JP2010222524A - Active energy ray-curable resin composition for film protective layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray-curable resin composition which can form a protective film in which there is no coating defect, and which excels in surface stainproof, and has high scratch resistance. <P>SOLUTION: The active energy ray-curable resin composition for a fluid protective layer includes: an active energy ray-curable resin composition; and a reactive fluorine antifouling agent, wherein the turbidity of the reactive fluorine antifouling agent is less than 20%, and the reactive fluorine antifouling agent includes: a perfluoropolyether which has one active hydrogen; and a monomer which has an active hydrogen and a carbon-carbon double bond. An optical sheet comprises a cured product of the active energy ray-curable resin composition for a film protective layer. A protecting adhesive film includes: a protective layer formed comprising a cured product of the active energy ray-curable resin composition for a film protective layer which is formed on a film; and an adhesive surface which is prepared on the back surface of the film. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an active energy ray-curable resin composition for a film that forms a hardened cured film suitable for use as a protective layer for a substrate such as a film or sheet. Further, the present invention relates to a film having a protective layer made of a cured film of the composition and a protective adhesive film made of a cured product of the composition.

  An article is affected by the contact between the articles, contact with other articles, or the environment in which the article is placed, and external changes that are damaged or deformed or internal changes that degrade the materials that make up the article Receive. In order to prevent such a change, a protective layer is provided on the surface of the article, or the article itself is strengthened.

  Plastics are used in various fields for reasons such as good processability, light weight, and low cost. However, the processability is good, but there are drawbacks such as softness and easy scratching on the surface. In order to improve this drawback, it is common to coat a hard coat material and provide a protective layer on the surface.

  As this hard coat material, there are advantages such as (1) fast curing, (2) low energy cost, (3) curing at low temperature, etc., active energy ray curable resin composition Is often adopted. In particular, the active energy ray-curable resin composition is cured immediately upon irradiation with active energy rays such as ultraviolet rays to form a hard film, so that the processing speed is fast, and the hardness, scratch resistance, stain resistance, etc. are excellent. Since it can be continuously processed, it has become the mainstream as a hard coat material for a film protective layer.

  In recent years, display bodies such as a liquid crystal display, a plasma display, and a touch panel display provided with a film having a hard coat material as a protective layer on the surface thereof are rapidly spreading. In addition to basic performance such as pencil hardness and steel wool, the hard coat material is required to have low curl for handling and improvement in yield. Furthermore, recently, there is an increasing demand for antifouling properties for a coating material used on the outermost surface of a display screen such as a touch panel or a mobile phone, on which a human fingerprint is easily attached.

  In order to solve the above problems, for example, it has been proposed to add a reactive fluorine antifouling agent. In order to impart antifouling properties such as fingerprint wiping properties, a fluorine antifouling agent having high water and oil repellency is effective (for example, see Patent Document 1). However, this results in poor compatibility with the resin and causes problems such as poor coating material stability and coating film defects. Further, when a reactive fluorine antifouling agent is added to the active energy ray-curable resin composition, the antifouling property is improved, but the defective rate of customer products due to coating film defects (for example, repellency). There was a problem that increased.

Japanese Patent No. 3963169

  The problem to be solved by the present invention is to provide an active energy ray-curable resin composition that is free of coating defects, has excellent surface antifouling properties, and can form a highly scratch-resistant protective film. .

  As a result of diligent research, the present inventor has found that a film protective layer free from coating film defects can be formed by reducing the turbidity of the reactive fluorine antifouling agent to less than a certain value, and has completed the present invention. It came to do.

  That is, the present invention is an active energy ray-curable resin composition for a film protective layer containing an active energy ray-curable resin composition and a reactive fluorine antifouling agent, and the turbidity of the reactive fluorine antifouling agent And a reactive fluorine antifouling agent containing a perfluoropolyether having one active hydrogen and a monomer having an active hydrogen and a carbon-carbon double bond. Active energy ray curable resin composition for film protective layer, optical sheet made of cured product of active energy ray curable resin composition for film protective layer, active energy ray curable resin composition for film protective layer on film A protective adhesive film is provided, in which a protective layer that is a cured product of the product is formed, and an adhesive surface is provided on the back surface of the film.

  The active energy ray-curable resin composition of the present invention has no coating film defects when cured by irradiation with active energy rays such as ultraviolet rays, excellent surface fingerprint wiping property, small curing shrinkage, high hardness, high A cured film having scratch resistance can be obtained, and is useful as a protective layer for a film. In addition, since the curing shrinkage is small, the occurrence of curling can be suppressed even with a large film, which is suitable as a protective film for an optical film of a large screen display such as a liquid crystal display.

  Moreover, it is also suitable as a protective adhesive film for protecting a screen panel provided on the surface of a display device such as a liquid crystal panel, a touch panel-mounted liquid crystal panel, or an EL display.

[Hard coat layer]
The active energy ray-curable resin composition used in the present invention is an addition reaction product of polyisocyanate (a1) and acrylate (a2) having one hydroxyl group and two or more (meth) acryloyl groups in one molecule. An α, β-unsaturated compound having a functional group capable of reacting with the reactive functional group in a urethane acrylate (A) and a (meth) acrylate polymer (b1) having a reactive functional group in the side chain ( and a polymer (B) having a (meth) acryloyl group reacted with b2).

  Examples of the polyisocyanate (a1) used in the present invention include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5- Aromatic isocyanate compounds such as naphthalene diisocyanate and 4,4′-diphenylmethane diisocyanate; alicyclic rings such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated methylenebisphenylene diisocyanate, and 1,4-cyclohexane diisocyanate A compound having two isocyanate groups bonded to a hydrocarbon (hereinafter abbreviated as alicyclic diisocyanate); trimethylene diisocyanate, hexamethyl Compounds having two isocyanate groups attached to aliphatic hydrocarbons such as emissions diisocyanate (hereinafter, abbreviated as aliphatic diisocyanates.) And the like. These polyisocyanates can be used alone or in combination of two or more.

  Of these polyisocyanates (a1), aliphatic diisocyanates or alicyclic diisocyanates are preferable, and among them, isophorone diisocyanate, norbornane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated methylene bisphenylene diisocyanate, and hexamethylene diisocyanate are preferable. In particular, norbornane diisocyanate is most preferable.

  Examples of the acrylate (a2) having one hydroxyl group and two or more (meth) acryloyl groups in one molecule used in the present invention include trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, And polyacrylates of polyhydric hydroxyl group-containing compounds such as pentaerythritol penta (meth) acrylate, adducts of these polyacrylates with ε-caprolactone, adducts of these polyacrylates with alkylene oxide, epoxy Examples include acrylates. These acrylates (a2) can be used alone or in combination of two or more. In the present invention, “(meth) acrylate” refers to one or both of methacrylate and acrylate, and the same applies to “(meth) acryloyl group” and “(meth) acrylic acid”.

  Of these acrylates (a2), an acrylate having one hydroxyl group and 3 to 5 (meth) acryloyl groups in one molecule is preferable. Examples of such acrylates include pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and the like, and these are particularly preferable because a cured film having high hardness can be obtained.

