JP2017052901A - Antifouling sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antifouling sheet using an optical transparent sheet consisting of a cured article of an allyl ester resin composition as a substrate and excellent in hardness, antifouling property and optical isotropy.SOLUTION: There is provided an antifouling sheet which forms an antifouling coat layer containing a fluorine-based compound on at least one surface of an allyl ester resin sheet. The allyl ester resin sheet is a cured article of an allyl ester resin composition, the allyl ester resin composition has a group represented by the formula (2) as a terminal group and contains an oligomer having a bivalent structure with dicarboxylic acid residue having an alicyclic and/or aromatic ring. (2), where Ris an allyl group or a methallyl group and Ais one or more organic residue having an alicyclic structure and/or an aromatic structure derived from dicarboxylic acid.SELECTED DRAWING: None

Description

  The present invention relates to an antifouling sheet useful as a protective film for various display device screens. More specifically, the present invention relates to an antifouling sheet excellent in hardness, antifouling properties and optical isotropy, which is based on a cured product of an allyl ester resin composition.

With the spread of mobile terminals such as smartphones and tablet terminals, a protective film and an anti-scattering film are affixed to the outermost surface for the purpose of preventing scattering of touch panels such as liquid crystal displays and organic EL displays.
These films require slipperiness and scratch resistance to maintain operability, transparency that does not impair the image quality of the terminal itself, and antifouling properties such as resistance to fingerprints and dirt, and ease of wiping. Is required.

As a film excellent in hardness and antifouling property, a hard coat film obtained by adding a fluorine-based additive to an active energy ray-curable hard coat solution and applying and curing to a base film (JP 2010- No. 168419; Patent Document 1), and a hard coat film (Japanese Patent Laid-Open No. 2014-134770; Patent Document 2) in which a fluorine-based compound is further laminated thereon is proposed.
However, in both Patent Document 1 and Patent Document 2, since an ethylenically unsaturated double bond-containing acrylic copolymer film is used as the base film, the optical isotropy is not sufficient, and when wearing polarized sunglasses Had problems such as rainbow unevenness. For this reason, materials having high levels of hardness, antifouling properties, and optical isotropy are required for anti-scattering films and protective films for smartphones and tablet terminals.

JP 2010-168419 A JP 2014-134770 A

  An object of the present invention is to provide an antifouling sheet having excellent hardness, antifouling properties and optical isotropy.

  As a result of intensive studies, the present inventors have found that the object can be achieved by forming an antifouling coating layer containing a fluorine compound on a sheet based on a cured product of an allyl ester resin composition. The present invention has been completed.

（式中、Ｒ³はアリル基またはメタリル基を表し、Ａ²はジカルボン酸に由来する脂環式構造及び／または芳香環構造を有する一種以上の有機残基を表す。）で示される基を末端基として有し、かつ一般式（３）

（式中、Ａ³はジカルボン酸に由来する脂環式構造及び／または芳香環構造を有する一種以上の有機残基を表し、Ｘは多価アルコールから誘導された一種以上の有機残基を表す。ただし、Ｘはエステル結合によって、さらに上記一般式（２）で示される基を末端基とし、上記一般式（３）で示される構造を構成単位とする分岐構造を有することができる。）で示される構造を構成単位として有するアリルエステルオリゴマーを含むものである前項１または２に記載の防汚性シート。
［４］ 前記アリルエステル樹脂シートの防汚コート層と反対側の面の少なくとも一部に粘着層が形成されている請求項１〜３のいずれかに記載の防汚性シート。
［５］ 両表面に表面保護の剥離フィルムが貼合されている前項１〜４のいずれかに記載の防汚性シート。
［６］ フッ素系化合物を含有する防汚コート剤をアリルエステル樹脂シート表面に真空蒸着して、防汚コート層を形成することを特徴とする防汚性シートの製造方法。
［７］ フッ素系化合物を含有する防汚コート剤をアリルエステル樹脂シート表面にウエットコートして、防汚コート層を形成することを特徴とする防汚性シートの製造方法。 That is, the present invention relates to the following antifouling sheets [1] to [5] and methods for producing the antifouling sheets [6] to [7].
[1] An antifouling sheet having an antifouling coating layer containing a fluorine compound on at least one surface of an allyl ester resin sheet.
[2] The antifouling sheet according to item 1, wherein the antifouling sheet has a primer layer between the allyl ester resin sheet and the antifouling coating layer mainly composed of a fluorine compound.
[3] The allyl ester resin sheet is a cured product of the allyl ester resin composition, and the allyl ester resin composition has the general formula (2)

Wherein R ³ represents an allyl group or a methallyl group, and A ² represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid. Having terminal groups and having the general formula (3)

(In the formula, A ³ represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from dicarboxylic acid, and X represents one or more organic residues derived from a polyhydric alcohol. However, X may have a branched structure having an ester bond and a group represented by the general formula (2) as a terminal group and a structure represented by the general formula (3) as a constituent unit. 3. The antifouling sheet according to item 1 or 2, which comprises an allyl ester oligomer having the structure shown as a structural unit.
[4] The antifouling sheet according to any one of claims 1 to 3, wherein an adhesive layer is formed on at least a part of the surface of the allyl ester resin sheet opposite to the antifouling coating layer.
[5] The antifouling sheet according to any one of items 1 to 4, wherein a release film for surface protection is bonded to both surfaces.
[6] A method for producing an antifouling sheet, comprising forming an antifouling coating layer by vacuum-depositing an antifouling coating agent containing a fluorine compound on the allyl ester resin sheet surface.
[7] A method for producing an antifouling sheet, comprising wet coating an antifouling coating agent containing a fluorine compound on the surface of an allyl ester resin sheet to form an antifouling coating layer.

  The antifouling sheet of the present invention having an antifouling coating layer containing an allyl ester resin sheet as a base material and containing a fluorine-based compound is excellent in hardness, antifouling properties and optical isotropy.

