained.

<Synthesis Example 2> [Preparation Example of Vinyl Polymer Segment Precursor (a2-1)]
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet, 20.1 parts by mass of PTMS as a silane compound, 24.4 parts by mass of DMDMS, 107.7 parts by mass of MIBK as a solvent, The temperature was raised to 95 ° C. while stirring under nitrogen gas.

  Next, AA 1.5 parts by mass, BA 1.5 parts by mass, MMA 30.6 parts by mass, CHMA 75 parts by mass, HEMA 7.5 parts by mass, MPTS 4.5 parts by mass, TBPEH 6.8 parts by mass, A mixture containing 15 parts by mass of MIBK was dropped into the reaction vessel over 4 hours while stirring at the same temperature under aeration of nitrogen gas, and further stirred for 2 hours at the same temperature. The number average molecular weight was 6800. A reaction solution containing a vinyl polymer having a hydroxyl value (OHv) of 21.6 mgKOH / g was obtained. In the reaction vessel, a mixture of 0.06 parts by mass of Phoslex A-4 and 12.8 parts by mass of deionized water was dropped over 5 minutes and stirred at the same temperature for 5 hours to hydrolyze the silane compound. The condensation reaction was allowed to proceed. When the reaction product was analyzed by 1H-NMR, almost 100% of the trimethoxysilyl group of the silane monomer in the reaction vessel was hydrolyzed. Subsequently, by stirring for 10 hours at the same temperature, a vinyl polymer segment precursor (a2-1) having a residual amount of TBPEH of 0.1% by mass or less was obtained. The residual amount of TBPEH was measured by an iodometric titration method.

<Synthesis Examples 3, 4, 5, 6> Synthesis of vinyl polymer segment precursors (a2-2), (a2-3), (a2-4), and (a2-5) Formulation of vinyl group-containing monomers and the like The vinyl polymer segment precursors (a2-2), (a2-3), (a2-4), (a2) are the same as in Synthesis Example 2 except that the formulation is changed to the formulation shown in Table 4 below. -5) was obtained.

<Preparation Example 1> [Preparation Example of Inorganic Fine Particle Dispersion (a3-1)]
MTMS 412.3 parts, MPTS 751.9 parts, Aerosil R-7200 1836 parts, Phoslex A-4 0.9 parts, deionized water 163.7 parts, MIBK 1836 parts Dispersion was carried out using Ultra Apex Mill UAM015 manufactured by Co., Ltd. In preparing the dispersion, the mill was filled with 100 μm zirconia beads as media to 70% of the volume of the mill, and the composition was circulated and ground at a peripheral speed of 10 m / s and a flow rate of 1.5 liters per minute. went. By carrying out the circulating pulverization for 30 minutes, an inorganic fine particle dispersion (a3-1) in which silica fine particles contained in Aerosil R-7200 were dispersed in a mixture was obtained.

<Preparation Example 2> Preparation of inorganic fine particle dispersion (a3-2) The composition was changed to the composition shown in Table 5 below, and the ROBOMIX made by Primix Co. was used instead of Ultra Apex Mill UAM015 Except for the above, an inorganic fine particle dispersion (a3-2) was obtained in the same manner as in Preparation Example 1.

<Preparation Examples 3 and 4> Preparation of inorganic fine particle dispersions (a3-3) and (a3-4) Inorganic fine particles were prepared in the same manner as in Preparation Example 1 except that the composition was changed to the composition described in Table 5 below. Dispersions (a3-3) and (a3-4) were obtained.

Synthesis of Inorganic Fine Particle Complex (M) <Synthesis Example 7> Inorganic Fine Particle Complex (M-1)
81.72 parts by mass of the inorganic fine particle dispersion (a3-1) is added to 336.8 parts by mass of the vinyl polymer segment precursor (a2-1), and the mixture is stirred for 5 minutes, and then deionized water. By adding 6 parts by mass and stirring at 80 ° C. for 4 hours, a hydrolysis condensation reaction between the vinyl polymer segment precursor (a2-1) and the silane compound was performed. The obtained reaction product was distilled under reduced pressure of 1 to 30 kPa at 40 to 60 ° C. for 2 hours to remove the produced methanol and water, and then MIBK 134.4 parts by mass, DAA By adding 557.1 parts by mass, an inorganic fine particle composite (M-1) solution (solid content: 34.2% by mass) having a silica content of 50% by mass as inorganic fine particles was obtained.

Synthesis of inorganic fine particle composite (M) <Synthesis Examples 8, 9, 10> Inorganic fine particle composite (M-2), (M-3), (M-4)
Inorganic fine particle composite bodies (M-1), (M-2) and (M-3) were obtained in the same manner as in Synthesis Example 1 except that the composition was changed to the composition shown in Table 6 below.