The urethane acrylate (A) used in the present invention is obtained by subjecting two components of the polyisocyanate (a1) and the acrylate (a2) to an addition reaction. The ratio of the acrylate (a2) to 1 equivalent of the isocyanate in the polyisocyanate (a1) is usually preferably 0.1 to 50, more preferably 0.1 to 10, and preferably 0.9 to 1.2 as the hydroxyl equivalent. Is more preferable. Moreover, 30-150 degreeC is preferable and, as for the reaction temperature of the said polyisocyanate (a1) and the said acrylate (a2), 50-100 degreeC is more preferable.
In addition, the end point of reaction can be confirmed by calculating | requiring an isocyanate group content rate by the loss | disappearance of the infrared absorption spectrum of 2250cm <-1> which shows an isocyanate group, or the method as described in JISK7301-1995, for example.

  Further, in the above addition reaction, a catalyst can be used for the purpose of shortening the reaction time. Examples of the catalyst include basic catalysts (amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine and ammonia, phosphines such as tributylphosphine and triphenylphosphine) and acidic catalysts (copper naphthenate, naphthene). Metal alkoxides such as cobalt acid, zinc naphthenate, tributoxyaluminum, tetrabutoxytrititanium and tetrabutoxyzirconium, Lewis acids such as aluminum chloride, and tin compounds such as dibutyltin dilaurate and dibutyltin diacetate). Of these, acidic catalysts are preferred, and tin compounds are most preferred. The catalyst is usually added in an amount of 0.1 to 1 part by mass with respect to 100 parts by mass of the polyisocyanate. If necessary, a solvent such as toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, or a radical polymerizable monomer that does not have a site that reacts with isocyanate, for example, radical polymerization described later. Monomers (C) that do not have a hydroxyl group or amino group may be used as the solvent. These solvents and monomers can be used alone or in combination of two or more.

The molecular weight of the urethane acrylate (A) is preferably in the range of 500 to 1,500.
When the molecular weight is within this range, a cured film having a sufficiently high hardness can be obtained and the curing shrinkage can be reduced, so that the curl of the film having the cured film can also be reduced.

  5-90 mass parts is preferable, as for the compounding quantity of the said urethane acrylate (A) in the total 100 mass parts of the resin component in a resin composition, 10-70 mass parts is more preferable, and 10-60 mass parts is further more preferable. . If the blending amount of the urethane acrylate (A) is within this range, a cured film having a sufficiently high hardness can be obtained, and there is no coating film defect, excellent surface antifouling properties, and curing shrinkage is reduced. Curling of a film having a cured coating can also be reduced.

  As the reactive functional group of the (meth) acrylate polymer (b1) having a reactive functional group in the side chain used in the present invention, a hydroxyl group, a carboxyl group, an epoxy group or the like is preferable. In addition, examples of the functional group of the α, β-unsaturated compound (b2) capable of reacting with these reactive functional groups include isocyanate groups, carboxyl groups, acid halide groups, hydroxyalkyl groups, hydroxyl groups, and epoxy groups. preferable. The (meth) acrylate polymer (b1) having a reactive functional group in the side chain was reacted with an α, β-unsaturated compound (b2) having a functional group capable of reacting with the reactive functional group. The production method of the polymer (B) having a (meth) acryloyl group is not particularly limited and can be produced by various methods. Examples thereof include the following production methods (1) to (3).

Manufacturing method (1)
As the (meth) acrylate polymer (b1), a (meth) acrylate polymer or copolymer having a hydroxyl group as a reactive functional group in the side chain is used. A method of introducing a (meth) acryloyl group by reacting (meth) acryloylethyl isocyanate, (meth) acrylic acid, (meth) acrylic acid chloride or the like as the β-unsaturated compound (b2).

Manufacturing method (2)
As the (meth) acrylate polymer (b1), using a (meth) acrylate polymer or copolymer having a carboxyl group as a reactive functional group in the side chain, a part or all of the carboxyl group, A method of introducing a (meth) acryloyl group by reacting an acrylate containing a hydroxyl group and a (meth) acryloyl group or an acrylate having an epoxy group and a (meth) acryloyl group as the α, β-unsaturated compound (b2).

Manufacturing method (3)
As the (meth) acrylate polymer (b1), using a (meth) acrylate polymer or copolymer having an epoxy group as a reactive functional group in the side chain, a part or all of the epoxy group, A method of introducing a (meth) acryloyl group by reacting (meth) acrylic acid or an acrylate having a carboxyl group and an acryloyl group as the α, β-unsaturated compound (b2).

  Taking the production method (3) as an example, the production method of the polymer (B) will be described more specifically. In the production method (3), the polymer (B) can be easily obtained by reacting the (meth) acrylate polymer or copolymer having an epoxy group with an α, β-unsaturated carboxylic acid. . Here, the (meth) acrylate polymer having an epoxy group includes, for example, glycidyl (meth) acrylate and (meth) acrylate having an alicyclic epoxy group (for example, “CYCLOMER manufactured by Daicel Chemical Industries, Ltd.). M100 ”,“ CYCLOMER A200 ”), and (meth) acrylate having an epoxy group such as 4-hydroxybutyl acrylate glycidyl ether, and these are obtained by homopolymerization.

  In addition, the (meth) acrylate-based copolymer having an epoxy group is an α, which does not have a carboxyl group such as (meth) acrylate, styrene, vinyl acetate, acrylonitrile, in addition to the (meth) acrylate having the epoxy group. It can be obtained by copolymerizing two or more monomers using a β-unsaturated monomer as a raw material. When an α, β-unsaturated monomer having a carboxyl group is used instead of the α, β-unsaturated monomer having no carboxyl group, the copolymerization reaction with glycidyl (meth) acrylate is carried out. At this time, it is not preferable because a crosslinking reaction is caused to increase the viscosity and gelation.

  Examples of the α, β-unsaturated carboxylic acid that reacts with the (meth) acrylate-based polymer or copolymer having an epoxy group include (meth) acrylic acid, a compound having a carboxyl group and an acryloyl group (for example, Osaka Organic Chemical Co., Ltd. “Biscoat 2100”) and the like.

  The weight average molecular weight of the polymer (B) obtained by the above production method is preferably 5,000 to 80,000, more preferably 5,000 to 50,000, and still more preferably 8,000 to 35,000. When the weight average molecular weight is 5,000 or more, the effect of reducing curing shrinkage is large, and when it is 80,000 or less, the hardness is sufficiently high.

  The (meth) acryloyl group equivalent of the polymer (B) is preferably 100 to 300 g / eq, more preferably 200 to 300 g / eq. When the (meth) acryloyl group equivalent of the polymer (B) is within this range, curing shrinkage can be reduced and the hardness can be sufficiently increased.

  When the polymer (B) is produced by the above production methods (1) to (3), the polymer (B) is used so as to satisfy the weight average molecular weight and (meth) acryloyl group equivalent. The kind of the polymer and polymer, the amount of use thereof, and the like may be appropriately selected.

  The blending amount of the polymer (B) in a total of 100 parts by mass of the resin components in the resin composition is preferably 20 parts by mass or less, and preferably 10 parts by mass or less from the viewpoint of easy occurrence of repelling. Is more preferable. If the blending amount of the polymer (B) is within this range, a cured film having a sufficiently high hardness can be obtained, and there is no coating film defect, excellent surface antifouling properties, and curing shrinkage is reduced. Curling of a film having a cured coating can also be reduced.

