WO2012077809A1 - Adhesive resin composition for image display device, adhesive sheet for image display device, and image display device - Google Patents

Adhesive resin composition for image display device, adhesive sheet for image display device, and image display device Download PDF

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Publication number
WO2012077809A1
WO2012077809A1 PCT/JP2011/078619 JP2011078619W WO2012077809A1 WO 2012077809 A1 WO2012077809 A1 WO 2012077809A1 JP 2011078619 W JP2011078619 W JP 2011078619W WO 2012077809 A1 WO2012077809 A1 WO 2012077809A1
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Prior art keywords
meth
image display
display device
acrylate
resin composition
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PCT/JP2011/078619
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French (fr)
Japanese (ja)
Inventor
聖司 春原
今泉　純一
中村　智之
中村　一
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日立化成工業株式会社
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Priority to JP2012547936A priority Critical patent/JP5790663B2/en
Publication of WO2012077809A1 publication Critical patent/WO2012077809A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/6725—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing ester groups other than acrylate or alkylacrylate ester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer

Definitions

  • the present invention relates to an adhesive resin composition for an image display device, an adhesive sheet for an image display device, and an image display device.
  • a liquid crystal display device (liquid crystal display (LCD)) is illustrated as an example of a typical image display device.
  • LCD liquid crystal display
  • a polarizing plate or a laminate of a polarizing plate and a retardation plate is attached to an optical component such as a liquid crystal display cell of a liquid crystal display device.
  • an optical component such as a liquid crystal display cell of a liquid crystal display device.
  • FIG. A liquid crystal display device with a built-in touch panel includes a transparent protective plate (glass or plastic substrate) 1, a touch panel 2, a polarizing plate 3, and a liquid crystal display cell 4. In recent liquid crystal display devices, the liquid crystal display device is cracked.
  • an adhesive layer 5 for bonding the transparent protective plate and the touch panel is provided, and further, an adhesive layer 6 for bonding the touch panel and the polarizing plate is provided. It has been. Since such a liquid crystal display device has been used for various purposes such as in-vehicle use, outdoor instruments, mobile phones, personal computers, etc., the use environment has become very severe. Under such severe conditions, the adhesive strength of the adhesive layers 5 and 6 to which the respective members are bonded is reduced, and air bubbles, peeling and the like are likely to occur. Therefore, a highly durable pressure-sensitive adhesive sheet that does not generate air bubbles, peeling, etc. even under the severe conditions as described above is required. In response to this requirement, Patent Document 1 is exemplified as a pressure-sensitive adhesive composition that does not foam, float, peel off, etc. at the bonding interface even when exposed to a high temperature and high temperature and high humidity for a long time.
  • the material described in Patent Document 1 contains a component having a carboxyl group in order to improve adhesion, and this acid component may corrode the ITO transparent electrode of the touch panel. Moreover, since the material described in Patent Document 1 has a low glass transition temperature, it is expected to be inferior in handleability.
  • INDUSTRIAL APPLICABILITY The present invention is useful for prevention of cracking, relaxation of stress and impact, has excellent transparency, improves fogging and flickering of a displayed image, and is particularly high temperature conditions (for example, 80 ° C. or higher) and high temperature and high humidity conditions.
  • the present invention (1) (A) (meth) acrylic acid derivative polymer, (B) (meth) acrylic acid derivative monomer having one (meth) acryloyl group in the molecule, (C) bifunctional (meth) acryloyl group And (D) a pressure-sensitive adhesive resin composition for an image display device comprising a photopolymerization initiator, wherein (C) the cross-linking agent having a bifunctional (meth) acryloyl group has a weight average molecular weight of 2 0.0 ⁇ 10 4 to 4.0 ⁇ 10 4 crosslinking agent (hereinafter sometimes referred to as “crosslinking agent Y”), and the blending amount of the crosslinking agent Y is based on the total amount of the adhesive resin composition.
  • crosslinking agent Y crosslinking agent
  • An adhesive resin composition for an image display device having a content of 4 to 8% by mass (2) An adhesive sheet for an image display device obtained by curing the adhesive resin composition for an image display device according to (1) above into a sheet, and (3) For an image display device according to (1) above An image display device having a layer formed from an adhesive resin composition on the viewing side is provided.
  • the adhesive strength between the transparent protective plate on the viewing side, such as glass, and the adhesive resin composition is high, and even when exposed to high temperature and high humidity such as 85 ° C./85% RH, it peels off, floats, bubbles, etc. It is possible to provide an adhesive resin composition for an image display device and an adhesive sheet for an image display device that do not reduce the visibility of the display.
  • a liquid crystal display unit and a touch panel for example, a liquid crystal display unit and a touch panel, a liquid crystal display unit and a transparent protective plate, a touch panel and a transparent protective plate, or other members that are considered necessary for the image display unit and other image display devices, or an image display
  • an adhesive sheet for an image display device capable of bonding members on the viewing side of the image display unit of the device.
  • Transparent protective plate glass or plastic substrate
  • Touch panel 3
  • Polarizing plate 4
  • Liquid crystal display cell 5
  • Adhesive layer for laminating the transparent protective plate and the touch panel 6
  • the adhesive resin composition for an image display device of the present invention comprises (A) (meth) acrylic acid derivative polymer, (B) (meth) acrylic acid derivative monomer, specific (C) bifunctional (meth) acryloyl.
  • a cross-linking agent having a group and (D) a polymerization initiator, and the pressure-sensitive adhesive sheet for an image display device of the present invention is obtained by processing the pressure-sensitive resin composition into a sheet shape and curing the image. An apparatus is manufactured using this adhesive resin composition or this adhesive sheet.
  • Adhesive resin composition for image display device each component contained in the adhesive resin composition for an image display device according to the present invention (hereinafter sometimes simply referred to as “adhesive resin composition”) will be described.
  • the (A) (meth) acrylic acid derivative polymer in the present invention refers to a polymer obtained by polymerizing one monomer having one (meth) acryloyl group in the molecule or copolymerizing two or more monomers.
  • a compound having two or more (meth) acryloyl groups in the molecule or a polymerizable compound not having a (meth) acryloyl group for example, acrylonitrile, styrene, acetic acid
  • a compound having one polymerizable unsaturated bond such as vinyl, ethylene or propylene in the molecule or a compound having two or more polymerizable unsaturated bonds in the molecule such as divinylbenzene may be copolymerized.
  • (A) Monomers forming the (meth) acrylic acid derivative polymer include, for example, (meth) acrylic acid, (meth) acrylic amide, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) 1 to 18 carbon atoms such as acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, stearyl (meth) acrylate, etc.
  • Alkyl (meth) acrylates benzyl (meth) acrylate, (meth) acrylate having an aromatic ring such as phenoxyethyl (meth) acrylate; butoxyethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate (Meth) acrylates having alkoxy groups such as methoxytriethylene glycol (meth) acrylates; (meth) s having alicyclic groups such as cyclohexyl (meth) acrylates, isobornyl (meth) acrylates, dicyclopentanyl (meth) acrylates Acrylate; (meth) acrylate having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; tetrahydrofurfuryl (meth) acrylate; tetraethylene glycol monomethyl Ether (meth
  • Examples include polyethylene glycol ethyl ether (meth) acrylate; tetraethylene glycol (meth) acrylate, hexaethylene glycol (meth) acrylate, and octapropylene glycol (meth) acrylate.
  • the alkyl group having 4 to 18 carbon atoms is preferable.
  • a polymer having such a copolymerization ratio can be generally obtained by blending each monomer at the same ratio as the above-mentioned copolymerization ratio and copolymerizing the monomers, so that the polymerization rate substantially approaches 100% by mass. It is preferable.
  • Monomers that copolymerize with (meth) acrylates having an alkyl group having 4 to 18 carbon atoms are not limited to those described above, but include hydroxyl groups, morpholine groups, amino groups, carboxyl groups, cyano groups, carbonyl groups, nitro groups, and the like.
  • Monomers having polar groups such as groups are preferred, that is, (meth) acrylates having these polar groups are preferred because they tend to improve the adhesion to transparent substrates such as plastics.
  • the weight average molecular weight of the (meth) acrylic acid derivative polymer is preferably 1 ⁇ 10 5 to 1 ⁇ 10 6 in terms of a value converted by gel permeation chromatography using a standard polystyrene calibration curve. More preferred is 1 ⁇ 10 5 to 5 ⁇ 10 5 .
  • the polymerization method of the (meth) acrylic acid derivative polymer may be a known polymerization method such as solution polymerization, emulsion polymerization, suspension polymerization, or bulk polymerization.
  • a compound that generates radicals by heat can be used.
  • the blending amount of the (meth) acrylic acid derivative polymer is preferably 10 to 70% by mass, and more preferably 15 to 60% by mass with respect to the total amount of the adhesive resin composition.
  • the (B) (meth) acrylic acid derivative monomer in the adhesive resin composition for an image display device of the present invention is not particularly limited as long as it is a monomer having one (meth) acryloyl group in the molecule, Known materials can be used, and two or more kinds may be used in combination.
  • CH 2 CXCOO (C m H 2m O) n H ⁇ (b) (Wherein X represents H or CH 3 , m represents an integer of 2 to 4, and n represents an integer of 1 to 10)
  • alkyl (meth) acrylate having 4 to 18 carbon atoms in the alkyl group examples include n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, and n-octyl (meth) acrylate. , Isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like.
  • N-butyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, n-octyl (meth) acrylate and the like are preferable, and ethylhexyl (meth) acrylate is particularly preferable. Also, acrylate is more preferable than methacrylate. These (meth) acrylates may be used in combination of two or more.
  • Examples of the hydroxyl group-containing (meth) acrylate represented by the general formula (b) include 2-hydroxyethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl ( Such as meth) acrylate, 1-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, etc.
  • Hydroxyl group-containing (meth) acrylate polyethylene glycol mono (meth) acrylate such as diethylene glycol mono (meth) acrylate and triethylene glycol mono (meth) acrylate; dipropylene glycol mono (meth) Polypropylene glycol mono (meth) acrylates such as acrylate and tripropylene glycol mono (meth) acrylate; polybutylene glycol mono (meth) acrylates such as dibutylene glycol mono (meth) acrylate and tributylene glycol mono (meth) acrylate It is done.
  • 2-hydroxyethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate and the like are preferable, 2-hydroxyethyl (meth) acrylate and 4-hydroxy Butyl (meth) acrylate is particularly preferred and 4-hydroxybutyl (meth) acrylate is very particularly preferred.
  • the (B) (meth) acrylic acid derivative monomer preferably contains (meth) acryloylmorpholine from the viewpoint of further improving the effects of the present invention.
  • the content is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, and particularly preferably 15 to 25% by mass with respect to the total amount of the adhesive resin composition.
  • the content of the (B) (meth) acrylic acid derivative monomer is preferably 15 to 80% by mass with respect to the total amount of the adhesive resin composition.
  • the content of the (meth) acrylic acid derivative monomer is in the range of 15 to 80% by mass, the obtained pressure-sensitive adhesive sheet is bonded between the glass substrate and the glass substrate at a high temperature (80 ° C. And the occurrence of bubbles after the reliability test under high temperature and high humidity (85 ° C./85% RH) is suppressed.
  • the content of the (B) (meth) acrylic acid derivative monomer is more preferably 30 to 80% by mass, and particularly preferably 40 to 80% by mass.
  • the (C) cross-linking agent having a bifunctional (meth) acryloyl group in the present invention is a monomer having two (meth) acryloyl groups in the molecule.
  • crosslinking agent Y having a bifunctional (meth) acryloyl group having such a weight average molecular weight known methods can be used, for example, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate.
  • diisocyanates such as alkylene glycol, polyalkylene glycol, polyester polyol and other diols, hydroxyalkyl (meth) acrylate, lactone-modified hydroxyalkyl (meth) acrylate, isocyanatoalkyl (meth) acrylate and other (meth)
  • the acrylate can be synthesized by reacting both ends to be (meth) acryloyl groups.
  • a skeleton derived from isophorone diisocyanate that is, urethane di (meth) acrylate having a skeleton represented by the following general formula (a) is preferable because it is excellent in suppressing the occurrence of bubbles, floats, peeling, etc. of the present invention. .
  • the crosslinking agent Y is required to be 4 to 8% by mass with respect to the total amount of the adhesive resin composition, but is preferably 5 to 7% by mass.
  • the content is less than 4% by mass, the crosslinking density is low and the dimensional stability of the pressure-sensitive adhesive sheet at high temperature is poor.
  • the content exceeds 8% by mass, the crosslinking density becomes too high.
  • crosslinking agent Y as the component (C)
  • other crosslinking agents that is, bifunctional (with a molecular weight deviating from the weight average molecular weight, within the range not impairing the effects of the present invention.
  • a crosslinking agent having a (meth) acryloyl group or a crosslinking agent having a tri- or higher functional (meth) acryloyl group may be used in combination.
  • the photopolymerization initiator (D) used in the present invention has a curing reaction that proceeds by irradiation with active energy rays.
  • the active energy rays are ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, ⁇ rays, and the like.
  • the selection of the photopolymerization initiator is not particularly limited, and known materials such as benzophenone series, anthraquinone series, benzoyl series, sulfonium salts, diazonium salts, and onium salts can be used.
  • benzophenone N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4,4′-dimethyl Aminobenzophenone, ⁇ -hydroxyisobutylphenone, 2-ethylanthraquinone, t-butylanthraquinone, 1,4-dimethylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 1,2 -Benzoanthraquinone, 2-phenylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl
  • polymerization initiators that do not color the adhesive resin composition include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2- ⁇ -hydroxyalkylphenone compounds such as hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one; bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis Acylphosphine oxide compounds such as (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; oligo (2-hydroxy- 2-Methyl-1- (4- (1-methylvinyl) phenyl) pro Non) and a combination thereof are preferred.
  • bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine
  • a photopolymerization initiator containing an acyl phosphine oxide compound such as oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide is preferable.
  • oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) is preferable.
  • a plurality of these photopolymerization initiators may be used in combination.
  • the blending amount of the photopolymerization initiator (D) is preferably 0.1 to 5% by mass with respect to the total amount of the adhesive resin composition.
  • permeability of the obtained adhesive sheet is high, and a hue does not become yellowish. From the above viewpoint, 3% by mass or less is more preferable.
