JP5472685B2 - Anti-scattering adhesive sheet - Google Patents

Description

  The present invention relates to an anti-scattering adhesive sheet that prevents scattering of a screen panel provided on the surface of a display device such as a liquid crystal panel or an EL display.

  Small electronic terminals such as mobile personal computers, electronic notebooks, and mobile phones are becoming smaller and thinner. In recent years, image display devices such as liquid crystal display devices that are used in such devices are increasingly required to be lighter, thinner, and smaller. ing. In addition, these small electronic terminals are often provided with a protective screen panel to prevent the image display device from being damaged or damaged. Particularly, the small electronic terminals are capable of touch input due to the multi-functionalization of the small electronic terminals. With the increase, there is an increasing demand for preventing damage and breakage.

  As a screen panel, a panel made of resin such as acrylic or polycarbonate has been used conventionally, but the resin panel lacks rigidity, so when the panel part is pressed with a finger, the display device is deformed and the display is defective. Or the screen panel is deformed in a high-temperature and high-humidity environment, and the image display panel partially sticks.

  For such a problem, for example, a glass panel has begun to be adopted as a highly rigid screen panel. However, when a glass panel is used for a small electronic terminal that is highly demanded of thinning, cracking may occur due to the thinning of the panel. Therefore, a protective adhesive film with a scattering prevention function is attached to the surface of the panel. Is being considered.

  As such a protective adhesive film, a film having a hard coat layer is used to prevent scratches and damage on the surface, for example, a protective adhesive film that realizes a high surface hardness by a specific layer configuration is disclosed. (See Patent Document 1). Since the protective adhesive film has a specific layer structure, even if it is thin, there is little decrease in surface hardness due to the adhesive layer, so that it is possible to realize a thin screen panel that is hardly damaged.

  The protective adhesive film has a suitable surface protection function due to the hard coat layer having a high hardness. However, cracks and breakage may occur in the hard coat portion during punching. In particular, processing of fine shapes has been widely performed by improving the workability of glass panels. However, in accordance with such fine processing of glass panels, for example, a fine shape such as a hole with a diameter of about several millimeters. When processed, a large amount of cracks may occur in the hard coat portion. When cracks occur in the hard coat layer as described above, the durability of the heart coat layer is remarkably reduced, so that scratches and peeling of the hard coat layer are likely to occur, and the visibility of the image display portion may be reduced.

JP 2008-095064 A

  The problem to be solved by the present invention is laminated with a glass panel or the like through an adhesive layer, and has excellent surface protection performance that is less likely to be damaged when a thin panel is formed, An object of the present invention is to provide an anti-scattering pressure-sensitive adhesive sheet in which cracks are unlikely to occur in a hard coat layer during processing of a fine shape.

  The anti-scattering pressure-sensitive adhesive sheet of the present invention has a high hardness by combining a hard coat pressure-sensitive adhesive film having a specific range of Martens hardness with a protective film and a release film so as to have a specific total thickness. Although it has a hard coat layer, cracks in the hard coat layer during punching can be made difficult to occur, and it is suitably used for fine shape processing.

That is, the present invention relates to a hard coat pressure-sensitive adhesive film provided with a pressure-sensitive adhesive layer on one side of a hard coat film having a hard coat layer on one side of the film substrate, and a protective film provided on the hard coat layer surface of the hard coat pressure-sensitive adhesive film. And an anti-scattering adhesive sheet comprising a release film provided on the surface of the adhesive layer of the hard coat adhesive film,
The pencil hardness of the hard coat layer surface of the hard coat film is 3H or more,
The Martens hardness is 240 to 300 N / mm ² measured by sticking the hard coat pressure-sensitive adhesive film on glass, and pressing a Vickers indenter with an edge angle of 136 ° into the hard coat layer surface with a load of 15 mN, and the total thickness Is an anti-scattering pressure-sensitive adhesive sheet characterized by having a thickness of 250 μm or less.

  The anti-scattering pressure-sensitive adhesive sheet of the present invention has the above-described configuration, so that the surface is hardly damaged and cracks are hardly generated in the hard coat layer during processing. For this reason, the damage at the time of use and peeling of a hard-coat layer can be prevented, and the screen panel and small electronic terminal which hold | maintained the visibility at the time of use suitably are realizable.

[Film substrate]
As the film substrate used in the present invention, various resin film substrates generally used as a substrate for pressure-sensitive adhesive sheets can be used. For example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetyl Cellulose, triacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyether ether ketone, polyether sulfone, poly Examples of the resin film include ether imide, polyimide, fluorine resin, nylon, and acrylic resin.
As the film substrate, a film substrate having an elastic modulus of 3 to 7 GPa is preferably used. When the elastic modulus is within this range, deformation of the film base material hardly occurs when the hard coat pressure-sensitive adhesive film is formed, and it becomes easy to suppress a decrease in surface hardness when the hard coat pressure-sensitive adhesive film is formed. Moreover, since the softness | flexibility of a film base material can be ensured, the tracking to a gentle curved surface becomes easy at the time of affixing a hard coat adhesive film.

  The film substrate used in the present invention may be a substrate composed only of the resin film, but a film substrate provided with a thin primer layer on the resin film in order to improve adhesion to the hard coat layer. It may be. In addition, for the purpose of improving the adhesion with the hard coat layer and the pressure-sensitive adhesive layer, surface roughening treatment such as sandblasting or solvent treatment, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone Surface treatments such as ultraviolet irradiation treatment and surface oxidation treatment can be performed.