  In the active energy ray-curable resin composition used in the present invention, in addition to the urethane acrylate (A) and the polymer (B), a radical polymerizable monomer other than the urethane acrylate (A) and the polymer (B). Body (C) may be added. Examples of the radically polymerizable monomers (C) include the following.

N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylcarbazole, vinylpyridine, acrylamide, N, N-dimethyl (meth) acrylamide, isobutoxymethyl (meth) acrylamide, t-octyl (meth) acrylamide, diacetone (meth) Acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, acryloylmorpholine, lauryl (meth) acrylate, dicyclopentadienyl (meth) acrylate , Dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethylene diethylene glycol (meth) Acrylate, butoxyethyl (meth) acrylate, monoacrylate such as methyl triethylene diglycol (meth) acrylate, phenoxyethyl (meth) acrylate;

Trimethylolpropane tri (meth) acrylate, triethylene oxide modified trimethylolpropane tri (meth) acrylate, tripropylene oxide modified glycerol tri (meth) acrylate, triethylene oxide modified glycerol tri (meth) acrylate, triepichlorohydrin modified glycerol tri (Meth) acrylate, 1,3,5-triacroylhexahydro-s-triazine, tris (acryloyloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetraethylene oxide modified Pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, diethylene oxide modified ditrimethylo Rupropanetetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol pentaacrylate (for example, “Kayarad D-310” manufactured by Nippon Kayaku Co., Ltd.), alkyl-modified dipentaerythritol tetraacrylate (for example, Nippon Kayaku Co., Ltd. “Kayarad D-320”), ε-caprolactone-modified dipentaerythritol hexaacrylate (for example, Nippon Kayaku Co., Ltd. “Kayarad DPCA-20”), dipentaerythritol pentamethacrylate, dipenta Erythritol hexa (meth) acrylate, hexaethylene oxide modified sorbitol hexa (meth) acrylate, hexakis (methacryloyloxyethyl) cyclotriphosphazene There are polyfunctional acrylates such as “PPZ” manufactured by Seisha Chemical Co., Ltd.

  Among the radical polymerizable monomers (C), a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule is preferable because it has an effect of increasing hardness. Examples of such polyfunctional (meth) acrylates include pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like. These may be used alone or in combination of two or more.

  Furthermore, as the radical polymerizable monomers (C), a monomer having an acid group such as a carboxyl group, a phosphoric acid group or a sulfonic acid group, a monomer having an amino group, an alkoxysilyl group, an alkoxy titanyl group It is preferable to use a monomer having, since the adhesion to the substrate can be improved. On the other hand, a monomer having a fluorocarbon chain, a dimethylsiloxane chain, or a hydrocarbon chain having 12 or more carbon atoms can improve the surface properties of the protective layer such as surface slipperiness, stain resistance, and fingerprint resistance. preferable.

  The amount of the radical polymerizable monomers (C) blended in the resin composition is 10 to 10 parts by mass with respect to 100 parts by mass of the total amount of the urethane acrylate (A) and the polymer (B). 300 parts by mass is preferred. Moreover, 20-200 mass parts is more preferable, and 20-100 mass parts is still more preferable in order to make hardening shrinkage small and to raise the surface hardness of a cured film.

  Moreover, in addition to the said urethane acrylate (A) and a polymer (B), urethane acrylate (D) other than the said urethane acrylate (A) may be added to the active energy ray-curable resin composition used for this invention. good. The urethane acrylate (D) is an acrylate (a2) having one hydroxyl group and two or more (meth) acryloyl groups in one molecule after addition reaction of the polyol and the polyisocyanate (a1). Can be added. As for the compounding quantity at the time of mix | blending this urethane acrylate (D) in a resin composition, 5-100 mass parts is preferable with respect to 100 mass parts of total amounts of the said urethane acrylate (A) and a polymer (B). 10 to 50 parts by mass is more preferable.

In addition to the urethane acrylate (A) and the polymer (B), a polyester acrylate (E) may be added. If the resin component composition is the following composition / range, a cured film having a sufficiently high hardness can be obtained. The resulting film is free from coating film defects, has excellent antifouling properties on the surface, and cure shrinkage is reduced, so that the curl of the film having this cured coating can also be reduced.
For example, the blending ratio of the urethane acrylate resin (A) and the polyester acrylate resin (E) in a total of 100 masses of resin components in the resin composition is (A) :( E) = 10: 90 to mass basis. The range of 90:10 is preferable, the range of (A) :( E) = 20: 80 to 80:20 is more preferable, and the range of (A) :( E) = 25: 75 to 75:25 is more preferable. .

  In addition to the urethane acrylate resin (A) and the polyester acrylate resin (E), the polymer (B) may be added. The amount of the polymer (B) blended in the resin composition is 25 parts by mass or less based on 100 parts by mass of the total amount of the urethane acrylate resin (A) and the polyester acrylate resin (E). Preferably, it is 12 parts by mass or less.

[Additive]
The reactive fluorine antifouling agent used in the present invention is required to have a turbidity of less than 20%, and a perfluoropolyether having one active hydrogen, and an active hydrogen and a carbon-carbon double bond. Since the reactive fluorine antifouling agent containing the monomer having the above is excellent in antifouling properties such as fingerprint wiping property, it can be suitably used.

As the reactive fluorine antifouling agent, for example, an activity comprising perfluoropolyether (I-1) having active hydrogen and a monomer (I-2) having active hydrogen and a carbon-carbon double bond as essential components. Examples thereof include a carbon-carbon double bond-containing composition obtained by reacting a hydrogen-containing compound (I) with a triisocyanate compound (II) obtained by trimerizing diisocyanate.

  The carbon-carbon double bond-containing composition includes an isocyanate group in the triisocyanate compound (II), an active hydrogen group in the perfluoropolyether (I-1), and the triisocyanate compound (II). The thing which the active hydrogen group in the monomer (I-2) which has the said isocyanate group and the said carbon-carbon double bond reacted is preferable.

The perfluoropolyether _{(I-1), -OCF 2} CF 2 CF 2 -, - OCFCF 3 CF 2 -, - OCF 2 CF 2 -, - OCF 2 - a repeating unit such as, the recurring units Is a compound having a total of 1 to 200, a hydroxyl group-containing group such as —CH ₂ OH at one end or both ends, and when only one end is a hydroxyl group-containing group, the other end is Compounds that are fluorine atoms can be used.

Monomers (I-2) having active hydrogen and carbon-carbon double bonds include hydroxyethyl (meth) acrylate, aminoethyl (meth) acrylate, HO (CH ₂ CH ₂ O) i-COC (R) C ═CH ₂ (R: H, CH ₃ , i = 2 to 10), CH ₃ CH (OH) CH ₂ OCOC (R) C═CH ₂ (R: H, CH ₃ ; 2-hydroxypropyl (meth) acrylate ), CH ₃ CH ₂ CH (OH) CH ₂ OCOC (R) C═CH ₂ (R: H, CH ₃ ; 2-hydroxybutyl (meth) acrylate), C ₆ H ₅ OCH ₂ CH (OH) CH _{2 OCOC (R) C = CH 2} (R: H, CH 3; 2- hydroxy-3-phenoxypropyl (meth) acrylate), allyl _{alcohol, HO (CH 2) kCH =} CH 2 (k = _{~20), (CH 3) 3} SiCH (OH) CH = CH2 . Of these, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylates such as A compound containing a hydroxyl group as the active hydrogen group is preferred.