Hereinafter, the present invention will be described in more detail.
The antifouling sheet of the present invention is characterized by having an antifouling coating layer containing a fluorine compound on at least one surface of an allyl ester resin sheet.
The allyl ester resin sheet is made of a cured product of the allyl ester resin composition, and the antifouling coating layer is applied to the surface of the allyl ester resin sheet by a vacuum deposition method or a wet coating method using a fluorine compound-containing antifouling coating agent. Can be formed. Further, an adhesive layer may be formed on a part or all of the surface of the allyl ester resin sheet opposite to the antifouling coating layer. Furthermore, a release film (protective film) is affixed for the purpose of preventing scratches during the storage and transfer of the antifouling sheet of the present invention (antifouling coating layer, adhesive layer), and adhesion of dirt and dust. May be combined.

  Here, the film usually indicates a film having a thickness of less than 250 μm, and the sheet indicates a film having a thickness of 250 μm or more, but the distinction between the two is not strict. In the present specification, the expression “sheet” includes the thickness of the film region, and the expression “film” includes the thickness of the sheet region.

[Allyl ester resin]
The allyl ester resin composition is a kind of thermosetting resin.
In general, an “allyl ester resin” may refer to a prepolymer (including an oligomer, an additive, and a monomer) before curing, and may indicate a cured product. Among them, “allyl ester resin” indicates a cured product, and “allyl ester resin composition” indicates a prepolymer before curing.

[Allyl ester resin composition]
The allyl ester resin composition is a composition containing an allyl group or a methallyl group (hereinafter, both may be collectively referred to as a (meth) allyl group) and a compound having an ester structure as main curing components.

  The compound having a (meth) allyl group and an ester structure is: (1) an esterification reaction between a compound containing a (meth) allyl group and a hydroxyl group (herein collectively referred to as allyl alcohol) and a compound containing a carboxyl group, (2 ) It can be obtained by esterification reaction between a compound containing (meth) allyl group and carboxyl group and a compound containing hydroxyl group, or (3) ester exchange reaction between ester compound consisting of allyl alcohol and dicarboxylic acid and polyhydric alcohol. . When the compound containing a carboxyl group is a polyester oligomer of a dicarboxylic acid and a diol, only the terminal can be an ester with allyl alcohol.

（Ｒ¹、Ｒ²は、それぞれ独立してアリル基またはメタリル基のいずれかの基を表し、Ａ¹はジカルボン酸に由来する脂環式構造及び／または芳香環構造を有する一種以上の有機残基を表す。）
で示される化合物の中から選ばれる少なくとも１種以上の化合物が挙げられる。この化合物は後述のアリルエステルオリゴマーの原料となるほか、反応性希釈剤（反応性モノマー）として本発明のアリルエステル樹脂組成物に含まれてもよい。一般式（１）中のＡ¹は後述の一般式（２）、一般式（３）におけるＡ²、Ａ³と同様のものが好ましい。 Specific examples of ester compounds composed of (meth) allyl alcohol and dicarboxylic acid include those represented by the general formula (1)

(R ¹ and R ² each independently represents either an allyl group or a methallyl group, and A ¹ represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid. Represents a group.)
And at least one compound selected from the compounds represented by formula (1). This compound may be contained in the allyl ester resin composition of the present invention as a reactive diluent (reactive monomer) as well as a raw material for the allyl ester oligomer described later. A ¹ in general formula (1) is preferably the same as A ² and A ³ in general formula (2) and general formula (3) described later.

As a compound having an (meth) allyl group and an ester structure, which is the main curing component of the allyl ester resin composition, an ester formed from a polyhydric alcohol and a dicarboxylic acid having an allyl group and / or a methallyl group as a terminal group It is preferably an allyl ester compound having a structure (hereinafter, this may be referred to as “allyl ester oligomer”).
Moreover, you may contain the hardening | curing agent mentioned later, a reactive monomer, an additive, other radical reactive resin components etc. as another component.

（式中、Ｒ³はアリル基またはメタリル基を表し、Ａ²はジカルボン酸に由来する脂環式構造及び／または芳香環構造を有する一種以上の有機残基を表す。）
で示される基を末端基として有し、かつ一般式（３）

（式中、Ａ³はジカルボン酸に由来する脂環式構造及び／または芳香環構造を有する一種以上の有機残基を表し、Ｘは多価アルコールから誘導された一種以上の有機残基を表す。ただし、Ｘはエステル結合によって、さらに上記一般式（２）で示される基を末端基とし、上記一般式（３）で示される構造を構成単位とする分岐構造を有することができる。）
で示される構造を構成単位として有する化合物が好ましい。 [Allyl ester oligomer]
As the allyl ester oligomer of the present invention, the general formula (2)

(Wherein R ³ represents an allyl group or a methallyl group, and A ² represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid.)
And a group represented by the general formula (3)

(In the formula, A ³ represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from dicarboxylic acid, and X represents one or more organic residues derived from a polyhydric alcohol. However, X may have a branched structure having a group represented by the above general formula (2) as a terminal group and a structure represented by the above general formula (3) as a constituent unit by an ester bond.
The compound which has a structure shown by as a structural unit is preferable.

In the allyl ester oligomer, the number of terminal groups represented by the general formula (2) is at least 2 or more, but when X in the general formula (3) has a branched structure, the number is 3 or more. In this case, although also R ³ at each end groups there are a plurality, each of these R ³ may not necessarily be the same type, some end there in the structure of an allyl group, the other terminal methallyl group May be.

Moreover, not all R ³ must be an allyl group or a methallyl group, and a part thereof may be a non-polymerizable group such as a methyl group or an ethyl group as long as the curability is not impaired.

Similarly, the structure represented by A ² may be different for each terminal group. For example, A ^{2 at} one terminal may be a benzene ring and the other may be a cyclohexane ring.
A ² in the general formula (2) is one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid. The moiety derived from the dicarboxylic acid is indicated by a carbonyl structure adjacent to A ² . Therefore, A ² represents a benzene skeleton or a cyclohexane skeleton.

There are no particular limitations on the dicarboxylic acid to induce A ² structure, from the viewpoint of ready availability of raw materials, terephthalic acid, isophthalic acid, phthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic Acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenyl-m, m′-dicarboxylic acid, diphenyl-p, p′-dicarboxylic acid, benzophenone-4, 4′-dicarboxylic acid, p-phenylenediacetic acid, p-carboxyphenylacetic acid, methyl terephthalic acid and tetrachlorophthalic acid are preferred, and terephthalic acid, isophthalic acid, phthalic acid and 1,4-cyclohexanedicarboxylic acid are particularly preferred.