  Moreover, it is also preferable to add an antistatic agent as a compounding material to the resin film to impart an antistatic function. As an antistatic agent, nonoxy-based polyoxyethylene alkyl ether, polyoxyethylene alkylphenol, polyoxyethylene alkylamine, polyoxyethylene alkylamide, fatty acid polyethylene glycol ester, fatty acid sorbitan ester, polyoxyethylene fatty acid sorbitan ester, fatty acid glycerin Examples thereof include esters and alkylpolyethyleneimines. Examples of the cationic system include alkylamine salts, alkyl quaternary ammonium salts, and alkyl imidazoline derivatives. An acrylate compound having ethylene oxide as a skeleton can also be used. Polyaniline, polypyrrole, polythiophene, poly3,4-ethylenedioxythiophene, and derivatives thereof can be used as the conductive polymer. As the metal oxide, antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), aluminum-doped zinc oxide, antimony suboxide, or the like can be used. In addition, an ion conduction type antistatic agent in which metal ions such as lithium ions are mixed can also be used.

[Hard coat layer]
When the hard coat layer used in the present invention is laminated with the film base material to form a hard coat film, the pencil hardness of the hard coat layer surface is 3H or more, and an adhesive layer is provided on the hard coat film. When the resulting hard coat adhesive film is formed, the Martens hardness measured by pushing a Vickers indenter with a corner angle of 136 ° into the hard coat adhesive film surface with a load of 15 mN is 240 to 300 N / mm ^2. Any hard coat layer may be used, and those made of cured hard coat agents can be used.

  As the hard coat agent for forming such a hard coat layer, an active energy ray-curable resin composition can be suitably used. Among them, polyisocyanate (a1), one hydroxyl group in one molecule, and two or more The reactive functional group is added to the urethane acrylate (A) which is an addition reaction product with the acrylate (a2) having a (meth) acryloyl group and the (meth) acrylate polymer (b1) having a reactive functional group in the side chain. And a polymer (B) having a (meth) acryloyl group obtained by reacting an α, β-unsaturated compound (b2) having a functional group capable of reacting with the compound (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.

  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 weight per 100 parts by weight 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.

  The blending amount of the urethane acrylate (A) in 100 parts by weight of the resin component in the resin composition is preferably 5 to 90 parts by weight, more preferably 10 to 70 parts by weight, and even more preferably 10 to 60 parts by weight. . 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. Moreover, as a functional group which the (alpha), (beta)-unsaturated compound (b2) which can react with these reactive functional groups has, an isocyanate group, a carboxyl group, an acid halide group, a hydroxyl group, an epoxy group etc. are 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 other (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.

  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 glycerin 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 (eg, 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.

  The amount of the radical polymerizable monomers (C) blended in the resin composition is 10 to 10 parts by weight based on 100 parts by weight of the total amount of the urethane acrylate (A) and the polymer (B). 300 parts by weight is preferred. Moreover, 20-200 weight part is more preferable and 20-100 weight part is further 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 weight part is preferable with respect to 100 weight part of total amounts of the said urethane acrylate (A) and a polymer (B). 10 to 50 parts by weight 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 weight parts of the resin components in the resin composition is (A) :( E) = 10: 90- 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 weight or less based on 100 parts by weight of the total amount of the urethane acrylate resin (A) and the polyester acrylate resin (E). The amount is preferably 12 parts by weight or less.

  For the purpose of enhancing the surface properties of the protective layer such as surface slipperiness, stain resistance, and fingerprint resistance, the above active energy ray-curable resin composition has a fluorocarbon chain, a dimethylsiloxane chain, and 12 or more carbon atoms. It is preferable to add an additive comprising a composition containing a compound having a hydrocarbon chain. The additive amount of the additive containing a compound having a fluorocarbon chain, a dimethylsiloxane chain and a hydrocarbon chain having 12 or more carbon atoms is preferably 0.05 to 5% by weight with respect to the active energy ray-curable resin composition. 0.1 to 2% by weight is more preferable.

  Among these, a compound containing a fluorocarbon chain can be suitably used because it is excellent in surface properties such as stain resistance, fingerprint resistance, and magic wiping property. Especially, it is preferable that they are the triisocyanate which trimerized diisoacinate, the perfluoropolyether compound which has a hydroxyl group in the terminal of at least one, and the monomer which has a hydroxyl group and a carbon-carbon double bond.

  Diisocyanates used to obtain triisocyanates include diisocyanates in which isocyanate groups are aliphatically bonded, such as hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate; Examples of the group-bonded diisocyanates include tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolidine diisocyanate, and naphthalene diisocyanate.

The perfluoropolyether compound having a hydroxyl group at at least one end, as repeating _{units, -C 3 F 6 O -,} - C 2 F 4 O -, - a repeating unit of the _CF 2 O-like, and its The total number of repeating units is 1 to 200, and at least one terminal has —CH ₂ OH, —CH ₂ — (OCH ₂ CH ₂ ) m—OH, —CH ₂ OCH ₂ CH (OH) CH ₂ OH. When a hydroxyl group is contained by a group such as one and only one of these is a hydroxyl group-containing group, a compound in which the other end is a fluorine atom can be used. The molecular weight of the perfluoropolyether compound is preferably a molecular weight having a weight average molecular weight of about 500 to 10,000.