  Examples of the triisocyanate compound (II) obtained by trimerizing diisocyanate include triisocyanate obtained by trimerizing the following diisocyanate. Examples of the diisocyanate include diisocyanates in which isocyanate groups are bonded aliphatically, such as hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate; diisocyanates in which isocyanate groups are bonded aromatically, Examples thereof include tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolidine diisocyanate, and naphthalene diisocyanate. Among these, diisocyanates in which isocyanate groups such as hexamethylene diisocyanate and isophorone diisocyanate are bonded to aliphatic groups are preferable from the viewpoint of compatibility of the reactants.

  In addition, the equivalent ratio at the time of reaction with the active hydrogen group in the perfluoropolyether (I-1) having active hydrogen to the isocyanate group in the triisocyanate (II) [in ((I-1) in Active hydrogen group / (isocyanate group in ((II)))] is preferably 0.01 to 1.2.

  Moreover, the equivalent at the time of reaction with the active hydrogen group in the active hydrogen group in the monomer (I-2) which has an active hydrogen and a carbon-carbon double bond with respect to the isocyanate group in the said triisocyanate (II) The ratio [(active hydrogen group in (I-2) / (isocyanate group in (II))]] is preferably 1.2 to 2.0.

  The equivalent ratio [(total active hydrogen groups in (I)) / (isocyanate groups in (II)]] when reacting the active hydrogen-containing compounds with the triisocyanate compound is 1.0 or more. In particular, it is preferably 1.0.

  Therefore, as a reactive fluorine antifouling agent containing a perfluoropolyether having one active hydrogen and a monomer having an active hydrogen and a carbon-carbon double bond, 1 mole of triisocyanate (II) is used. Particularly preferred is a product obtained by reacting 1 mol of perfluoropolyether (I-1) having active hydrogen and 2 mol of a monomer having a carbon-carbon double bond containing a hydroxyl group.

  Fluorine antifouling agents generally have poor compatibility with the active energy ray-curable resin composition and the dilution solvent, and the antifouling property is improved when added to the active energy ray-curable resin composition. However, there is a problem that a coating film defect (for example, repellency / pox) occurs. Especially, in the case of the reactive fluorine antifouling agent, coating film defects are likely to occur. In particular, when the reactive fluorine antifouling agent itself has a high turbidity, coating film defects tend to occur remarkably even with a small addition amount.

  In particular, the reactive fluorine antifouling agent has a turbidity of 30% or more and generates a coating film defect [fine coating film defect and coating film defect (for example, repellency / defects)] described later. Moreover, in 20-30%, a coating-film defect does not generate | occur | produce, but a fine coating-film defect generate | occur | produces. Therefore, the reactive fluorine antifouling agent used in the present invention can be suitably used since a turbidity of less than 20% can form a film protective layer free of coating film defects.

  Factors that increase the turbidity include, for example, generation of impurities with high fluorine concentration (as an example of impurities, perfluoropolyether (I-1) having two or more active hydrogens in 1 mol of triisocyanate (II) ) In a non-uniform composition). Controlling the impurities and the like is one way to reduce turbidity.

  The reactive fluorine antifouling agent is preferably added in an amount of 0.05 parts by mass or more with respect to 100 parts by mass of the active energy ray-curable resin composition because the antifouling property becomes remarkable. It is preferable that the amount is not more than part by mass because it is difficult to cause coating film defects (for example, repellency / pops). Furthermore, it is especially preferable that it is 0.1-2 mass parts.

  The active energy ray-curable resin composition used in the present invention refers to a resin composition that cures when irradiated with active energy rays. Active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used, a photopolymerization initiator is added to the active energy ray-curable resin composition. If necessary, a photosensitizer is further added. On the other hand, when ionizing radiation such as electron beam, α-ray, β-ray, and γ-ray is used, it cures quickly without using a photopolymerization initiator or photosensitizer. There is no.

  When curing with ultraviolet rays, effective photopolymerization initiators can be broadly classified into intramolecular cleavage type photopolymerization initiators and hydrogen abstraction type photopolymerization initiators. Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy. 2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino- (4-thio Acetophenone compounds such as methylphenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone; benzoin compounds such as benzoin, benzoin methyl ether and benzoin isopropyl ether; 4,6-trimethylbenzoyldiphenyl Scan fins oxide, bis (2,4,6-trimethylbenzoyl) - acyl phosphine oxide-based compounds such as triphenylphosphine oxide; benzyl, compounds such as methyl phenylglyoxylate ester.

  On the other hand, examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, methyl 4-phenylbenzophenone, o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide. Benzophenone compounds such as acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4 A thioxanthone compound such as dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; an aminobenzophenone compound such as Michler's ketone and 4,4′-diethylaminobenzophenone; 2-chloro acridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, include compounds such as camphor quinone.

  Further, the photosensitizer suitably used for the active energy ray-curable resin composition used in the present invention is not particularly limited, but examples thereof include amines such as aliphatic amines and aromatic amines, o-tolylthiourea. And the like, and sulfur compounds such as sodium diethyldithiophosphate, s-benzylisothiouronium-p-toluenesulfonate, and the like.

  The amount of these photopolymerization initiators and photosensitizers used is preferably 0.1 to 20% by weight, preferably 0.5 to 10%, based on 100 parts by weight of the resin component in the active energy ray-curable resin composition. The mass% is more preferable.

  Moreover, various additives may be mix | blended with the active energy ray hardening-type resin composition used for this invention as needed, and you may dilute with a solvent if desired. Examples of the additive include a polymerization inhibitor, an antioxidant, a leveling agent, an antifoaming agent, a coating surface improver (wetting property, slip property improving agent, etc.), a plasticizer, and a colorant.

[solvent]
Solvents used for dilution include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol and isopropyl alcohol; esters such as ethyl acetate and ethyl sorbacetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone Etc. These solvents may be used alone or in combination of two or more.

[Film substrate]
Examples of the film substrate used in the present invention include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, diacetylcellulose film, triacetylcellulose film, acetylcellulose butyrate film, and polyvinyl chloride film. , Polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyetherimide film, polyimide Film, fluorine resin film, nylon film, acrylic resin And the like can be given Irumu. The cured coating of the active energy ray-curable resin composition of the present invention has a small curing shrinkage and is excellent in high hardness and high scratch resistance, so that it can protect without affecting the film base material due to curling. . Furthermore, since the cut surface is not cracked or chipped when the film having the cured film is cut, the defective product rate at the time of cutting can be reduced. For this reason, the cured film of the active energy ray-curable resin composition of the present invention is effective as a protective layer for various film substrates. As this film base material, a pattern or an easily adhesive layer may be provided. In order to exhibit high hardness and high scratch resistance, the thickness of the cured coating is usually preferably 0.5 to 500 μm, more preferably 3 to 50 μm, and particularly preferably 4 to 30 μm.