  In addition, within the range that does not impair the effects of the present invention, acyclic dicarboxylic acids (during the reaction) such as maleic acid, fumaric acid, itaconic acid, citraconic acid, endic acid anhydride and chlorendic acid are used. Also good.

  At least one structural unit represented by the general formula (3) is necessary in the allyl ester oligomer. However, when this structure is repeated, the molecular weight of the allyl ester oligomer as a whole increases to some extent. Since it is obtained, workability is improved, and the toughness of the cured product is also improved, which is preferable. However, if the molecular weight is too large, the molecular weight between cross-linking points is too large, so that Tg is lowered and heat resistance may be lowered. It is important to adjust to an appropriate molecular weight according to the application.

  The weight average molecular weight of the allyl ester oligomer is preferably 500 to 200,000, more preferably 1,000 to 100,000.

A ³ in the general formula (3) is one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid. The same as A ² in FIG. X in the general formula (3) represents one or more organic residues derived from a polyhydric alcohol.

  The polyhydric alcohol is a compound having two or more hydroxyl groups, and X represents a skeleton portion other than the hydroxyl groups of the polyhydric alcohol.

  Further, the number of hydroxyl groups in the polyhydric alcohol may be at least two. When the polyhydric alcohol used as a raw material is trivalent or more, that is, when there are three or more hydroxyl groups, an unreacted hydroxyl group may remain. .

  Specific examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6 -Hexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, ethylene oxide 3 mol adduct of isocyanuric acid, pentaerythritol, tricyclodecane dimethanol, glycerin, trimethylolpropane, pentaerythritol ethylene oxide 3 mol adduct, D-sorbitol And hydrogenated bisphenol A and the like. Although there is no restriction | limiting in particular as a manufacturing method of these compounds, For example, it can manufacture by the method mentioned in Japanese Patent Publication No. 6-74239.

As the structural unit represented by the general formula (3) in the allyl ester oligomer, the same structural unit may be repeated, but different structural units may be included. That is, the allyl ester oligomer may be a copolymer type. In this case, several types of X exist in one allyl ester oligomer. For example, the structure may be such that one of X is a residue derived from propylene glycol and the other X is a residue derived from trimethylolpropane. In this case, the allyl ester oligomer will be branched at the trimethylolpropane residue. There may be several types of A ³ as well. The structural formulas in the case where R ³ is an allyl group, A ² and A ³ are residues derived from isophthalic acid, and X is propylene glycol and trimethylolpropane are shown below.

[Curing agent]
A curing agent may be used in the allyl ester resin composition. There is no restriction | limiting in particular as a hardening | curing agent which can be used, What is generally used as a hardening | curing agent of polymeric resin can be used. Among these, it is desirable to add a radical polymerization initiator from the viewpoint of starting polymerization of the allyl group. Examples of the radical polymerization initiator include organic peroxides, photopolymerization initiators, azo compounds and the like.

  As the organic peroxide, known compounds such as dialkyl peroxides, acyl peroxides, hydroperoxides, ketone peroxides, peroxyesters and the like can be used. Specific examples thereof include benzoyl peroxide, 1,1 -Bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-dibutylperoxycyclohexyl) propane, t-butylperoxy-2-ethylhexanate, 2,5-dimethyl-2,5-di (T-butylperoxy) hexane, 2,5-dimethyl2,5-di (benzoylperoxy) hexane, t-butylperoxybenzoate, t-butylcumyl peroxide, p-methylhydroperoxide, t-butyl Hydroperoxide, cumene hydroperoxide, dicumyl Over peroxide, di -t- butyl peroxide, t-hexyl peroxy isopropyl monocarbonate, t- butyl peroxy isopropyl monocarbonate and 2,5-dimethyl-2,5-dibutyl peroxy f relaxin -3, and the like.

  Examples of the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2-methyl-1- (4-methylthiophenyl) -2- Morpholinopropane-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2,4,6- And trimethylbenzoyldiphenylphosphine oxide.

  These radical polymerization initiators may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular in the compounding quantity of these hardening | curing agents, 0.1-10 mass parts is preferable with respect to 100 mass parts of allyl ester resin compositions, and 0.5-5 mass parts is more preferable. When the blending amount of the curing agent is less than 0.1 parts by mass, it is difficult to obtain a sufficient curing rate. When the blending amount exceeds 10 parts by mass, the final cured product becomes brittle and the mechanical strength decreases. May be.

[Reactive monomer]
In the present invention, a reactive monomer (reactive diluent) may be added to the allyl ester resin composition for the purpose of controlling the curing reaction rate, adjusting the viscosity (improving workability), improving the crosslinking density, and adding functions. it can.

  There is no restriction | limiting in particular as a reactive monomer, In order to make it react with an allyl ester oligomer, the monomer which has radically polymerizable carbon-carbon double bonds, such as a vinyl group and an allyl group, is preferable. Examples thereof include unsaturated fatty acid esters, aromatic vinyl compounds, vinyl esters of saturated fatty acids or aromatic carboxylic acids and derivatives thereof, crosslinkable polyfunctional monomers, and the like. Especially, if a crosslinkable polyfunctional monomer is used, the crosslinking density of hardened | cured material can also be controlled. Preferred specific examples of the reactive monomer are shown below.

As unsaturated fatty acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate Alkyl (meth) acrylates such as cyclohexyl (meth) acrylate and methylcyclohexyl (meth) acrylate;
Phenyl (meth) acrylate, benzyl (meth) acrylate, 1-naphthyl (meth) acrylate, fluorophenyl (meth) acrylate, chlorophenyl (meth) acrylate, cyanophenyl (meth) acrylate, methoxyphenyl (meth) acrylate and biphenyl (meth) ) Acrylic acid aromatic esters such as acrylates;
Haloalkyl (meth) acrylates such as fluoromethyl (meth) acrylate and chloromethyl (meth) acrylate;
Furthermore, glycidyl (meth) acrylate, alkylamino (meth) acrylate, α-cyanoacrylic acid ester and the like can be mentioned.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, chlorostyrene, styrene sulfonic acid, 4-hydroxystyrene, vinyltoluene and the like.
Examples of vinyl esters of saturated fatty acids or aromatic carboxylic acids and derivatives thereof include vinyl acetate, vinyl propionate and vinyl benzoate.