  The monomer having a hydroxyl group and a carbon-carbon double bond is particularly preferably a (meth) acrylate monomer having a hydroxyl group or a vinyl monomer having a hydroxyl group. Examples of such monomers include hydroxyethyl (meth) acrylate, aminoethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl ( (Meth) acrylate), allyl alcohol, styrylphenol and the like.

  In the protective adhesive film of the present invention, since it is used for a small electronic terminal such as a mobile phone, a film particularly excellent in anti-fingerprint adhesion and repetitive fingerprint wiping properties is preferably used, and is represented by the following structural formula. Isocyanurate type perfluoropolyether urethane acrylate is most preferred.

In the formula, n is an integer of 1 to 20.

  Moreover, the composition containing the compound which has a dimethylsiloxane chain can be preferably used from being excellent in the surface slipperiness etc. As the compound, for example, an additive containing a compound composed of an acrylate or the like in which a (meth) acryloyl group is introduced into a dimethylsiloxane skeleton through a spacer composed of an alkylene group such as an ethylene group or a polypropylene group is preferably used. it can. Examples of these acrylates include BYK-UV3500 and BYK-UV3570 manufactured by Big Chemie, Ebecryl 1360 manufactured by Daicel UCB Corporation, and the like.

[Hard coat film]
The hard coat film used in the present invention has a hard coat layer composed of the above hard coat agent on at least the film base, and the pencil hardness of the hard coat layer surface of the hard coat film is at least 3H, preferably 3H. ~ 4H. When the glass panel and the hard coat film are laminated with the hard coat film having a surface hardness within the above range via the pressure-sensitive adhesive layer, the surface pencil hardness is hardly lowered.

  The hard coat film used in the present invention can be produced by applying a hard coat agent on a film substrate and curing it.

  Examples of methods for applying a hard coating agent to a film substrate include gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, transfer coating, dip coating, spinner coating, wheeler coating, brush coating, and silk. Examples thereof include a solid coat using a screen, a wire bar coat, and a flow coat. 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.

  Curing of the hard coating agent may be appropriately performed according to the hard coating agent to be used, but when the active energy ray-curable resin composition is used as the hard coating agent, the activity of light, electron beam, radiation, etc. What is necessary is just to harden with an energy ray. Specific energy sources or curing devices include, for example, germicidal lamps, ultraviolet fluorescent lamps, carbon arc, xenon lamps, high pressure mercury lamps for copying, medium or high pressure mercury lamps, ultrahigh pressure mercury lamps, electrodeless lamps, metal halide lamps, natural light, etc. Or an electron beam using a scanning type or curtain type electron beam accelerator.

  Among these, ultraviolet rays are particularly preferable, and irradiation in an inert gas atmosphere such as nitrogen gas is preferable in terms of increasing the polymerization efficiency. Further, if necessary, heat may be used as an energy source and heat treatment may be performed after curing with active energy rays.

  When ultraviolet rays are used as a device for irradiating active energy rays, the light source is a low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, electrodeless lamp (fusion lamp), chemical lamp, black light. Lamps, mercury-xenon lamps, short arc lamps, helium / cadmium lasers, argon lasers, sunlight, LEDs and the like can be mentioned. In addition, when the active energy ray-curable resin composition used in the present invention is applied to a film substrate to form a cured film, a flashing xenon-flash lamp is used. This is preferable because the influence of heat can be reduced.

[Adhesive layer]
For the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer used in the present invention, known acrylic, rubber-based, and silicone-based pressure-sensitive resins can be used. Among them, an acrylic copolymer containing a (meth) acrylate monomer having an alkyl group having 2 to 14 carbon atoms as a repeating unit as a main monomer component is preferable from the viewpoint of light resistance and heat resistance.

  Specific examples of the (meth) acrylate monomer having 2 to 14 carbon atoms include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, and n-hexyl. Acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, isodecyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec -Butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, n-o Chill methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, isononyl methacrylate, isodecyl methacrylate, lauryl methacrylate and the like.

  Among them, an alkyl methacrylate having an alkyl side chain having 4 to 9 carbon atoms or an alkyl acrylate having an alkyl side chain having 4 to 9 carbon atoms is preferable, and an alkyl acrylate having an alkyl side chain having 4 to 9 carbon atoms. Is more preferable. Of these, n-butyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, and ethyl acrylate are particularly preferable. By using an alkyl (meth) acrylate having an alkyl side chain with a carbon number within the range, it is easy to ensure a suitable adhesive force.

  The content of the (meth) acrylate having 2 to 14 carbon atoms in the monomer constituting the acrylic copolymer used in the pressure-sensitive adhesive layer of the present invention is preferably 90 to 99% by weight, More preferably, it is 96 wt%. It becomes easy to ensure suitable adhesive force by setting it as content of the said C2-C14 (meth) acrylate in the carboxyl group-containing (meth) acrylic acid ester copolymer of the said range.

  Acrylic copolymers further contain (meth) acrylic acid ester monomers and other vinyl monomers having polar groups such as hydroxyl, carboxyl and amino groups in the side chain as monomer components. It is preferable to do.

  Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, hydroxypropyl (meth) acrylate, and caprolactone-modified (meth) acrylate. Hydroxyl group-containing (meth) acrylates such as polyethylene glycol mono (meth) acrylate and polypropylene glycol (meth) acrylate can be used, among which 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxy It is preferred to use hexyl (meth) acrylate as a copolymerization component.

  As the monomer having a carboxyl group, acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, (meth) acrylic acid dimer, ethylene oxide-modified succinic acid acrylate, etc. can be used. It is preferable to use it as a copolymerization component.

  Examples of the monomer having a nitrogen atom include N-vinyl-2-pyrrolidone, N-vinylcaprolactam, acryloylmorpholine, acrylamide, N, N-dimethylacrylamide, and 2- (perhydrophthalimido-N-yl) ethyl acrylate. An amide group-containing vinyl monomer can be used, and among these, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, and acryloylmorpholine are preferably used as the copolymerization component.

  Examples of vinyl monomers having other polar groups include vinyl acetate, acrylonitrile, maleic anhydride, itaconic anhydride and the like.

  The content of the monomer having a polar group is preferably 0.1 to 20% by weight of the monomer component constituting the acrylic copolymer, more preferably 1 to 13% by weight, More preferably, it is 1.5 to 8% by weight. By containing in the said range, it is easy to adjust the cohesive force, holding force, and adhesiveness of an adhesive to a suitable range.

  The weight average molecular weight Mw of the acrylic copolymer used for the pressure-sensitive adhesive layer is preferably 400,000 to 1,400,000, and more preferably 600,000 to 1,200,000. When the weight average molecular weight Mw of the acrylic copolymer is within the above range, it is easy to adjust the adhesive force to a specific range, and when the hard coat adhesive film is formed, the load on the film surface is suitably reduced. Cheap.

The weight average molecular weight Mw of the acrylic copolymer can be measured by gel permeation chromatograph (GPC). More specifically, as a GPC measurement device, “SC8020” manufactured by Tosoh Corporation can be used to measure and obtain the following GPC measurement conditions based on polystyrene conversion values.
(GPC measurement conditions)
Sample concentration: 0.5% by weight (tetrahydrofuran solution)
Sample injection volume: 100 μL
・ Eluent: Tetrahydrofuran (THF)
・ Flow rate: 1.0 mL / min
Column temperature (measurement temperature): 40 ° C
Column: “TSKgel GMHHR-H” manufactured by Tosoh Corporation
・ Detector: Differential refraction

  Further, in order to increase the cohesive strength of the pressure-sensitive adhesive layer, it is preferable to add a crosslinking agent in 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 of the original weight by measuring the weight after drying the insoluble content remaining after 24 hours of immersion in the adhesive layer after curing.

  Furthermore, in order to improve the adhesive strength of the pressure-sensitive adhesive layer, a tackifier resin may be added. The tackifying resin to be added to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape of the present invention is an acrylic copolymer, a rosin resin such as rosin or an esterified rosin; a terpene such as a diterpene polymer or an α-pinene-phenol copolymer. Examples of such resins include: petroleum resins such as aliphatic (C5) and aromatic (C9); styrene resins, phenolic 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 the addition amount of the tackifier resin, when the pressure-sensitive adhesive resin is an acrylic copolymer, it is preferable to add 10 to 60 parts by weight with respect to 100 parts by weight of the acrylic copolymer. When importance is attached to adhesiveness, it is most preferable to add 20 to 50 parts by weight. Further, when the pressure-sensitive adhesive resin is a rubber-based resin, it is preferable to add 80 to 150 parts by weight of the tackifier resin with respect to 100 parts by weight of the rubber-based resin. In general, when the adhesive resin is a silicone resin, no tackifying resin is added.

  In addition to the above, known and commonly used additives 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 pressure-sensitive adhesive layer can be formed on the film substrate by a method generally used for application of the pressure-sensitive adhesive sheet. The composition of the pressure-sensitive adhesive layer is directly applied to the substrate film and dried, or once applied onto the release film, dried, and then bonded to the substrate film.

The storage elastic modulus (20 ° C.) of the pressure-sensitive adhesive layer is preferably 2.0 × 10 ⁵ Pa or more, and more preferably 2.5 × 10 ⁵ Pa or more. By setting the pressure to 2.0 × 10 ⁵ Pa or more, the pressure-sensitive adhesive does not become too soft, and even when a pressure-sensitive adhesive layer is provided, a protective pressure-sensitive adhesive film having a high surface hardness can be realized and the adhesive force can be easily adjusted.

  As the pressure-sensitive adhesive layer used in the present invention, a pressure-sensitive adhesive tape formed by providing a pressure-sensitive adhesive layer with a thickness of 10 μm on a PET substrate having a thickness of 100 μm is applied to a glass plate in an environment of a temperature of 23 ° C. and a relative humidity of 50% RH. On the other hand, 180 ° peeling adhesion at a peeling speed of 300 mm / min after leaving for 2 hours in a 60 ° C. and 90% environment using a 2 kg roller is 4 N or more / 25 mm. It is preferable to use an adhesive layer. In the present invention, when the adhesive layer is peeled off by 180 ° and the adhesive strength is set to the adhesive strength, even if a hard coat pressure-sensitive adhesive film is used for a long time, the film end is not lifted or peeled off. it can.