The film having a cured coating of the active energy ray-curable resin composition of the present invention is usually 0.5% as the mass of the active energy ray-curable resin composition on the film substrate after drying the resin composition. ˜500 g / m ² (coat thickness 0.5 to 500 μm), preferably 3 to 50 g / m ² (coat thickness 3 to 50 μm), particularly preferably 4 to 30 g / m ² (coat thickness 4 to 30 μm) It can apply | coat, and after drying, it can obtain by irradiating an active energy ray and forming a cured film. In addition, when the mass after drying of the resin composition is less than 0.5 g / m ² , the hardness is not increased due to the influence of the substrate, and when it is 500 g / m ² or more, the deformation of the substrate is caused by the polymerization heat at the time of curing. Therefore, when forming a film thickness of 500 g / m ² or more, a device such as cooling is required.

  Examples of the material for the film substrate include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin resins such as polypropylene, polyethylene, and polymethylpentene-1; and cellulose resins such as triacetyl cellulose. Polystyrene resin, polyamide resin, polycarbonate resin, norbornene resin (for example, “Zeonor” manufactured by Nippon Zeon Co., Ltd.), modified norbornene resin (for example, “Arton” manufactured by JSR Corporation), cyclic olefin copolymer (for example, And “Apel” manufactured by Mitsui Chemicals, Inc.) Among these materials, triacetyl cellulose exhibits excellent adhesion with the cured film of the active energy ray-curable resin composition of the present invention. So preferable Further, a substrate made of these resins may be used by laminating two or more. These film substrate may be a sheet, the thickness of the film substrate, 20 to 500 [mu] m is preferred.

  Examples of the method for applying the active energy ray-curable resin composition of the present invention to a film substrate include gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, transfer coating, dip coating, and spinner coating. Wheeler coat, brush coating, solid coating with silk screen, wire bar coat, flow coat and the like. Also, printing methods such as offset printing and letterpress printing may be used. Among these, gravure coating, roll coating, comma coating, air knife coating, kiss coating, wire bar coating, and flow coating are preferable because a coating film having a more constant thickness can be obtained.

  Further, as a method of protecting the plastic molded body with the cured film of the active energy ray-curable resin composition of the present invention, the cured film is formed on the outermost surface before molding the plastic. There is also a method of sticking to the plastic surface so that the plastic is molded with the film. The film may be attached to the plastic surface by melting and bonding the film and the plastic at a high temperature or by using an adhesive. Moreover, you may affix on the molded object which shape | molded the plastics what carried out the secondary shaping | molding of the film in which the cured film was formed according to the external shape of this molded object.

  Further, as a method of providing a protective layer on an article formed of a material such as plastic or metal, there is a method of using a transfer film provided with a protective layer made of a cured coating of the active energy ray-curable resin composition of the present invention in advance. . In this case, the transfer material is attached to the surface of the article using a transfer method such as a hydraulic transfer method so that the protective layer of the transfer material becomes the outermost layer of the article after the transfer. When a pattern or a thin metal layer is provided on this transfer material, it is possible to impart design properties to the article and at the same time impart high hardness and high scratch resistance to the surface. Moreover, since the active energy ray-curable resin composition of the present invention has a small cure shrinkage, the curl of the transfer film using the resin composition is small, and the workability at the time of transfer is high.

  On the other hand, the optical sheet comprising the cured product of the active energy ray-curable resin composition of the present invention is cured by irradiation with active energy rays such as ultraviolet rays while the resin composition is in contact with the mold. And obtained by transferring the mold. Since the mold can be transferred as it is, it can be applied to an optical sheet such as a Fresnel lens sheet having a special shape. The optical sheet obtained by this method is very useful because it has little curling due to curing shrinkage and is excellent in high hardness and high scratch resistance, and is not damaged by contact with other articles. .

  When the active energy ray-curable resin composition of the present invention is irradiated with ultraviolet rays as an active energy ray, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a chemical lamp, black is used as a light generation source. Examples thereof include a light lamp, a mercury-xenon lamp, a short arc lamp, a helium / cadmium laser, an argon laser, sunlight, and an LED. Use of a flashing xenon-flash lamp is effective because the influence of heat on the film substrate is reduced.

  When irradiating an electron beam as an active energy ray, it is preferable to use an electron beam accelerator having an acceleration voltage of 30 to 300 kV. In addition, when the resin of the film base has an aromatic skeleton that is easily yellowed by an electron beam or when the resin is easily deteriorated by an electron beam, for example, a cellulose-based resin, a polyester-based resin, a polystyrene-based resin, a polyamide In the case of using a system resin, a polycarbonate system resin, or the like, when the acceleration voltage is set to 30 to 150 kV, yellowing or deterioration of the film base material can be prevented.

[Adhesive layer]
As the pressure-sensitive adhesive layer used in the present invention, a pressure-sensitive adhesive layer having a thickness of 5 to 20 μm is used. In the present invention, by setting the thickness of the pressure-sensitive adhesive layer to the thickness, sufficient adhesive strength with the object to be adhered can be expressed, and even when stress concentration occurs on the surface of the protective adhesive film, the protective adhesive Since the elasticity modulus of the whole film can be kept high, it is thought that the fall of the hardness of the hard-coat layer provided in the adhesive film surface can be suppressed.

  As the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer used in the present invention, various acrylic, rubber-based, and silicone-based pressure-sensitive resins can be used. Among them, an acrylic copolymer containing a repeating unit derived from an acrylate ester having an alkyl group having 2 to 14 carbon atoms as a repeating unit is preferable from the viewpoint of light resistance and heat resistance. Examples thereof include acrylic copolymers containing repeating units derived from n-butyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, ethyl acrylate and the like.

  Furthermore, as a repeating unit, a repeating unit derived from an acrylic ester having a polar group such as a hydroxyl group, a carboxyl group, or an amino group in the side chain and other vinyl monomers is contained in the range of 0.01 to 15% by mass. Is preferred. The acrylic copolymer can be obtained by copolymerization by a solution polymerization method, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, an ultraviolet irradiation method, or an electron beam irradiation method. The average molecular weight of the acrylic copolymer is preferably 400,000 to 1,400,000, and more preferably 600,000 to 1,200,000.

  Furthermore, it is preferable to add a crosslinking agent in order to increase the cohesive strength of the pressure-sensitive adhesive. As a crosslinking agent, an isocyanate type crosslinking agent, an epoxy type crosslinking agent, a chelate type crosslinking agent etc. are mentioned, for example. The addition amount of the crosslinking agent is preferably adjusted so that the pressure-sensitive adhesive layer has a gel fraction of 25 to 80%. A more preferable gel fraction is 40 to 75%. Among these, 50 to 70% is most preferable. When the gel fraction is less than 25%, the surface pencil hardness when the protective adhesive film is attached to the panel is lowered. On the other hand, if the gel fraction exceeds 80%, the adhesiveness decreases. The gel fraction is expressed as a percentage with respect to the original mass by immersing the cured adhesive layer in toluene, measuring the mass after drying of the insoluble matter left after standing for 24 hours, and measuring the mass.