  • additives may be blended in the adhesive resin composition for image display of the present invention as necessary.
  • various additives that can be blended in the present invention for example, it is added for the purpose of enhancing the storage stability of the adhesive resin composition obtained by blending (A), (B), (C) and (D).
  • Polymerization inhibitors such as paramethoxyphenol, antioxidants such as triphenylphosphine added for the purpose of increasing the heat resistance of the pressure-sensitive adhesive sheet obtained by curing the adhesive resin composition with light, and ultraviolet light
  • examples thereof include a light stabilizer such as HALS (Hindered Amine Light Stabilizer) added for the purpose of increasing resistance, and a silane coupling agent added for improving adhesion to glass or the like.
  • HALS Hindered Amine Light Stabilizer
  • silane coupling agent added for improving adhesion to glass or the like.
  • Surfactants such as polydimethylsiloxane and fluorine can be blended.
  • the above additives may be used alone or in combination with a plurality of additives.
  • the compounding quantity of these other additives is usually small compared with the total compounding quantity of said (A), (B), (C), and (D), and generally with respect to the whole quantity of adhesive resin composition. About 0.01 to 5% by mass.
  • the adhesive sheet obtained by irradiating and curing the adhesive resin composition for image display with active energy will be described below.
  • the adhesive resin composition for image display of the present invention can be used as it is in the liquid state as it is, but it is preferably used as a sheet-like adhesive sheet.
  • the production method of the adhesive sheet in this invention is illustrated below.
  • the pressure-sensitive adhesive sheet in the present invention is obtained by applying a pressure-sensitive resin composition on a base material in a sheet shape and irradiating it with an active energy ray to cure.
  • a light source of the active energy ray a light source having a light emission distribution at a wavelength of 400 nm or less is preferable. Can be used.
  • the irradiation energy is not particularly limited, but is usually about 500 to 5000 mJ / cm 2 .
  • the pressure-sensitive adhesive sheet for image display device of the present invention (hereinafter sometimes simply referred to as “pressure-sensitive adhesive sheet”) has an appropriate pressure-sensitive adhesive force and reworkability, does not contain bubbles or the like with respect to a desired thickness, and has excellent impact.
  • the thickness can be set so as to exhibit relaxation properties.
  • the thickness of the pressure-sensitive adhesive sheet of the present invention is not particularly limited depending on the intended use and method, but a thickness of about 0.05 to 2 mm is preferable. When used in this range, it exhibits particularly excellent effects as a transparent adhesive sheet for laminating an optical member on a display.
  • the glass transition temperature of the pressure-sensitive adhesive sheet is preferably 10 ° C. to 30 ° C.
  • the pressure-sensitive adhesive resin composition and pressure-sensitive adhesive sheet of the present invention can be applied to various image display devices.
  • the image display device include a plasma display (PDP), a liquid crystal display (LCD), a cathode ray tube (CRT), a field emission display (FED), an organic EL display (OELD), a 3D display, and electronic paper (EP).
  • PDP plasma display
  • LCD liquid crystal display
  • CRT cathode ray tube
  • FED field emission display
  • OELD organic EL display
  • 3D display electronic paper
  • the adhesive resin composition and the adhesive sheet of the present invention are, for example, a functional layer having functionality such as an antireflection layer, an antifouling layer, a dye layer, and a hard coat layer of the image display device, or a polyethylene film,
  • a multilayer product formed or laminated on an optical filter substrate such as a base film such as a polyester film, a transparent protective plate such as glass, acrylic or polycarbonate, or a multilayer product obtained by forming or laminating a functional layer having various functions thereoncan be used to combine and paste them together.
  • it can also be used as an optical filter combined with such a multilayer product.
  • the adhesive resin composition of the present invention can be cured after being applied to, or filled in, these multilayer products.
  • the antireflection layer may be a layer having an antireflection property with a visible light reflectance of 5% or less, and is a layer treated by a known antireflection method on a transparent substrate such as a transparent plastic film. Can be used.
  • the antifouling layer is for preventing the surface from getting dirty, and a known layer composed of a fluorine-based resin or a silicone-based resin can be used to reduce the surface tension.
  • the dye layer is used to increase color purity, and is used to reduce unnecessary light when the color purity of light emitted from an image display unit such as a liquid crystal display unit is low.
  • dye which absorbs the light of an unnecessary part can be melt
  • the hard coat layer is used to increase the surface hardness.
  • a hard-coat layer what formed or laminated
  • the adhesive resin composition and the adhesive sheet of the present invention can be used by being laminated on a polarizing plate. In this case, it can also laminate
  • an antireflection layer, an antifouling layer, and a hard coat layer can be laminated on the viewing surface side of the pressure-sensitive adhesive sheet.
  • a functional layer can be laminated on the viewing surface side of the polarizing plate.
  • an adhesive sheet can be laminated
  • the pressure-sensitive adhesive sheet is preferably disposed at an appropriate position on the viewing side between the image display unit of the image display device and the transparent protective plate (front plate) on the foremost viewing side. Specifically, it is preferably applied between the image display unit and the transparent protective plate. Further, in the image display device in which the touch panel is combined with the image display unit, it is preferable that the touch panel is applied between the touch panel and the image display unit and / or between the touch panel and the transparent protective plate (front plate). If the adhesive sheet of this invention is applicable on the structure of an image display apparatus, it will not restrict to the position described above.
  • the adhesive sheet is placed between the transparent protective plate and the touch panel, the touch panel and the image display unit, or between the transparent protective plate and the image display unit. From the viewpoint of further removing air bubbles in the vicinity of the step after the step of laminating in step 40 to 80 ° C. (preferably 50 ° C. to 70 ° C.), 0.3 to 0.8 MPa (preferably 0.4 to 0.7 MPa). It is preferable to heat and pressurize (autoclave treatment) for 5 to 60 minutes (preferably 10 to 50 minutes).
  • a general optical transparent substrate can be used as the transparent protective plate (front plate) of the image display device.
  • Specific examples include glass plates, inorganic plates such as quartz, plastic (organic) plates such as acrylic plates, polycarbonate plates, and polyethylene terephthalate plates, and resin sheets such as thick polyester sheets.
  • a general liquid crystal display cell can be used as the liquid crystal display cell.
  • Liquid crystal display cells are classified into TN (Twisted Nematic) method, STN (Super-twisted nematic) method, VA (Virtual Alignment) method, IPS (In-Place-Switching) method, etc., depending on the control method of the liquid crystal material.
  • a liquid crystal display cell using any control method may be used.
  • Each pressure-sensitive adhesive sheet obtained in each example and comparative example was evaluated by the following test method.
  • 1. Glass transition temperature A pressure-sensitive adhesive sheet having a thickness of 0.5 mm, a width of 10 mm, and a length of 10 mm was prepared, and using a wide-range dynamic viscoelasticity measuring apparatus (Peometric Scientific, Solids Analyzer RSA-II), a shear sandwich mode, frequency 1
  • the glass transition temperature was measured at 0.0 Hz, a measurement temperature range of ⁇ 40 to 80 ° C., and a heating rate of 5 ° C./min.
  • the glass transition temperature (Tg) was a temperature at which tan ⁇ exhibited a peak in the above measurement temperature range. When two or more tan ⁇ peaks were observed in this temperature range, the temperature at which the value of tan ⁇ was the largest was taken as the glass transition temperature. 2. Appearance evaluation The prepared pressure-sensitive adhesive sheet was cut into a size of 50 mm in width and 100 mm in length, and affixed to a glass substrate having dimensions of 50 mm ⁇ 100 mm ⁇ t 0.7 mm using a roller. Subsequently, the same glass substrate was bonded together using the roller, and the thing of the structure which pinched
  • the produced adhesive sheet was cut out into a size of 25 mm wide ⁇ 25 mm long.
  • the pressure-sensitive adhesive sheet was attached to a stainless steel plate of 25 mm ⁇ 100 mm, a PET film cut into 25 mm ⁇ 100 mm was attached thereto, and a 100 g weight was attached to the end of the PET film. Then, the stainless steel plate was fixed so that a 100-g weight might hang in a 80 degreeC thermostat dryer, and the dimensional change amount of the adhesive sheet 24 hours after was measured. If the dimensional change was 0.5 mm or less, it was determined as OK.
  • the weight average molecular weight was measured using gel permeation chromatography using THF as a solvent, and determined using a standard polystyrene calibration curve using the following apparatus and measurement conditions.
  • Apparatus Hitachi, Ltd.
  • RI detector L-3350
  • Solvent THF
  • Column Gelpac GL-R420 + R430 + R440 manufactured by Hitachi Chemical Co., Ltd.
  • Comparative production example 1 ⁇ (C) Synthesis 1 of a crosslinking agent having a bifunctional (meth) acryloyl group>
  • a reaction vessel equipped with a condenser, a thermometer, a stirrer, a dropping funnel and an air injection tube 223.12 g of polypropylene glycol (molecular weight 2,000), 76.29 g of lactone-modified hydroxyethyl acrylate, 99.68 g of 2-ethylhexyl acrylate, Taking 0.12 g of p-methoxyphenol as a polymerization inhibitor and 0.5 g of dibutyltin dilaurate as a catalyst, the temperature was raised to 75 ° C.
  • Polyurethane acrylate having a repeating unit of polypropylene glycol and isophorone diisocyanate and having a polymerizable unsaturated bond at both ends (weight average molecular weight 8,500) (Hereinafter, this polyurethane acrylate is referred to as “polyurethane diacrylate 1”).
  • Polyurethane acrylate having a repeating unit of polypropylene glycol and isophorone diisocyanate and having a polymerizable unsaturated bond at both ends (weight average molecular weight 20,000) (Hereinafter, this polyurethane acrylate is referred to as “polyurethane diacrylate 2”).
  • Comparative production example 2 ⁇ (C) Synthesis 4 of Crosslinking Agent Having Bifunctional (Meth) acryloyl Group>
  • a reaction vessel equipped with a condenser, a thermometer, a stirrer, a dropping funnel and an air injection tube 285.3 g of polypropylene glycol (molecular weight 2,000), 2-ethylhexyl acrylate 100. g, 0.13 g of p-methoxyphenol as a polymerization inhibitor and 0.5 g of dibutyltin dilaurate as a catalyst, the temperature was raised to 75 ° C. while flowing air, and 39.6 g of isophorone diisocyanate was stirred for 2 hours at 75 ° C.
  • Example 1 ⁇ Sample formulation and adhesive sheet preparation> 30.8 g of acrylic acid derivative polymer obtained in Production Example 1, 38.7 g of 2-ethylhexyl acrylate (EHA), 18.5 g of acryloylmorpholine (ACMO), 5.0 g of 4-hydroxybutyl acrylate (4-HBA), 6.5 g of polyurethane diacrylate 2 obtained in Production Example 2 and 0.5 g of 1-hydroxycyclohexyl phenyl ketone (I-184) were weighed and mixed by stirring to obtain an adhesive resin composition.
  • EHA 2-ethylhexyl acrylate
  • ACMO acryloylmorpholine
  • 4-HBA 4-hydroxybutyl acrylate
  • I-184 1-hydroxycyclohexyl phenyl ketone
  • the adhesive resin composition obtained above is dropped onto a polyethylene terephthalate film, and further covered with polyethylene terephthalate, and the adhesive resin composition is applied in a sheet form with a roller, and an ultraviolet irradiation device is used.
  • a transparent adhesive sheet was obtained by irradiating ultraviolet rays at 2,000 mJ / cm 2 .
  • Examples 2 and 3 and Comparative Examples 1 to 4 A pressure-sensitive adhesive resin composition and a pressure-sensitive adhesive sheet were prepared in the same manner as in Example 1 with the blending components and blending amounts shown in Tables 1 and 2.
  • an image display device having impact resistance and excellent visibility can be provided.
  • the adhesive strength between the transparent protective plate on the viewing side, such as glass, and the adhesive resin composition is high, and even when exposed to high temperature and high humidity such as 85 ° C./85% RH, it peels off, floats, bubbles, etc. And the visibility of the display is not reduced. That is, it is possible to bond the members that are considered necessary for the image display unit and the image display device, and it is possible to bond the members that are closer to the viewing side than the image display unit of the image display device.

Abstract

The present invention is an adhesive resin composition for an image display device, the adhesive resin composition containing (A) a (meth)acrylic acid derivative polymer, (B) a (meth)acrylic acid derivative monomer having one (meth)acryloyl group in the molecule, (C) a bifunctional crosslinking agent having a (meth)acryloyl group, and (D) a photoinitiator. The (C) bifunctional crosslinking agent having a (meth)acryloyl group contains a crosslinking agent (Y) having a weight average molecular weight of 2.0×104-4.0×104. The amount of the crosslinking agent (Y) admixed is 4-8 mass% with respect to the total adhesive resin composition. The present invention is able to provide an adhesive sheet and the adhesive resin composition that is for an image device and that does not decrease the visibility of a display and resists the occurrence of peeling, lifting, air bubbles, and the like even when exposed to a high temperature and high humidity.

Description

画像表示装置用粘着性樹脂組成物、画像表示装置用粘着シート及び画像表示装置Adhesive resin composition for image display device, adhesive sheet for image display device, and image display device
　本発明は、画像表示装置用粘着性樹脂組成物、画像表示装置用粘着シート及び画像表示装置に関する。 The present invention relates to an adhesive resin composition for an image display device, an adhesive sheet for an image display device, and an image display device.