[Hard coat adhesive film]
The hard coat pressure-sensitive adhesive film used in the present invention has a structure in which a pressure-sensitive adhesive layer is provided on a hard coat film having a hard coat layer on one surface of the above-mentioned film base material, and is stuck on a glass surface. Further, it is a hard coat adhesive film having a Martens hardness of 240 to 300 N / mm ² measured by pushing a Vickers indenter having a ridge angle of 136 ° with a load of 15 mN.

  In the present invention, it is desirable that the hard coat pressure-sensitive adhesive film to be attached to the display surface or the like has a thickness of at least 150 μm or less because of problems in appearance and peeling due to the film edge portion being caught.

  For this reason, the film base material needs to be a thin base material, and from the viewpoint that lamination with other layers is required, the thickness of the film base material is preferably at least 100 μm or less, 38 to 100 μm. It is preferable to use a film base material, more preferably 50 to 100 μm. By setting it as the said thickness range, a film base material cannot change easily and it becomes easy to suppress the fall of the surface hardness of a hard coat adhesive film.

  The thickness of the hard coat layer in the hard coat pressure-sensitive adhesive film is preferably 5-5 in order to easily exhibit a hard coat function even when a hard coat pressure-sensitive adhesive film having a thickness of 150 μm or less is formed. The thickness is preferably 25 μm. More preferably, it is 5-20 micrometers, More preferably, it is 5-10 micrometers. By setting the thickness of the hard coat within the above range, it is easy to suppress a decrease in surface pencil hardness of the hard coat adhesive film and curing shrinkage of the hard coat layer.

  Also, by setting the thickness of the pressure-sensitive adhesive layer in the hard coat pressure-sensitive adhesive film to 5 to 20 μm, even when stress concentration occurs on the surface of the hard coat pressure-sensitive adhesive film, the elastic modulus of the entire hard coat pressure-sensitive adhesive film is kept high. Therefore, it is considered that the decrease in the hardness of the hard coat layer can be suppressed.

  The hard coat pressure-sensitive adhesive film used in the present invention easily secures particularly suitable hardness by the above-exemplified configuration, and can have a surface pencil hardness of 2H or more, preferably 2H to 3H even in the state having an adhesive layer. . Further, while being a thin thickness, preferably 150 μm or less, it is possible to prevent scratches and deformation at the time of stress concentration, and it is easy to achieve both high hardness and rigidity and suitable workability.

[Protective film]
The protective film used in the present invention is not particularly limited, and a known protective film may be used.

  As the structure of the protective film, a substrate provided with a pressure-sensitive adhesive layer is preferably used. Examples of the base material include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polyvinyl chloride film, and 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 film, etc. It can be. In particular, a polyethylene film and a polypropylene film that do not require a release film for a protective film are preferably used.

  As the pressure-sensitive adhesive used for the protective film, known acrylic, rubber-based, and silicone-based pressure-sensitive resins can be used.

  Moreover, you may color the said protective film as needed in order to improve the visibility of a protective film. For coloring the protective film, a known and commonly used method such as a method of mixing a colorant into a substrate or an adhesive or printing on a substrate can be used.

[Peeling film]
As a peeling film used for this invention, it does not specifically limit, The well-known peeling film generally laminated | stacked and used for the adhesive layer of an adhesive sheet can be used.

  As a configuration of the release film, a substrate having a release agent layer provided on a substrate is preferably used. It does not specifically limit as a base material, From what is conventionally used as a base material of a peeling film, arbitrary things can be selected suitably and can be used. Examples of such a substrate include plastic films such as a polyethylene terephthalate film, a polybutylene terephthalate film, a polyethylene film, a polypropylene film, a polymethylpentene film, and a polycarbonate film. As the release agent layer, known and commonly used ones such as a thermosetting type or irradiation curing type silicone release agent, a long-chain alkyl polymer type or an olefin type non-silicone release agent can be used. In the present invention, a silicone-based release agent having particularly excellent releasability is particularly preferably used.

[Splash-proof adhesive sheet]
The structure of the anti-scattering adhesive sheet of the present invention is an anti-scattering adhesive sheet in which the protective film is provided on the surface of the hard coat layer of the hard coat adhesive film and the release film is provided on the surface of the adhesive layer.

  When the total thickness of the anti-scattering adhesive sheet is 250 μm or less, preferably 180 to 220 μm, it can be suitably punched even during microfabrication.

  In the structure of the anti-scattering adhesive sheet of the present invention, the thickness of the protective film constituting the anti-scattering adhesive sheet is preferably 40 to 100 μm, and most preferably 45 to 70 μm. By making the said protective film into 100 micrometers or less, the stress concerning a scattering prevention adhesive sheet at the time of a punching process does not become large too much, and it can become difficult to produce the deformation | transformation and damage of a scattering prevention adhesive sheet, and the crack of a hard-coat layer. Moreover, by setting it as 40 micrometers or more, it can become difficult to extend a protective film at the time of sticking to a hard coat adhesive film, and can curl of the scattering prevention adhesive sheet after sticking suitably.

  The thickness of the release film constituting the anti-scattering pressure-sensitive adhesive sheet is preferably 10 to 75 μm, and particularly preferably 25 to 38 μm, in order to facilitate removal of the anti-scattering pressure-sensitive adhesive sheet into the release film. . When the release film is 75 μm or less, it is difficult for the processing blade to penetrate deeply during punching, and it is possible to suppress the stress on the anti-scattering adhesive sheet, particularly the hard coat layer, deformation and breakage of the anti-scattering adhesive sheet, cracks in the hard coat layer Can be made difficult to occur.