  Furthermore, in order to improve the adhesive strength of the pressure-sensitive adhesive layer, a tackifier resin may be added. The tackifier resin to be added to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape of the present invention is a rosin resin such as rosin or an esterified product of rosin; a terpene resin such as a diterpene polymer or an α-pinene-phenol copolymer; Petroleum resins such as (C5) and aromatic (C9); styrene resins, phenol resins, xylene resins, and the like. In order to reduce the b * value of the pressure-sensitive adhesive layer after standing at 100 ° C. for 14 days to 6 or less, there are few unsaturated double bonds, esterified products of hydrogenated rosin and disproportionated rosin, aliphatic and aromatic series It is preferable to add petroleum tree or the like to the adhesive layer.

  In order to achieve both adhesion and yellowing resistance, it is preferable to use a highly disproportionated rosin ester, a polymerized rosin ester, and a petroleum resin in combination.

  As addition amount of tackifying resin, when an adhesive resin is an acrylic copolymer, it is preferable to add 10-60 mass parts with respect to 100 mass parts of acrylic copolymers. When attaching importance to adhesiveness, it is most preferable to add 20 to 50 parts by mass. When the adhesive resin is a rubber-based resin, it is preferable to add 80 to 150 parts by mass of the tackifier resin to 100 parts by mass of the rubber-based resin. In general, when the adhesive resin is a silicone resin, no tackifying resin is added.

  Various additives other than the above can be added to the adhesive. For example, in order to improve the adhesion to glass, a silane coupling agent can be added in the range of 0.001 to 0.005. In addition, plasticizers, softeners, fillers, pigments, flame retardants, and the like can be added.

The storage elastic modulus (20 ° C.) of the pressure-sensitive adhesive layer is preferably 1.0 × 10 ⁵ Pa or more, and more preferably 2.5 × 10 ⁵ Pa or more. If the pressure is less than 1.0 × 10 ⁵ Pa, the pressure-sensitive adhesive is soft, and thus when the laminate is 20 μm or more, the surface hardness of the protective film is significantly reduced.

[Protective adhesive film]
The protective adhesive film is a protective adhesive film in which at least the film substrate, the hard coat layer, and the adhesive layer are laminated. The protective adhesive film having such a configuration has high surface hardness and small deformation of the film due to curing shrinkage, and therefore can realize excellent surface hardness and deformation prevention that cannot be obtained by conventional protective adhesive films.

  By setting the thickness of the protective adhesive film to 150 μm or less, preferably 120 μm or less, the protective adhesive film is useful as a protective film provided on a display portion of a display device or the like for surface protection or glass scattering prevention. The thickness of the base film is preferably 38 to 100 μm. Further, the thickness of the hard coat layer is adjusted to a thickness of 5 to 25 μm in order to develop a hard coat function when the total thickness is 150 μm or less. Preferably it is 5-20 micrometers, More preferably, it is 5-10 micrometers. If the thickness is less than 5 μm, the surface pencil hardness decreases, and if it exceeds 25 μm, the adhesive coating becomes difficult due to curing shrinkage of the hard coat layer.

  The protective adhesive film of the present invention can achieve high surface hardness even when applied to an object to be applied via an adhesive layer, and preferably can achieve a hardness of 2H or more when attached to a glass plate.

[Production method]
The protective adhesive film of the present invention is formed by applying and curing the active energy ray-curable resin composition on a film substrate to form a hard coat layer, and then reverse the surface of the film substrate having the hard coat layer. It can be produced by forming an adhesive layer on the surface.

  In formation of an adhesive layer, it can form on a film base material by the method generally used for application | coating of an adhesive. The composition of the pressure-sensitive adhesive layer is directly applied to the base film and dried, or once applied on a separator (release sheet), dried, and then bonded to the base film.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these.

<Synthesis of urethane acrylate (A-1)>
In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 254 parts by mass of butyl acetate, 222 parts by mass of isophorone diisocyanate (hereinafter referred to as “IPDI”), 0.5 parts by mass of p-methoxyphenol, dibutyl After charging 0.5 parts by mass of tin diacetate and raising the temperature to 70 ° C., a mixture of pentaerythritol triacrylate (hereinafter referred to as “PE3A”) / pentaerythritol tetraacrylate (hereinafter referred to as “PE4A”) (mass ratio). 75/25 mixture) 795 parts by mass were added dropwise over 1 hour. After completion of the dropwise addition, the mixture is reacted at 70 ° C. for 3 hours, further reacted until the infrared absorption spectrum of 2250 cm −1 indicating the isocyanate group disappears, and then a urethane acrylate (A-1) / PE4A mixture (a mixture having a mass ratio of 80/20). Thus, a butyl acetate solution having a nonvolatile content of 80% by mass was obtained. The molecular weight of urethane acrylate (A-1) was 818.

<Synthesis of urethane acrylate (A-2)>
In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 161.8 parts by mass of butyl acetate, 222 parts by mass of IPDI, 0.5 parts by mass of p-methoxyphenol, and 0.5 parts by mass of dibutyltin diacetate After charging and heating to 70 ° C., 461.3 parts by mass of a butyl acetate solution of 80% non-volatile content of bis (acryloxyethyl) hydroxyethyl isocyanurate was added dropwise over 1 hour, and after completion of the addition at 70 ° C. for 3 hours. Reacted. Thereafter, 434 parts by mass of a PE3A / PE4A mixture (a mixture having a mass ratio of 75/25) was added dropwise over 1 hour, reacted at 70 ° C. for 3 hours after completion of the addition, and an infrared absorption spectrum of 2250 cm −1 indicating an isocyanate group. The reaction was carried out until it disappeared to obtain a urethane acrylate (A-2) / PE4A mixture (a mixture with a mass ratio of 87/13, a butyl acetate solution with a nonvolatile content of 80% by mass). The molecular weight of urethane acrylate (A-2) was 889.

<Synthesis of polymer (B)>
In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 250 parts by mass of glycidyl methacrylate (hereinafter referred to as “GMA”), 1.3 parts by mass of lauryl mercaptan, and methyl isobutyl ketone (hereinafter, “MIBK”). 1000 parts by mass and 7.5 parts by mass of 2,2′-azobisisobutyronitrile (hereinafter referred to as “AIBN”) were added and stirred at 90 ° C. over 1 hour while stirring under a nitrogen stream. The temperature was raised and reacted at 90 ° C. for 1 hour. Next, while stirring at 90 ° C., a mixed solution consisting of 750 parts by mass of GMA, 3.7 parts by mass of lauryl mercaptan, and 22.5 parts by mass of AIBN was dropped over 2 hours, and then reacted at 100 ° C. for 3 hours. Thereafter, 10 parts by weight of AIBN was charged, and further reacted at 100 ° C. for 1 hour, then heated to around 120 ° C. and reacted for 2 hours. Cool to 60 ° C., replace the nitrogen introduction tube with an air introduction tube, add 507 parts by mass of acrylic acid (hereinafter referred to as “AA”), 2 parts by mass of p-methoxyphenol, and 5.4 parts by mass of triphenylphosphine. After mixing, the reaction solution was bubbled with air, heated to 110 ° C., and reacted for 8 hours. Thereafter, 1.4 parts by mass of p-methoxyphenol was added, and after cooling to room temperature, MIBK was added so that the nonvolatile content was 50% by mass, and the polymer (B) (MIBK solution having a nonvolatile content of 50% by mass) was added. Obtained. In addition, the weight average molecular weight of the obtained polymer (B) was 31,000 (in terms of polystyrene by GPC), and the (meth) acryloyl group equivalent was 300 g / eq.