　代表的な画像表示装置の例として液晶表示装置（液晶ディスプレイ（ＬＣＤ））が例示される。液晶表示装置の液晶表示セル等の光学部品には、一般に偏光板や偏光板と位相差板の積層体などが貼付けられているが、近年タッチパネルを内蔵した液晶表示装置の需要が伸びている。この構造の略図例を図１に示す。タッチパネルを内蔵した液晶表示装置は、透明保護板（ガラスまたはプラスチック基材）１、タッチパネル２、偏光板３、液晶表示セル４で構成されており、最近の液晶表示装置では、液晶表示装置の割れ防止、応力及び衝撃の緩和、並びに、視認性の向上のために、透明保護板とタッチパネルを貼合わせるための粘着層５が設けられ、さらにタッチパネルと偏光板を貼合わせるための粘着層６が設けられている。このような液晶表示装置は、車載用、屋外計器、携帯電話、パーソナルコンピュータ等多用途に使用されてきているため、これに伴い使用環境も非常に過酷になってきている。このような過酷な条件下では、各部材を貼合わせる粘着層５及び６の粘着力低下が発生し、気泡、剥がれ等が発生し易くなる。そのため、上記のような過酷条件下においても気泡、剥がれ等が発生しない耐久性の高い粘着シートが要求される。
　この要求に対して、高温下、高温高湿下に長期間暴露されても貼合界面に発泡、浮き、剥がれ等が生じない粘着材組成物として特許文献１が例示される。 A liquid crystal display device (liquid crystal display (LCD)) is illustrated as an example of a typical image display device. In general, a polarizing plate or a laminate of a polarizing plate and a retardation plate is attached to an optical component such as a liquid crystal display cell of a liquid crystal display device. Recently, however, the demand for a liquid crystal display device having a built-in touch panel is increasing. A schematic example of this structure is shown in FIG. A liquid crystal display device with a built-in touch panel includes a transparent protective plate (glass or plastic substrate) 1, a touch panel 2, a polarizing plate 3, and a liquid crystal display cell 4. In recent liquid crystal display devices, the liquid crystal display device is cracked. In order to prevent, relieve stress and impact, and improve visibility, an adhesive layer 5 for bonding the transparent protective plate and the touch panel is provided, and further, an adhesive layer 6 for bonding the touch panel and the polarizing plate is provided. It has been. Since such a liquid crystal display device has been used for various purposes such as in-vehicle use, outdoor instruments, mobile phones, personal computers, etc., the use environment has become very severe. Under such severe conditions, the adhesive strength of the adhesive layers 5 and 6 to which the respective members are bonded is reduced, and air bubbles, peeling and the like are likely to occur. Therefore, a highly durable pressure-sensitive adhesive sheet that does not generate air bubbles, peeling, etc. even under the severe conditions as described above is required.
In response to this requirement, Patent Document 1 is exemplified as a pressure-sensitive adhesive composition that does not foam, float, peel off, etc. at the bonding interface even when exposed to a high temperature and high temperature and high humidity for a long time.
特開２００７－２３８８５３号公報JP 2007-238853 A
　しかしながら、特許文献１に記載されている材料は、密着性を向上させるためにカルボキシル基を有する成分を含有しており、この酸成分がタッチパネルのＩＴＯ透明電極を腐食する恐れがある。また、特許文献１に記載されている材料は、ガラス転移温度が低いため、取り扱い性に劣ることが予想される。
　本発明は、割れ防止、応力及び衝撃の緩和に有用で、透明性に優れ、表示画像の曇り、チラツキなどが改善されると共に、特に、高温条件下（例えば８０℃以上）及び高温高湿条件下（例えば８５℃／８５％ＲＨ）での、気泡、浮き、剥がれ等の発生が抑制された取り扱い性にも優れる画像表示装置用粘着性樹脂組成物、これを用いた画像表示装置用粘着シート及び画像表示装置に関する。 However, the material described in Patent Document 1 contains a component having a carboxyl group in order to improve adhesion, and this acid component may corrode the ITO transparent electrode of the touch panel. Moreover, since the material described in Patent Document 1 has a low glass transition temperature, it is expected to be inferior in handleability.
INDUSTRIAL APPLICABILITY The present invention is useful for prevention of cracking, relaxation of stress and impact, has excellent transparency, improves fogging and flickering of a displayed image, and is particularly high temperature conditions (for example, 80 ° C. or higher) and high temperature and high humidity conditions. Adhesive resin composition for an image display device excellent in handleability in which generation of bubbles, floats, peeling, etc. is suppressed at a lower temperature (for example, 85 ° C./85% RH), and an adhesive sheet for an image display device using the same And an image display device.
　本発明者等は上記の課題を解決するために鋭意研究した結果、（メタ）アクリル酸系誘導体ポリマ、（メタ）アクリロイル基を分子内に１つ有する（メタ）アクリル酸系誘導体モノマに、特定の２官能の（メタ）アクリロイル基を有する架橋剤、及び光重合開始剤を含有する樹脂組成物により上記課題が解決し得ることを見出した。本発明は、かかる知見にもとづいて完成したものである。
　すなわち、本発明は、
（１）（Ａ）（メタ）アクリル酸系誘導体ポリマ、（Ｂ）（メタ）アクリロイル基を分子内に１つ有する（メタ）アクリル酸系誘導体モノマ、（Ｃ）２官能の（メタ）アクリロイル基を有する架橋剤及び（Ｄ）光重合開始剤を含有する画像表示装置用粘着性樹脂組成物であって、前記（Ｃ）２官能の（メタ）アクリロイル基を有する架橋剤が、重量平均分子量２．０×１０4～４．０×１０4の架橋剤（以下「架橋剤Ｙ」と記載することがある。）を含み、該架橋剤Ｙの配合量が、該粘着性樹脂組成物全量に対して４～８質量％である画像表示装置用粘着性樹脂組成物、
（２）上記（１）に記載の画像表示装置用粘着性樹脂組成物をシート状に硬化して得られる画像表示装置用粘着シート、及び
（３）上記（１）に記載の画像表示装置用粘着性樹脂組成物から形成される層を視認側に有する画像表示装置を提供するものである。 As a result of intensive studies to solve the above problems, the present inventors have identified a (meth) acrylic acid derivative polymer and a (meth) acrylic acid derivative monomer having one (meth) acryloyl group in the molecule. It has been found that the above-mentioned problems can be solved by a resin composition containing a crosslinking agent having a bifunctional (meth) acryloyl group and a photopolymerization initiator. The present invention has been completed based on such knowledge.
That is, the present invention
(1) (A) (meth) acrylic acid derivative polymer, (B) (meth) acrylic acid derivative monomer having one (meth) acryloyl group in the molecule, (C) bifunctional (meth) acryloyl group And (D) a pressure-sensitive adhesive resin composition for an image display device comprising a photopolymerization initiator, wherein (C) the cross-linking agent having a bifunctional (meth) acryloyl group has a weight average molecular weight of 2 0.0 × 10 4 to 4.0 × 10 4 crosslinking agent (hereinafter sometimes referred to as “crosslinking agent Y”), and the blending amount of the crosslinking agent Y is based on the total amount of the adhesive resin composition. An adhesive resin composition for an image display device having a content of 4 to 8% by mass,
(2) An adhesive sheet for an image display device obtained by curing the adhesive resin composition for an image display device according to (1) above into a sheet, and (3) For an image display device according to (1) above An image display device having a layer formed from an adhesive resin composition on the viewing side is provided.
　本発明によれば、耐衝撃性を有し、視認性に優れる画像表示装置を提供することができる。特に、視認側の透明保護板、例えばガラスと、粘着性樹脂組成物との密着力が高く、８５℃／８５％ＲＨのような高温高湿下に曝されても、剥がれ、浮き、気泡等を発生することなく、ディスプレイの視認性を低下させない画像表示装置用粘着性樹脂組成物及び画像表示装置用粘着シートを提供することができる。
　すなわち本発明によれば、例えば液晶表示ユニットとタッチパネル、液晶表示ユニットと透明保護板、タッチパネルと透明保護板など、画像表示ユニットとその他の画像表示装置に必要と思われる部材と、又は、画像表示装置の画像表示ユニットより視認側にある部材同士を貼合することが可能な画像表示装置用粘着シートを提供することができる。 According to the present invention, it is possible to provide an image display device having impact resistance and excellent visibility. In particular, the adhesive strength between the transparent protective plate on the viewing side, such as glass, and the adhesive resin composition is high, and even when exposed to high temperature and high humidity such as 85 ° C./85% RH, it peels off, floats, bubbles, etc. It is possible to provide an adhesive resin composition for an image display device and an adhesive sheet for an image display device that do not reduce the visibility of the display.
That is, according to the present invention, for example, a liquid crystal display unit and a touch panel, a liquid crystal display unit and a transparent protective plate, a touch panel and a transparent protective plate, or other members that are considered necessary for the image display unit and other image display devices, or an image display It is possible to provide an adhesive sheet for an image display device capable of bonding members on the viewing side of the image display unit of the device.
本発明の画像表示装置の断面構造を示す概略図である。It is the schematic which shows the cross-section of the image display apparatus of this invention.
１　透明保護板（ガラスまたはプラスチック基材）
２　タッチパネル
３　偏光板
４　液晶表示セル
５　透明保護板とタッチパネルを貼合わせるための粘着層
６　タッチパネルと偏光板を貼合わせるための粘着層 1 Transparent protective plate (glass or plastic substrate)
2 Touch panel 3 Polarizing plate 4 Liquid crystal display cell 5 Adhesive layer for laminating the transparent protective plate and the touch panel 6 Adhesive layer for laminating the touch panel and the polarizing plate
　本発明の画像表示装置用粘着性樹脂組成物は、（Ａ）（メタ）アクリル酸系誘導体ポリマ、（Ｂ）（メタ）アクリル酸系誘導体モノマ、特定の（Ｃ）２官能の（メタ）アクリロイル基を有する架橋剤及び（Ｄ）重合開始剤を含有するものであり、本発明の画像表示装置用粘着シートは該粘着性樹脂組成物をシート状に加工して硬化したものであり、画像表示装置は、該粘着性樹脂組成物又は該粘着シートを用いて製造したものである。以下、本発明の実施形態について、詳細に説明する。 The adhesive resin composition for an image display device of the present invention comprises (A) (meth) acrylic acid derivative polymer, (B) (meth) acrylic acid derivative monomer, specific (C) bifunctional (meth) acryloyl. A cross-linking agent having a group and (D) a polymerization initiator, and the pressure-sensitive adhesive sheet for an image display device of the present invention is obtained by processing the pressure-sensitive resin composition into a sheet shape and curing the image. An apparatus is manufactured using this adhesive resin composition or this adhesive sheet. Hereinafter, embodiments of the present invention will be described in detail.
＜画像表示装置用粘着性樹脂組成物＞
　以下、本発明に係わる画像表示装置用粘着性樹脂組成物（以下単に「粘着性樹脂組成物」ということがある）に含有される成分ごとに説明をする。 <Adhesive resin composition for image display device>
Hereinafter, each component contained in the adhesive resin composition for an image display device according to the present invention (hereinafter sometimes simply referred to as “adhesive resin composition”) will be described.
［（Ａ）（メタ）アクリル酸系誘導体ポリマ］
　本発明における（Ａ）（メタ）アクリル酸系誘導体ポリマとは、（メタ）アクリロイル基を分子内に１つ有するモノマを１種で重合するか又は２種以上組み合わせて共重合したものをいう。なお、本発明の効果を損なわない範囲であれば、（メタ）アクリロイル基を分子内に２個以上有する化合物や（メタ）アクリロイル基を有していない重合性化合物（例えば、アクリロニトリル、スチレン、酢酸ビニル、エチレン、プロピレン等の重合性不飽和結合を分子内に１個有する化合物やジビニルベンゼン等の重合性不飽和結合を分子内に２個以上有する化合物）を共重合させてもよい。 [(A) (Meth) acrylic acid derivative polymer]
The (A) (meth) acrylic acid derivative polymer in the present invention refers to a polymer obtained by polymerizing one monomer having one (meth) acryloyl group in the molecule or copolymerizing two or more monomers. In addition, as long as the effect of the present invention is not impaired, a compound having two or more (meth) acryloyl groups in the molecule or a polymerizable compound not having a (meth) acryloyl group (for example, acrylonitrile, styrene, acetic acid) A compound having one polymerizable unsaturated bond such as vinyl, ethylene or propylene in the molecule or a compound having two or more polymerizable unsaturated bonds in the molecule such as divinylbenzene may be copolymerized.
　（Ａ）（メタ）アクリル酸系誘導体ポリマを形成するモノマとして、例えば、（メタ）アクリル酸、（メタ）アクリル酸アミド、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ｎ－ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート等の炭素数１から１８のアルキル（メタ）アクリレート；ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート等の芳香環を有する（メタ）アクリレート；ブトキシエチレングリコール（メタ）アクリレート、ブトキシジエチレングリコール（メタ）アクリレート、メトキシトリエチレングリコール（メタ）アクリレート等のアルコキシ基を有する（メタ）アクリレート；シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート等の脂環式基を有する（メタ）アクリレート；２－ヒドロキシエチル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等の水酸基を有する（メタ）アクリレート；テトラヒドロフルフリル（メタ）アクリレート；テトラエチレングリコールモノメチルエーテル（メタ）アクリレート、ヘキサエチレングリコールモノメチルエーテル（メタ）アクリレート、オクタエチレングリコールモノメチルエーテル（メタ）アクリレート、ノナエチレングリコールメチルエーテル（メタ）アクリレート等のポリエチレングリコールモノメチルエーテル（メタ）アクリレート；ヘプタプロピレングリコールモノメチルエーテル（メタ）アクリレート等のポリプロピレングリコールモノメチルエーテル（メタ）アクリレート；テトラエチレングリコールエチルエーテル（メタ）アクリレート等のポリエチレングリコールエチルエーテル（メタ）アクリレート；テトラエチレングリコール（メタ）アクリレート、ヘキサエチレングリコール（メタ）アクリレート、オクタプロピレングリコール（メタ）アクリレートなどが挙げられる。 (A) Monomers forming the (meth) acrylic acid derivative polymer include, for example, (meth) acrylic acid, (meth) acrylic amide, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) 1 to 18 carbon atoms such as acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, stearyl (meth) acrylate, etc. Alkyl (meth) acrylates; benzyl (meth) acrylate, (meth) acrylate having an aromatic ring such as phenoxyethyl (meth) acrylate; butoxyethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate (Meth) acrylates having alkoxy groups such as methoxytriethylene glycol (meth) acrylates; (meth) s having alicyclic groups such as cyclohexyl (meth) acrylates, isobornyl (meth) acrylates, dicyclopentanyl (meth) acrylates Acrylate; (meth) acrylate having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; tetrahydrofurfuryl (meth) acrylate; tetraethylene glycol monomethyl Ether (meth) acrylate, hexaethylene glycol monomethyl ether (meth) acrylate, octaethylene glycol monomethyl ether (meth) acrylate, nonaethylene glycol Polyethylene glycol monomethyl ether (meth) acrylate such as methyl ether (meth) acrylate; polypropylene glycol monomethyl ether (meth) acrylate such as heptapropylene glycol monomethyl ether (meth) acrylate; tetraethylene glycol ethyl ether (meth) acrylate, etc. Examples include polyethylene glycol ethyl ether (meth) acrylate; tetraethylene glycol (meth) acrylate, hexaethylene glycol (meth) acrylate, and octapropylene glycol (meth) acrylate.
