KR101380850B1 - Protective adhesive film, screen panel and mobile electronic terminal - Google Patents

Abstract

This invention is a protective adhesive film provided with the adhesive layer in the hard coat film which consists of a film base material which has a hard coat layer, The elasticity modulus of the said film base material is 3-7 GPa, the thickness is 38-100 micrometers, and the thickness of the said hard coat layer is 5-100. 25 micrometers, the pencil hardness of the hard-coat layer surface of the said hard coat film is 3H or more, the thickness of the said adhesive layer is 5-20 micrometers, the total thickness is 60-150 micrometers, and at the frequency of 1 Hz of the said adhesive layer The storage modulus at 80 ° C. in the dynamic viscoelastic spectrum is 1.0 × 10 ⁵ It provides the protective adhesive film which is Pa or more.

Hard coating layer, protective adhesive film, screen panel, portable electronic terminal

Description

Protective Adhesive Film, Screen Panel and Mobile Electronic Terminals {PROTECTIVE ADHESIVE FILM, SCREEN PANEL AND MOBILE ELECTRONIC TERMINAL}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a protective adhesive film for protecting a screen panel provided on a surface of a display device such as a liquid crystal panel or an EL display, a screen panel having a protective adhesive film, and a portable electronic terminal having the screen panel.

In response to requests of portable electronic terminals for miniaturization and miniaturization, thinning of image display apparatuses (hereinafter, display apparatuses) has been advanced. In order to prevent damage of display devices, such as a liquid crystal, a protective screen panel (following panel) is provided. For thinning, thinning of the panel and reducing the gap between the display device and the panel are effective.

However, in conventional panels made of resin such as acrylic or polycarbonate, the rigidity is insufficient, so when the panel portion is pressed with a finger, the display device is deformed to cause display defects, or when a long-term durability test is performed under moist heat conditions. There arises a problem that the panel partially sticks to the image display panel.

Therefore, instead of the conventional resin screen panel, a high rigid screen panel is required, for example, glass panels are beginning to be adopted. However, glass panels require safety measures in case of breakage. Therefore, adhesion of the protective adhesive film with a scattering prevention function is examined on the surface of a panel. As a protective adhesive film, the hard coat film for polarizing plates in a liquid crystal display body, or various display protection is disclosed by patent document 1. As shown in FIG. The disclosed hard film exhibits a surface pencil hardness of 4H using a 188 μm PET film as the base film, but the film thickness is thick, which is not suitable for the purpose of thinning. In addition, when the same hard coating agent is provided in a thin base film, it has a high surface pencil hardness, such as 3H, if it does not have an adhesive layer, but when an adhesive layer passes through when laminating | stacking on a panel, an adhesive layer will deform | transform and surface pencil as a panel There was a problem that the hardness greatly decreased.

In addition, at the time of thinning of the image display apparatus, the request for thinning of the protective adhesive film itself is also high. As a thin surface protection sheet, the adhesive sheet for surface protections used for image paper, such as a photograph which has scratch resistance and chemical-resistance, etc. is disclosed (refer patent document 2). However, the adhesive sheet did not have sufficient surface hardness, and further improvement was required in order to apply it to an image display apparatus. In addition, since the protective adhesive sheet is used as the outermost layer of the image display device, it is required to have excellent peeling resistance, but when a flexible adhesive is used to secure the adhesive force, foaming occurs in a decrease in surface hardness or in a high temperature and high humidity environment. There was a case.

[Patent Document 1] Japanese Patent Laid-Open No. 2005-320522

[Patent Document 2] Japanese Patent Laid-Open No. 2003-96410

The problem to be solved by the present invention is to provide a protective adhesive film that can be laminated by a glass plate or the like through an adhesive layer to maintain a high surface hardness even when a thin panel is formed, and that foaming is unlikely to occur even at a high temperature and high humidity environment. To provide a screen panel that combines thin, moderate elasticity and high surface hardness and is excellent in visibility, and provides a portable electronic terminal that is hard to scratch on the surface of the panel and is excellent in visibility.

In the present invention, an object to be attached is provided via a pressure-sensitive adhesive layer by a protective pressure-sensitive adhesive film in which a pressure-sensitive adhesive layer having a specific thickness is provided on a hard hard coating film obtained by combining a base material having a specific elastic modulus with a hard hard coating layer at a specific thickness. Hard coating when there is no pressure-sensitive adhesive layer by appropriately relieving the dent of the film caused by the presence of the pressure-sensitive adhesive layer even when the pressure is locally applied to the surface of the protective pressure-sensitive adhesive film by impact or the like even when attached to the surface. The characteristic of a film can be expressed favorably. In addition, by adjusting the viscoelasticity of the pressure-sensitive adhesive layer, suitable adhesive force can be realized while maintaining the above excellent surface hardness, and generation of bubbles can be suppressed even when the adhesive layer is attached to an object to be attached.

That is, this invention is a protective adhesive film in which the adhesive layer was provided in the hard coat film which consists of a film base material which has a hard coat layer, The elasticity modulus of the said film base material is 3-7 GPa, the thickness is 38-100 micrometers, and the thickness of the said hard coat layer Is 5 to 25 µm, the pencil hardness of the surface of the hard coating layer of the hard coating film is 3H or more, the thickness of the pressure-sensitive adhesive layer is 5 to 20 µm, and the total thickness is 60 to 150 µm. To provide.

When the protective adhesive film of this invention is used for the protection of the thin glass panel of a portable electronic terminal, for example, since it has high surface pencil hardness, it can be used suitably. Or it can use suitably for protection of various displays.

Moreover, when a sticking object is a thing which a crack, such as glass, arises, it is useful as a scattering prevention film which prevents scattering when a sticking object is broken.

[Film substrate]

In this invention, the film base material whose elasticity modulus is 3-7 GPa, thickness is 38-100 micrometers, and light transmittance is 85% or more is used. As a protective adhesive film which protects the surface of a display body, etc., it is desired to make thickness at least 150 micrometers or less because of a problem with an external appearance and the problem of peeling by the latching of an edge part. For this reason, it is necessary to be at least 100 micrometers or less from a viewpoint that a base film needs to be a thin base material, and lamination with another layer is needed. In this case, when an elasticity modulus is less than 3 GPa, when a protective adhesive film is formed, deformation of a film base material will arise easily, and when a protective adhesive film is formed, the fall of surface hardness cannot be suppressed. Moreover, if it is 7 GPa or more, a film base material will become hard too much and it will become impossible to follow a gentle curved surface at the time of sticking of a protective adhesive film. Moreover, when thickness is less than 38 micrometers, even if it is the range of the said elasticity modulus, since the deformation | transformation of a film base material arises easily, when a pressure-sensitive adhesive layer is provided, the fall of surface hardness cannot be suppressed. Moreover, 85% or more of light transmittance is preferable, More preferably, it is 90% or more.

As a film base material used for this invention, a polyethylene terephthalate, a polybutylene terephthalate, a polyethylene naphthalate, a polyethylene film, a polypropylene film, a cellophane, a diacetyl cellulose film, a triacetyl cellulose film, acetyl cellulose, for example Butylate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyether ether ketone film, A polyether sulfone film, a polyetherimide film, a polyimide film, a fluororesin film, a nylon film, an acrylic resin film, etc. are mentioned.

Moreover, in order to improve the adhesiveness with a hard coating layer or an adhesive layer, the surface uneven | corrugated treatment by the sand blasting method, the solvent treatment method, etc., or corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone, ultraviolet irradiation treatment, etc. Surface treatment, such as oxidation treatment of the surface, can be performed.

As the other compounding material, an antistatic agent may be added to impart an antistatic function. As nonionic polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol, polyoxyethylene alkylamine, polyoxyethylene alkylamide, fatty acid polyethylene glycol ester, fatty acid sorbitan ester, polyoxyethylene fatty acid sorbitan ester, fatty acid glycerine ester, Alkyl polyethyleneimine etc. are mentioned. Examples of the cationic system include alkylamine salts, alkyl quaternary ammonium salts and alkylimidazoline derivatives. Moreover, the acrylate compound etc. which have ethylene oxide as frame | skeleton can also be used. As the conductive polymer, polyaniline, polypyrrole, polythiophene, poly 3,4-ethylenedioxythiophene and derivatives thereof can be used. As the metal oxide, antimony doped tin oxide (ATO), tin doped indium oxide (ITO), aluminum doped zinc oxide, antimony double oxide and the like can be used. In addition, an ion-conducting antistatic agent that mixes metal ions such as lithium ions can be used.

[Hard Coating Layer]

The hard coat layer used by this invention should just have a hardness of 3H or more, when laminated | stacked with the said film base material, and what consists of hardened | cured material of various hard coat agents can be used.