  Using the urethane acrylates (A-1) to (A-2) and the polymer (B) obtained above, an active energy ray-curable resin composition (main agent) was prepared as follows.

(Preparation of main agent 1)
35.2 parts by mass of ethyl acetate, 50.0 parts by mass of a butyl acetate solution (non-volatile content 80%) of a urethane acrylate (A-1) / PE4A mixture (mixture having a mass ratio of 87/13), dipentaerythritol hexaacrylate , "DPHA") 40.0 parts by mass, photoinitiator 1-hydroxycyclohexyl phenyl ketone (hereinafter referred to as "HCPK") 3.2 parts by mass, photoinitiator diphenyl-2,4,6-trimethylbenzoyl 0.8 parts by mass of phosphine = oxide (hereinafter referred to as “TPO”) was uniformly mixed to prepare main agent 1 (nonvolatile content: 65%).

(Preparation 2 of main ingredient)
35.2 parts by mass of ethyl acetate, 50.0 parts by mass of a butyl acetate solution (non-volatile content 80%) of urethane acrylate (A-2) / PE4A mixture (mixture of mass ratio 87/13), 40.0 parts by mass of DPHA, light An initiator HCPK (3.2 parts by mass) and a photoinitiator TPO (0.8 parts by mass) were uniformly mixed to prepare a main agent 2 (nonvolatile content: 65%).

(Preparation of main agent 3)
28.2 parts by mass of ethyl acetate, 16.0 parts by mass of MIBK solution of polymer (B) (non-volatile content 50%), butyl acetate of urethane acrylate (A-2) / PE4A mixture (mixture of mass ratio 87/13) 45.0 parts by mass of solution (non-volatile content: 80%), 36.0 parts by mass of DPHA, 3.2 parts by mass of photoinitiator HCPK, and 0.8 parts by mass of photoinitiator TPO were mixed uniformly, and main agent 3 (non-volatile content: 65%) Was prepared.

(Preparation of main agent 4)
5.2 parts by mass of ethyl acetate, 80.0 parts by mass of MIBK solution of polymer (B) (non-volatile content 50%), 40.0 parts by mass of DPHA, 3.2 parts by mass of photoinitiator HCPK, 0.8 parts by mass of photoinitiator TPO Parts were mixed uniformly to prepare main agent 4 (nonvolatile content: 65%).

(Preparation of hard coat material 1)
100 parts by weight of the main agent 1 (nonvolatile content 65% by mass) prepared in Preparation 1 of the main agent, 2 parts by mass of reactive fluorine antifouling agent having a turbidity of 13% (OPTOOL DAC; manufactured by Daikin Industries, Ltd., 20% by mass nonvolatile content) Were mixed with propylene glycol monomethyl ether (hereinafter referred to as “PGME”) so that the nonvolatile content was 40% by mass to obtain a hard coat material (1).

(Preparation of hard coat material 2)
100 parts by mass of main agent 2 (nonvolatile content: 65% by mass) prepared in Preparation 2 of main agent, 2 parts by mass of reactive fluorine antifouling agent having a turbidity of 16% (Optool DAC; manufactured by Daikin Industries, Ltd., nonvolatile content: 20% by mass) Were uniformly mixed and then diluted with PGME so that the non-volatile content was 40% by mass to obtain a hard coat material (2).

(Preparation of hard coat material 3)
100 parts by mass of main agent 3 (nonvolatile content 65% by mass) prepared in Preparation 3 of main agent, 2 parts by mass of reactive fluorine antifouling agent with 10% turbidity (Optool DAC; manufactured by Daikin Industries, Ltd., nonvolatile content 20% by mass) Were uniformly mixed and then diluted with PGME so that the non-volatile content was 40% by mass to obtain a hard coat material (3).

(Preparation of hard coat material 4)
SUMIDUR N3300 (hexamethylene diisocyanate cyclic trimer, manufactured by Sumitomo Bayer Urethane Co., Ltd., NCO group content 21.9% by mass) is added to a 1 L three-necked flask equipped with a dropping funnel, condenser, thermometer and stirrer. Is dissolved in 165 g of HCFC225, 0.4 g of dibutyltin dilaurate (first grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) is added, and DEMNUM (CF ₃ CF ₂ O— (CF ₂ ) is added for 4.5 hours with stirring at room temperature in air. dissolved _{CF 2 CF 2 O) 10.9 -CF} 2 CF 2 CH 2 OH, purity 86.9% and 19F-NMR, PFPE monoalcohol identified from IH-NMR, the Daikin Industries, Ltd.) 244 g in HCFC225 160 g The solution was added dropwise and stirred at room temperature for 6 hours. The mixture was heated to 40 to 45 ° C., and 24.4 g of hydroxyethyl acrylate was added dropwise over 10 minutes, followed by stirring for 3 hours. The absorption of NCO was confirmed to be completely disappeared by IR (the disappearance of —CF ₃ —CH ₂ OH was also confirmed from ¹⁹ F-NMR of the product), and the 50 wt% HCFC225 of the perfluoropolyether urethane acrylate composition was confirmed. A solution was obtained. The obtained perfluoropolyether urethane acrylate composition has a turbidity of 3%. A hard coat material (4) was obtained in the same manner as in Preparation 2 of the hard coat material, except that 2 parts by mass of the obtained composition was changed to a reactive fluorine antifouling agent (OPTOOL DAC; manufactured by Daikin Industries, Ltd.). It was.

(Preparation of hard coat material 5)
100 parts by mass of main agent 3 (nonvolatile content 65% by mass) prepared in Preparation 3 of main agent, 2 parts by mass of reactive fluorine antifouling agent with 54% turbidity (Optool DAC; manufactured by Daikin Industries, Ltd., nonvolatile content 20% by mass) Were mixed uniformly, and then diluted with PGME so that the non-volatile content was 40% by mass to obtain a hard coat material (5).

(Preparation of hard coat material 6)
100 parts by mass of main agent 3 (non-volatile content 65% by mass) prepared in Preparation 3 of main agent, 2 parts by mass of reactive fluorine antifouling agent with 25% turbidity (OPTOOL DAC; manufactured by Daikin Industries, Ltd., non-volatile content 20% by mass) Were uniformly mixed and then diluted with PGME so that the non-volatile content was 40% by mass to obtain a hard coat material (6).

(Preparation of hard coat material 7)
100 parts by mass of main agent 3 (nonvolatile content 65% by mass) prepared in Preparation 3 of main agent, 2 parts by mass of reactive fluorine antifouling agent having a turbidity of 31% (Optool DAC; manufactured by Daikin Industries, Ltd., 20% by mass nonvolatile content) Were uniformly mixed, and then diluted with PGME so that the nonvolatile content was 40% by mass to obtain a hard coat material (7).