　上記化合物の中でも、炭素数４から１８のアルキル基を有する（メタ）アクリレートを含有することが好ましく、共重合された１分子のポリマを１００質量％とした場合、炭素数４から１８のアルキル基を有する（メタ）アクリレートの割合は、５質量％～９５質量％であることが好ましく、１０質量％から９０質量％であることがさらに好ましい。５質量％から９５質量％であれば粘着シートを形成した後の加工性において、ガラスやプラスチックなどの透明基材の密着性が向上する傾向にある。
　このような共重合割合のポリマは、一般に、各モノマを上記共重合割合と同じ割合で配合し、共重合させることで得ることができ、重合率を実質的に１００質量％に近づくようにすることが好ましい。 Among the above compounds, it is preferable to contain a (meth) acrylate having an alkyl group having 4 to 18 carbon atoms. When the copolymerized one molecule polymer is 100% by mass, the alkyl group having 4 to 18 carbon atoms is preferable. The proportion of the (meth) acrylate having a content of preferably 5% to 95% by mass, and more preferably 10% to 90% by mass. If it is 5 mass% to 95 mass%, in the workability after forming an adhesive sheet, it exists in the tendency for the adhesiveness of transparent base materials, such as glass and a plastic, to improve.
A polymer having such a copolymerization ratio can be generally obtained by blending each monomer at the same ratio as the above-mentioned copolymerization ratio and copolymerizing the monomers, so that the polymerization rate substantially approaches 100% by mass. It is preferable.
　炭素数４から１８のアルキル基を有する（メタ）アクリレートと共重合するモノマとしては、上記に記載したものに限定されないが、水酸基、モルホリン基、アミノ基、カルボキシル基、シアノ基、カルボニル基、ニトロ基等の極性基を有するモノマが好ましく、すなわちこれら極性基を有する（メタ）アクリレートは、プラスチックなどの透明基材との粘着性が向上する傾向にあるので好ましい。 Monomers that copolymerize with (meth) acrylates having an alkyl group having 4 to 18 carbon atoms are not limited to those described above, but include hydroxyl groups, morpholine groups, amino groups, carboxyl groups, cyano groups, carbonyl groups, nitro groups, and the like. Monomers having polar groups such as groups are preferred, that is, (meth) acrylates having these polar groups are preferred because they tend to improve the adhesion to transparent substrates such as plastics.
　（Ａ）（メタ）アクリル酸系誘導体ポリマの重量平均分子量は、ゲルパーミッションクロマトグラフィーにより標準ポリスチレンの検量線を用いて換算した値が、１×１０5～１×１０6であるものが好ましく、１×１０5～５×１０5であるものがより好ましい。重量平均分子量を１×１０5以上にすることで、高温（例えば８０℃以上）、高温高湿（例えば８５℃／８５％ＲＨ）の環境下で、透明基材などに剥がれの発生しない粘着力を得ることができ、１×１０6以下にすることで、画像表示装置用粘着性樹脂組成物の粘度が高くなり過ぎず、粘着シートにする際の加工性が良好になる。
　また、（メタ）アクリル酸誘導体ポリマの重合方法は、溶液重合、乳化重合、懸濁重合、塊状重合等の既知の重合方法を用いることができる。 (A) The weight average molecular weight of the (meth) acrylic acid derivative polymer is preferably 1 × 10 5 to 1 × 10 6 in terms of a value converted by gel permeation chromatography using a standard polystyrene calibration curve. More preferred is 1 × 10 5 to 5 × 10 5 . By setting the weight average molecular weight to 1 × 10 5 or more, the adhesive strength that does not cause peeling on a transparent substrate or the like in an environment of high temperature (for example, 80 ° C. or more) and high temperature and high humidity (for example, 85 ° C./85% RH). By making it 1 × 10 6 or less, the viscosity of the pressure-sensitive adhesive resin composition for an image display device does not become too high, and the processability when making a pressure-sensitive adhesive sheet is improved.
The polymerization method of the (meth) acrylic acid derivative polymer may be a known polymerization method such as solution polymerization, emulsion polymerization, suspension polymerization, or bulk polymerization.
　重合開始剤としては、熱によりラジカルを発生する化合物を用いることができ、具体的には、過酸化ベンゾイル、ｔ－ブチルパーベンゾエイト、クメンヒドロパーオキシド、ジイソプロピルパーオキシジカーボネート、ジ－ｎ－プロピルパーオキシジカーボネート、ジ（２―エトキシエチル）パーオキシジカーボネート、ｔ－ブチルパーオキシネオデカノエート、ｔ－ブチルパーオキシビバレート、（３，５，５－トリメチルヘキサノイル）パーオキシド、ジプロピオニルパーオキシド、ジアセチルパーオキシド、ジドデシルパーオキシドのような有機過酸化物や、２，２'－アゾビスイソブチロニトリル、２，２'－アゾビス（２－メチルブチロニトリル）、１，１'―アゾビス（シクロヘキサン－１－カルボニル）、２．２'―アゾビス（２，４－ジメチルバレロニトリル）、２，２'―アゾビス（２，４－ジメチル－４－メトキシバレロニトリル）、ジメチル２，２'－アゾビス（２－メチルプロピオネート）、４，４'―アゾビス（４－シアノバレリック酸）、２，２'―アゾビス（２－ヒドロキシメチルプロピオニトリル）、２，２'―アゾビス［２－（イミダゾリン－２－イル）プロパン］のようなアゾ系化合物などが挙げられる。 As the polymerization initiator, a compound that generates radicals by heat can be used. Specifically, benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n- Propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, t-butylperoxyneodecanoate, t-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, di Organic peroxides such as propionyl peroxide, diacetyl peroxide, didodecyl peroxide, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1, 1′-azobis (cyclohexane-1-carbonyl), 2.2′-azobis (2 , 4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate), 4,4′-azobis Azo compounds such as (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (imidazolin-2-yl) propane] Is mentioned.
　（メタ）アクリル酸系誘導体ポリマの配合量は、粘着性樹脂組成物の全量に対して、１０～７０質量％であることが好ましく、１５～６０質量％であることがより好ましい。（Ａ）（メタ）アクリル酸系誘導体ポリマの配合量が１０～７０質量％であると、画像表示装置用粘着性樹脂組成物の粘度が粘着シートを作製する際の適正粘度範囲に入り、加工性がよい。また、得られた粘着シートは、ガラスやプラスチックなどの透明基材への粘着性が良好である。 The blending amount of the (meth) acrylic acid derivative polymer is preferably 10 to 70% by mass, and more preferably 15 to 60% by mass with respect to the total amount of the adhesive resin composition. (A) When the blending amount of the (meth) acrylic acid derivative polymer is 10 to 70% by mass, the viscosity of the pressure-sensitive adhesive resin composition for an image display device falls within an appropriate viscosity range for producing a pressure-sensitive adhesive sheet, and processing Good sex. Moreover, the obtained adhesive sheet has good adhesiveness to transparent substrates such as glass and plastic.
［（Ｂ）（メタ）アクリル酸系誘導体モノマ］
　本発明の画像表示装置用粘着性樹脂組成物における（Ｂ）（メタ）アクリル酸系誘導体モノマは、（メタ）アクリロイル基を分子内に１つ有するモノマであれば、特に限定するものではなく、公知の材料を使用することが可能であり、２種以上を組み合わせて用いてもよい。その具体例としては、（メタ）アクリル酸、（メタ）アクリル酸アミド、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ｎ－ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート等の炭素数１から１８のアルキル（メタ）アクリレート；ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート等の芳香環を有する（メタ）アクリレート；ブトキシエチレングリコール（メタ）アクリレート、ブトキシジエチレングリコール（メタ）アクリレート、メトキシトリエチレングリコール（メタ）アクリレートなどの（メタ）アクリレート；シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート等の脂環式基を有する（メタ）アクリレート；２－ヒドロキシエチル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等の水酸基を有する（メタ）アクリレート；テトラヒドロフルフリル（メタ）アクリレート；Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノプロピルアクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド、（メタ）アクリロイルモルホリン、Ｎ－イソプロピルアクリルアミド、Ｎ，Ｎ－ジエチルアクリルアミド、Ｎ－ヒドロキシエチルアクリルアミドなど、アミド基を有する（メタ）アクリレート；２－（２－メタクリロイルオキシエチルオキシ）エチルイソシアネート、２－（メタ）アクリロイルオキシエチルイソシアネートなど、イソシアネート基を有する（メタ）アクリレート；テトラエチレングリコールモノメチルエーテル（メタ）アクリレート、ヘキサエチレングリコールモノメチルエーテル（メタ）アクリレート、オクタエチレングリコールモノメチルエーテル（メタ）アクリレート、ノナエチレングリコールメチルエーテル（メタ）アクリレート等のポリエチレングリコールモノメチルエーテル（メタ）アクリレート；ヘプタプロピレングリコールモノメチルエーテル（メタ）アクリレート等のポリプロピレングリコールモノメチルエーテル（メタ）アクリレート；テトラエチレングリコールエチルエーテル（メタ）アクリレート等のポリエチレングリコールエチルエーテル（メタ）アクリレート；テトラエチレングリコール（メタ）アクリレート、ヘキサエチレングリコール（メタ）アクリレート、オクタプロピレングリコール（メタ）アクリレートなどが挙げられる。
　特に、アルキル基の炭素数が４～１８であるアルキル（メタ）アクリレートと下記一般式（ｂ）で示されるヒドロキシル基含有アクリレートを併用することが好ましい。 [(B) (Meth) acrylic acid derivative monomer]
The (B) (meth) acrylic acid derivative monomer in the adhesive resin composition for an image display device of the present invention is not particularly limited as long as it is a monomer having one (meth) acryloyl group in the molecule, Known materials can be used, and two or more kinds may be used in combination. Specific examples thereof include (meth) acrylic acid, (meth) acrylic amide, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) ) Acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, stearyl (meth) acrylate and the like alkyl (meth) acrylate having 1 to 18 carbon atoms; benzyl (meth) acrylate, (Meth) acrylate having an aromatic ring such as phenoxyethyl (meth) acrylate; butoxyethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate Any (meth) acrylate; (meth) acrylate having an alicyclic group such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 3- (Meth) acrylate having a hydroxyl group such as hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; tetrahydrofurfuryl (meth) acrylate; N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethyl Has an amide group such as aminopropylacrylamide, N, N-dimethylacrylamide, (meth) acryloylmorpholine, N-isopropylacrylamide, N, N-diethylacrylamide, N-hydroxyethylacrylamide, etc. (Meth) acrylate; 2- (2-methacryloyloxyethyloxy) ethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, etc. (meth) acrylate having an isocyanate group; tetraethylene glycol monomethyl ether (meth) acrylate, hexaethylene Polyethylene glycol monomethyl ether (meth) acrylates such as glycol monomethyl ether (meth) acrylate, octaethylene glycol monomethyl ether (meth) acrylate, nonaethylene glycol methyl ether (meth) acrylate; polypropylene such as heptapropylene glycol monomethyl ether (meth) acrylate Glycol monomethyl ether (meth) acrylate; tetraethylene glycol ethyl Examples include polyethylene glycol ethyl ether (meth) acrylate such as ether (meth) acrylate; tetraethylene glycol (meth) acrylate, hexaethylene glycol (meth) acrylate, octapropylene glycol (meth) acrylate, and the like.
In particular, it is preferable to use together an alkyl (meth) acrylate having an alkyl group with 4 to 18 carbon atoms and a hydroxyl group-containing acrylate represented by the following general formula (b).
　ＣＨ2＝ＣＸＣＯＯ（ＣmＨ2mＯ）nＨ     ・・・（ｂ）
（式中、ＸはＨ又はＣＨ3であり、ｍは２～４の整数、ｎは１～１０の整数を示す。） CH 2 = CXCOO (C m H 2m O) n H ··· (b)
(Wherein X represents H or CH 3 , m represents an integer of 2 to 4, and n represents an integer of 1 to 10)
　アルキル基の炭素数が４～１８であるアルキル（メタ）アクリレートとしては、ｎ－ブチル（メタ）アクリレート、ｎ－ペンチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ステアリル（メタ）アクリレート等が挙げられるが、ｎ－ブチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート等が好ましく、エチルヘキシル（メタ）アクリレートが特に好ましい。
　また、メタクリレートよりもアクリレートの方がより好ましい。これらの（メタ）アクリレートは２種類以上を組み合わせて使用してもよい。 Examples of the alkyl (meth) acrylate having 4 to 18 carbon atoms in the alkyl group include n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, and n-octyl (meth) acrylate. , Isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like. N-butyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, n-octyl (meth) acrylate and the like are preferable, and ethylhexyl (meth) acrylate is particularly preferable.
Also, acrylate is more preferable than methacrylate. These (meth) acrylates may be used in combination of two or more.