As the crosslinkable polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5-pentadiol di (meth) acrylate, 1,6-hexadiol di (meth) acrylate, neopentyl Glycol di (meth) acrylate, tricyclodecane di (meth) acrylate, oligoester di (meth) acrylate, polybutadiene di (meth) acrylate, 2,2-bis (4- (meth) acryloyloxyphenyl) pro Emissions and 2,2-bis (4-.omega. (meth) acryloyloxy pyridinium) phenyl) di (meth) acrylates such as propane;
Diallyl phthalate, diallyl isophthalate, dimethallyl isophthalate, diallyl terephthalate, triallyl trimellitic acid, diallyl 2,6-naphthalenedicarboxylate, diallyl 1,5-naphthalenedicarboxylate, allyl 1,4-xylenedicarboxylate and 4, Difunctional aromatic carboxylates such as diallyl 4'-diphenyldicarboxylate; bifunctional such as diallyl 1,4-cyclohexanedicarboxylate, diallyl 1,2-cyclohexanedicarboxylate, diallyl 1,3-cyclohexanedicarboxylate and divinylbenzene Crosslinkable monomer: trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri (meth) allyl isocyanurate, tri (meth) Trifunctional crosslinkable monomers such as allyl cyanurate, triallyl trimellitate and diallyl chlorendate;
Furthermore, monomers having a tetrafunctional or higher functional crosslinkable group, such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropane poly (meth) acrylate, dipentaerythritol poly (meth) acrylate, and the like can be given.

  Said reactive monomer can be used individually by 1 type or in mixture of 2 or more types. Although there is no restriction | limiting in particular in the usage-amount of the resin component of these reactive monomers, 1-1000 mass parts is preferable with respect to 100 mass parts of allyl ester oligomers, 2-500 mass parts is more preferable, 5-100 masses Part is particularly preferred. When the amount of the reactive monomer used is less than 1 part by mass, the effect of decreasing the viscosity is small and workability is not improved. Moreover, when a monofunctional monomer is used as the reactive monomer, the crosslinking density may be lowered and the hardness may be insufficient. Moreover, when the usage-amount exceeds 1000 mass parts, the outstanding transparency and mechanical strength of allyl ester resin itself may fall.

[Radically reactive resin composition]
The allyl ester resin composition may contain a radical reactive resin component for the purpose of improving various physical properties. Examples of these resin components include unsaturated polyester resins and vinyl ester resins.
Unsaturated polyester resin can be obtained by converting a condensation product obtained by esterification reaction of a polyhydric alcohol and an unsaturated polybasic acid (and a saturated polybasic acid if necessary) into a polymerizable unsaturated compound such as styrene. For example, the resins described in “Polyester Resin Handbook”, published by Nikkan Kogyo Shimbun, 1988, pages 16 to 18, pages 29 to 37, and the like can be mentioned. This unsaturated polyester resin can be produced by a known method.

  Vinyl ester resin, also called epoxy (meth) acrylate, is a ring-opening reaction between a compound having an epoxy group typically represented by an epoxy resin and a carboxyl group of a carboxyl compound having a polymerizable unsaturated group such as (meth) acrylic acid. Polymerized by a ring-opening reaction between a resin having a polymerizable unsaturated group produced by the above, or a compound having a carboxyl group and an epoxy group of a polymerizable unsaturated compound having an epoxy group in the molecule such as glycidyl (meth) acrylate It refers to a resin having a polymerizable unsaturated group. Details are described in “Polyester Resin Handbook”, Nikkan Kogyo Shimbun, published in 1988, pp. 336 to 357, and can be produced by a known method.

  The epoxy resin used as the raw material for the vinyl ester resin includes bisphenol A diglycidyl ether and its high molecular weight homologue, glycidyl ether of bisphenol A alkylene oxide adduct, bisphenol F diglycidyl ether and its high molecular weight homologue, and bisphenol F alkylene oxide. Examples include adduct glycidyl ethers and novolac-type polyglycidyl ethers.

The above radical-reactive resin components can be used singly or in combination of two or more.
Although there is no restriction | limiting in particular in the usage-amount of these radical reactive resin components, 1-1000 mass parts is preferable with respect to 100 mass parts of allyl ester oligomers, 2-500 mass parts is more preferable, 5-100 masses Part is particularly preferred.

  When the amount of the reactive monomer used is less than 1 part by mass, effects such as improvement of mechanical strength derived from radical reactive resin components are small, and workability deteriorates or moldability deteriorates. Moreover, when the usage-amount exceeds 1000 mass parts, the heat resistance of allyl ester resin itself may not appear.

[Additive]
For the purpose of improving hardness, strength, moldability, durability, and water resistance, allyl ester resin compositions include antioxidants, lubricants, ultraviolet absorbers, colorants, flame retardants, crosslinking aids, inorganic fillers, Additives such as organic fillers, antifoaming agents and leveling agents can be added as necessary.

  There is no restriction | limiting in particular as antioxidant, What is generally used can be used. Among them, phenolic antioxidants and amine antioxidants that are radical chain inhibitors are preferable, and phenolic antioxidants are particularly preferable. Examples of phenolic antioxidants include 2,6-t-butyl-p-cresol, 2,6-t-butyl-4-ethylphenol, and 2,2′-methylenebis (4-methyl-6-t-butylphenol). And 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane.

  There is no restriction | limiting in particular as a lubricant, What is generally used can be used. Among these, metal soap lubricants, fatty acid ester lubricants, aliphatic hydrocarbon lubricants and the like are preferable, and metal soap lubricants are particularly preferable. Examples of the metal soap lubricant include barium stearate, calcium stearate, zinc stearate, barium stearate, magnesium stearate, and aluminum stearate. These may be used as a complex.