(Preparation of hard coat material 8)
100 parts by mass of main agent 4 (nonvolatile content 65% by mass) prepared in Preparation 4 of main agent, 2 parts by mass of reactive fluorine antifouling agent with 10% turbidity (Optool DAC; manufactured by Daikin Industries, Ltd., 20% by mass nonvolatile content) Were uniformly mixed and then diluted with PGME so that the non-volatile content was 40% by mass to obtain a hard coat material (8).

(Preparation of hard coat film)
The hard coat materials (1) to (8) obtained above are made of polyethylene terephthalate (hereinafter referred to as “PET”) film base (“Cosmo Shine A4300 # 100” manufactured by Toyobo Co., Ltd., thickness: 100 μm). Is applied to one side using a wire bar (# 4), heated at 60 ° C. for 1 minute, and then exposed to an ultraviolet irradiation device (“GS30 type UV irradiation device” manufactured by Nihon Battery Co., Ltd.), lamp: 120 W / cm under an air atmosphere. Hard coat films (1) to (8) having a cured coating with a thickness of 10 μm were obtained by irradiating with ultraviolet rays using two metal halide lamps, lamp height: 20 cm, irradiation light quantity: 0.5 J / cm 2.

(Preparation of adhesive layer)
After applying a DIC adhesive PPS1030B to a release liner in which a silicone compound release layer is formed on the non-hard coat treated surfaces of the hard coat films (1) to (8), drying at 90 ° C. for 90 seconds and then drying A pressure-sensitive adhesive layer having a thickness of 10 μm was formed.

Example 1
The surface having no hard coat layer of the hard coat film (1) obtained above is subjected to a corona treatment apparatus and surface-treated so as to have a surface tension of 55 dynes / cm (unit confirmation required),
Adhesive layer A is bonded at a pressure of 4 kg / cm, cured at 40 ° C. for 2 days, and then 93 μm thick
A protective adhesive film (1) was obtained.

(Examples 2 to 4)
The hard coat film (1) in Example 1 was replaced with the hard coat film (2) to
Protective adhesive films (2) to (4) were obtained in the same manner except for (4).

(Comparative Examples 1-4)
The hard coat film (1) in Example 1 above, the hard coat film (5) to
Protective adhesive films (5) to (8) were obtained in the same manner except for (8).

(Measurement of turbidity of reactive fluorine antifouling agent)
A 1 mm cell was filled with a reactive fluorine antifouling agent, and the turbidity was measured. The turbidity was measured with a turbidimeter NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with the above JIS K7136.

(Evaluation of coating film defects of hard coat film)
After visually counting the number of coating film defects in the hard coat film 5 cm × 5 cm obtained above, it was evaluated according to the following criteria.
○: 0 coating film defects Δ: 1 to 10 coating film defects ×: 10 or more coating film defects

(Evaluation of fine coating film defects of hard coat film)
After visually counting the number of fine coating film defects in the hard coat film 10 cm × 10 cm obtained above, it was evaluated according to the following criteria. The fine coating film defect is a coating film defect in the coating film that is not completely repelled but is slightly repelled.
○: 0 coating film defects ×: 10 or more coating film defects

(Fingerprint wiping evaluation)
An index finger fingerprint was attached to the surface of the hard coat film obtained above. The number of times that the fingerprint was wiped off with Bencott S-2 (manufactured by Asahi Kasei Fibers Co., Ltd.) was measured. The evaluation criteria are as follows.
○: Number of wipes 1 to 10 times Δ: Number of wipes 11 to 20 times ×: Number of wipes 30 or more

(Measurement of surface pencil hardness)
The hard coat film obtained above and the protective adhesive film obtained in the above examples and comparative examples were attached to a glass plate, and the surface pencil hardness was measured according to JIS K 5600-5-4 (1999 edition). Based on the regulations, measurement was performed using a pencil scratch tester (manual type) for coating film manufactured by Imoto Seisakusho Co., Ltd. In the test of the hard coat film alone, the four corners of the film were fixed to a glass plate with a cellophane tape and measured.

(Measurement of weight average molecular weight)
In addition, the measurement of the weight average molecular weight (polystyrene conversion) by GPC in this invention was performed on condition of the following using the HLC8220 system by Tosoh Corporation.
Separation column: 4 TSKgelGMH _HR- N manufactured by Tosoh Corporation are used. Column temperature: 40 ° C. Moving layer: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow rate: 1.0 ml / min. Sample concentration: 1.0% by weight. Sample injection volume: 100 microliters. Detector: differential refractometer.

  The evaluation results are shown in Table 1.

  From the evaluation results shown in Table 1, the hard coat films of the present invention of Examples 1 to 4 were free from coating film defects and fine coating film defects, and had a suitable coating film appearance. In addition, it was confirmed that the surface hardness was high, the surface was not damaged, and the antifouling property and fingerprint wiping performance of the surface were good. On the other hand, in the hard coat films of Comparative Example 1 and Comparative Examples 3 to 4, many coating film defects and fine coating film defects were observed, and a good appearance was not obtained. Moreover, although the hard coat film of Comparative Example 2 had no coating film defects, fine coating film defects were observed and a good appearance was not obtained.

Claims (8)

  An active energy ray-curable resin composition for a film protective layer comprising an active energy ray-curable resin composition and a reactive fluorine antifouling agent, wherein the reactive fluorine antifouling agent has a turbidity of less than 20% And a reactive fluorine antifouling agent comprising a perfluoropolyether having one active hydrogen and a monomer having an active hydrogen and a carbon-carbon double bond. Active energy ray-curable resin composition for use.   The active energy ray-curable resin composition is a urethane acrylate (a reaction product of polyisocyanate (a1) and an acrylate (a2) having one hydroxyl group and two or more (meth) acryloyl groups in one molecule) A) and a (meth) acrylate polymer (b1) having a reactive functional group in the side chain are reacted with an α, β-unsaturated compound (b2) having a functional group capable of reacting with the reactive functional group. The active energy ray-curable resin composition for a film protective layer according to claim 1, which is an active energy ray-curable resin composition comprising a polymer (B) having a (meth) acryloyl group.   The active energy ray-curable resin composition for a film protective layer according to claim 2, wherein the polyisocyanate (a1) is an aliphatic diisocyanate and / or an alicyclic diisocyanate.   The active energy ray-curable resin composition for a film protective layer according to claim 2 or 3, wherein the acrylate (a2) is an acrylate having one hydroxyl group and 3 to 5 (meth) acryloyl groups in one molecule.   The active energy for a film protective layer according to claim 2, 3 or 4, wherein the polymer (B) is a reaction product obtained by reacting a glycidyl (meth) acrylate polymer with an α, β-unsaturated carboxylic acid. A linear curable resin composition.   6. The active energy ray curing for film protective layer according to claim 5, wherein the polymer (B) has a weight average molecular weight of 5,000 to 80,000 and a (meth) acryloyl group equivalent of 100 to 300 g / eq. Mold resin composition.   Film protection as described in any one of Claims 1-6 which contains radically polymerizable monomers (C) other than said (A) and (B) in the said active energy ray hardening-type resin composition further. Active energy ray-curable resin composition for layer.   The protection which provided the hard-coat layer which consists of an active energy ray hardening-type resin composition for film protective layers as described in any one of Claims 1-7 in the single side | surface of a base film, and provided the adhesive layer in the opposite surface Adhesive film.