　一般式（ｂ）で示されるヒドロキシル基含有（メタ）アクリレートとしては、２－ヒドロキシエチル（メタ）アクリレート、１－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、１－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、３－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、１－ヒドロキシブチル（メタ）アクリレート等の水酸基含有（メタ）アクリレート；ジエチレングリコールモノ（メタ）アクリレートやトリエチレングリコールモノ（メタ）アクリレート等のポリエチレングリコールモノ（メタ）アクリレート；ジプロピレングリコールモノ（メタ）アクリレートやトリプロピレングリコールモノ（メタ）アクリレート等のポリプロピレングリコールモノ（メタ）アクリレート；ジブチレングリコールモノ（メタ）アクリレートやトリブチレングリコールモノ（メタ）アクリレート等のポリブチレングリコールモノ（メタ）アクリレートなどが挙げられる。これらのうち、２－ヒドロキシエチル（メタ）アクリレート、１－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、１－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、３－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、１－ヒドロキシブチル（メタ）アクリレート等が好ましく、２－ヒドロキシエチル（メタ）アクリレート及び４－ヒドロキシブチル（メタ）アクリレートが特に好ましく、４－ヒドロキシブチル（メタ）アクリレートが極めて好ましい。また、これらの（メタ）アクリレートは２種類以上を組み合わせて使用してもよい。
　また、（Ｂ）（メタ）アクリル酸系誘導体モノマは、本発明の効果をより向上できる観点から、（メタ）アクリロイルモルホリンを含有することが好ましい。
　（メタ）アクリロイルモルホリンを用いる場合の含有量は、粘着性樹脂組成物の全量に対して５～４０質量％が好ましく、１０～３０質量％がより好ましく、１５～２５質量％が特に好ましい。 Examples of the hydroxyl group-containing (meth) acrylate represented by the general formula (b) include 2-hydroxyethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl ( Such as meth) acrylate, 1-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, etc. Hydroxyl group-containing (meth) acrylate; polyethylene glycol mono (meth) acrylate such as diethylene glycol mono (meth) acrylate and triethylene glycol mono (meth) acrylate; dipropylene glycol mono (meth) Polypropylene glycol mono (meth) acrylates such as acrylate and tripropylene glycol mono (meth) acrylate; polybutylene glycol mono (meth) acrylates such as dibutylene glycol mono (meth) acrylate and tributylene glycol mono (meth) acrylate It is done. Of these, 2-hydroxyethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate and the like are preferable, 2-hydroxyethyl (meth) acrylate and 4-hydroxy Butyl (meth) acrylate is particularly preferred and 4-hydroxybutyl (meth) acrylate is very particularly preferred. These (meth) acrylates may be used in combination of two or more.
The (B) (meth) acrylic acid derivative monomer preferably contains (meth) acryloylmorpholine from the viewpoint of further improving the effects of the present invention.
When (meth) acryloylmorpholine is used, the content is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, and particularly preferably 15 to 25% by mass with respect to the total amount of the adhesive resin composition.
　本発明における（Ｂ）（メタ）アクリル酸系誘導体モノマの含有量は、粘着性樹脂組成物の全量に対して１５～８０質量％が好ましい。（Ｂ）（メタ）アクリル酸誘導体モノマの含有量が、１５～８０質量％の範囲であると、得られた粘着シートをガラス基板とガラス基板の間に貼り合せた後、高温下（８０℃以上）および高温高湿下（８５℃／８５％ＲＨ）での信頼性試験実施後の気泡の発生、剥がれが抑制される。以上の観点から、（Ｂ）（メタ）アクリル酸誘導体モノマの含有量は、３０～８０質量％がより好ましく、４０～８０質量％が特に好ましい。 In the present invention, the content of the (B) (meth) acrylic acid derivative monomer is preferably 15 to 80% by mass with respect to the total amount of the adhesive resin composition. (B) When the content of the (meth) acrylic acid derivative monomer is in the range of 15 to 80% by mass, the obtained pressure-sensitive adhesive sheet is bonded between the glass substrate and the glass substrate at a high temperature (80 ° C. And the occurrence of bubbles after the reliability test under high temperature and high humidity (85 ° C./85% RH) is suppressed. From the above viewpoint, the content of the (B) (meth) acrylic acid derivative monomer is more preferably 30 to 80% by mass, and particularly preferably 40 to 80% by mass.
［（Ｃ）２官能の（メタ）アクリロイル基を有する架橋剤］
　本発明における（Ｃ）２官能の（メタ）アクリロイル基を有する架橋剤は、（メタ）アクリロイル基を分子内に２つ有するモノマである。本発明においては、重量平均分子量が２．０×１０4～以上４．０×１０4である架橋剤Ｙを特定量含むことが必要である。これにより高温条件下及び高湿条件下での、気泡、浮き、剥がれ等の発生を抑制することができる。
　このような重量平均分子量を有する２官能の（メタ）アクリロイル基を有する架橋剤Ｙを製造する方法としては、公知の方法が使用でき、例えば、イソホロンジイソシアネート、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート等の各種ジイソシアネートと、アルキレングリコール、ポリアルキレングリコール、ポリエステルポリオール等の各種ジオールと、ヒドロキシアルキル（メタ）アクリレート、ラクトン変性ヒドロキシアルキル（メタ）アクリレート、イソシアナトアルキル（メタ）アクリレート等の各種（メタ）アクリレートを、両末端が（メタ）アクリロイル基となるように反応させることによって合成することができる。
なかでも、イソホロンジイソシアネートに起因する骨格、即ち、下記一般式（ａ）で示される骨格を有するウレタンジ（メタ）アクリレートであると本発明の、気泡、浮き、剥がれ等の発生抑制効果に優れるので好ましい。 [(C) Cross-linking agent having a bifunctional (meth) acryloyl group]
The (C) cross-linking agent having a bifunctional (meth) acryloyl group in the present invention is a monomer having two (meth) acryloyl groups in the molecule. In the present invention, it is necessary to include a specific amount of the crosslinking agent Y having a weight average molecular weight of 2.0 × 10 4 to 4.0 × 10 4 or more. Thereby, generation | occurrence | production of a bubble, a float, peeling, etc. on high temperature conditions and high humidity conditions can be suppressed.
As a method for producing the crosslinking agent Y having a bifunctional (meth) acryloyl group having such a weight average molecular weight, known methods can be used, for example, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate. Various diisocyanates such as alkylene glycol, polyalkylene glycol, polyester polyol and other diols, hydroxyalkyl (meth) acrylate, lactone-modified hydroxyalkyl (meth) acrylate, isocyanatoalkyl (meth) acrylate and other (meth) The acrylate can be synthesized by reacting both ends to be (meth) acryloyl groups.
Among them, a skeleton derived from isophorone diisocyanate, that is, urethane di (meth) acrylate having a skeleton represented by the following general formula (a) is preferable because it is excellent in suppressing the occurrence of bubbles, floats, peeling, etc. of the present invention. .
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　また、前記架橋剤Ｙは、粘着性樹脂組成物全量に対して、４～８質量％であることが必要であるが、５～７質量％であることが好ましい。４質量％未満である場合は、架橋密度が低く、粘着シートの高温での寸法安定性が悪く、８質量％を超える場合、架橋密度が高くなり過ぎ、得られた粘着シートをガラス基板等の透明保護板と、タッチパネル、液晶ユニット等の貼り合わせ対象部材との間に貼り合せた後、高温下（８０℃以上）および高湿下（８５℃／８５％ＲＨ）での信頼性試験実施後の気泡の発生や剥がれが生じる。
　なお、本発明においては、（Ｃ）成分として前記架橋剤Ｙの他に、本発明の効果を損なわない範囲内で、その他の架橋剤、即ち前記重量平均分子量をはずれた分子量の２官能の（メタ）アクリロイル基を有する架橋剤や３官能以上の（メタ）アクリロイル基を有する架橋剤などを併用することもできる。 The crosslinking agent Y is required to be 4 to 8% by mass with respect to the total amount of the adhesive resin composition, but is preferably 5 to 7% by mass. When the content is less than 4% by mass, the crosslinking density is low and the dimensional stability of the pressure-sensitive adhesive sheet at high temperature is poor. When the content exceeds 8% by mass, the crosslinking density becomes too high. After bonding between a transparent protective plate and a member to be bonded, such as a touch panel or a liquid crystal unit, after performing a reliability test under high temperature (80 ° C or higher) and high humidity (85 ° C / 85% RH) Generation and peeling of bubbles occur.
In the present invention, in addition to the crosslinking agent Y as the component (C), other crosslinking agents, that is, bifunctional (with a molecular weight deviating from the weight average molecular weight, within the range not impairing the effects of the present invention. A crosslinking agent having a (meth) acryloyl group or a crosslinking agent having a tri- or higher functional (meth) acryloyl group may be used in combination.
［（Ｄ）光重合開始剤］
　本発明に使用する（Ｄ）光重合開始剤は、活性エネルギー線の照射により硬化反応が進むものであり、ここで活性エネルギー線とは、紫外線、電子線、α線、β線、γ線等をいう。
　光重合開始剤の選定は特に限定するものではなく、ベンゾフェノン系、アントラキノン系、ベンゾイル系、スルホニウム塩、ジアゾニウム塩、オニウム塩など公知の材料を使用することが可能である。 [(D) Photopolymerization initiator]
The photopolymerization initiator (D) used in the present invention has a curing reaction that proceeds by irradiation with active energy rays. Here, the active energy rays are ultraviolet rays, electron beams, α rays, β rays, γ rays, and the like. Say.
The selection of the photopolymerization initiator is not particularly limited, and known materials such as benzophenone series, anthraquinone series, benzoyl series, sulfonium salts, diazonium salts, and onium salts can be used.
　具体的には、ベンゾフェノン、Ｎ，Ｎ'－テトラメチル－４，４'－ジアミノベンゾフェノン（ミヒラーケトン）、Ｎ，Ｎ－テトラエチル－４，４'－ジアミノベンゾフェノン、４－メトキシ－４，４’－ジメチルアミノベンゾフェノン、α－ヒドロキシイソブチルフェノン、２－エチルアントラキノン、ｔ－ブチルアントラキノン、１，４－ジメチルアントラキノン、１－クロロアントラキノン、２，３－ジクロロアントラキノン、３－クロル－２－メチルアントラキノン、１，２－ベンゾアントラキノン、２－フェニルアントラキノン、１，４－ナフトキノン、９，１０－フェナントラキノン、チオキサントン、２－クロロチオキサントン、１－ヒドロキシシクロヘキシルフェニルケトン、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、２，２－ジエトキシアセトフェノン等の芳香族ケトン化合物；ベンゾイン、メチルベンゾイン、エチルベンゾイン等のベンゾイン化合物；ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソブチルエーテル、ベンゾインフェニルエーテル等のベンゾインエーテル化合物；ベンジル、ベンジルジメチルケタール等のベンジル化合物；β－（アクリジン－９－イル）（メタ）アクリル酸のエステル化合物；９－フェニルアクリジン、９－ピリジルアクリジン、１，７－ジアクリジノヘプタン等のアクリジン化合物、２－（ｏ－クロロフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｏ－クロロフェニル）－４，５－ジ（ｍ－メトキシフェニル）イミダゾール二量体、２－（ｏ－フルオロフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｏ－メトキシフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｐ－メトキシフェニル）－４，５－ジフェニルイミダゾール二量体、２，４－ジ（ｐ－メトキシフェニル）５－フェニルイミダゾール二量体、２－（２，４－ジメトキシフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｐ－メチルメルカプトフェニル）－４，５－ジフェニルイミダゾール二量体等の２，４，５－トリアリールイミダゾール二量体、２－ベンジル－２－ジメチルアミノ－１－（４－モリホリノフェニル）－１－ブタノン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノ－１－プロパン、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド、オリゴ（２－ヒドロキシ－２－メチル－１－（４－（１－メチルビニル）フェニル）プロパノン）等が挙げられる。 Specifically, benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4,4′-dimethyl Aminobenzophenone, α-hydroxyisobutylphenone, 2-ethylanthraquinone, t-butylanthraquinone, 1,4-dimethylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 1,2 -Benzoanthraquinone, 2-phenylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane Aromatic ketone compounds such as 1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2,2-diethoxyacetophenone; Benzoin compounds such as benzoin, methylbenzoin and ethylbenzoin; Benzoin methyl ether Benzoin ether compounds such as benzoin ethyl ether, benzoin isobutyl ether and benzoin phenyl ether; benzyl compounds such as benzyl and benzyldimethyl ketal; ester compounds of β- (acridin-9-yl) (meth) acrylic acid; 9-phenylacridine , 9-pyridylacridine, acridine compounds such as 1,7-diacridinoheptane, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (M-methoxy Phenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p- Methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) 5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole Dimer, 2,4,5-triarylimidazole dimer such as 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer, 2-benzyl-2-dimethylamino-1- ( 4-Morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane, bis (2,4 6- trimethyl benzoyl) - phenyl phosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), and the like.
　また、特に、粘着性樹脂組成物を着色させない重合開始剤としては１－ヒドロキシシクロヘキシルフェニルケトン、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン等のα－ヒドロキシアルキルフェノン系化合物；ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド、ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチル－ペンチルフォスフィンオキサイド、２，４，６－トリメチルベンゾイル－ジフェニルフォスフィンオキサイド等のアシルフォスフィンオキサイド系化合物；オリゴ（２－ヒドロキシ－２－メチル－１－（４－（１－メチルビニル）フェニル）プロパノン）及びこれらを組み合わせたものが好ましい。
　また、特に厚いシートを作製するためには、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド、ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチル－ペンチルフォスフィンオキサイド、２，４，６－トリメチルベンゾイル－ジフェニルフォスフィンオキサイド等のアシルフォスフィンオキサイド系化合物を含む光重合開始剤が好ましい。
　また、シートの臭気を減らすためにはオリゴ（２－ヒドロキシ－２－メチル－１－（４－（１－メチルビニル）フェニル）プロパノン）が好ましい。これらの光重合開始剤は複数を組み合わせて使用してもよい。 In particular, polymerization initiators that do not color the adhesive resin composition include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2- Α-hydroxyalkylphenone compounds such as hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one; bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis Acylphosphine oxide compounds such as (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; oligo (2-hydroxy- 2-Methyl-1- (4- (1-methylvinyl) phenyl) pro Non) and a combination thereof are preferred.
In order to produce particularly thick sheets, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine A photopolymerization initiator containing an acyl phosphine oxide compound such as oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide is preferable.
In order to reduce the odor of the sheet, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) is preferable. A plurality of these photopolymerization initiators may be used in combination.
　本発明における（Ｄ）光重合開始剤の配合量は、粘着性樹脂組成物の全量に対して、０．１～５質量％であることが好ましい。５質量％以下とすることで、得られた粘着シートの透過率が高く、また色相も黄味を帯びることがない。以上の観点から、３質量％以下がさらに好ましい。 In the present invention, the blending amount of the photopolymerization initiator (D) is preferably 0.1 to 5% by mass with respect to the total amount of the adhesive resin composition. By setting it as 5 mass% or less, the transmittance | permeability of the obtained adhesive sheet is high, and a hue does not become yellowish. From the above viewpoint, 3% by mass or less is more preferable.