  The scattering-preventing pressure-sensitive adhesive sheet of the present invention is a scattering-preventing pressure-sensitive adhesive sheet that is less scratched and excellent in fine workability by adjusting the physical properties of the constituent members to a specific range and combining them. For this reason, the scattering prevention pressure-sensitive adhesive sheet of the present invention can be punched into a fine hole for a speaker or a microphone terminal, particularly a minimum width of 3 mm or less, preferably about 1 to 3 mm, and is required to be finely processed. It can be suitably applied to a screen panel application of a portable electronic terminal.

[Embodiment]
As a preferred embodiment of the scattering prevention pressure-sensitive adhesive sheet of the present invention, for example, the scattering prevention pressure-sensitive adhesive sheet having the above-described configuration is provided with a fine hole having a minimum width of 3 mm or less at a position suitable for various terminals such as a portable electronic terminal to be applied. Then, after peeling off the protective film and the release film, the screen panel can be formed by laminating with a glass plate. The screen panel is particularly useful as a display application for various portable electronic terminals having the screen panel on the surface of the image display unit because damage to the glass plate is particularly reduced.
The laminated glass plate is preferably a tempered glass plate. Examples of the tempered glass include tempered glass manufactured by HOYA, Gorilla glass manufactured by Corning, and IG3 manufactured by Ishizuka Glass. Examples of a method for strengthening the glass plate include a physical strengthening method and a chemical strengthening method. In particular, chemical strengthening methods include an ion exchange method and an air cooling strengthening method. Examples of the material of the glass plate include float glass, alkali glass, and alkali-free glass.
The screen panel configured as described above can be suitably applied as, for example, a portable electronic terminal having a configuration in which the screen panel is fixed to a housing having an LCD module with a gap from the LCD module surface. In this configuration, since there is a gap at the bottom of the screen panel, the screen panel on the surface of the image display unit may be bent when an impact or the like is applied to the surface. When the bending occurs, stress concentrates on the concave portion and it is easy to be damaged, but according to the configuration, it is possible to suitably prevent the damage.

  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.

(Preparation Example 1)
<Synthesis of urethane acrylate (UA1)>
In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 254 parts by weight of butyl acetate, 222 parts by weight of isophorone diisocyanate (hereinafter referred to as “IPDI”), 0.5 part by weight of p-methoxyphenol, dibutyl After charging 0.5 parts by weight 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”) (weight ratio). 75/25 mixture) 795 parts by weight were added dropwise over 1 hour. After completion of the dropwise addition, the mixture is reacted at 70 ° C. for 3 hours, and further reacted until the infrared absorption spectrum of 2250 cm −1 indicating an isocyanate group disappears, and a urethane acrylate (UA1) / PE4A mixture (a mixture of 80/20 by weight, non-volatile) 80% by weight butyl acetate solution). The molecular weight of urethane acrylate (UA1) was 818.

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

  Using the urethane acrylate (UA1) and polymer (A) obtained above, an active energy ray-curable resin composition (resin composition 1), which is the main component of the hard coat agent, was prepared as follows.

  3.1 parts by weight of ethyl acetate, 40.0 parts by weight of a butyl acetate solution (80% of non-volatile content) of a urethane acrylate (UA1) / PE4A mixture (80/20 by weight), a MIBK solution of polymer (a) ( Non-volatile content 50%) 64.0 parts by weight, dipentaerythritol hexaacrylate (hereinafter referred to as “DPHA”) 16.0 parts by weight, photoinitiator 1-hydroxycyclohexyl phenyl ketone (hereinafter referred to as “HCKK”) 1 .63 parts by weight, 1.16 parts by weight of photoinitiator diphenyl-2,4,6-trimethylbenzoylphosphine oxide (hereinafter referred to as “TPO”) were uniformly mixed to obtain resin composition 1 (non-volatile content: 65%) ) Was prepared.

(Preparation Example 2)
<Synthesis of urethane acrylate (UA2)>
In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 161.8 parts by weight of butyl acetate, 222 parts by weight of isophorone diisocyanate (hereinafter referred to as “IPDI”), 0.5 parts by weight of p-methoxyphenol After charging 0.5 parts by weight of dibutyltin diacetate and heating to 70 ° C., 461.3 parts by weight of a butyl acetate solution of 80% non-volatile content of bis (acryloxyethyl) hydroxyethyl isocyanurate was added over 1 hour. The solution was added dropwise, and reacted at 70 ° C. for 3 hours after completion of the addition. Then, 434 parts by weight of a PE3A / PE4A mixture (mixture of 75/25 by weight) 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 was further obtained. The reaction was continued until disappearance to obtain a urethane acrylate (UA2) / PE4A mixture (a mixture with a weight ratio of 87/13, a butyl acetate solution having a nonvolatile content of 80% by weight). The molecular weight of urethane acrylate (UA2) was 889.

  Using the urethane acrylate (UA2) obtained above, an active energy ray-curable resin composition (resin composition 2), which is the main component of the hard coat agent, was prepared as follows.