(Preparation Example 5 Preparation of Resin Layer Forming Composition (P-1))
102.3 parts by mass of the inorganic fine particle composite body (M-1) obtained in Synthesis Example 1, 35 parts by mass of A9300, 2.8 parts by mass of Irg184, 2.8 parts by mass of Ti400, and 0.7 parts by mass of Ti123 are mixed. Thus, a resin layer forming composition (P-1) was obtained.

(Preparation Examples 6, 7, 8 Preparation of Resin Layer Forming Composition (P-2), (P-3), (P-4))
Inorganic fine particle composite bodies (M-1), (M-2) and (M-3) were obtained in the same manner as in Synthesis Example 1 except that the composition was changed to the composition shown in Table 7 below.

<Comparative Synthesis Example 1> Synthesis of Composite Resin for Comparative Example (A-1) In the same apparatus as in Synthesis Example 1, 178.8 parts by mass of polysiloxane segment precursor (a1-1), vinyl polymer segment precursor After adding 371.2 parts by mass of (a2-5) and stirring for 5 minutes, 41.0 parts by mass of deionized water was added, and the mixture was stirred at 80 ° C. for 4 hours. A decomposition condensation reaction was performed. The resulting reaction product is distilled under reduced pressure of 10 to 300 kPa under conditions of 40 to 60 ° C. for 2 hours to remove the produced methanol and water, and then 195.0 parts by mass of MIBK is added. By this, 600 mass parts of composite resin (A-1) whose non volatile matter is 45.1 mass% was obtained.

(Preparation Example 9 Preparation of Curable Resin Composition (Ratio P-1))
Resin by mixing 100 parts by mass of composite resin (A-1) obtained in Comparative Synthesis Example 1, 35 parts by mass of A9300, 2.8 parts by mass of Irg184, 2.8 parts by mass of Ti400, and 0.7 parts by mass of Ti123 A layer forming composition (ratio P-1) was obtained.

(Preparation Example 10 Preparation of Comparative Resin Layer Forming Composition (Ratio P-2))
Unidic 17-813 (DIC Corporation, polyfunctional urethane acrylate, nonvolatile content 80 mass%) 39 parts by mass, dipentaerythritol hexaacrylate (Toagosei Co., Ltd., Aronix M402) 31 parts by mass, as a photopolymerization initiator A composition (ratio P-2) was obtained by mixing 4 parts by mass of Irgacure 184 (manufactured by BASF, hydroxycyclohexyl phenyl ketone) and 26 parts by mass of ethyl acetate as an organic solvent.

Example 1
The resin layer forming composition (P-1) is mixed with MIBK and the solid content thereof is adjusted to 45% by mass, and then a group consisting of U48-100 (manufactured by Toray Industries, Inc., thickness 100 μm, highly transparent polyethylene terephthalate film). A coating was formed on one side of the material by applying it using a bar coater so that the thickness after drying was 5 μm, and drying for 4 minutes in an environment at a temperature of 80 ° C.

Next, on the surface of the coating film, an H bulb manufactured by Fusion is used, and UV irradiation is performed so that the UV intensity is 550 mW / cm ² and the UV integrated light quantity is 1000 mJ / cm ² in the air. A resin layer (X′-1) in which a part of the (meth) acryloyl group contained in the coating film was polymerized was formed.

  Next, on the resin layer (X′-1), “P-5062” (manufactured by JGC Catalysts & Chemicals, Inc., hollow silica fine particle dispersion, nonvolatile content 3% by mass) has a thickness after drying of 0.1 μm. The coating film (low refractive index layer (Y-1)) was formed by applying using a bar coater and drying for 2 minutes in an environment at a temperature of 80 ° C.

Next, the surface of the coating film (low refractive index layer (Y-1)) is irradiated with ultraviolet rays so as to have an irradiation amount of 400 mJ / cm ² under a nitrogen atmosphere using an H bulb manufactured by Fusion. The antireflection which the said resin layer (X-1) in which all or most of the (meth) acryloyl group contained in the said coating film superposed | polymerized and the low-refractive-index layer (Y-1) on the surface laminated | stacked. A film was obtained.

(Example 2)
The resin layer forming composition (P-1) is mixed with MIBK and the solid content thereof is adjusted to 45% by mass, and then a group consisting of U48-100 (manufactured by Toray Industries, Inc., thickness 100 μm, highly transparent polyethylene terephthalate film). A coating was formed on one side of the material by applying it using a bar coater so that the thickness after drying was 5 μm, and drying for 4 minutes in an environment at a temperature of 80 ° C.

Next, the surface of the coating film is irradiated with ultraviolet rays so that the UV intensity is 550 mW / cm ² and the UV integrated light intensity is 1000 mJ / cm ² in an oxygen atmosphere using an H bulb manufactured by Fusion. Thus, a resin layer (X′-1) in which a part of the (meth) acryloyl group contained in the coating film was polymerized was formed.