［その他添加剤］
　本発明の画像表示用粘着性樹脂組成物には、必要に応じて上記の（Ａ）、（Ｂ）、（Ｃ）、及び（Ｄ）とは別に、各種添加剤を配合してもよい。本発明に配合可能な各種添加剤としては、例えば、（Ａ）、（Ｂ）、（Ｃ）及び（Ｄ）を配合して得られた粘着性樹脂組成物の保存安定性を高める目的で添加するパラメトキシフェノールなどの重合禁止剤、粘着性樹脂組成物を光により硬化させ得られた粘着シートの耐熱性を高める目的で添加するトリフェニルホスフィンなどの酸化防止剤、紫外線など光に対しての耐性を高める目的で添加するＨＡＬＳ（Ｈｉｎｄｅｒｅｄ　Ａｍｉｎｅ　Ｌｉｇｈｔ　Ｓｔａｂｉｌｉｚｅｒ）などの光安定化剤、ガラスなどへの密着性を高めるために添加するシランカップリング剤などが挙げられる。
　また、本発明の画像表示用粘着性樹脂組成物を用いて粘着シートを得る際にポリエチレンテレフタレートフィルム等で挟む構成となるが、そのポリエチレンテレフタレートフィルム等の基材との剥離性を制御するために、ポリジメチルシロキサン系、フッ素系などの界面活性剤を配合することができる。
　上記添加剤は、単独で用いてもよくまた、複数の添加剤を組み合わせて配合してもよい。なお、これらのその他添加剤の配合量は、通常、上記の（Ａ）、（Ｂ）、（Ｃ）及び（Ｄ）の合計配合量と比較すると小さく、一般に粘着性樹脂組成物の全量に対して０．０１～５質量％程度である。 [Other additives]
In addition to the above (A), (B), (C), and (D), various additives may be blended in the adhesive resin composition for image display of the present invention as necessary. As various additives that can be blended in the present invention, for example, it is added for the purpose of enhancing the storage stability of the adhesive resin composition obtained by blending (A), (B), (C) and (D). Polymerization inhibitors such as paramethoxyphenol, antioxidants such as triphenylphosphine added for the purpose of increasing the heat resistance of the pressure-sensitive adhesive sheet obtained by curing the adhesive resin composition with light, and ultraviolet light Examples thereof include a light stabilizer such as HALS (Hindered Amine Light Stabilizer) added for the purpose of increasing resistance, and a silane coupling agent added for improving adhesion to glass or the like.
In addition, when the pressure-sensitive adhesive composition for image display of the present invention is used to obtain a pressure-sensitive adhesive sheet, it is sandwiched between polyethylene terephthalate films, etc., in order to control the peelability from the substrate such as the polyethylene terephthalate film. , Surfactants such as polydimethylsiloxane and fluorine can be blended.
The above additives may be used alone or in combination with a plurality of additives. In addition, the compounding quantity of these other additives is usually small compared with the total compounding quantity of said (A), (B), (C), and (D), and generally with respect to the whole quantity of adhesive resin composition. About 0.01 to 5% by mass.
＜粘着シート＞
　次に、画像表示用粘着性樹脂組成物に活性エネルギーを照射し、硬化させ得られた粘着シートについて以下に説明する。本発明の画像表示用粘着性樹脂組成物は、そのまま液状の状態で粘着剤として用いることもできるが、シート状の粘着シートとして用いることが好ましい。
　本発明における粘着シートの作製方法を以下に例示する。 <Adhesive sheet>
Next, the adhesive sheet obtained by irradiating and curing the adhesive resin composition for image display with active energy will be described below. The adhesive resin composition for image display of the present invention can be used as it is in the liquid state as it is, but it is preferably used as a sheet-like adhesive sheet.
The production method of the adhesive sheet in this invention is illustrated below.
　本発明における粘着シートは、基材上に粘着性樹脂組成物をシート状に塗布し、これに活性エネルギー線を照射して硬化させることにより得られる。活性エネルギー線の光源としては、波長４００ｎｍ以下に発光分布を有するものが好ましく、例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、ブラックライトランプ、メタルハライドランプ及びマイクロウェーブ励起水銀灯が使用できる。また照射エネルギーは特に限定されないが、通常５００～５０００ｍＪ／ｃｍ2程度である。
　本発明の画像表示装置用粘着シート（以下単に「粘着シート」ということがある）は、適度な粘着力とリワーク性を兼ね備え、かつ所望の厚みに対して気泡等を含まず、また優れた衝撃緩和性を発揮できる厚さにすることができる。本発明の粘着シートの厚さは、使用用途及び方法により特に限定されないが、０．０５～２ｍｍ程度の厚さが好ましい。この範囲で使用した場合、ディスプレイ上に光学部材を貼合せるための透明な粘着シートとして特に優れた効果を発揮する。
　また、粘着シートのガラス転移温度は、１０℃～３０℃であることが好ましい。 The pressure-sensitive adhesive sheet in the present invention is obtained by applying a pressure-sensitive resin composition on a base material in a sheet shape and irradiating it with an active energy ray to cure. As the light source of the active energy ray, a light source having a light emission distribution at a wavelength of 400 nm or less is preferable. Can be used. The irradiation energy is not particularly limited, but is usually about 500 to 5000 mJ / cm 2 .
The pressure-sensitive adhesive sheet for image display device of the present invention (hereinafter sometimes simply referred to as “pressure-sensitive adhesive sheet”) has an appropriate pressure-sensitive adhesive force and reworkability, does not contain bubbles or the like with respect to a desired thickness, and has excellent impact. The thickness can be set so as to exhibit relaxation properties. The thickness of the pressure-sensitive adhesive sheet of the present invention is not particularly limited depending on the intended use and method, but a thickness of about 0.05 to 2 mm is preferable. When used in this range, it exhibits particularly excellent effects as a transparent adhesive sheet for laminating an optical member on a display.
The glass transition temperature of the pressure-sensitive adhesive sheet is preferably 10 ° C. to 30 ° C.
＜画像表示装置＞
　次に、本発明の粘着性樹脂組成物又は粘着シートを用いた画像表示装置について説明する。
　本発明の粘着性樹脂組成物及び粘着シートは、各種画像表示装置に適用することができる。画像表示装置としては、プラズマディスプレイ（ＰＤＰ）、液晶ディスプレイ（ＬＣＤ）、陰極線管（ＣＲＴ）、電界放出ディスプレイ（ＦＥＤ）、有機ＥＬディスプレイ（ＯＥＬＤ）、３Ｄディスプレイ、電子ペーパー（ＥＰ）などが挙げられる。本発明の粘着性樹脂組成物及び粘着シートは、例えば、前記画像表示装置の反射防止層、防汚層、色素層、ハードコート層などの機能性を有する機能層、またはこの層をポリエチレンフィルム、ポリエステルフィルム等の基材フィルムなどの光学フィルタ基材に製膜または積層した多層物、ガラス、アクリル、ポリカーボネート等の透明保護板、またはこれに各種機能を有する機能層を製膜または積層した多層物などを、組み合わせて貼り合わせるために使用することができる。また、このような多層物と組み合わせた光学フィルタとして使用することもできる。さらに、本発明の粘着性樹脂組成物はこれらの多層物に塗布、充填などしてから硬化することも可能である。 <Image display device>
Next, an image display device using the adhesive resin composition or the adhesive sheet of the present invention will be described.
The pressure-sensitive adhesive resin composition and pressure-sensitive adhesive sheet of the present invention can be applied to various image display devices. Examples of the image display device include a plasma display (PDP), a liquid crystal display (LCD), a cathode ray tube (CRT), a field emission display (FED), an organic EL display (OELD), a 3D display, and electronic paper (EP). . The adhesive resin composition and the adhesive sheet of the present invention are, for example, a functional layer having functionality such as an antireflection layer, an antifouling layer, a dye layer, and a hard coat layer of the image display device, or a polyethylene film, A multilayer product formed or laminated on an optical filter substrate such as a base film such as a polyester film, a transparent protective plate such as glass, acrylic or polycarbonate, or a multilayer product obtained by forming or laminating a functional layer having various functions thereon Can be used to combine and paste them together. Moreover, it can also be used as an optical filter combined with such a multilayer product. Furthermore, the adhesive resin composition of the present invention can be cured after being applied to, or filled in, these multilayer products.
　前記反射防止層は、可視光反射率が５％以下となる反射防止性を有している層であればよく、透明なプラスチックフィルム等の透明基材に既知の反射防止方法で処理された層を用いることができる。
　前記防汚層は、表面に汚れがつきにくくするためのもので、表面張力を下げるためにフッ素系樹脂やシリコーン系樹脂で構成される既知の層を用いることができる。 The antireflection layer may be a layer having an antireflection property with a visible light reflectance of 5% or less, and is a layer treated by a known antireflection method on a transparent substrate such as a transparent plastic film. Can be used.
The antifouling layer is for preventing the surface from getting dirty, and a known layer composed of a fluorine-based resin or a silicone-based resin can be used to reduce the surface tension.
　前記色素層は、色純度を高めるために使用されたもので、液晶表示ユニット等の画像表示ユニットから発する光の色純度が低い場合に不要な光を低減するために使用される。不要な部分の光を吸収する色素を樹脂に溶解させ、ポリエチレンフィルム、ポリエステルフィルム等の基材フィルムに製膜または積層して得ることができる。
　前記ハードコート層は、表面硬度を高くするために使用される。ハードコート層としては、ウレタンアクリレートやエポキシアクリレートなどのアクリル樹脂やエポキシ樹脂等をポリエチレンフィルム等の基材フィルムに製膜または積層したものを使用することができる。同様に表面硬度を高めるために、ガラス、アクリル、ポリカーボネート等の透明保護基板またはこれらの板にハードコート層を製膜または積層したものを使用することもできる。 The dye layer is used to increase color purity, and is used to reduce unnecessary light when the color purity of light emitted from an image display unit such as a liquid crystal display unit is low. The pigment | dye which absorbs the light of an unnecessary part can be melt | dissolved in resin, and it can obtain by forming or laminating | stacking on base films, such as a polyethylene film and a polyester film.
The hard coat layer is used to increase the surface hardness. As a hard-coat layer, what formed or laminated | stacked acrylic resin, epoxy resins, etc., such as urethane acrylate and epoxy acrylate, on base films, such as a polyethylene film, can be used. Similarly, in order to increase the surface hardness, a transparent protective substrate made of glass, acrylic, polycarbonate, or the like, or a hard coat layer formed or laminated on these plates can also be used.
　本発明の粘着性樹脂組成物及び粘着シートは、偏光板に積層して使用することができる。この場合、偏光板の視認面側に積層することもでき、その反対側に積層することもできる。
　偏光板の視認面側に使用する場合には、粘着シートのさらに視認面側に反射防止層、防汚層、ハードコート層を積層することができ、偏光板と液晶セルの間に使用する場合には、偏光板の視認面側に機能性を有する層を積層することができる。
　このような積層物とする場合、粘着シートは、ロールラミネートや真空貼合機、また枚葉貼合機を用いて積層することができる。 The adhesive resin composition and the adhesive sheet of the present invention can be used by being laminated on a polarizing plate. In this case, it can also laminate | stack on the visual recognition surface side of a polarizing plate, and can also laminate | stack on the opposite side.
When used on the viewing surface side of the polarizing plate, an antireflection layer, an antifouling layer, and a hard coat layer can be laminated on the viewing surface side of the pressure-sensitive adhesive sheet. When used between the polarizing plate and the liquid crystal cell A functional layer can be laminated on the viewing surface side of the polarizing plate.
When setting it as such a laminated body, an adhesive sheet can be laminated | stacked using a roll lamination, a vacuum bonding machine, and a single wafer bonding machine.
　粘着シートは、画像表示装置の画像表示ユニットと視認側最前面の透明保護板（前面板）の間であって、視認側の適切な位置に配置されることが好ましい。具体的には、画像表示用ユニットと透明保護板の間に応用（ｕｓｅ）されることが好ましい。
　また、タッチパネルを画像表示ユニットに組み合わせた画像表示装置においては、タッチパネルと画像表示ユニットの間及び／又はタッチパネルと前記透明保護板（前面板）の間に応用（ｕｓｅ）されることが好ましいが、画像表示装置の構成上、本発明の粘着シートが適用可能であれば、上記に記載した位置に限るものではない。
　なお、透明保護板、タッチパネル、又は画像表示ユニットに１０～８０μｍの段差を有する場合は、透明保護板とタッチパネル、タッチパネルと画像表示ユニット、又は透明保護板と画像表示ユニットとの間を、粘着シートで貼り合わせる工程後に、段差近傍の気泡をより除去できる観点から、４０℃～８０℃（好ましくは５０℃～７０℃）、０．３～０．８ＭＰａ（好ましくは０．４～０．７ＭＰａ）、５～６０分（好ましくは、１０～５０分）の条件で加熱加圧処理（オートクレーブ処理）することが好ましい。 The pressure-sensitive adhesive sheet is preferably disposed at an appropriate position on the viewing side between the image display unit of the image display device and the transparent protective plate (front plate) on the foremost viewing side. Specifically, it is preferably applied between the image display unit and the transparent protective plate.
Further, in the image display device in which the touch panel is combined with the image display unit, it is preferable that the touch panel is applied between the touch panel and the image display unit and / or between the touch panel and the transparent protective plate (front plate). If the adhesive sheet of this invention is applicable on the structure of an image display apparatus, it will not restrict to the position described above.
If the transparent protective plate, touch panel, or image display unit has a step of 10 to 80 μm, the adhesive sheet is placed between the transparent protective plate and the touch panel, the touch panel and the image display unit, or between the transparent protective plate and the image display unit. From the viewpoint of further removing air bubbles in the vicinity of the step after the step of laminating in step 40 to 80 ° C. (preferably 50 ° C. to 70 ° C.), 0.3 to 0.8 MPa (preferably 0.4 to 0.7 MPa). It is preferable to heat and pressurize (autoclave treatment) for 5 to 60 minutes (preferably 10 to 50 minutes).