  23.1 parts by weight of ethyl acetate, 50.0 parts by weight of a butyl acetate solution (80% non-volatile content) of a urethane acrylate (UA2) / PE4A mixture (mixture having a weight ratio of 87/13), dipentaerythritol hexaacrylate (hereinafter, “ DPHA ”)) 40.0 parts by weight, photoinitiator 1-hydroxycyclohexyl phenyl ketone (hereinafter referred to as“ HCPK ”) 3.2 parts by weight, photoinitiator diphenyl-2,4,6-trimethylbenzoylphosphine = 0.8 parts by weight of oxide (hereinafter referred to as “TPO”) was uniformly mixed to prepare Resin Composition 2 (nonvolatile content: 65%).

(Hard coat agent 1)
100 parts by weight of MIBK solution (non-volatile content 50% by weight) of the resin composition 1 prepared in Preparation 1 of the main agent, 2 parts by weight of reactive fluorine antifouling agent (Optool DAC; manufactured by Daikin Industries, Ltd., non-volatile content 20% by weight) Were uniformly mixed and then diluted with ethyl acetate so that the non-volatile content was 40% by weight to obtain a hard coat agent (1).

(Hard coat agent 2)
100 parts by weight of MIBK solution (non-volatile content: 50% by weight) of the resin composition 1 prepared in Preparation 2 of the main agent, silicon hexaacrylate (“Ebecryl 1360” manufactured by Daicel UCB Ltd .; hereinafter referred to as “SiA”) 1 After the parts by weight were uniformly mixed, the hard coating agent (2) was obtained by diluting with ethyl acetate so that the nonvolatile content was 40% by weight.

(Adhesive layer 1)
0.7 parts by weight of an isocyanate-based crosslinking agent (Coronate L-45 manufactured by Nippon Polyurethane Co., Ltd., 45% solid content) is added to the adhesive SK-909A / 100 parts by weight of Soken Co., Ltd., and stirred for 15 minutes. Was prepared. Then, the prepared pressure-sensitive adhesive was applied to a release film having a silicone compound release layer formed on one side of a 38 μm-thick polyethylene terephthalate film, dried at 90 ° C. for 90 seconds, and the thickness after drying was 10 μm. The agent layer (1) was formed.

Example 1
The hard coating agent (1) prepared above was applied to one side of a 75 μm thick polyethylene terephthalate film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.), dried at 60 ° C. for 90 seconds, and then irradiated with an ultraviolet irradiation device ( Using "F450" manufactured by Fusion UV Systems Japan Co., Ltd., lamp: 120 W / cm, H bulb), ultraviolet light was irradiated at an irradiation light amount of 0.5 J / cm ² to form a hard coat layer having a thickness of 7 μm. . Next, the non-hard-coated surface was surface-treated with a corona treatment device so that the surface tension was 55 dynes / cm to obtain a hard-coated film. The pressure-sensitive adhesive (1) was bonded to the corona-treated surface of this hard coat film at a pressure of 4 kg / cm, and after curing at 40 ° C. for 2 days, a hard coat pressure-sensitive adhesive film having a thickness of 92 μm was obtained. Further, a protective film R-100 manufactured by Nitto Denko Corporation with a thickness of 65 μm was bonded to the obtained hard coat pressure-sensitive adhesive film to obtain a scattering prevention pressure-sensitive adhesive sheet having a total thickness of 195 μm.

(Example 2)
The anti-scattering pressure-sensitive adhesive sheet having a total thickness of 210 μm was the same as in Example (1) except that the hard coat layer thickness of the hard coat film (1) was 10 μm and the release film thickness of the pressure-sensitive adhesive layer (1) was 50 μm. Got.

(Example 3)
A scattering prevention pressure-sensitive adhesive sheet having a total thickness of 210 μm was obtained in the same manner as in Example (2) except that the hard coat agent (2) was used as the hard coat agent.

Example 4
The hard coat film (1) has a total thickness of 223 μm in the same manner as in Example (1) except that a polyethylene terephthalate film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.) having a hard coat layer thickness of 10 μm and a thickness of 100 μm was used. An anti-scattering adhesive sheet was obtained.

(Comparative Example 1)
Except for using a polyethylene terephthalate film (Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.) having a hard coat layer thickness of 12 μm and a thickness of 125 μm, the hard coat film (1) has a total thickness of 250 μm. An anti-scattering adhesive sheet was obtained.

(Comparative Example 2)
A scattering-preventing pressure-sensitive adhesive sheet having a total thickness of 260 μm was obtained in the same manner as in Example (4) except that the release film thickness was 75 μm.

(Comparative Example 3)
A scattering prevention pressure-sensitive adhesive sheet having a total thickness of 260 μm was obtained in the same manner as in Example (1) except that B310 (100 μm) manufactured by Sanei Kaken Co., Ltd. was used as the protective film and the thickness of the release film was 75 μm.

(Comparative Example 4)
Scattering with a thickness of 306 μm in the same manner as in Example (1) except that a polyethylene terephthalate film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.) having a hard coat layer thickness of 5 μm and a thickness of 188 μm was used. A prevention adhesive sheet was obtained.

(Comparative Example 5)
A scattering-preventing pressure-sensitive adhesive sheet having a thickness of 191 μm was obtained in the same manner as in Example (1) except that the hard coat layer thickness of the hard coat film (1) was 3 μm.

  The following evaluation was performed about the scattering prevention adhesive sheet obtained by the said Example and comparative example. The obtained results are shown in Table 1 and FIGS.