As the hard coat agent, α can be suitably used an active energy ray-curable resin composition, and among these, α having a functional group capable of reacting with the reactive functional group in the (meth) acrylate polymer (a1) having a reactive functional group in the side chain. A polymer (A) having a (meth) acryloyl group to which a,?-unsaturated compound (a2) is reacted, and a polyfunctional (meth) acrylate (B) having three or more (meth) acryloyl groups in one molecule Since the curvature of the active energy ray-curable resin composition to contain hardly arises, and also when the adhesive layer is provided in the hard coat film which makes the hardened | cured material of this composition a hard coat layer, since the fall of surface hardness hardly occurs, Especially suitable. In the present invention, "(meth) acrylate" refers to one or both of methacrylate and acrylate, and the same as for "(meth) acryloyl group" and "(meth) acrylic acid". to be.

As a reactive functional group of the (meth) acrylate type polymer (a1) which has a reactive functional group in a side chain, a hydroxyl group, a carboxy group, an epoxy group, etc. are preferable. Moreover, as a functional group which the (alpha), (beta)-unsaturated compound (a2) which can react with these reactive functional groups is preferable, an isocyanate group, a carboxy group, an acid halide group, a hydroxyl group, an epoxy group, etc. are preferable. Moreover, the polymer which has a (meth) acryloyl group which made the (meth) acrylate type polymer (a1) which has a reactive functional group in a side chain react with the (alpha), (beta)-unsaturated compound (a2) which has a functional group which can react with the said reactive functional group. The manufacturing method of (A) is not specifically limited, Although it can manufacture by a conventionally well-known method, For example, the following manufacturing methods (1)-(3) are mentioned.

Manufacturing method (1) As said (meth) acrylate type polymer (a1), (meth) acrylate type polymer or copolymer which has a hydroxyl group as a reactive functional group in a side chain is used, and a part or all of the hydroxyl groups are alpha, A method of introducing a (meth) acryloyl group by reacting (meth) acryloylethyl isocyanate, (meth) acrylic acid, (meth) acrylic acid chloride and the like as the β-unsaturated compound (a2).

Manufacturing method (2) As said (meth) acrylate type polymer (a1), (meth) acrylate type polymer or copolymer which has a carboxyl group as a reactive functional group in a side chain is used, and part or all of the carboxyl group is (alpha), 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 β-unsaturated compound (a2). .

Manufacturing method (3) As said (meth) acrylate type polymer (a1), (meth) acrylate type polymer or copolymer which has an epoxy group as a reactive functional group in a side chain is used, and a part or all of the epoxy group is (alpha), A method of introducing a (meth) acryloyl group by reacting (meth) acrylic acid or a carboxyl group with an acrylate having an acryloyl group as the β-unsaturated compound (a2).

The manufacturing method of a polymer (A) is demonstrated more concretely as an example of said manufacturing method (3). In the manufacturing method (3), a polymer (A) can be obtained easily by making (alpha), (beta)-unsaturated carboxylic acid react with the (meth) acrylate type polymer or copolymer which has an epoxy group. Here, as a raw material, the (meth) acrylate type polymer which has an epoxy group is glycidyl (meth) acrylate and the (meth) acrylate which has an alicyclic epoxy group (for example, Daicel Chemical Industries, Ltd.) It is obtained by homopolymerizing these using (meth) acrylate which has epoxy groups, such as "CYCLOMER M100", "CYCLOMER a200"), and 4-hydroxybutyl acrylate glycidyl ether by the company.

Moreover, the (meth) acrylate type copolymer which has an epoxy group is (alpha), (beta) which does not have carboxyl groups, such as (meth) acrylic acid ester, styrene, vinyl acetate, and acrylonitrile, in addition to the (meth) acrylate which has the said epoxy group. It is obtained by copolymerizing 2 or more types of monomers using a unsaturated monomer as a raw material. In addition, when an α, β-unsaturated monomer having a carboxyl group is used in place of the α, β-unsaturated monomer not having the carboxyl group, a crosslinking reaction occurs during the copolymerization reaction with glycidyl (meth) acrylate, resulting in high viscosity or It is not preferable because it causes gelation.

As (alpha), (beta)-unsaturated carboxylic acid which reacts with the (meth) acrylate type polymer or copolymer which has the said epoxy group, For example, the compound which has (meth) acrylic acid, a carboxy group, and an acryloyl group (for example, Osaka "Biscoat 2100" by Yuki Chemical Co., Ltd.) etc. are mentioned.

5,000-80,000 are preferable, as for the weight average molecular weight of the polymer (A) obtained by said manufacturing method, 5,000-50,000 are more preferable, 8,000-35,000 are further more preferable. When the weight average molecular weight is 5,000 or more, the effect of reducing the cure shrinkage is great, and the hardness becomes sufficiently high at 80,000 or less.

Moreover, as for the (meth) acryloyl group equivalent of a polymer (A), 100-300 g / eq is preferable, More preferably, it is 200-300 g / eq. When the (meth) acryloyl group equivalent of a polymer (A) is this range, hardening shrinkage can be made small and hardness can also be made high enough.

When manufacturing a polymer (A) by said manufacturing method (1)-(3), a kind of monomer and polymer to be used so that the weight average molecular weight and (meth) acryloyl group equivalent of said polymer (A) may be satisfied. What is necessary is just to select these usage amounts suitably.

As a polyfunctional (meth) acrylate (B) which has three or more (meth) acryloyl groups in said one molecule, For example, trimethylol propane tri (meth) acrylate and triethylene oxide modified trimethylol propane tree (Meth) acrylate, tripropylene oxide modified glycerin tri (meth) acrylate, triethylene oxide modified glycerin tri (meth) acrylate, triepichlorohydrin modified glycerin tri (meth) acrylate, 1,3,5- Triacryloylhexahydro-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 ditrimethylolpropane Tra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipentaestitol tol acrylate (for example, "Kayarad D-310" by Nihon Kayaku Co., Ltd.), alkyl modified di Pentaerythritol tetraacrylate (for example, "Kayalad D-320" made by Nihon Kayaku Co., Ltd.), epsilon -caprolactone modified dipentaerythritol hexaacrylate (for example, Nihon Kayaku Co., Ltd.) Kayarad DPCA-20), dipentaerythritol pentamethacrylate, dipentaerythritol hexa (meth) acrylate, hexaethylene oxide modified sorbitol hexa (meth) acrylate, hexakis (methacryloyloxy Ethyl) cyclotriphosphazene (for example, "PPZ" by Kyoeisha Chemical Co., Ltd.) etc. are mentioned. These may be used independently or may use 2 or more types together.

Moreover, when said pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are used among the said polyfunctional (meth) acrylate (B), the composition Since the fall of surface hardness hardly arises even when an adhesive layer is provided in the hard coat film which makes hardened | cured material of a hard coat layer, it is especially suitable.

As for the compounding ratio of the said polymer (A) and a polyfunctional (meth) acrylate (B), the range of (A) :( B) = 10: 90-90: 10 is preferable on a mass basis, and (A) :( The range of B) = 20: 80-80: 20 is more preferable, The range of (A) :( B) = 30: 70-70: 30 is further more preferable. When the compounding ratio of the said polymer (A) and a polyfunctional (meth) acrylate (B) is this range, curvature hardly arises in the hardened | cured material obtained, Furthermore, an adhesive is used for the hard-coating film which makes the hardened | cured material of the composition a hard-coat layer. Since the fall of surface hardness hardly arises even when a layer is provided, it is especially suitable.

A radically polymerizable monomer (C) can be mix | blended with said active energy ray hardening type resin composition other than said polymer (A) and polyfunctional (meth) acrylate (B). As this radically polymerizable monomer (C), N-vinyl caprolactam, 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, acryloyl morpholine, lauryl (meth) acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acryl Ethylene, tetrahydrofurfuryl (meth) acrylate, ethylenediethylene glycol (meth) acrylate, butoxyethyl (meth) acrylate, methyl triethylene diglycol (meth) acrylate, phenoxyethyl (meth) acrylate , 2-hydroxypropyl (meta) Acrylates and the like.

When mix | blending the said radically polymerizable monomer (C) with said active energy ray hardening-type resin composition, the compounding quantity is 100 mass parts in total with respect to the said polymer (A) and a polyfunctional (meth) acrylate (B). , 1-50 mass parts is preferable, 1-30 mass parts is more preferable, 1-10 mass parts is more preferable.