　画像表示装置の透明保護板（前面板）は、一般的な光学用透明基板を使用することができる。具体的には、ガラス板、石英等の無機物の板、アクリル板、ポリカーボネート板、ポリエチレンテレフタレート板等のプラスチック（有機物）板、厚手のポリエステルシート等の樹脂シートなどが挙げられる。
　前記画像表示装置が液晶表示装置の場合、液晶表示セルは、一般的な液晶表示セルを使用することができる。液晶表示セルは液晶材料の制御方法によって、ＴＮ（Ｔｗｉｓｔｅｄ　Ｎｅｍａｔｉｃ）方式、ＳＴＮ（Ｓｕｐｅｒ－ｔｗｉｓｔｅｄ　ｎｅｍａｔｉｃ）方式、ＶＡ（Ｖｉｒｔｉｃａｌ　Ａｌｉｇｎｍｅｎｔ）方式、ＩＰＳ（Ｉｎ－Ｐｌａｃｅ－Ｓｗｉｔｃｈｉｎｇ）方式等に分類されるが、本発明では、いずれの制御方法を使用した液晶表示セルであってもよい。 As the transparent protective plate (front plate) of the image display device, a general optical transparent substrate can be used. Specific examples include glass plates, inorganic plates such as quartz, plastic (organic) plates such as acrylic plates, polycarbonate plates, and polyethylene terephthalate plates, and resin sheets such as thick polyester sheets.
When the image display device is a liquid crystal display device, a general liquid crystal display cell can be used as the liquid crystal display cell. Liquid crystal display cells are classified into TN (Twisted Nematic) method, STN (Super-twisted nematic) method, VA (Virtual Alignment) method, IPS (In-Place-Switching) method, etc., depending on the control method of the liquid crystal material. In the present invention, a liquid crystal display cell using any control method may be used.
　以下、実施例により本発明の説明をする。なお、本発明はこれらの実施例に制限されるものではない。
＜評価＞
　各実施例及び比較例で得られた各粘着シートについて以下の試験方法で評価した。
１．ガラス転移温度
　厚み０．５ｍｍ、幅１０ｍｍ、長さ１０ｍｍの粘着シートを作製し、広域動的粘弾性測定装置（Ｐｈｅｏｍｅｔｒｉｃ　Ｓｃｉｅｎｔｉｆｉｃ社製、Ｓｏｌｉｄｓ　Ａｎａｌｙｚｅｒ　ＲＳＡ－II）を用いて、シェアサンドイッチモード、周波数１．０Ｈｚ、測定温度範囲－４０～８０℃で昇温速度５℃／分によりガラス転移温度を測定した。
　ガラス転移温度（Ｔｇ）は、上記測定温度範囲において、ｔａｎδがピークを示す温度とした。この温度範囲に２つ以上のｔａｎδピークが観測されるときは、最もｔａｎδの値が大きい値を示す温度をガラス転移温度とした。
２．外観評価
　作製した粘着シートを幅５０ｍｍ、長さ１００ｍｍのサイズに切り出し、５０ｍｍ×１００ｍｍ×ｔ０．７ｍｍの寸法のガラス基板にローラーを用いて貼付した。次いで、その上に同様のガラス基板を、ローラーを用いて貼り合わせ、ガラス基板とガラス基板の間に粘着シートを挟んだ構造のものを作製した。その後オートクレーブ処理（６０℃、０．５ＭＰａ）を３０分間行いサンプルとした。
　完成したサンプルは、以下の環境条件に設定時間放置され、取り出した後外観評価（気泡、剥がれ）を行った。評価基準は、目視にて気泡及び剥がれが発生しない場合はＡ、発生した場合はＢとした。
・高温高湿試験（以下、「８５／８５」と記載する。）；
　サンプルを８５℃、８５％ＲＨの条件下で２４時間放置した。
・高温試験（以下、「１００」と記載する。）
　サンプルを１００℃の条件下で２４時間放置した。
・ヒートサイクル試験（以下、「ＴＣＴ」と記載する。）
　サンプルを－４０℃雰囲気に３０分間放置し、１００℃雰囲気に３０分間放置するヒートサイクルを１００回施した。
３．ズリ評価
　作製した粘着シートを幅２５ｍｍ×長さ２５ｍｍのサイズに切り出した。２５ｍｍ×１００ｍｍのステンレス板に該粘着シートを貼り、その上から２５ｍｍ×１００ｍｍにカットしたＰＥＴフィルムを貼り合せ、ＰＥＴフィルムの端に１００ｇの重りを付けた。その後、８０℃の恒温乾燥機内に１００ｇの重りがぶら下がるように、ステンレス板を固定し、２４時間後の粘着シートの寸法変化量を測定した。その寸法変化量が０．５ｍｍ以下であればＯＫとした。 Hereinafter, the present invention will be described by way of examples. In addition, this invention is not restrict | limited to these Examples.
<Evaluation>
Each pressure-sensitive adhesive sheet obtained in each example and comparative example was evaluated by the following test method.
1. Glass transition temperature A pressure-sensitive adhesive sheet having a thickness of 0.5 mm, a width of 10 mm, and a length of 10 mm was prepared, and using a wide-range dynamic viscoelasticity measuring apparatus (Peometric Scientific, Solids Analyzer RSA-II), a shear sandwich mode, frequency 1 The glass transition temperature was measured at 0.0 Hz, a measurement temperature range of −40 to 80 ° C., and a heating rate of 5 ° C./min.
The glass transition temperature (Tg) was a temperature at which tan δ exhibited a peak in the above measurement temperature range. When two or more tan δ peaks were observed in this temperature range, the temperature at which the value of tan δ was the largest was taken as the glass transition temperature.
2. Appearance evaluation The prepared pressure-sensitive adhesive sheet was cut into a size of 50 mm in width and 100 mm in length, and affixed to a glass substrate having dimensions of 50 mm × 100 mm × t 0.7 mm using a roller. Subsequently, the same glass substrate was bonded together using the roller, and the thing of the structure which pinched | interposed the adhesive sheet between the glass substrate and the glass substrate was produced. Thereafter, autoclaving (60 ° C., 0.5 MPa) was performed for 30 minutes to obtain a sample.
The completed sample was allowed to stand for the set time under the following environmental conditions, and after taking out, appearance evaluation (bubbles and peeling) was performed. The evaluation criteria were A when no bubble or peeling occurred visually, and B when it occurred.
High temperature and high humidity test (hereinafter referred to as “85/85”);
The sample was left under conditions of 85 ° C. and 85% RH for 24 hours.
High temperature test (hereinafter referred to as “100”)
The sample was left at 100 ° C. for 24 hours.
Heat cycle test (hereinafter referred to as “TCT”)
The sample was allowed to stand in a −40 ° C. atmosphere for 30 minutes and subjected to 100 heat cycles in which it was left in a 100 ° C. atmosphere for 30 minutes.
3. Slip evaluation The produced adhesive sheet was cut out into a size of 25 mm wide × 25 mm long. The pressure-sensitive adhesive sheet was attached to a stainless steel plate of 25 mm × 100 mm, a PET film cut into 25 mm × 100 mm was attached thereto, and a 100 g weight was attached to the end of the PET film. Then, the stainless steel plate was fixed so that a 100-g weight might hang in a 80 degreeC thermostat dryer, and the dimensional change amount of the adhesive sheet 24 hours after was measured. If the dimensional change was 0.5 mm or less, it was determined as OK.
製造例１　＜（Ａ）（メタ）アクリル酸系誘導体ポリマの合成＞
　冷却管、温度計、攪拌装置、滴下漏斗及び窒素導入管の付いた反応容器に、初期モノマとして２－エチルヘキシルアクリレート８４．０ｇ、２－ヒドロキシエチルアクリレート３６．０ｇ及びメチルエチルケトン１５０．０ｇをとり１００ｍｌ／分の風量で窒素置換しながら、１５分間で常温（２５℃）から７０℃まで加熱した。
　その後、この温度に保ちながら、追加モノマとして、２－エチルヘキシルアクリレート２１．０ｇ及び２－ヒドロキシエチルアクリレート９．０ｇを使用し、これらにラウロイルパーオキシド１．０ｇを溶解した溶液を準備し、この溶液を６０分間かけて滴下し滴下終了後さらに２時間反応させた。
　続いて、メチルエチルケトンを溜去することにより２－エチルヘキシルアクリレートと２－ヒドロキシエチルアクリレートの共重合体（重量平均分子量１５０，０００）を得た（以下、この共重合体を「アクリル酸系誘導体ポリマ」と称する）。
　なお、重量平均分子量の測定は、ＴＨＦを溶媒としたゲルパーミッションクロマトグラフィーを使用して行い、下記の装置及び測定条件を用いて標準ポリスチレンの検量線を使用して決定した。
　装置：（株）日立製作所
　ＲＩ検出器：Ｌ－３３５０
　使用溶媒：ＴＨＦ
　カラム：日立化成工業（株）製　Ｇｅｌｐａｃ　ＧＬ－Ｒ４２０＋Ｒ４３０＋Ｒ４４０
　カラム温度：４０℃
　流量：２．０ｍｌ／分 Production Example 1 <Synthesis of (A) (meth) acrylic acid derivative polymer>
Into a reaction vessel equipped with a condenser, a thermometer, a stirrer, a dropping funnel and a nitrogen introducing tube, 84.0 g of 2-ethylhexyl acrylate, 36.0 g of 2-hydroxyethyl acrylate, and 150.0 g of methyl ethyl ketone were taken as initial monomers to 100 ml / Heating was performed from room temperature (25 ° C.) to 70 ° C. in 15 minutes while replacing the nitrogen with the air volume of minutes.
Thereafter, while maintaining this temperature, 21.0 g of 2-ethylhexyl acrylate and 9.0 g of 2-hydroxyethyl acrylate were used as additional monomers, and a solution in which 1.0 g of lauroyl peroxide was dissolved therein was prepared. Was added dropwise over 60 minutes, and the reaction was further continued for 2 hours after the completion of the dropwise addition.
Subsequently, methyl ethyl ketone was distilled off to obtain a copolymer of 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate (weight average molecular weight 150,000) (hereinafter, this copolymer was referred to as “acrylic acid derivative polymer”). Called).
The weight average molecular weight was measured using gel permeation chromatography using THF as a solvent, and determined using a standard polystyrene calibration curve using the following apparatus and measurement conditions.
Apparatus: Hitachi, Ltd. RI detector: L-3350
Solvent: THF
Column: Gelpac GL-R420 + R430 + R440 manufactured by Hitachi Chemical Co., Ltd.
Column temperature: 40 ° C
Flow rate: 2.0ml / min
比較製造例１
＜（Ｃ）２官能の（メタ）アクリロイル基を有する架橋剤の合成１＞
　冷却管、温度計、攪拌装置、滴下漏斗及び空気注入管のついた反応容器にポリプロピレングリコール（分子量２，０００）２２３．１２ｇ、ラクトン変性ヒドロキシエチルアクリレート７６．２９ｇ、２－エチルヘキシルアクリレート９９．６８ｇ、重合禁止剤としてｐ－メトキシフェノール０．１２ｇおよび触媒としてジブチル錫ジラウレート０．５ｇをとり、空気を流しながら７５℃に昇温後、７５℃で攪拌しつつイソホロンジイソシアネート４９．３５ｇを２時間かけて均一滴下し、反応を行った。
　滴下終了後、５時間反応させたところで、さらに２－ヒドロキシエチルアクリレート４４．８５ｇを追加し、１時間反応させた。ＩＲ測定の結果、イソシアネートが消失したことを確認して反応を終了し、ポリプロピレングリコールとイソホロンジイソシアネートを繰り返し単位として有し、両末端に重合性不飽和結合を有するポリウレタンアクリレート（重量平均分子量８，５００）を得た（以下、このポリウレタンアクリレートを「ポリウレタンジアクリレート１」とする）。 Comparative production example 1
<(C) Synthesis 1 of a crosslinking agent having a bifunctional (meth) acryloyl group>
In a reaction vessel equipped with a condenser, a thermometer, a stirrer, a dropping funnel and an air injection tube, 223.12 g of polypropylene glycol (molecular weight 2,000), 76.29 g of lactone-modified hydroxyethyl acrylate, 99.68 g of 2-ethylhexyl acrylate, Taking 0.12 g of p-methoxyphenol as a polymerization inhibitor and 0.5 g of dibutyltin dilaurate as a catalyst, the temperature was raised to 75 ° C. while flowing air, and then 49.35 g of isophorone diisocyanate was stirred for 2 hours while stirring at 75 ° C. The reaction was carried out uniformly.
When the reaction was completed for 5 hours after completion of the dropwise addition, 44.85 g of 2-hydroxyethyl acrylate was further added, and the reaction was performed for 1 hour. As a result of IR measurement, it was confirmed that the isocyanate had disappeared, and the reaction was completed. Polyurethane acrylate having a repeating unit of polypropylene glycol and isophorone diisocyanate and having a polymerizable unsaturated bond at both ends (weight average molecular weight 8,500) (Hereinafter, this polyurethane acrylate is referred to as “polyurethane diacrylate 1”).
製造例２
＜（Ｃ）２官能の（メタ）アクリロイル基を有する架橋剤の合成２＞
　冷却管、温度計、攪拌装置、滴下漏斗及び空気注入管のついた反応容器にポリプロピレングリコール（分子量２，０００）３０３．９２ｇ、ラクトン変性ヒドロキシエチルアクリレート８．６６ｇ、２－エチルヘキシルアクリレート９９．７４ｇ、重合禁止剤としてｐ－メトキシフェノール０．１２ｇおよび触媒としてジブチル錫ジラウレート０．５ｇをとり、空気を流しながら７５℃に昇温後、７５℃で攪拌しつつイソホロンジイソシアネート３６．４１ｇを２時間かけて均一滴下し、反応を行った。
　滴下終了後、５時間反応させたところで、さらに２－ヒドロキシエチルアクリレート４４．８８ｇを追加し、１時間反応させた。ＩＲ測定の結果、イソシアネートが消失したことを確認して反応を終了し、ポリプロピレングリコールとイソホロンジイソシアネートを繰り返し単位として有し、両末端に重合性不飽和結合を有するポリウレタンアクリレート（重量平均分子量２０，０００）を得た（以下、このポリウレタンアクリレートを「ポリウレタンジアクリレート２」とする）。 Production Example 2
<(C) Synthesis 2 of a crosslinking agent having a bifunctional (meth) acryloyl group>
In a reaction vessel equipped with a condenser, a thermometer, a stirrer, a dropping funnel and an air injection tube, 303.92 g of polypropylene glycol (molecular weight 2,000), 8.66 g of lactone-modified hydroxyethyl acrylate, 99.74 g of 2-ethylhexyl acrylate, Taking 0.12 g of p-methoxyphenol as a polymerization inhibitor and 0.5 g of dibutyltin dilaurate as a catalyst, the temperature was raised to 75 ° C. while flowing air, and then 36.41 g of isophorone diisocyanate was stirred for 2 hours while stirring at 75 ° C. The reaction was carried out uniformly.