  There is no restriction | limiting in particular as a ultraviolet absorber, The thing generally used can be used. Among these, benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, and cyanoacrylate ultraviolet absorbers are preferable, and benzophenone ultraviolet absorbers are particularly preferable. Examples of benzophenone ultraviolet absorbers include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-butylphenyl) benzotriazole and 2- (2-hydroxy-3). '-T-butylphenyl) benzotriazole and the like.

  Colorants include anthraquinone, azo, carbonium, quinacridone, quinoline, quinoneimine, indigoid, phthalocyanine and other organic pigments, azoic dyes, sulfur dyes and other organic dyes, titanium yellow, ultramarine blue, yellow oxidation Examples thereof include inorganic pigments such as iron, zinc yellow, chrome orange, molybdenum red, cobalt violet, cobalt blue, cobalt green, chromium oxide, titanium oxide, zinc sulfide, and carbon black. The blending amount is not particularly limited.

  Examples of the flame retardant include brominated epoxy compounds, acid-modified brominated epoxy compounds, brominated epoxy compounds having an acryloyl group, bromine-containing compounds such as acid-modified brominated epoxy compounds having an acryloyl group, red phosphorus, tin oxide, Antimony compounds, zirconium hydroxide, barium metaborate, aluminum hydroxide, magnesium hydroxide and other inorganic flame retardants, ammonium phosphate compounds, phosphate compounds, aromatic condensed phosphate esters, halogen-containing condensed phosphate esters, nitrogen-containing compounds Examples thereof include phosphorus compounds such as phosphorus compounds and phosphazene compounds. As a compounding quantity of a flame retardant, although it changes with the kind of another compound, quantity, etc., generally 10-50 mass parts with respect to 100 mass parts of all the radically polymerizable components in an allyl ester resin composition. preferable. If the flame retardant is less than 10 parts by mass, a sufficient flame retardant effect cannot be expected.

Specific examples of the crosslinking aid are compounds that act as a crosslinking aid in the partial crosslinking treatment with the thermal polymerization initiator, and examples thereof include polyfunctional vinyl monomers such as divinylbenzene and triallyl isocyanurate.
The compounding amount of the crosslinking aid varies depending on the type and amount of the other compound, but generally 1-30 parts by mass with respect to 100 parts by mass of all radical polymerizable components in the allyl ester resin composition. If the crosslinking aid is less than 1 part by mass, a sufficient effect cannot be expected. If it exceeds 30 parts by mass, the flexibility of the film is lowered, which is not preferable.

Inorganic fillers include barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, crystalline silica, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica powder, Although well-known and usual inorganic fillers, such as glass sphere, glass fiber, and carbon fiber, can be illustrated, it is not limited to these.
Specific examples of the organic filler include known and commonly used organic fillers such as an acrylic resin, a melamine resin, a styrene resin, a silicone resin, a silicone rubber, and a fluorine resin, but are not limited thereto.
These inorganic fillers and organic fillers can be used alone or in combination of two or more, and do not impair the gist of the present invention, that is, all radically polymerizable components in the allyl ester resin composition of the present invention. It can add at 1-50 mass parts with respect to 100 mass parts.

  Furthermore, if necessary, known and commonly used additives such as silicone-based, fluorine-based, acrylic-based, and polymer-based antifoaming agents and / or leveling agents are added within a range that does not impair the gist of the present invention. can do.

  However, these additives are not limited to the specific examples described above, and any additive can be added within a range that does not impair the object or effect of the present invention.

[Curing of allyl ester resin composition]
By curing the allyl ester resin composition by applying light and / or heat, an antifouling sheet substrate having excellent transparency and heat resistance can be obtained.

  There are no particular restrictions on the conditions for curing the allyl ester resin composition, but it can be applied to transparent plastic films such as PET (polyethylene terephthalate) films and PEN (polyethylene naphthalate) films, metal sheets, or glass plates. After casting and casting, it is preferable to carry out photocuring and heat curing, or heat curing.

In the case of photocuring, an ultraviolet irradiation method is generally used. For example, ultraviolet rays can be generated and irradiated using an ultraviolet lamp. Examples of ultraviolet lamps include metal halide lamps, high-pressure mercury lamps, low-pressure mercury lamps, pulse-type xenon lamps, xenon / mercury mixed lamps, low-pressure sterilization lamps, electrodeless lamps, and LED lamps, all of which can be used. Among these ultraviolet lamps, a metal halide lamp or a high-pressure mercury lamp is preferable. Irradiation conditions vary depending on the respective lamp conditions, but the irradiation exposure dose is preferably about ²⁰ to 5000 mJ / cm ² . In addition, it is preferable to attach an elliptical, parabolic, diffusive or the like reflector to the ultraviolet lamp, and a heat cut filter or the like as a cooling measure. Moreover, in order to accelerate | stimulate hardening, you may heat to 30-80 degreeC previously, and may irradiate this with an ultraviolet-ray.

  In the case of thermosetting, the heating method is not particularly limited, but a heating method excellent in uniformity such as a hot air oven or a far infrared oven is preferable. The curing temperature is about 100 to 200 ° C, preferably 120 to 180 ° C. Although the curing time varies depending on the curing method, it is preferably 0.5 to 5 hours for a hot-air oven and 0.5 to 60 minutes for a far-infrared oven.

  In addition, ultraviolet curing using a photopolymerization initiator and thermal curing using an organic peroxide or an azo compound are radical reactions and thus are susceptible to reaction inhibition by oxygen. In order to prevent oxygen inhibition during the curing reaction, the curable composition is applied onto a transparent plastic film, a metal sheet, or a glass plate, and after casting, onto the curable composition before performing photocuring. It is preferable to apply a transparent cover film and reduce the oxygen concentration on the surface of the cast curable composition to 1% or less. It is necessary to use a transparent cover film that does not have pores on the surface, has a low oxygen permeability, and can withstand the heat generated during ultraviolet curing or thermal curing. For example, PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PC (polycarbonate), PP (polypropylene), acetate resin, acrylic resin, vinyl fluoride, polyamide, polyarylate, polyethersulfone, cycloolefin polymer (norbornene resin) ) And the like, and these can be used alone or in combination of two or more. However, since it must be possible to peel from the cured product after curing, the surface of these transparent cover films may be subjected to easy peeling treatment such as silicone resin coating or fluororesin coating.

