WO2012077809A1 - 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 - Google Patents

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 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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English (en)
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/ja
Publication of WO2012077809A1 publication Critical patent/WO2012077809A1/ja

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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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Liquid Crystal (AREA)
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JP2014133812A (ja) * 2013-01-10 2014-07-24 Hitachi Maxell Ltd 硬化性粘着剤組成物、粘着剤および粘着シート
JP2014189723A (ja) * 2013-03-28 2014-10-06 Hitachi Chemical Co Ltd 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、画像表示装置の製造方法及び画像表示装置
JP2014201705A (ja) * 2013-04-08 2014-10-27 日立化成株式会社 接着剤組成物
WO2016013510A1 (ja) * 2014-07-22 2016-01-28 日本合成化学工業株式会社 活性エネルギー線硬化性粘着剤組成物、これを用いてなる粘着剤、及び粘着シート
JPWO2014069134A1 (ja) * 2012-10-31 2016-09-08 昭和電工株式会社 重合性組成物、重合物、光学用粘着シート、画像表示装置およびその製造方法
JP5997405B1 (ja) * 2016-04-06 2016-09-28 大日精化工業株式会社 粘着剤組成物及び積層体
WO2016185262A1 (ja) * 2015-05-18 2016-11-24 藤森工業株式会社 接着性樹脂層及び接着性樹脂フィルム
WO2019124255A1 (ja) * 2017-12-18 2019-06-27 株式会社クラレ 液晶ディスプレイ保護板の製造方法

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JP2010163591A (ja) * 2008-04-11 2010-07-29 Three M Innovative Properties Co 透明粘着シート及びそれを含む画像表示装置
JP2010189545A (ja) * 2009-02-18 2010-09-02 Nitto Denko Corp 両面粘着シートおよび粘着型光学部材

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JPH10265743A (ja) * 1997-03-26 1998-10-06 Toppan Forms Co Ltd 感圧接着性プリント用シート
JP2010163591A (ja) * 2008-04-11 2010-07-29 Three M Innovative Properties Co 透明粘着シート及びそれを含む画像表示装置
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Cited By (17)

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JPWO2014069134A1 (ja) * 2012-10-31 2016-09-08 昭和電工株式会社 重合性組成物、重合物、光学用粘着シート、画像表示装置およびその製造方法
JP2014133812A (ja) * 2013-01-10 2014-07-24 Hitachi Maxell Ltd 硬化性粘着剤組成物、粘着剤および粘着シート
JP2014189723A (ja) * 2013-03-28 2014-10-06 Hitachi Chemical Co Ltd 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、画像表示装置の製造方法及び画像表示装置
JP2014201705A (ja) * 2013-04-08 2014-10-27 日立化成株式会社 接着剤組成物
KR20170033331A (ko) * 2014-07-22 2017-03-24 닛폰고세이가가쿠고교 가부시키가이샤 활성 에너지선 경화성 점착제 조성물, 이를 포함하는 점착제, 및 점착 시트
CN106536653A (zh) * 2014-07-22 2017-03-22 日本合成化学工业株式会社 活性能量射线固化性粘合剂组合物、使用其而得到的粘合剂和粘合片
WO2016013510A1 (ja) * 2014-07-22 2016-01-28 日本合成化学工業株式会社 活性エネルギー線硬化性粘着剤組成物、これを用いてなる粘着剤、及び粘着シート
JPWO2016013510A1 (ja) * 2014-07-22 2017-04-27 日本合成化学工業株式会社 活性エネルギー線硬化性粘着剤組成物、これを用いてなる粘着剤、及び粘着シート
KR102245657B1 (ko) * 2014-07-22 2021-04-28 미쯔비시 케미컬 주식회사 활성 에너지선 경화성 점착제 조성물, 이를 포함하는 점착제, 및 점착 시트
WO2016185262A1 (ja) * 2015-05-18 2016-11-24 藤森工業株式会社 接着性樹脂層及び接着性樹脂フィルム
EP3239259A4 (en) * 2015-05-18 2018-06-27 Fujimori Kogyo Co., Ltd. Adhesive resin layer and adhesive resin film
US10604683B2 (en) 2015-05-18 2020-03-31 Fujimori Kogyo Co., Ltd. Adhesive resin layer and adhesive resin film
JP5997405B1 (ja) * 2016-04-06 2016-09-28 大日精化工業株式会社 粘着剤組成物及び積層体
JP2017186450A (ja) * 2016-04-06 2017-10-12 大日精化工業株式会社 粘着剤組成物及び積層体
WO2019124255A1 (ja) * 2017-12-18 2019-06-27 株式会社クラレ 液晶ディスプレイ保護板の製造方法
JPWO2019124255A1 (ja) * 2017-12-18 2021-01-14 株式会社クラレ 液晶ディスプレイ保護板の製造方法
JP7160838B2 (ja) 2017-12-18 2022-10-25 株式会社クラレ 液晶ディスプレイ保護板の製造方法

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