When the reaction was completed for 5 hours after completion of the dropwise addition, 44.88 g of 2-hydroxyethyl acrylate was further added, and the reaction was performed for 1 hour. As a result of IR measurement, it was confirmed that the isocyanate had disappeared, and the reaction was terminated. Polyurethane acrylate having a repeating unit of polypropylene glycol and isophorone diisocyanate and having a polymerizable unsaturated bond at both ends (weight average molecular weight 20,000) (Hereinafter, this polyurethane acrylate is referred to as “polyurethane diacrylate 2”).
製造例３
＜（Ｃ）２官能の（メタ）アクリロイル基を有する架橋剤の合成３＞
　冷却管、温度計、攪拌装置、滴下漏斗及び空気注入管のついた反応容器にポリプロピレングリコール（分子量２，０００）２８５．３ｇ、２－エチルヘキシルアクリレート１００．ｇ、重合禁止剤としてｐ－メトキシフェノール０．１３ｇおよび触媒としてジブチル錫ジラウレート０．５ｇをとり、空気を流しながら７５℃に昇温後、７５℃で攪拌しつつイソホロンジイソシアネート３９．６ｇを２時間かけて均一滴下し、反応を行った。
　滴下終了後、４時間反応させたところで、ラクトン変性ヒドロキシエチルアクリレート２４．５ｇを投入し、さらに１時間後に２－ヒドロキシエチルアクリレート４５．０ｇを追加し、１時間反応させた。ＩＲ測定の結果、イソシアネートが消失したことを確認して反応を終了し、ポリプロピレングリコールとイソホロンジイソシアネートを繰り返し単位として有し、両末端に重合性不飽和結合を有するポリウレタンアクリレート（重量平均分子量３５，０００）を得た（以下、このポリウレタンアクリレートを「ポリウレタンジアクリレート３」とする）。 Production Example 3
<(C) Synthesis 3 of a crosslinking agent having a bifunctional (meth) acryloyl group>
In a reaction vessel equipped with a condenser, a thermometer, a stirrer, a dropping funnel and an air injection tube, 285.3 g of polypropylene glycol (molecular weight 2,000), 2-ethylhexyl acrylate 100. g, 0.13 g of p-methoxyphenol as a polymerization inhibitor and 0.5 g of dibutyltin dilaurate as a catalyst, the temperature was raised to 75 ° C. while flowing air, and 39.6 g of isophorone diisocyanate was stirred for 2 hours at 75 ° C. The solution was uniformly dropped over the course of the reaction.
When the reaction was completed for 4 hours after the completion of the dropwise addition, 24.5 g of lactone-modified hydroxyethyl acrylate was added, and 45.0 g of 2-hydroxyethyl acrylate was further added after 1 hour and reacted for 1 hour. As a result of IR measurement, it was confirmed that the isocyanate had disappeared, and the reaction was terminated. Polyurethane acrylate having a repeating unit of polypropylene glycol and isophorone diisocyanate and having a polymerizable unsaturated bond at both ends (weight average molecular weight 35,000). (Hereinafter, this polyurethane acrylate is referred to as “polyurethane diacrylate 3”).
比較製造例２
＜（Ｃ）２官能の（メタ）アクリロイル基を有する架橋剤の合成４＞
　冷却管、温度計、攪拌装置、滴下漏斗及び空気注入管のついた反応容器にポリプロピレングリコール（分子量２，０００）２８５．３ｇ、２－エチルヘキシルアクリレート１００．ｇ、重合禁止剤としてｐ－メトキシフェノール０．１３ｇおよび触媒としてジブチル錫ジラウレート０．５ｇをとり、空気を流しながら７５℃に昇温後、７５℃で攪拌しつつイソホロンジイソシアネート３９．６ｇを２時間かけて均一滴下し、反応を行った。
　滴下終了後、５時間反応させたところで、ラクトン変性ヒドロキシエチルアクリレート２４．５ｇを投入し、さらに１時間後に２－ヒドロキシエチルアクリレート４５．０ｇを追加し、１時間反応させた。ＩＲ測定の結果、イソシアネートが消失したことを確認して反応を終了し、ポリプロピレングリコールとイソホロンジイソシアネートを繰り返し単位として有し、両末端に重合性不飽和結合を有するポリウレタンアクリレート（重量平均分子量５６，０００）を得た（以下、このポリウレタンアクリレートを「ポリウレタンジアクリレート４」とする）。 Comparative production example 2
<(C) Synthesis 4 of Crosslinking Agent Having Bifunctional (Meth) acryloyl Group>
In a reaction vessel equipped with a condenser, a thermometer, a stirrer, a dropping funnel and an air injection tube, 285.3 g of polypropylene glycol (molecular weight 2,000), 2-ethylhexyl acrylate 100. g, 0.13 g of p-methoxyphenol as a polymerization inhibitor and 0.5 g of dibutyltin dilaurate as a catalyst, the temperature was raised to 75 ° C. while flowing air, and 39.6 g of isophorone diisocyanate was stirred for 2 hours at 75 ° C. The solution was uniformly dropped over the course of the reaction.
When the reaction was completed for 5 hours after completion of the dropwise addition, 24.5 g of lactone-modified hydroxyethyl acrylate was added, and 45.0 g of 2-hydroxyethyl acrylate was further added after 1 hour and reacted for 1 hour. As a result of IR measurement, it was confirmed that the isocyanate had disappeared, and the reaction was terminated. Polyurethane acrylate having a repeating unit of polypropylene glycol and isophorone diisocyanate and having a polymerizable unsaturated bond at both ends (weight average molecular weight 56,000) (Hereinafter, this polyurethane acrylate is referred to as “polyurethane diacrylate 4”).
実施例１
＜サンプル配合及び粘着シート作製＞
　製造例１で得られたアクリル酸系誘導体ポリマ３０．８ｇ、２－エチルヘキシルアクリレート（ＥＨＡ）３８．７ｇ、アクリロイルモルホリン（ＡＣＭＯ）１８．５ｇ、４－ヒドロキシブチルアクリレート（４－ＨＢＡ）５．０ｇ、製造例２で得られたポリウレタンジアクリレート２を６．５ｇ、１－ヒドロキシシクロヘキシルフェニルケトン（Ｉ－１８４）０．５ｇを秤量し、攪拌混合して粘着性樹脂組成物を得た。
　その後、ポリエチレンテレフタレートフィルムに上記で得られた粘着性樹脂組成物を滴下し、さらにポリエチレンテレフタレートをその上から被せ、ローラーにて粘着性樹脂組成物をシート状に塗布し、紫外線照射装置を用いて紫外線を２，０００ｍＪ／ｃｍ2照射して透明な粘着シートを得た。 Example 1
<Sample formulation and adhesive sheet preparation>
30.8 g of acrylic acid derivative polymer obtained in Production Example 1, 38.7 g of 2-ethylhexyl acrylate (EHA), 18.5 g of acryloylmorpholine (ACMO), 5.0 g of 4-hydroxybutyl acrylate (4-HBA), 6.5 g of polyurethane diacrylate 2 obtained in Production Example 2 and 0.5 g of 1-hydroxycyclohexyl phenyl ketone (I-184) were weighed and mixed by stirring to obtain an adhesive resin composition.
Then, the adhesive resin composition obtained above is dropped onto a polyethylene terephthalate film, and further covered with polyethylene terephthalate, and the adhesive resin composition is applied in a sheet form with a roller, and an ultraviolet irradiation device is used. A transparent adhesive sheet was obtained by irradiating ultraviolet rays at 2,000 mJ / cm 2 .
実施例２、３及び比較例１～４
　表１及び表２に記載の配合成分及び配合量で、実施例１と同様の方法で粘着性樹脂組成物及び粘着シートを作製した。 Examples 2 and 3 and Comparative Examples 1 to 4
A pressure-sensitive adhesive resin composition and a pressure-sensitive adhesive sheet were prepared in the same manner as in Example 1 with the blending components and blending amounts shown in Tables 1 and 2.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　本発明の画像表示装置用粘着性樹脂組成物を用いることで、耐衝撃性を有し、視認性に優れる画像表示装置を提供することができる。特に、視認側の透明保護板、例えばガラスと、粘着性樹脂組成物との密着力が高く、８５℃／８５％ＲＨのような高温高湿下に曝されても、剥がれ、浮き、気泡等を発生することなく、ディスプレイの視認性を低下させない。すなわち、画像表示ユニットと画像表示装置に必要と思われる部材を貼合することが可能であり、また画像表示装置の画像表示ユニットより視認側にある部材同士を貼合することが可能である。特に、液晶表示ユニットとタッチパネル、液晶表示ユニットと透明保護板、タッチパネルと透明保護板などを貼着させる粘着シートとして有用である。 By using the adhesive resin composition for an image display device of the present invention, an image display device having impact resistance and excellent visibility can be provided. In particular, the adhesive strength between the transparent protective plate on the viewing side, such as glass, and the adhesive resin composition is high, and even when exposed to high temperature and high humidity such as 85 ° C./85% RH, it peels off, floats, bubbles, etc. And the visibility of the display is not reduced. That is, it is possible to bond the members that are considered necessary for the image display unit and the image display device, and it is possible to bond the members that are closer to the viewing side than the image display unit of the image display device. In particular, it is useful as an adhesive sheet for attaching a liquid crystal display unit and a touch panel, a liquid crystal display unit and a transparent protective plate, a touch panel and a transparent protective plate, and the like.

Claims (9)

  1. 　（Ａ）（メタ）アクリル酸系誘導体ポリマ、（Ｂ）（メタ）アクリロイル基を分子内に１つ有する（メタ）アクリル酸系誘導体モノマ、（Ｃ）２官能の（メタ）アクリロイル基を有する架橋剤及び（Ｄ）光重合開始剤を含有する画像表示装置用粘着性樹脂組成物であって、前記（Ｃ）２官能の（メタ）アクリロイル基を有する架橋剤が、重量平均分子量が２．０×１０4～４．０×１０4の架橋剤Ｙを含み、該架橋剤Ｙの配合量が、該粘着性樹脂組成物全量に対して４～８質量％である画像表示装置用粘着性樹脂組成物。 (A) (meth) acrylic acid derivative polymer, (B) (meth) acrylic acid derivative monomer having one (meth) acryloyl group in the molecule, (C) cross-linking having a bifunctional (meth) acryloyl group A cross-linking agent having a bifunctional (meth) acryloyl group (2.0) having a weight average molecular weight of 2.0. A pressure-sensitive adhesive resin for an image display device comprising a cross-linking agent Y of × 10 4 to 4.0 × 10 4 , wherein the amount of the cross-linking agent Y is 4 to 8% by mass with respect to the total amount of the pressure-sensitive adhesive resin composition Composition.
  2. 　前記架橋剤Ｙが、下記一般式（ａ）の骨格を有するウレタンジアクリレートである請求項１記載の画像表示装置用粘着性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
         The pressure-sensitive adhesive resin composition for an image display device according to claim 1, wherein the crosslinking agent Y is a urethane diacrylate having a skeleton of the following general formula (a).
    Figure JPOXMLDOC01-appb-C000001
  3. 　（Ｂ）（メタ）アクリル酸系誘導体モノマが、下記一般式（ｂ）で表されるモノマを含有する請求項１又は２に記載の画像表示装置用粘着性樹脂組成物。
    　ＣＨ2＝ＣＸＣＯＯ（ＣmＨ2mＯ）nＨ     ・・・（ｂ）
    （式中、ＸはＨ又はＣＨ3であり、ｍは２～４の整数、ｎは１～１０の整数を示す。）     The adhesive resin composition for an image display device according to claim 1 or 2, wherein the (B) (meth) acrylic acid derivative monomer contains a monomer represented by the following general formula (b).
    CH 2 = CXCOO (C m H 2m O) n H ··· (b)
    (Wherein X represents H or CH 3 , m represents an integer of 2 to 4, and n represents an integer of 1 to 10)
  4. 　一般式（ｂ）で表されるモノマの配合量が、粘着性樹脂組成物全量に対して２～２０質量％である請求項３に記載の画像表示装置用粘着性樹脂組成物。 4. The adhesive resin composition for an image display device according to claim 3, wherein the amount of the monomer represented by the general formula (b) is 2 to 20% by mass with respect to the total amount of the adhesive resin composition.
  5. 　請求項１～４のいずれか１項に記載の画像表示装置用粘着性樹脂組成物をシート状に硬化して得られる画像表示装置用粘着シート。 5. An adhesive sheet for an image display device obtained by curing the adhesive resin composition for an image display device according to any one of claims 1 to 4 into a sheet shape.
  6. 　ガラス転移温度が１０℃～３０℃である請求項５に記載の画像表示装置用粘着シート。 The pressure-sensitive adhesive sheet for an image display device according to claim 5, wherein the glass transition temperature is 10 ° C to 30 ° C.
  7. 　請求項１～４のいずれか１項に記載の画像表示装置用粘着性樹脂組成物から形成される層を視認側に有する画像表示装置。 An image display device having a layer formed from the adhesive resin composition for an image display device according to any one of claims 1 to 4 on a viewing side.
  8. 　画像表示装置用粘着性樹脂組成物から形成される層が、視認側の保護板と画像表示パネルの間に形成されているものである請求項７記載の画像表示装置。 The image display device according to claim 7, wherein the layer formed from the adhesive resin composition for an image display device is formed between the protective plate on the viewing side and the image display panel.
  9. 　透明保護板とタッチパネル、タッチパネルと画像表示ユニット、又は透明保護板と画像表示ユニットとの間を、請求項５又は６に記載の画像表示装置用粘着シートで貼り合わせる工程、前記貼り合わせる工程後、４０℃～８０℃、０．３～０．８ＭＰａ、及び５～６０分の条件で処理する工程と、を含む、画像表示装置の製造方法。 The step of bonding the transparent protective plate and the touch panel, the touch panel and the image display unit, or the transparent protective plate and the image display unit with the adhesive sheet for an image display device according to claim 5 or 6, after the bonding step, And a process of treating under conditions of 40 to 80 ° C., 0.3 to 0.8 MPa, and 5 to 60 minutes.
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