  Since the allyl ester resin composition of the present invention is in a liquid state, it can be applied, coated, and the like so as to have a predetermined shape and form using a known coating apparatus. Examples of the coating method include gravure coating, roll coating, reverse coating, knife coating, die coating, lip coating, doctor coating, extrusion coating, slide coating, wire bar coating, curtain coating, and spinner coating. In addition, as a preferable viscosity range of the allyl ester resin composition at the time of application | coating, coating, and shaping | molding, it is the range of 100-100,000 mPa * s at normal temperature.

[Structure of allyl ester resin]
The allyl ester resin is a cured product of the allyl ester resin composition as described above. The allyl ester oligomer which is the main component of the allyl ester resin composition has a plurality of allyl groups like the allyl ester oligomer of the formula (4). In the curing reaction, these allyl groups undergo addition polymerization. Since there are a plurality of allyl groups in one molecule, the polymer is not simply a linear polymer, but a crosslinked polymer (cured product) having a very complicated molecular structure such as branching or intermolecular crosslinking is formed. In addition, when reactive monomers and other cross-linking agents (such as cross-linkable polyfunctional monomers) are also cured, the crosslinking structure by the reactive monomer polymer and the cross-linking points by the cross-linking agent are added. It becomes more complicated and it is practically impossible or impractical to express it in chemical or structural formulas.

[Allyl ester resin sheet]
The thickness of the allyl ester resin sheet comprising the cured product of the allyl ester resin composition is preferably 0.1 to 1 mm, more preferably 0.1 to 0.8 mm, and 0.1 to 0.5 mm. Is more preferable. When the thickness is 0.1 mm or more, the protective performance of the glass plate such as falling ball characteristics is good, and when it is 1 mm or less, the product cost can be suppressed.

[Anti-fouling coating layer]
The antifouling coating agent used for forming the antifouling coating layer contains a fluorine compound. A fluorine-containing silane compound is suitable for the fluorine compound. In particular, a perfluoropolyether group-containing silane compound having a perfluoropolyether group in the molecular main chain and a hydrolyzable group bonded to a Si atom at the molecular terminal or terminal part is preferred. When the antifouling coating agent containing this perfluoropolyether group-containing silane compound is applied to the substrate, the hydrolyzable group bonded to the Si atom is bonded by reacting with the substrate and between the compounds, An antifouling coating layer can be formed. Specific examples of such fluorine-based compounds include Daikin Industries, Ltd. OPTOOL (registered trademark) DSX, Shin-Etsu Chemical Co., Ltd., KY-164, Fluoro Technology, Inc. Fluorosurf (registered trademark) FG-5000, DON Corporation SH-HT made by CE, Top CleanSafe made by CEKO, etc. are mentioned.

  Examples of the film formation method for the antifouling coating layer using a fluorine compound include a dry method and a wet method. As the dry method, a vacuum deposition method is preferable, and specific examples include a resistance heating method, an electron beam method, a high frequency heating method, an ion beam method, and similar methods. Specific examples of the wet method (wet coating method) include dip coating, spin coating, flow coating, spray coating, micro spray coating, roll coating, gravure coating, and similar methods.

In the case of a wet method, the fluorine-based compound can be diluted with a volatile solvent and coated as necessary. Volatile solvents include C5-C12 perfluoroaliphatic hydrocarbons (eg, perfluorohexane, perfluoromethylcyclohexane and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (eg, bis (Trifluoromethyl) benzene); polyfluoroaliphatic hydrocarbons; hydrofluoroethers (HFE) (for example, perfluoropropyl methyl ether (C ₃ F ₇ OCH ₃ ), perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃₎ ), Perfluorobutyl ether (C ₄ F ₉ OC ₂ H ₅ ), perfluorohexyl methyl ether (C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ ) and other alkyl perfluoroalkyl ethers (perfluoroalkyl groups) And the alkyl group may be linear or branched. ), And the like. These solvents can be used alone or as a mixture of two or more. Among them, hydrofluoroether is preferable, and perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) and / or perfluorobutyl ethyl ether (C ₄ F ₉ OC ₂ H ₅ ) is particularly preferable. After the wet coating, the above-mentioned solvent is removed from the allyl ester resin sheet surface under heating and / or reduced pressure conditions.

In the wet method, heat treatment is preferably performed to fix the fluorine-based compound on the surface of the allyl ester resin sheet. The temperature is preferably 40 to 150 ° C, more preferably 60 to 120 ° C.
In the case of the dry method, a porous compound, metal powder carbon fiber or the like may be impregnated with a fluorine compound.

[Primer layer]
In the antifouling sheet of the present invention, a primer layer is preferably provided between the allyl ester resin sheet and the antifouling coating layer for the purpose of improving the adhesion between the allyl ester resin sheet and the fluorine compound of the antifouling coating layer. The primer layer can be organic or inorganic. Specific examples of the organic primer include acrylic resin, curable acrylic resin, urethane resin, epoxy resin, and polyester resin. If necessary, fine particles such as silica may be contained. Examples of the method for applying the organic primer layer include a coating method and a transfer method.

Examples of inorganic primers include SiO ₂ , ZrO ₂ , TiO ₂ , carbon compounds and the like. These inorganic substances may be used alone or in combination of two or more thereof (for example, as a mixture). Examples of the method for applying the inorganic primer include a vacuum deposition method and a CVD method.

[Preprocessing]
In the production of the antifouling sheet of the present invention, plasma treatment (for example, corona discharge) or ion beam irradiation or the like is applied to the allyl ester resin sheet surface before primer treatment or fluorine compound film formation as necessary. Can do. This has the effect of improving the adhesion between the layers by introducing or increasing polar groups such as hydroxyl groups and carboxyl groups on the sheet surface.

[Adhesive layer]
Since the antifouling sheet of the present invention is attached to the display of a smartphone or tablet terminal, an adhesive layer may be formed on at least a part of the surface of the allyl ester resin sheet opposite to the antifouling coating layer. The antifouling sheet having an adhesive layer formed on the other surface of the allyl ester resin sheet can be used as a protective film for various touch panel display devices including smartphones and tablet PCs.