Moreover, as said polyfunctional (meth) acrylate (B) or radically polymerizable monomer (C), it has a monomer which has acid groups, such as a carboxyl group, a phosphoric acid group, and a sulfonic acid group, the monomer which has an amino group, the alkoxysilyl group, and the alkoxy titanyl group When a monomer is used, since adhesiveness with a base material can be improved, it is preferable. On the other hand, monomers having a fluorocarbon chain, a dimethylsiloxane chain and a hydrocarbon chain having 12 or more carbon atoms are preferable because they can improve the surface properties such as surface sliding properties, stain resistance, and fingerprint adhesion of the protective layer. 0.01-5 mass% is preferable, and, as for the addition amount of the monomer which has a fluorocarbon chain, a dimethylsiloxane chain, and a hydrocarbon chain of 12 or more carbon atoms, 0.1-3 mass% is more preferable.

The monomer having a fluorocarbon chain is excellent in surface properties such as stain resistance and anti-fingerprint property, but among them, the following general formula (1)

[In Formula (1), R is a hydrogen atom or a C1-C4 alkyl group, X is the alkylene chain which may have a hetero atom, or following General formula (2)

{In formula (2), Y is an oxygen atom or a sulfur atom, m and n are integers of 1 to 4, which may be the same or different, and Rf ¹ is a fluorinated alkyl group.} And Rf is a fluorinated alkyl group. .]

Since the functional group which has a fluorinated alkyl group at the terminal represented by this, and the fluorinated alkyl group containing (meth) acrylate which has two or more (meth) acryloyl groups contribute to surface surface improvement and also improve surface hardness, it is especially preferable. Can be used.

Since the structure represented by the said General formula (1) has an alkylene chain etc. between the carbonyl carbon and fluorinated alkyl group in an ester bond, there is little problem of deterioration by hydrolysis, and it is excellent in the long-term stability of the performance of hardened | cured material. will be. In addition, since the fluorinated alkyl group in the structure exists in the terminal of a molecule | numerator, it does not enter as a part of the net at the time of crosslinking. It also has a -CF ₃ group which contributes greatly to the surface tension lowering ability. For this reason, when used as a coating material, for example, a fluorine atom can be arrange | positioned effectively on the surface, and it becomes possible to express the surface characteristic derived from a fluorine atom efficiently.

In addition, the fluorinated alkyl group-containing (meth) acrylate used in the present invention is required to have two or more (meth) acryloyl groups. This has two or more crosslinking points in one molecule during the curing reaction, and is required for forming a strong three-dimensional network structure.

Moreover, since the surface characteristic and optical characteristic derived from a fluorine atom are easy to express when the fluorine atom content rate in 1 molecule is 25 weight% or more, it is preferable. When the content of the fluorine atom is 25% by weight or more, the amount of the fluorinated alkyl group-containing (meth) acrylate for expressing the surface and optical properties can be reduced, and other reactive compounds having a high content of other fluorine atoms and / or ratios Sufficient characteristics can be expressed without using a reactive compound together. In addition, compatibility is sufficiently obtained and suitable optical properties are easily obtained.

Moreover, it is preferable that it is 500-4000 as molecular weight of this (meth) acrylate. If the molecular weight is in the above range, the crosslinking density becomes good, the mechanical properties can be easily obtained, and the amount of fluorine atoms capable of expressing the effect can be introduced.

By using such a fluorinated alkyl group-containing (meth) acrylate, while exhibiting excellent surface properties and optical properties of the cured product which are performances derived from fluorine atoms, a crosslinking density is high, and a rigid three-dimensional network structure can be formed. The characteristics (mechanical strength) improve, and as a result, a cured product having these performances can be obtained, and a cured product excellent in hydrolysis resistance is further obtained.

Among these, in particular, it is preferable that the content of the fluorine atom in one molecule of the fluorinated alkyl group-containing (meth) acrylate is 25% by weight or more, and particularly preferably 30 to 65% by weight in terms of the above-mentioned performance. Moreover, it is preferable that molecular weights are 500-4000, and it is especially preferable that it is 600-3500.

In addition, the functional group and the two or more (meth) acryloyl groups are each independently a quaternary carbon or cyanurate ring via an alkylene chain having 1 to 5 carbon atoms which may have the same or different oxygen atoms. Or at least one of the two or more (meth) acrylate groups in the quaternary carbon, cyanurate ring or phosphoryl group, which is bonded to a phosphoryl group and the functional group is bonded via the alkylene chain; When the three-dimensional network structure is formed, the structure that is bonded through the chain is capable of arranging low degree of freedom quaternary carbon, cyanurate ring or phosphoryl group at the portion connecting the crosslinking points. By making itself more rigid, expressing the mechanical properties of the cured product, and placing a fluorinated alkyl group in the vicinity of the crosslinking point, It is preferred from the point that combines the learning characteristics and optical characteristics. For the above reasons, the alkylene chain is preferably a short one, particularly preferably an alkylene chain having 1 to 3 carbon atoms or an oxyalkylene chain having 1 to 3 carbon atoms.

As X in the said General formula (1), following General formula (3)

-(CH ₂ ) _p -Z _q- (CH ₂ ) _r- (3)

Equation (3) of the, Z is a nitrogen atom, an oxygen atom, a sulfur atom, or -NR-SO ₂ having a hydrogen atom or an alkyl group of 1 to 24 carbon atoms - an alkyl group (R is a 1 to 24 hydrogen atoms, or carbon atoms being P is an integer of 0 to 4, q is 0 or 1, r is an integer of 0 to 20, and 1 ≦ p + r ≦ 20.].

It is preferable that it is the alkylene chain represented by the point which is excellent in the hydrolysis resistance of the hardened | cured material obtained, Especially, the alkylene chain in which X in the said General formula (1) is represented with the said General formula (3) [where Z is a hydrogen atom or A nitrogen atom, an oxygen atom, a sulfur atom, or -NR-SO _2- (R is a hydrogen atom or a C1-C24 alkyl group) having an alkyl group having 1 to 24 carbon atoms, p is 1, q is 1 And r is an integer of 0 to 19. Or, the linking group represented by the general formula (2), provided that Rf ¹ is -C _n F _{2n +1} (n is an integer of 1 to 20), In addition, a compound in which Rf in General Formula (1) is -C _n F _{2n +1} (n is an integer of 1 to 20), which is the same as or different from Rf ¹ , may be prepared by the Michael addition reaction described below. It is suitable for industrial production, and since the fluorinated alkyl group is a perfluoroalkyl group, it is preferable in that it can effectively express the performance derived from a fluorine atom. A. In addition, when using a fluorinated alkyl group other than a perfluoroalkyl group, it has the effect of improving compatibility with the other components mentioned later that are mix | blended as needed, and also light transmittance etc., and also the flexible toughness of hardened | cured material, It has an effect when using for the use etc. for which adhesiveness is calculated | required, and it is preferable to select the structure and type of a fluorinated alkyl group according to the level of use, use, etc. which are required.

Further, the above-mentioned formula (3) Z is a nitrogen atom, a sulfur atom, or -NR-SO ₂ having a hydrogen atom or an alkyl group having 1 to 6 carbon atoms in the - (R being an alkyl group of 1 to 6 carbon atoms) and, or When Y in General Formula (2) is a sulfur atom, Rf ¹ has 4, 6, or 8 carbon atoms, and when Rf in General Formula (1) has 4, 6, or 8 compounds, The surface properties, the optical properties, and the mechanical properties are particularly excellent, and therefore the most preferable ones. Moreover, as R in the said General formula (1), it is preferable that it is a hydrogen atom or a methyl group from the point of industrial availability of a raw material, and the point which can be manufactured by Michael addition reaction.

As a fluorinated alkyl group containing (meth) acrylate used by this invention, the compound represented by the following general formula (I)-(X) is mentioned, for example.

Of the formula (I) ~ (III), R 1 is a hydroxyl group, an alkyl group of a straight chain having a carbon number of _{1~4, CH 2 = CHCO 2 CH} 2 -, CH 2 = C (CH 3) CO 2 CH 2 -, or It is a C1-C3 alkylol group, R <^2> is a (meth) acryloyl group, m and n are the integers of 1-4 which may be same or different, t is 4, 6, or 8, i is 1 or 2 And j is 2 or 3 and i + j = 4.]

Of the formula ^{(IV), R 1, R} 2 is the same as that in the formula (I) ~ (III), R 4 is a (meth) acrylate as HS (CH ₂₎ a journal ₂ C _t F _{2t +1} or Is a group added by HN (C ₃ H ₇ ) (CH ₂ ) ₂ C _t F _{2t +1} (where t represents 4, 6 or 8).]

[In Formula (V), R <^2> , R <^4> is the same as that in Formula (I)-(IV), m is 1 or 2, n is 2 or 3, and m + n = 4.]