  Next, on the resin layer (X′-1), “DX-1057ZRC” (manufactured by JGC Catalysts & Chemicals, Inc., zirconia fine particle dispersion, nonvolatile content 3% by mass) is dried as a composition for forming a high refractive index layer. The coating film was formed by applying using a bar coater so that the subsequent thickness would be 0.15 μm, and drying in an environment at a temperature of 80 ° C. for 2 minutes.

Next, the surface of the coating film is contained in the coating film by using an H bulb manufactured by Fusion and irradiating with ultraviolet rays so that the irradiation amount is 600 mJ / cm ² in air. The resin layer (X-1) in which all or most of the acryloyl group was polymerized and the high refractive index layer (Z-1) were formed on the surface thereof.

  Next, the thickness after drying “P-5062” (manufactured by JGC Catalysts & Chemicals Co., Ltd., hollow silica fine particle dispersion, nonvolatile content 3 mass%) on the high refractive index layer (Z-1) is 0.00. The coating film (low refractive index layer (Y-1)) was formed by applying using a bar coater so as to be 1 μm, and drying for 2 minutes in an environment at a temperature of 80 ° C.

Next, the surface of the coating film (low refractive index layer (Y-1)) is irradiated with ultraviolet rays so as to have an irradiation amount of 400 mJ / cm ² under a nitrogen atmosphere using an H bulb manufactured by Fusion. Thus, an antireflection film in which a low refractive index layer (Y-1) was laminated on the high refractive index layer (Z-1) was obtained.

(Example 3)
Example 1 except that UVTAC80 (manufactured by Fuji Film, 80 μm thick, highly transparent triacetylcellulose) was used instead of U48-100 (manufactured by Toray Industries, Inc., thickness 100 μm, highly transparent polyethylene terephthalate film) In the same manner as above, an antireflection film was obtained.

Example 4
Example 2 except that UVTAC80 (manufactured by Fuji Film, 80 μm thick, highly transparent triacetylcellulose) was used instead of U48-100 (manufactured by Toray Industries, Inc., thickness 100 μm, highly transparent polyethylene terephthalate film) In the same manner as above, an antireflection film was obtained.

(Examples 5 to 8)
Examples 1 to 4 except that the resin layer forming composition (P-2) was used instead of the resin layer forming composition (P-1) as the resin layer (X) forming composition. An antireflection film was formed in the same manner.

(Examples 9 to 12)
Examples 1 to 4 except that the resin layer forming composition (P-3) was used instead of the resin layer forming composition (P-1) as the resin layer (X) forming composition. An antireflection film was formed in the same manner.

(Examples 13 to 16)
Examples 1-4 with the exception that the resin layer forming composition (P-4) was used instead of the resin layer forming composition (P-1) as the resin layer (X) forming composition. An antireflection film was formed in the same manner.

(Comparative Examples 1-4)
The same method as in Examples 1 to 4 except that the composition (ratio P-1) was used as the resin layer (X) forming composition instead of the resin layer forming composition (P-1). An antireflection film was formed respectively.

(Comparative Examples 5 to 8)
In the same manner as in Examples 1 to 4, except that the composition (P-2) was used in place of the resin layer forming composition (P-1) as the resin layer (X) forming composition. Each antireflection film was formed.

[Measurement method of pencil hardness]
The pencil hardness of the surface comprising the antireflection film constituting the antireflection film was measured under a load of 750 g according to the method described in JIS K-5400. From the value of the pencil hardness, the surface hardness of the antireflection film was evaluated according to the following criteria.
○: 2H or more △: H
×: F or less

[Weather resistance test]
The weather resistance of the antireflection film is 4 hours irradiation (irradiation hardness 90 mW, black panel temperature 63 ° C. humidity 70%) using an ultra accelerated weathering tester Super UV Tester (SUV) manufactured by Iwasaki Electric Co., Ltd. for 4 hours. Darkness (black panel temperature 63 ° C, humidity 90%) and 4-hour condensation (black panel temperature 30 ° C, humidity 95%) 12 hours as one cycle, appearance after 100 cycles (visual evaluation, change in haze value) and Evaluation was based on adhesion. The visual appearance evaluation was carried out by comparing the appearance of the unexposed specimen and the appearance of the specimen after the 100-cycle test on the reflection reduction layer side by visual observation.

(crack)
Those with no change in surface condition etc. (○)
Some cracks have occurred but there are no practical problems (△)
Those with cracks on the entire surface (×)
(Yellowing)
Those with no change in surface condition etc. (○)
Some are yellowed but have no practical problems (△)
Those that have yellowing on the entire surface (×)

[Weather resistance adhesion test]
The adhesion between the base material constituting the antireflection film after the test, the resin layer, and the reflection reducing layer was evaluated by the following method.