  The adhesive layer is formed of a conventional transparent adhesive. Examples of the pressure-sensitive adhesive include rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, olefin-based pressure-sensitive adhesives (modified olefin-based pressure-sensitive adhesives), and silicone-based pressure-sensitive adhesives.

  Examples of rubber adhesives include a combination of a rubber component (natural rubber, synthetic rubber, thermoplastic elastomer, etc.) and a tackifier (terpene resin, rosin resin, petroleum resin, modified olefin resin, etc.). Be mentioned.

  As an acrylic adhesive, the adhesive comprised with the acrylic copolymer which has acrylic acid C2-C10 alkylester as a main component, such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, can be used, for example. Examples of the copolymerizable monomer of the acrylic copolymer include (meth) acrylic monomers [for example, (meth) acrylic acid, methyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) ) Acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, acrylamide, N-methylolacrylamide etc.], polymerizable nitrile compound [eg (meth) acrylonitrile etc.], unsaturated dicarboxylic acid or derivative thereof (for example, Maleic anhydride, itaconic acid, etc.), vinyl esters (eg, vinyl acetate, vinyl propionate, etc.), aromatic vinyls (eg, styrene, etc.) and the like.

  Examples of the olefin pressure-sensitive adhesive include ethylene- (meth) acrylic acid copolymer, ethylene-2-hydroxyethyl (meth) acrylate copolymer, ethylene-glycidyl (meth) acrylate copolymer, ethylene-vinyl acetate- (Meth) acrylic acid copolymer, ethylene-ethyl (meth) acrylate- (anhydrous) maleic acid copolymer, partially saponified product of ethylene-vinyl acetate copolymer, and the like.

Examples of the silicone-based pressure-sensitive adhesive include a silicone rubber component [monofunctional R ₃ SiO _1/2 (wherein R represents an alkyl group such as a methyl group, an aryl group such as a phenyl group, and the like. The same applies hereinafter). And MQ resin comprising tetrafunctional SiO ₂ ] and a silicone resin component (bifunctional R ₂ SiO alone, or oily or gum combining bifunctional R ₂ SiO and monofunctional R ₃ SiO _1/2) And the like can be used. The silicone rubber component may be cross-linked.
Among these pressure-sensitive adhesives, silicone pressure-sensitive adhesives are preferable from the viewpoint of optical properties and reworkability.

  The thickness of the pressure-sensitive adhesive layer is, for example, about 1 to 150 μm, preferably about 10 to 100 μm, and more preferably about 20 to 70 μm (especially 25 to 50 μm).

[Peeling film]
The antifouling sheet of the present invention may be protected on both sides (antifouling coat layer, adhesive layer) with a release film in order to prevent scratches during storage and transfer, and adhesion of dirt and dust. . That is, it is good also as a structure of peeling film A / antifouling coating layer / allyl ester resin sheet / adhesion layer / release film B. This release film is peeled off when the antifouling sheet of the present invention is applied to a display device or the like.

Examples of the release film A to be applied to the antifouling coating layer include a film made of polyethylene, polypropylene, polyethylene terephthalate, etc., and a self-adhesive film.
The release film B to be attached to the adhesive layer can be made of polyethylene, polypropylene or polyethylene terephthalate.

  In general, when a protective film is to be applied to a display device screen, if the screen size is large or the shape is complicated, positioning of the protective film is difficult even if the protective film is applied to the entire screen at once. In some cases, dust may be mixed between the adhesive layer and the display screen. In such a case, a part of the peeling film (peeling film B) can be divided, only a part of the adhesive layer is exposed, only a part of the protective film is attached to the screen, and temporarily fixed. Adhesion can be prevented and alignment accuracy can be increased.

  Examples of the splittable release film include a case where the release film itself has an easy tear property and a case where the release film is further processed to improve the easy tear property.

  As a specific example of the peelable release film, a uniaxially stretched film obtained by adding uniaxial stretching to polyethylene, polypropylene, or polyethylene terephthalate to impart anisotropy of tear strength can be used. By tearing in the stretching direction, only a part of the adhesive layer of the antifouling sheet can be easily exposed. Further, as the release film, a film in which a different polymer such as an amorphous polyolefin polymer is mixed at the time of forming the polyethylene film to improve the tearing processability can also be used. This type of film can adjust the tear strength by changing the amount of the different polymer added. Such a splittable release film may be a single layer, but may have a structure in which a plurality of polymer films are laminated as required.

  As a specific example of the process for improving easy tearability, there is a method of slitting or imprinting the release film. As a specific example of the slit processing, there is a method of giving a transverse cut, groove (half cut) or imprint on the surface of the release film opposite to the adhesive layer with a knife or laser. When the release film to be used is a uniaxially stretched film, it is preferable to provide a groove | channel and a press mark in the same direction as the extending direction of a film.

EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example demonstrate this invention concretely, this invention is not limited by these description.
The total light transmittance, pencil hardness and the like of the examples and comparative examples and the described sheets were measured by the following methods.

[Total light transmittance]
The total light transmittance was measured based on JIS K-7361-1 using a Nippon Denshoku Industries Co., Ltd. haze meter NDH5000.

[Haze]
The total light transmittance was measured according to JIS K-7136 using a Nippon Denshoku Industries Co., Ltd. haze meter NDH5000.

[Optical isotropy]
A film was placed on the liquid crystal display, and a polarizing plate was placed thereon to check for the presence of rainbow unevenness. The evaluation criteria are as follows.
○: No rainbow unevenness
X: There is rainbow unevenness.

[Pencil hardness]
The pencil hardness is an electric pencil scratch hardness tester No. 553-M was used and measured according to JIS K5600-5-4.

[Anti-fouling]
Antifouling property was evaluated by water contact angle. The contact angle was measured using DropMaster DM-301 manufactured by Kyowa Interface Science Co., Ltd.
Measurement environment: 23 ° C ± 1 ° C, humidity 50% ± 10%
Analysis method: θ / 2 method Drop volume: 3.0 μL
Evaluation criteria: water contact angle of 110 ° or more (high antifouling property),
Water contact angle of 100 ° or more and less than 110 ° (antifouling property),
Water contact angle less than 100 ° (low antifouling property).