[In Formula (VI), R <^2> , R <^4> is the same as that of Formula (I)-(IV), p is an integer of 1-4, q is an integer of 2-5, r is 0-3 Is an integer of and p + q + r = 6.]

[In Formula (VII)-(VIII), R <^2> , R <^4> is the same as that in Formula (I)-(IV), w is an integer of 1-4, w 'is an integer of 2-5, W + w '= 6, y is an integer of 1 to 8, y' is an integer of 2 to 9, and y + y '= 10.]

[In Formula (IX), R <^2> , R <^4> is the same as that of Formula (I)-(IV).]

[In Formula (X), R <^2> , R <^4> is the same as that of Formula (I)-(IV).]

The following compounds are mentioned as a specific example of the said fluorinated alkyl group containing (meth) acrylate. In addition, the following specific example shows the case where it is all an acrylate, and all the acryloyl group in a formula can be changed into a methacryloyl group. In addition, the following specific example describes only what is a hydrogen atom as R in the said General formula (1), One of the hydrogen atoms in the methylene group couple | bonded with carbonyl carbon can be changed into a methyl group.

Although it does not specifically limit as a manufacturing method of the said fluorinated alkyl group containing (meth) acrylate, For example, Michael of the compound containing three or more (meth) acryloyl groups, and the compound which has a fluorinated alkyl group and active hydrogen In the presence of acid catalysts such as hydrochloric acid and sulfuric acid, a method of synthesizing by addition reaction, an alkyl carboxylic acid having a fluorinated alkyl group, a polyhydric alcohol, and (meth) acrylic acid are used as raw materials, and a polymerization inhibitor such as hydroquinone is added thereto, The method of making it react for 3 to 10 hours, removing water produced | generated by condensation reaction at 80-120 degreeC, etc. are mentioned.

In particular, the production method using the former Michael addition reaction is an addition reaction, so that there is no compound by-produced by the reaction, and it is possible to proceed under mild conditions as described later, and the content of fluorine atoms in the molecule (( Since the functional group etc. of a meta) acryloyl group can be adjusted easily, it is preferable as a method of obtaining the fluorinated alkyl group containing (meth) acrylate used for the fluorine-containing photocurable composition of this invention.

Moreover, the monomer which has a dimethylsiloxane chain is excellent in the sliding property of a surface, etc., As this monomer, for example, the monomer is made to the dimethylsiloxane skeleton via the spacer which consists of alkylene groups, such as an ethylene group and a polypropylene group, etc. Acrylate etc. into which the acryloyl group was introduce | transduced can be used preferably. Examples of these acrylates include BYK-UV3500 and BYK-UV3570 manufactured by BYK Chemi Corporation, and Ebecryl 1360 manufactured by Daicel Yushibi Corporation.

In addition, said active energy ray curable resin composition has one hydroxyl group and two or more (meth) acryloyl groups in polyisocyanate (d1) and 1 molecule as components other than said (A)-(C). You may mix | blend urethane acrylate (D) which is an addition reaction of acrylate (d2).

As the polyisocyanate (d1), for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene Aromatic isocyanate compounds such as diisocyanate and 4,4'-diphenylmethane diisocyanate; Isocyanate groups bonded to alicyclic hydrocarbons such as dicyclohexyl methane diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated methylene bisphenylene diisocyanate and 1,4-cyclohexane diisocyanate Two having compounds (hereinafter referred to as alicyclic diisocyanates); The compound which has two isocyanate groups couple | bonded with aliphatic hydrocarbons, such as trimethylene diisocyanate and hexamethylene diisocyanate (henceforth aliphatic diisocyanate), etc. are mentioned. These polyisocyanates may be used independently and may use 2 or more types together.

Among these polyisocyanates (d1), aliphatic diisocyanates or alicyclic diisocyanates are preferable, and among them, isophorone diisocyanate, norbornane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated methylene bisphenylenedi isocyanate and hexa Methylene diisocyanate is preferred. In particular, norbornane diisocyanate is the most preferable.

As an acrylate (d2) which has one hydroxyl group and two or more (meth) acryloyl groups in 1 molecule used by this invention, a trimethylol propane di (meth) acrylate and a pentaerythritol tree (meth) are, for example. Polyacrylates of polyhydric hydroxyl group containing compounds, such as an acrylate and dipentaerythritol penta (meth) acrylate, These polyacrylates and the adduct of (epsilon) -caprolactone, these polyacrylates, The adduct of alkylene oxide, epoxy acrylates, etc. are mentioned. These acrylates (d2) may be used independently or may use 2 or more types together.

Moreover, the acrylate which has one hydroxyl group and 3-5 (meth) acryloyl groups in 1 molecule among these acrylates (d2) is preferable. Pentaerythritol triacrylate, dipentaerythritol pentaacrylate, etc. are mentioned as such an acrylate, These are especially preferable because a hardened film of high hardness is obtained.

The urethane acrylate (D) used by this invention is obtained by addition-reacting two components of the said polyisocyanate (d1) and the said acrylate (d2). As for the hydroxyl equivalent, as for the ratio with respect to 1 equivalent of isocyanate in polyisocyanate (d1) of the said acrylate (d2), 0.1-50 are preferable normally, 0.1-10 are more preferable, and 0.9-1.2 are more preferable. Moreover, 30-150 degreeC is preferable and, as for the reaction temperature of the said polyisocyanate (d1) and the said acrylate (d2), 50-100 degreeC is more preferable. In addition, the end point of reaction can be confirmed by finding the isocyanate group content rate by the loss | disappearance of the 2250 cm <^-1> infrared absorption spectrum which shows an isocyanate group, and the method of JISK7301-995, for example.

In addition, in the said addition reaction, a catalyst can be used for the purpose of shortening reaction time. As the catalyst, for example, a basic catalyst (amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine, ammonia, phosphines such as tributylphosphine and triphenylphosphine) and an acidic catalyst ( Metal alkoxides such as copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, tetrabutoxytrititanium, tetrabutoxyzirconium, Lewis acids such as aluminum chloride, dibutyltin dilaurate, dibutyltin Tin compounds such as diacetate). Among these, an acidic catalyst is preferable and a tin compound is the most preferable. A catalyst is normally 0.1-1 mass part with respect to 100 mass parts of 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 having no site reacting with isocyanate, for example, You may use as a solvent the thing which does not have a hydroxyl group or an amino group in the radically polymerizable monomers (C). These solvents and monomers may be used independently or may use 2 or more types together.

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

When mix | blending the said urethane acrylate (D) with said active energy ray hardening-type resin composition, the compounding quantity is 100 mass parts in total with respect to the said polymer (A) and a polyfunctional (meth) acrylate (B) in total, 1-100 mass parts is preferable.

In this invention, when using said active energy ray hardening-type resin composition as a hard coating agent, hardened | cured material is obtained by irradiating an active energy ray. The active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. In addition, when hardening this resin composition with an ultraviolet-ray, a photoinitiator is added to active-energy-ray-curable resin composition. In addition, if necessary, further photosensitizer is added. On the other hand, in the case of using ionizing radiation such as electron beams, alpha rays, beta rays, and gamma rays, curing is performed quickly without using a photoinitiator or a photosensitizer, and therefore it is not particularly necessary to add them.

In the case of curing with ultraviolet rays, an effective photopolymerization initiator can be broadly classified into an intramolecular cleavage type photopolymerization initiator and a hydrogen drawing type photopolymerization initiator. Examples of the intramolecular cleavage type photopolymerization initiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, and 1- (4-isopropylphenyl)-. 2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl Acetophenone compounds such as 2-morpholino- (4-thiomethylphenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone; Benzoin compounds such as benzoin, benzoin methyl ether and benzoin isopropyl ether; Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; Benzyl, methylphenylglyoxyester, oligo2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone, 1- [4- (2-hydroxyethoxy) -phenyl]- 2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-pronionyl) -benzyl] -phenyl} And compounds such as 2-methyl-propan-1-one.

On the other hand, as a hydrogen drawing type | mold photoinitiator, benzophenone, methyl 4-phenylbenzophenone o-benzoyl benzoate, 4,4'- dichloro benzophenone, hydroxy benzophenone, 4-benzoyl-4'- is mentioned, for example. Benzophenes such as methyl-diphenylsulfide, acrylated benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and 3,3'-dimethyl-4-methoxybenzophenone Non-based compounds; Thioxanthone type compounds, such as 2-isopropyl thioxanthone, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, and 2, 4- dichloro thioxanthone; Aminobenzophenone compounds such as Michler's ketone and 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, phenylglyoxylic acid methyl ester, oxyphenylacetic acid 2- [2-oxo-2- And compounds such as a mixture of phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester.