(Martens hardness)
The release film of the anti-scattering adhesive sheet obtained in the above Examples and Comparative Examples was peeled off and attached to a glass plate. Further, the protective film was peeled off, and the Martens hardness was measured on the hard coat layer surface using a Fischer scope H100CXY with a Vickers indenter with a ridge angle of 136 °, a maximum indentation depth of 1 μm, a maximum load of 15 mN, and a load time of 15 seconds.

(Measurement of surface pencil hardness of hard coat film)
The hard coat films obtained in the above examples and comparative examples were cut into 10 cm squares, and the four corners were attached to a glass plate with a cellophane tape, 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.
(Measurement of surface pencil hardness of hard coat adhesive film)
The release film of the anti-scattering adhesive sheet obtained in the above Examples and Comparative Examples was peeled off and attached to a glass plate. Further, the protective film is peeled off, and the pencil hardness of the hard coat layer surface is measured using a pencil scratch tester (manual type) for coating film manufactured by Imoto Seisakusho Co., Ltd. based on the provisions of JIS K 5600-5-4 (1999 edition). Measured.

(Processability)
Using a bi-blade (blade angle 42 degrees), the release film was punched out in a 3 mm diameter circle from the protective film surface of the anti-scattering adhesive sheet. Then, the hard coat adhesive film which peeled off the protective film and the peeling film was affixed on the glass plate, and the crack of the hard coat layer was observed with the microscope (150 times) from the hard coat layer surface. The judgment criteria are as follows. Moreover, the microscope (150 times) photograph of the hard-coat layer surface after the punching in Example 2 and Comparative Example 2 was shown in FIGS.
A: There is no crack in the hard coat layer, and there is no defect such as peeling off in the hard coat adhesive film. ○: There is no crack in the hard coat layer, and there is no remarkable defect in the hard coat adhesive film. The coated adhesive film has problems such as peeling.

  As is clear from the above table, the anti-scattering pressure-sensitive adhesive sheet of the present invention was able to be suitably punched while having a high surface hardness of 2H or higher as a hard coat pressure-sensitive adhesive film (FIG. 1). On the other hand, although the adhesive sheets of Comparative Examples 1 to 4 had high surface hardness, cracks occurred in the hard coat layer of the punched portion (FIG. 2). In addition, the pressure-sensitive adhesive sheet of Comparative Example 5 has good processability, but did not have sufficient surface hardness.

It is a microscope (150 times) photograph of the hard-coat layer surface after stamping in the scattering prevention adhesive sheet of Example 2. FIG. 5 is a microscope (150 times) photograph of a hard coat layer surface after punching in the anti-scattering adhesive sheet of Comparative Example 2. FIG.

Claims (6)

A hard coat pressure-sensitive adhesive film in which a pressure-sensitive adhesive layer having a thickness of 5 to 20 μm is provided on one surface of a hard coat film having a hard coat layer having a thickness of 5 to 25 μm on one surface of a film substrate having a thickness of 100 μm or less ; An anti-scattering adhesive sheet comprising a protective film having a thickness of 40 to 100 μm provided on the surface of the hard coat adhesive film and a release film having a thickness of 10 to 75 μm provided on the surface of the adhesive layer of the hard coat adhesive film. Because
The pencil hardness of the hard coat layer surface of the hard coat film is 3H or more,
The hard coat adhesive film is pasted on glass, and the Martens hardness measured by pushing a Vickers indenter with a corner angle of 136 ° into the hard coat layer surface with a load of 15 mN is 240 to 300 N / mm ² .
An anti-scattering adhesive sheet having a total thickness of 250 μm or less. The thickness of the hard coat layer is 5 to 25 µm, the thickness of the film substrate is 38 to 100 µm, the elastic modulus is 3 to 7 GPa, and the thickness of the pressure-sensitive adhesive layer is 5 to 20 µm. The scattering prevention adhesive sheet of 1. The pressure-sensitive adhesive layer was formed by providing a pressure-sensitive adhesive tape formed by providing a pressure-sensitive adhesive layer with a thickness of 10 μm on a PET substrate having a thickness of 100 μm. Is a pressure-sensitive adhesive layer having a peel adhesive strength of 4N or more / 25 mm at a peeling speed of 300 mm / min after being crimped once in one reciprocation cycle and left in an environment of 60 ° C. and 90% for 240 hours. The scattering prevention adhesive sheet of Claim 1 or 2 . The anti-scattering adhesion sheet according to any one of claims 1 to 3 , wherein a storage elastic modulus at 20 ° C in a dynamic viscoelastic spectrum at a frequency of 1 Hz of the pressure-sensitive adhesive layer is 2.0 x 10 ⁵ Pa or more. The hard coat layer of the hard coat film includes a triisocyanate obtained by trimerizing diisocyanate, a perfluoropolyether compound having a hydroxyl group at at least one terminal, and a single group having a hydroxyl group and a carbon-carbon double bond. It is a layer which consists of a hardened | cured material of the active energy ray hardening-type resin composition containing the compound which consists of a monomer, The scattering prevention adhesive sheet of Claims 1-4 . It is a processing method which forms a micro hole by punching in a scattering prevention adhesive sheet, Comprising: The minimum width of the said micro hole is 3 mm or less, The said scattering prevention adhesive sheet is a scattering prevention in any one of Claims 1-5. A processing method characterized by being an adhesive sheet.