Synthesis example 1:
A 2-liter three-necked flask equipped with a distillation apparatus is charged with 1625 g of diallyl 1,4-cyclohexanedicarboxylate, 167 g of trimethylolpropane, and 0.8 g of dibutyltin oxide, and allyl alcohol produced at 180 ° C. in a nitrogen stream. It heated while distilling out of the system. When the distilled allyl alcohol reached about 170 g, the pressure in the reaction system was gradually reduced to 6.6 kPa over 4 hours to increase the distillation rate of allyl alcohol. When almost no distillation occurred, the pressure was adjusted to 0.5 kPa, and the reaction was performed for 1 hour, followed by cooling to room temperature to obtain allyl ester oligomer A. The structural formula of allyl ester oligomer A is shown below.

Example 1:
80 parts by weight of allyl ester oligomer A, 20 parts by weight of trimethylolpropane triacrylate, 1 part by weight of Perhexyl (registered trademark) I (manufactured by NOF Corporation), 0.5 part by weight of Irgacure (registered trademark) TPO (manufactured by BASF) Parts were mixed until uniform, and an allyl ester resin composition B was prepared. The resin composition B was applied onto a PET film having a thickness of 100 μm so that the thickness after curing was 0.2 mm. The coating liquid surface is covered with a PET cover film having a thickness of 100 μm, irradiated with ultraviolet rays using an ultraviolet irradiation device (metal halide lamp) at 200 mW / cm ² and 800 mJ / cm ² , and then heated at 150 ° C. The furnace was charged so that the residence time was 10 minutes. After taking out from the heating furnace and cooling, the PET films on both sides were peeled off to obtain an allyl ester resin sheet C.
On the surface of the obtained allyl ester resin sheet C, a carbon primer “Nano primer” manufactured by Seko Corporation was formed as a primer layer by vacuum deposition. Subsequently, a fluorine-based compound “Top CleanSafe” manufactured by Seko Co., Ltd. was formed by vacuum vapor deposition to obtain an antifouling sheet D.

Example 2:
Primer coating agent PC-3B (manufactured by Fluoro Technology Co., Ltd.) containing a silane compound was applied to the allyl ester resin sheet C obtained in Example 1, and heated at 100 ° C. for 30 minutes. Next, an antifouling coating agent FG5080-SH (manufactured by Fluoro Technology Co., Ltd.) containing a fluorine compound was applied and heated at 100 ° C. for 30 minutes to obtain an antifouling sheet E.

Comparative Example 1:
In a container equipped with a stirrer, 4.0 parts by mass of an ethylenically unsaturated double bond-containing acrylic copolymer composed of isobornyl methacrylate, methyl methacrylate and methacrylic acid as the first component, and methyl isobutyl ketone 50 as the organic solvent. 0.02 parts by mass and stirring, followed by 75.0 parts by mass of a mixture of dipentaerythritol hexaacrylate and pentaacrylate as a second component and 25.0 parts by mass of a mixture of pentaerythritol triacrylate and tetraacrylate, As the three components, 2.0 parts by mass of a polyether skeleton-containing urethane acrylate composed of isophorone diisocyanate and pentaerythritol triacrylate, 4 parts by mass of a reactive fluorine antifouling agent (Optool DAC: manufactured by Daikin Industries, Ltd.), and an organic solvent 118.0 parts by mass of propyl alcohol, 5.0 parts by mass of 1-hydroxycyclohexyl phenyl ketone as photopolymerization initiator and α-hydroxy- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl- 1-phenyl)]} propan-1-one was added in an amount of 1.0 part by mass to obtain an antifouling hard coat agent F. Next, at room temperature (20 ° C.), the antifouling hard coat agent F was applied onto PET (Lumirror (registered trademark) (188 μm thickness) manufactured by Toray Industries, Inc.) so that the dry film thickness was 6 μm. The solvent in the coating film was dried and removed by heating for a minute, and then cured by irradiation and exposure in an air environment at an energy of 500 mJ / cm ² with an ultra-high pressure mercury lamp (Fusion, H-bulb type). Hard coat film G was obtained.

Comparative Example 2:
The characteristics of the allyl ester resin sheet C before applying the antifouling coating were evaluated.

  Since the antifouling sheet of the present invention has a high level of hardness, antifouling property, and optical isotropy, it is particularly a liquid crystal protective film such as a smartphone or a tablet PC, a decoration / scattering prevention film, and an apparatus main body. It is useful as a transparent member used for a case, a cover, a flip case, a jacket, and the like.

Claims (7)

  An antifouling sheet having an antifouling coating layer containing a fluorine compound on at least one surface of an allyl ester resin sheet.   The antifouling sheet according to claim 1, further comprising a primer layer between the allyl ester resin sheet and the antifouling coating layer containing a fluorine compound as a main component. The allyl ester resin sheet is a cured product of the allyl ester resin composition, and the allyl ester resin composition has the general formula (2)

Wherein R ³ represents an allyl group or a methallyl group, and A ² represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from a dicarboxylic acid. Having terminal groups and having the general formula (3)

(In the formula, A ³ represents one or more organic residues having an alicyclic structure and / or an aromatic ring structure derived from dicarboxylic acid, and X represents one or more organic residues derived from a polyhydric alcohol. However, X may have a branched structure having an ester bond and a group represented by the general formula (2) as a terminal group and a structure represented by the general formula (3) as a constituent unit. The antifouling sheet according to claim 1 or 2, comprising an allyl ester oligomer having the structure shown as a structural unit.   The antifouling sheet according to any one of claims 1 to 3, wherein an adhesive layer is formed on at least a part of the surface of the allyl ester resin sheet opposite to the antifouling coating layer.   The antifouling sheet according to any one of claims 1 to 4, wherein a protective release film is bonded to both surfaces.   A method for producing an antifouling sheet, comprising forming an antifouling coating layer by vacuum-depositing an antifouling coating agent containing a fluorine compound on the surface of an allyl ester resin sheet.   A method for producing an antifouling sheet, comprising wet coating an antifouling coating agent containing a fluorine-based compound on the surface of an allyl ester resin sheet to form an antifouling coating layer.