Moreover, it does not specifically limit as a photosensitizer used suitably for the active energy ray hardening type resin composition used by this invention, For example, amines, such as aliphatic amine and aromatic amine, urea, such as o-tolyl thiourea, Sulfur compounds, such as sodium diethyldiophosphate and s-benzylisothiuronium-p-toluenesulfonate, etc. are mentioned.

0.1-20 mass% is preferable with respect to 100 mass parts of resin components in an active-energy-ray-curable resin composition, and, as for the usage-amount of these photoinitiators and a photosensitizer, 0.5-10 mass% is more preferable.

Moreover, you may mix | blend various additives with the active energy ray hardening-type resin composition used for this invention as needed, and you may dilute with a solvent as needed. As an additive, a polymerization inhibitor, antioxidant, a leveling agent, an antifoamer, a coating surface modifier (wetting property, a slip improver, etc.), a plasticizer, a coloring agent, inorganic fine particles, etc. are mentioned, for example.

Examples of the inorganic fine particles include metal oxides such as titanium oxide, silicon oxide, aluminum oxide, zinc oxide, calcium oxide, magnesium oxide, zirconium oxide, and tin oxide. The average particle diameter of the said inorganic fine particle is 1 micrometer or less, Preferably it is 300 nm or less, More preferably, it is 100 nm or less.

Moreover, in order to ensure adhesiveness to various film base materials etc. of a hard coat layer, you may mix | blend suitable tackifying resin (henceforth TF).

As TF, resins, such as phenols, such as modified rosin, polymerization rosin, a phenol resin, an alkylphenol resin, an aromatic petroleum type, such as a coumarone indene system, an aliphatic hydrocarbon type, and a terpene resin, can be used. The thing which modified | denatured carboxyl and hydroxyl group can also be used.

As a solvent used for dilution, Aromatic hydrocarbons, such as toluene and xylene; Alcohols such as methanol, ethanol and isopropyl alcohol; Esters such as ethyl acetate, butyl acetate and ethyl solve acetate; Ketones, such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, etc. are mentioned. These solvents may be used independently or may use 2 or more types together.

[Manufacturing Method of Hard Coating Film]

The protective pressure-sensitive adhesive film of the present invention is applied to the active energy ray-curable resin composition on a film substrate and cured to form a hard coating layer to form a hard coating film. It can manufacture by forming.

As a method of apply | coating an active-energy-ray-curable resin composition to a film base material, For example, gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, dip coating, spinner coating, wheeler coating , Blush coating, solid coating by silk screen, wire bar coating, flow coating, and the like. In addition, a printing method such as offset printing or 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 more uniform coating film is obtained.

As an apparatus for irradiating active energy rays, when using ultraviolet rays, as a light source, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an electrodeless lamp (fusion lamp), a chemical lamp, a black light lamp, Mercury-xenon lamps, short arc lamps, helium cadmium lasers, argon lasers, sunlight, LEDs and the like. In addition, when the active energy ray-curable resin composition used in the present invention is applied to a film base material and a cured film is formed, the influence of heat to the film base material can be reduced by using a xenon-flash lamp irradiated with flash. It is preferable because it is.

The thickness of the hard coat layer used in the present invention is adjusted to a thickness of 5 to 25 µm in order to suitably express the hard coating function even when a protective adhesive film having a total thickness of 150 µm or less is formed. Preferably it is 5-20 micrometers, More preferably, it is 5-15 micrometers. If it is less than 5 micrometers, surface pencil hardness will fall and when it exceeds 25 micrometers, adhesive coating will become difficult by hardening shrinkage of a hard coat layer.

[Hard Coating Film]

The hard coat film used in the present invention has at least the film base material and the hard coat layer, in view of exhibiting a substantially scratch-resistant effect when laminated via a pressure-sensitive adhesive layer on a display portion of an image display device or the like for use as a mobile application. , The pencil hardness of the hard coat layer surface is at least 3H or more, preferably 4H or more. If it is less than 3H, when a glass panel and the hard coat film of this invention are laminated | stacked through an adhesive layer, surface pencil hardness will fall. The light transmittance of the hard coat film is preferably 85% or more, more preferably 90% or more.

Moreover, in order to improve adhesiveness with a hard-coat layer, you may provide a thin primer layer in the film base material surface in the range which does not exceed 150 micrometers in total thickness.

[Pressure sensitive adhesive layer]

As an adhesive layer used by this invention, the adhesive layer of 5-20 micrometers in thickness is used. In this invention, by making thickness of an adhesive layer into the said thickness, sufficient adhesive force with a to-be-adhered object can be expressed, and even if stress concentration arises on the surface of a protective adhesive film, the elasticity modulus of the whole protective adhesive film can be kept high. Since it exists, it is thought that the fall of the hardness of the hard-coat layer provided in the adhesive film surface can be suppressed.

A well-known acryl-type, rubber type, silicone type adhesive resin can be used for the adhesive used for the adhesive layer used by this invention. Especially, the acryl-type copolymer containing the repeating unit derived from the acrylic acid ester which has a C2-C14 alkyl group as a repeating unit is preferable from a light resistance and heat resistance viewpoint. For example, the acryl-type copolymer containing the repeating unit derived from n-butyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, ethyl acrylate, etc. are mentioned.

Moreover, it is preferable to contain in the range of 0.01-15 mass% of repeating units derived from the acrylic acid ester and other vinylic monomer which have polar groups, such as a hydroxyl group, a carboxy group, and an amino group, in a side chain. An acryl-type copolymer can be obtained by copolymerizing by solution polymerization method, block polymerization method, suspension polymerization method, emulsion polymerization method, ultraviolet irradiation method, and electron beam irradiation method. The average molecular weight of the acrylic copolymer is preferably 400,000 to 1.4 million, more preferably 600,000 to 1.2 million.

Moreover, in order to raise the cohesion force of an adhesive, it is preferable to add a crosslinking agent. As a crosslinking agent, an isocyanate crosslinking agent, an epoxy crosslinking agent, a chelate crosslinking agent, etc. are mentioned, for example. As addition amount of a crosslinking agent, it is preferable to adjust so that it may become the gel fraction of 25 to 80% of an adhesive layer. In addition, a preferable gel fraction is 40 to 75%. Especially, 50 to 70% is the most preferable. If the gel fraction is less than 25%, the surface pencil hardness when the protective pressure-sensitive adhesive film is attached to the panel decreases. On the other hand, when a gel fraction exceeds 80%, adhesiveness will fall. The gel fraction is obtained by dipping the pressure-sensitive adhesive layer in toluene, measuring the mass after drying of the insolubles remaining after 24 hours of storage, and expressing it as a percentage with respect to the original mass.

Moreover, in order to improve the adhesive force of an adhesive layer, you may add tackifying resin. Tackifying resin added to the adhesive layer of the adhesive tape of this invention is rosin-type resin, such as rosin and rosin esterified substance; Terpene resins such as diterpene polymers and? -Pinene-phenol copolymers; Petroleum resins such as aliphatic (C5) and aromatic (C9); Other examples include styrene resins, phenol resins, and xylene resins. In order to make b * value of the adhesive layer after leaving 100 degreeC for 14 days to 6 or less, the esterified substance of hydrogenated rosin and disproportionated rosin, aliphatic, aromatic petroleum resin, etc. which have few unsaturated double bonds are added to an adhesive layer. It is preferable. The b * value is a value indicating yellowness in the L * a * b * color system established in JIS Z 8729, and a large b * value indicates strong yellowness.

In order to make adhesiveness and yellowing resistance compatible, it is preferable to use high disproportionation rosin ester, superposition | polymerization rosin ester, and petroleum resin together.

As addition amount of tackifying resin, when adhesive resin is an acrylic copolymer, it is preferable to add 10-60 mass parts with respect to 100 mass parts of acrylic copolymers. In the case of focusing on adhesiveness, it is most preferable to add 20 to 50 parts by mass. In addition, when adhesive resin is rubber-based resin, it is preferable to add 80-150 mass parts of tackifying resin with respect to 100 mass parts of rubber-type resins. In addition, generally, when adhesive resin is silicone resin, tackifying resin is not added.

In addition to the above, a well-known usual additive can be added to an adhesive. For example, in order to improve the adhesiveness to glass, a silane coupling agent can be added in the range of 0.001-0.005 mass part with respect to 100 mass parts of adhesives. In addition, plasticizers, softeners, fillers, pigments, flame retardants and the like can be added.

An adhesive layer can be formed on a film base material by the method generally used for application | coating of an adhesive sheet. The composition of an adhesive layer is apply | coated directly to a base film, it is dried, or it is apply | coated on a separator (peel sheet) once, and after drying, it is bonded to a base film.