A cross-cut test (JIS K5600) of 100 mm of 1 mm × 1 mm was performed on the surface of the reflection reducing layer of the antireflection film after the test. When the cellophane adhesive tape was affixed to the cross-cut surface and peeled off, the number of lattices remaining on the surface was calculated, and the adhesion was evaluated according to the following criteria.
○: 95-100 pieces Δ: 60-94 pieces x: 59 pieces or less

[Heat resistance adhesion test]
After heating the antireflection film in an electric oven at 110 ° C. for 240 hours, the adhesion between the base material, the resin layer and the reflection reducing layer constituting the antireflection film after the test is the same as in the weather resistance adhesion test. The method was evaluated.

[Water adhesion test]
The obtained antireflection film is immersed in warm water of 60 ° C. together with the base material for 240 hours, and the adhesion between the base material, the resin layer, and the reflection reducing layer constituting the antireflection film after the test is determined according to the weather resistance adhesiveness. Evaluation was performed in the same manner as in the test.

[Antireflection Evaluation Method (Evaluation Method Based on Visibility Reflectance)]
Using a spectrophotometer (V-650 manufactured by JASCO Corporation), the spectral reflectance of the antireflection film was measured by dispersing light in the wavelength range of 380 nm to 780 nm and irradiating the antireflection film. . The spectral reflectance at a wavelength of 550 nm is shown in Tables 8 to 10 as luminous reflectance. If the visibility reflectance was 2% or less, it was determined that sufficient antireflection performance was obtained.

  “PET” in the table represents U48-100 (Toray Industries, Inc., thickness 100 μm, highly transparent polyethylene terephthalate film), and “TAC” in the table represents UVTAC80 (Fuji Film, thickness 80 μm, highly transparent). Triacetyl cellulose).

DESCRIPTION OF SYMBOLS 10 Low refractive index layer 11 Resin layer 12 Base material 13 Optical film 14 High refractive index layer 15 Optical film

Claims (9)

An optical film having a resin layer (X) on at least one side of a substrate and a reflection reducing layer (Y) on the surface of the resin layer (X), wherein the resin layer (X) is represented by the general formula ( 1) and / or a polysiloxane segment (a1) having a structural unit represented by the general formula (2), a silanol group and / or a hydrolyzable silyl group, and a vinyl polymer segment (a2) An inorganic fine particle composite (A) in which the composite resin (A) bonded with the structure represented by the formula (4) and the inorganic fine particles (m) are bonded via the siloxane bond in the polysiloxane segment (a1). An optical film which is a layer containing M).

(In the general formulas (1) and (2), R ¹ , R ² and R ³ are each independently -R ⁴ -CH = CH ₂ , -R ⁴ -C (CH ₃ ) = CH ₂ ,- R ⁴ —O—CO—C (CH ₃ ) ═CH ₂ and —R ⁴ —O—CO—CH═CH ₂ or a polymerizable group selected from the group consisting of groups represented by the following formula (3): A group having a heavy bond (wherein R ⁴ represents a single bond or an alkylene group having 1 to 6 carbon atoms).

(In general formula (3), n is an integer represented by 1 to 5, and the structure Q represents either —CH═CH ₂ or —C (CH ₃ ) ═CH ₂ ).
An alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, an aralkyl group having 7 to 12 carbon atoms, and an epoxy group are represented. )

(In the general formula (4), carbon atoms constitute a part of the vinyl polymer segment (a2), and silicon atoms bonded only to oxygen atoms constitute a part of the polysiloxane segment (a1). To do.) The optical film according to claim 1, wherein the resin layer (X) has a thickness of 0.1 μm to 50 μm, and the reflection reducing layer (Y) has a thickness of 80 nm to 400 nm. The optical film according to claim 1, wherein the resin layer (X) has a refractive index of 1.45 to 1.55. The optical film according to claim 1 or 2, wherein the reflection reducing layer (Y) is a low refractive index layer (b1) or a laminate of a high refractive index layer (b2) and a low refractive index layer (b1). The low refractive index layer (b1) has a refractive index of 1.2 to 1.45, and the high refractive index layer (b2) has a refractive index layer of 1.55 to 2. 3. The optical film as described in 3. The optical film according to any one of claims 1 to 4, wherein a refractive index of the substrate is in a range of 1.45 to 1.7. The optical film according to claim 1, wherein the inorganic fine particles (m) are silica. 7. An information display device, wherein the optical film according to claim 1 is provided on a surface of an information display unit. An in-vehicle information display device, wherein the optical film according to any one of claims 1 to 6 is provided on a surface of an information display unit.

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