The pressure-sensitive adhesive used as the pressure-sensitive adhesive layer can be suitably adjusted to the stress relaxation of the pressure-sensitive adhesive in a high temperature environment by setting the storage modulus at 80 ° C. in the dynamic viscoelastic spectrum at a frequency of 1 Hz to 1.0 × 10 ⁵ Pa or more. Foaming can be suppressed. The upper limit of the storage modulus is not particularly limited as long as it is a range in which the pressure-sensitive adhesive can be produced, but from the viewpoint of preventing practical adhesive force, bleeding during processing, etc., about 5.0 × 10 ⁵ Pa is preferable, and 3 × 10 ⁵ Pa or less Is particularly preferred.

The storage modulus at 20 ° C. in the dynamic viscoelastic spectrum at a frequency of 1 Hz of the adhesive used as the adhesive layer is preferably 1.0 × 10 ⁵ Pa or more, more preferably 2.5 × 10 ⁵ Pa or more. By setting storage elastic modulus to 1.0 * 10 <^5> Pa or more, the fall of the surface hardness of the protective adhesive film by an adhesive can be suppressed suitably.

[Protective adhesive film]

The structure of the protective adhesive film of this invention is a protective adhesive film in which the adhesive layer was provided in the said hard coat film, The total thickness is 60-150 micrometers, Preferably it is a protective film of 80-120 micrometers.

The protective film of the present invention is a very thin film of 150 µm or less, which is compatible with the contrary characteristics of preventing deformation during scratching and stress concentration by forming a configuration in which the physical property values of the structural members are adjusted to a specific range and combined. . Thereby, the outstanding surface hardness which was not obtained with the conventional protective film is realized, without providing the special hard coating layer and film base material with very high hardness and rigidity. Moreover, since the protective film of this invention does not need to use a hard-coating layer and film base material with very high hardness and rigidity, peeling by repulsion hardly arises even if it is made to adhere to an attachment object.

The protective adhesive film of this invention can implement | achieve a high surface hardness, even if it adheres to an attachment object via an adhesive layer, and can implement | achieve the hardness of 2H or more, More preferably, 3H or more preferably in the state attached to a glass plate. It can be used suitably as a protective film of the thin glass panel of a portable electronic terminal, or a protective film of various displays. Moreover, when a sticking object is a thing which a crack, such as glass, arises, it is useful as a scattering prevention film which prevents scattering when a sticking object is broken.

As for 180 degree peel adhesive force in the tensile velocity of 300 mm / min with respect to glass of the protective adhesive film of this invention, 4-12 N / 25 mm is preferable. By making adhesive force into the said range, peeling at the edge part of a protective adhesion film hardly arises even when it uses for a portable electronic terminal. Moreover, 85% or more is preferable and, as for the light transmittance of the protective adhesive film of this invention, More preferably, it is 90% or more. By making light transmittance 85% or more, the visibility of the display part of an image display apparatus becomes favorable.

[Screen panel]

The screen panel of this invention consists of a laminated body of a glass plate and the protective adhesive film of this invention. Since the screen panel is hardly scratched on the surface layer, it can be usefully used for the image display part of various displays. Among them, the screen panel, which is a laminate of a protective adhesive film and a glass plate having a surface hardness of 3H or more in a state of being attached to a glass plate, Since the scratch of a glass plate is especially reduced, it is very useful as various display uses which have this screen panel on the image display part surface.

It is preferable that a glass plate is a tempered glass plate. As a method of strengthening the glass plate, there may be mentioned a physical strengthening method and a chemical strengthening method. In particular, chemical strengthening methods include ion exchange and wind-cooled strengthening. Examples of the material of the glass plate include float glass, alkali glass, alkali free glass, and tempered glass.

[Mobile Electronic Terminal]

The portable electronic terminal of the present invention has a structure in which a screen panel, which is a laminate of the protective film of the present invention, is fixed to a case having an LCD module with a gap between the LCD module surface (FIG. 1). In the above configuration, since the space is provided under the screen panel, the screen panel on the surface of the image display portion may be curved when an impact or the like is applied to the surface. If curvature occurs, the stress concentrates on the concave portion, and scratches tend to occur, but even in this case, according to the protective pressure-sensitive adhesive film of the present invention, it is possible to suitably prevent scratch generation. For this reason, the protective adhesive film and screen panel of this invention can be used especially suitably for the portable electronic terminal of the structure.

In particular, as an example of a mobile electronic terminal, there is a mobile phone whose screen panel is made of glass. Since the surface of the mobile phone carried in a pocket or bag of pants is likely to be scratched, the mobile phone having the protective adhesive film of the present invention having a surface hardness of 3H or more attached to the screen panel is less likely to be scratched on the screen panel. Since the fall of the visibility of an image display part can be reduced, it can use preferably.

[Example]

Although an Example and a comparative example demonstrate this invention further more concretely below, this invention is not limited to these at all.

(Synthesis Example 1)

<Synthesis of Polymer (A1)>

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"), 1.6 parts by mass of lauryl mercaptan, and methyl isobutyl ketone (hereinafter referred to as "gma"). And 1000 parts by mass of 2,2'-azobisisobutyronitrile (hereinafter referred to as AIBN) and 1000 parts by mass of `` MIBK '' are injected at 90 ° C over 1 hour while stirring under a nitrogen stream. It heated up and made it react at 90 degreeC for 1 hour. Then, while stirring at 90 degreeC, the liquid mixture which consists of 750 mass parts of GMA, 4.4 mass parts of lauryl mercaptans, and 22.5 mass parts of AIBN was dripped over 2 hours, and it was made to react at 100 degreeC for 3 hours. Then, 10 mass parts of AIBNs were inject | poured, and it made it react at 100 degreeC for 1 hour, and then heated up around 120 degreeC and made it react for 2 hours. Cool to 60 ° C, replace the nitrogen introduction pipe with an air introduction pipe, 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 mixture was heated up to 110 ° C while bubbling the reaction solution with air, and allowed to react for 8 hours. Then, after adding 1.4 mass parts of p-methoxy phenols, and cooling to room temperature, MIBK was added so that a non volatile matter might be 50 mass%, and the polymer (A1) (MIBK solution of 50 mass% non volatile matters) was obtained. . In addition, the weight average molecular weight of the obtained polymer (A1) was 11,000 (by polystyrene conversion by GPC), and the (meth) acryloyl group equivalent was 300 g / eq.

(Synthesis Example 2)

<Synthesis of Polymer (A2)>

In a flask equipped with a stirrer, a gas inlet tube, a cooling tube, and a thermometer, 200 parts by mass of GMA, 50 parts by mass of n-butyl methacrylate (hereinafter referred to as "nBMA"), lauryl mercaptan 1.8 parts by mass, 1000 parts by mass of MIBK '' and 7.5 parts by mass of AIBN were injected, and the mixture was heated at 90 ° C over 1 hour while stirring under a nitrogen stream, and allowed to react at 90 ° C for 1 hour. Subsequently, after stirring at 90 degreeC, the liquid mixture which consists of 600 mass parts of GMA, 150 mass parts of nBMA, 4.8 mass parts of lauryl mercaptans, and 22.5 mass parts of AIBN was dripped over 2 hours, and it was made to react at 100 degreeC for 3 hours. . Then, 10 mass parts of AIBNs were inject | poured, and after making it react at 100 degreeC for 1 hour, it heated up to near 120 degreeC and made it react for 2 hours. After cooling to 60 ° C, the nitrogen inlet pipe was replaced with an air inlet pipe, 406 parts by mass of AA, 2 parts by mass of p-methoxyphenol, and 5.4 parts by mass of triphenylphosphine were added and mixed. It heated up to 110 degreeC, bubbling, and made it react for 8 hours. Then, after adding 1.4 mass parts of p-methoxy phenols, and cooling to room temperature, MIBK was added so that a non volatile matter might be 50 mass%, and the polymer (A2) (MIBK solution of 50 mass% non volatile matters) was obtained. . In addition, the weight average molecular weight of the obtained polymer (A2) was 8,800 (by polystyrene conversion by GPC), and the (meth) acryloyl group equivalent was 240 g / eq.

(Synthesis Example 3)

<Synthesis of fluorinated alkyl group-containing acrylate (average number of added functional groups 2)>

28.9 g (0.05 mol) of dipentaerythritol hexaacrylate (LUMICURE DPA-600 manufactured by Dainippon Inky Chemical Co., Ltd.), 1.0 g of triethylamine, and 20 g of methyl isobutyl ketone (MIBK) are mixed in a 200 ml reaction flask. To the solution, 48.2 g (0.1 mol) of perfluorooctylethyl mercaptan was added dropwise while stirring at room temperature. After completion of the dropwise addition, the mixture was further stirred at 50 ° C for 3 hours, and the fluorinated alkyl group-containing acrylate represented by the structural formula (xxi) was contained by distilling off MIBK and triethylamine under reduced pressure in an evaporator (bath temperature of 50 ° C or lower). Then, 76.8 g of product (A3) consisting of a mixture in which the position of addition reaction of the acryloyl group and the perfluorooctylethyl mercaptan further comprises a compound different from the above formula (xxi) was obtained. Peaks and integrals of the ¹ H-NMR spectrum of the product supported the synthesis.

¹ H-NMR:

δ

2.20-2.90 (m, 16 H),

3.30-3.50 (m, 4H),

4.10-4.40 (m, 12H),

5.84 (d, J = 10.2 Hz, 4H),

6.10 (dd, J = 10.2, 17.2 Hz, 4H),

6.42 (d, J = 17.2 Hz, 4H)

(Manufacture of Hard Coating Agent (1))

100 mass parts of MIBK solution (50 mass% of non volatile matters) of the polymer (A1) synthesize | combined by the synthesis example 1, 50 mass parts of pentaerythritol tetraacrylate (henceforth "PETA"), and silicone hexaacrylate (diesel) 1 part by mass of "Ebecryl 1360" manufactured by Yushibi Corporation, hereinafter referred to as "SiA", and 4 parts by mass of a photoinitiator (1-hydroxycyclohexylphenyl ketone; hereinafter referred to as "HCPK"). After mixing, the mixture was diluted with ethyl acetate so that the nonvolatile content became 40 mass%, to obtain a hard coating agent (1).

(Manufacture of Hard Coating Agent (2))

After mixing 100 mass parts of MIBK solution (50 mass% of non volatile matters), 50 mass parts of PETA, 1 mass part of SiA, and 4 mass parts of HCPK of the polymer (A2) synthesize | combined by the synthesis example 2, 40 mass of non volatile matters were uniformly mixed. It diluted with ethyl acetate so that it might become% and the hard coat agent (2) was obtained.

(Manufacture of Hard Coating Agent (3))

100 mass parts of MIBK solution (50 mass% of non volatile matters) of the polymer (A1) synthesize | combined by the synthesis example 1, 50 mass parts of pentaerythritol tetraacrylate (henceforth "PETA"), and A3 synthesize | combined above Example 3) After mixing 1 mass part and 4 mass parts of HCPK uniformly, it diluted with ethyl acetate so that a non volatile matter might be 40 mass%, and the hard coat agent (3) was obtained.

(Manufacture of Hard Coating Film 1)

On one side of the polyethylene terephthalate film having an elastic modulus of 4.5 GPa and a thickness of 75 μm, the above-described hard coating agent (1) was applied and dried at 60 ° C. for 90 seconds, followed by an ultraviolet irradiation device (Fusion UV Systems, Zepen). Ultraviolet light was irradiated with 0.5 J / cm <2> of irradiation light quantity using "F450" by a company, lamp | ramp: 120W / cm, H valve), and the hard-coat layer with a thickness of 8 micrometers was formed. Subsequently, the non-hard coating surface was treated with a corona treatment apparatus so as to have a surface tension of 55 dyne / cm to obtain a hard coat film (1).

(Manufacture of Hard Coating Film 2)

The hard coat film (2) was obtained by the same method except having used the hard coat agent (2) produced above instead of the hard coat agent (1) used by manufacture of said hard coat film (1).

(Manufacture of the hard coat film 3)

On one side of the polyethylene terephthalate film having an elastic modulus of 4.5 GPa and a thickness of 75 μm, the above-described hard coating agent (1) was applied and dried at 60 ° C. for 90 seconds, followed by an ultraviolet irradiation device (Fusion UV Systems, Zepen). Ultraviolet was irradiated with the irradiation light amount of 0.5 J / cm <2> using "F450" by a company, lamp | ramp: 120W / cm, H valve), and the hard-coat layer which is 15 micrometers in thickness was formed. Subsequently, the non-hard coated surface was treated with a corona treatment device so as to have a surface tension of 55 dyne / cm to obtain a hard coat film (3).

(Manufacture of the hard coat film 4)

After applying a hard coating agent (1) to one side of a polyethylene terephthalate film having an elastic modulus of 4.5 GPa and a thickness of 50 μm, and drying at 60 ° C. for 90 seconds, an ultraviolet irradiation device (manufactured by Fusion UV Systems Zepen Co., Ltd.) under an air atmosphere F450 ", lamp: 120W / cm, H valve), and irradiated with the ultraviolet-ray by irradiation amount 0.5J / cm <2>, and formed the hard-coat layer which is 15 micrometers in thickness. Next, the hard-hardened coating surface was surface-treated by the corona treatment apparatus so that it might become surface tension 55 dyne / cm, and the hard coat film 4 was obtained.

(Manufacture of the hard coat film 5)

After applying a hard coating agent (1) to one side of a polyethylene terephthalate film having an elastic modulus of 4.5 CPa and a thickness of 75 µm, and drying at 60 ° C. for 90 seconds, an ultraviolet irradiation device (manufactured by Fusion UV Systems & Zepen Co., Ltd.) under an air atmosphere F450 ", lamp: 120W / cm, H valve), and irradiated with ultraviolet-ray at the irradiation amount of 0.5J / cm <2>, and formed the hard-coat layer which is 3 micrometers in thickness. Then, the hard-hardened coating surface was surface-treated by the corona treatment apparatus so that it might become surface tension 55 dyne / cm, and the hard coat film 5 was obtained.

(Manufacture of the hard coat film 6)

On one surface of a polyethylene terephthalate film having an elastic modulus of 4.5 GPa and a thickness of 50 µm, a hard-coated surface of a hard coating film (surface pencil hardness 3H) manufactured by Toray Film Co., Ltd., having a hard coating layer having a thickness of 2 µm, By the corona treatment apparatus, it surface-treated so that it might become surface tension 55 dyne / cm, and obtained the hard coat film (6).

(Manufacture of the hard coat film 7)

On one side of a polyethylene terephthalate film having an elastic modulus of 4.5 GPa and a thickness of 100 μm, the hard coating agent (3) prepared above was applied and dried at 60 ° C. for 90 seconds, followed by an ultraviolet irradiation device (Fusion UV Systems & Zepen Co., Ltd.) under an air atmosphere. Ultraviolet was irradiated with the irradiation light amount of 0.5 J / cm <2> using "F450" by a company, lamp | ramp: 120W / cm, H valve), and the hard-coat layer which is 15 micrometers in thickness was formed. Then, the hard-hardened coating surface was surface-treated by the corona treatment apparatus so that it might become surface tension 55 dyne / cm, and the hard coat film 7 was obtained.

(Measurement of Surface Pencil Hardness of Hard Coating Film)

Based on the provisions of JIS K 5600-5-4 (1999 edition), the surface pencil hardness of the hard coat films (1) to (7) obtained above is a pencil scratch tester for coating film manufactured by Imoto Seisakusho Co., Ltd. ( Manual). In addition, the measured surface pencil hardness is shown in Table 1.

(Manufacture of adhesive layer 1)

Isocyanate type crosslinking agent (coronate L made by Nippon Polyurethane Co., Ltd.) with respect to the adhesive SPS1030B / 100 weight part made by Dainippon Inge Chemical Co., Ltd. in the peeling liner which formed the peeling layer of the silicone compound in the one surface of the polyethylene terephthalate film of 75 micrometers in thickness. -45, solid content 45%) was coated with an adhesive solution containing 1.3 parts by weight of the adhesive solution, and dried at 90 ° C. for 90 seconds to form an adhesive layer 1 having a thickness of 10 μm after drying.

(Manufacture of adhesive layer 2)

Isocyanate type crosslinking agent (coronate L made by Nippon Polyurethane Co., Ltd.) with respect to adhesive SPS1030B / 100 weight part made by Dainippon Inge Chemical Co., Ltd. in the release liner which formed the peeling layer of the silicone compound in the one surface of the polyethylene terephthalate film of 75 micrometers in thickness. -45, solid content 45%), the pressure-sensitive adhesive solution blended with 1.3 parts by weight was coated and dried at 90 ° C. for 90 seconds to form a pressure-sensitive adhesive layer 2 having a thickness of 30 μm after drying.

(Manufacture of adhesive layer 3)

The adhesive solution which mix | blended 1.6 weight part of hardening agents BXX5627 with respect to 100 weight part of adhesives BPS5762K by Toyo Inky Co., Ltd. was made to the peeling liner which formed the peeling layer of a silicone compound on one side of the polyethylene terephthalate film of thickness 75micrometer, and 90 degreeC After drying for 90 seconds, the pressure-sensitive adhesive layer 3 having a thickness of 10 µm after drying was formed.

(Example 1)

The pressure-sensitive adhesive layer 1 was bonded to the corona treated surface of the hard coat film 1 by 4 kg / cm pressure, and then cured at 40 ° C. for 2 days to obtain a protective adhesive film having a thickness of 93 μm. It was 270 N / mm <2> when the obtained protective adhesion film was affixed on the glass plate and the microhardness was measured on the conditions of a press-in depth of 1 micrometer, and a press-in time of 15 second as Fischer Instruments ultra-micro hardness tester Fisher scope H100C X-Yprog.

(Example 2)

The pressure-sensitive adhesive layer 1 was bonded to the corona treated surface of the hard coat film 2 by 4 kg / cm pressure, and then cured at 40 ° C. for 2 days to obtain a protective adhesive film having a thickness of 93 μm.

(Example 3)

The pressure-sensitive adhesive layer 1 was bonded to the corona treated surface of the hard coat film 3 by 4 kg / cm pressure, and then cured at 40 ° C. for 2 days to obtain a protective adhesive film having a thickness of 100 μm.

(Example 4)

The adhesive layer 1 was adhere | attached on the corona treatment surface of the hard coat film 4 by pressure of 4 kg / cm, and then cured at 40 degreeC for 2 days, and the protective adhesive film of thickness 75micrometer was obtained.

(Example 5)

The pressure-sensitive adhesive layer 1 was adhered to the corona treated surface of the hard coat film 7 by 4 kg / cm pressure, and then cured at 40 ° C. for 2 days to obtain a protective adhesive film having a thickness of 125 μm. It was 310 N / mm <2> when the obtained protective adhesive film was affixed on the glass plate and the micro hardness was measured similarly to the above.

(Comparative Example 1)

The adhesive layer 1 was adhere | attached on the corona treatment surface of the hard coat film 5 by pressure of 4 kg / cm, and then cured at 40 degreeC for 2 days, and the protective adhesive film of thickness 88micrometer was obtained.

(Comparative Example 2)

The pressure-sensitive adhesive layer 2 was adhered to the corona treated surface of the hard coat film 1 by 4 kg / cm pressure, and then cured at 40 ° C. for 2 days to obtain a protective adhesive film having a thickness of 113 μm.

(Comparative Example 3)

After the adhesive layer 1 was adhere | attached on the corona treatment surface of the hard coat film 6 by the pressure of 4 kg / cm, after curing for 2 days at 40 degreeC, the protective adhesive film of thickness 62micrometer was obtained.

(Comparative Example 4)

The pressure-sensitive adhesive layer 3 was adhered to the corona treated surface of the hard coat film 1 by 4 kg / cm pressure, and then cured at 40 ° C. for 2 days to obtain a protective adhesive film having a thickness of 113 μm.

[Measurement of Surface Pencil Hardness of Protective Adhesive Film]

The protective adhesive film obtained by the said Example and the comparative example is affixed on a glass plate, and the surface pencil hardness is made by Imoto Seisakusho Co., Ltd. based on JIS K 5600-5-4 (1999 edition). It measured using the pencil scraping tester (manual type) for coating films.

[Measurement of Viscoelastic Spectrum]

The pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples were bonded to a thickness of 2 mm to form a test piece, a parallel disk having a diameter of 7.9 mm was mounted on a viscoelastic tester Ares 2 KSTD manufactured by Leometrics, and the test piece was inserted into the parallel disk. The temperature dispersion method, frequency 1 Hz, and the measurement temperature range measured viscoelastic spectrum at -30-100 degreeC, and read the storage modulus G 'of 20 degreeC and 80 degreeC.

[Observation of bubble presence]

The adhesive sheet of the Example and the comparative example of the same size was adhere | attached with the hand roll under normal temperature and normal pressure to the diagonal 2-inch-thick 0.8 mm thick ishizuka glass-furistor and IG3, and it was set as the test piece.

The test piece was subjected to autoclave treatment at 50 ° C. 5 kgf / m 2 for 20 minutes, and the number of bubbles at the time of adhesion at five points in the center and four corners of the test piece was measured under a microscope of 50 times. Then, it was left to stand in an environmental test machine of 60 degreeC 90% RH. After standing, the presence or absence of bubbles at five points in total in the center and four corners of the sample was observed under a microscope of 50 times. It was set as (circle): no bubble and x: bubble existed.

[Adhesiveness]

The adhesive force of the adhesive tape of this invention was calculated | required by the following procedure according to the test method of the adhesive force pulled 180 degree of JIS-Z0237 (2000).

(1) The adhesive tape of the 25 mm width | variety Example and the comparative example which added 25 micrometers of polyester films was made to pressurize 1 round-trip with a 2 kg roller, and left to stand for 1 hour on the glass plate on conditions of 23 degreeC of environment temperature, and 50% of humidity. The adhesive force (N) when peeling off a 25 mm wide tape pulled at a speed of 300 mm / min under the same temperature and humidity conditions using a Tenshiron universal tensile tester (RTA100, manufactured by Orientech). Was measured.

[Table 1]

As is apparent from Table 1, the protective adhesive film of the present invention was able to maintain high surface hardness and suitable adhesion even at a thin total thickness, and it was difficult to generate foaming even at a high temperature environment.

When the protective adhesive film of this invention is used for the protection of the thin glass panel of a portable electronic terminal, for example, since it has high surface pencil hardness, it can be used suitably. Or it can use suitably for protection of various displays. In addition, in the case where the attaching object is a crack such as glass, it is useful as a scattering prevention film that prevents scattering when the attaching object is broken, and there is significant industrial significance.

1 is a cross-sectional view showing an example of a portable electronic terminal of the present invention.

[Description of Symbols]

1: protective adhesive film 2: glass plate 3: case 4: LCD module 5: air gap

Claims (11)

As a protective adhesive film in which the adhesive layer was provided in the hard coat film which consists of a film base material which has a hard coat layer, The film base material has an elastic modulus of 3 to 7 GPa and a thickness of 38 to 100 µm. The hard coating layer has a thickness of 5 to 25 μm, The pencil hardness of the hard coat layer surface of the hard coat film is 3H or more, The thickness of the said adhesive layer is 5-20 micrometers, Total thickness is 60-150㎛, The storage elastic modulus in 80 degreeC in the dynamic viscoelasticity spectrum at the frequency of 1 Hz of the said adhesive layer is 1.0 * 10 <^5> Pa or more 5.0 * 10 <^5> Pa or less The protective adhesive film characterized by the above-mentioned. delete The method according to claim 1, The protective adhesive film whose 180 degree peeling adhesive force with a tensile speed of 300 mm / min with respect to a glass plate is 4-12 N / 25 mm. The method according to claim 1, The (meth) acryloyl group which the said hard-coat layer reacted the (meth) acrylate type polymer (a1) which has a reactive functional group in a side chain with the (alpha), (beta)-unsaturated compound (a2) which has a functional group which can react with the said reactive functional group The protective adhesive film which is a layer which consists of a hardened | cured material of the polymer (A) which has, and the polyfunctional (meth) acrylate (B) which has three or more (meth) acryloyl groups in 1 molecule. 5. The method of claim 4, The protective adhesive film whose said polymer (A) is a reaction product which made (alpha), (beta)-unsaturated carboxylic acid react with the glycidyl (meth) acrylate type polymer. 5. The method of claim 4, The protective adhesive film whose weight average molecular weights of the said polymer (A) are 5,000-80,000, and the (meth) acryloyl group equivalent is 100-300 g / eq. 5. The method of claim 4, The active energy ray-curable resin composition has the following general formula (1)

[In Formula (1), R is a hydrogen atom or a C1-C4 alkyl group, X is the alkylene chain which may have a hetero atom, or following General formula (2)

{In formula (2), Y is an oxygen atom or a sulfur atom, m and n are integers of 1 to 4, which may be the same or different, and Rf ¹ is a fluorinated alkyl group.} And Rf is a fluorinated alkyl group. .] The protective adhesive film containing the functional group which has a fluorinated alkyl group in the terminal represented by and the fluorinated alkyl group containing (meth) acrylate which has two or more (meth) acryloyl groups. 8. The method of claim 7, The fluorinated alkyl group-containing (meth) acrylate has a fluorine atom content in one molecule of 25% by weight or more, and a protective adhesive film having a molecular weight of 500 to 4000. The method according to claim 1, The protective adhesive film whose light transmittance is 85% or more. It consists of a laminated body of the protective adhesive film in any one of Claims 1 and 3-9, and the glass plate whose thickness is 0.1-1 mm, The screen panel characterized by the above-mentioned. A portable electronic terminal, wherein the screen panel according to claim 10 is fixed to a case having an LCD module with a gap between the LCD module surface.

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