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WO2012035958A1 - Light-curing composition for use in transparent pressure-sensitive adhesive sheet - Google Patents

Light-curing composition for use in transparent pressure-sensitive adhesive sheet Download PDF

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Publication number
WO2012035958A1
WO2012035958A1 PCT/JP2011/069288 JP2011069288W WO2012035958A1 WO 2012035958 A1 WO2012035958 A1 WO 2012035958A1 JP 2011069288 W JP2011069288 W JP 2011069288W WO 2012035958 A1 WO2012035958 A1 WO 2012035958A1
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WO
WIPO (PCT)
Prior art keywords
meth
adhesive sheet
composition
acrylate
transparent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2011/069288
Other languages
French (fr)
Japanese (ja)
Inventor
中西　健一
篤 海野
一博 佐々木
雄太 竹内
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Holdings Corp
Original Assignee
Showa Denko KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Showa Denko KK filed Critical Showa Denko KK
Priority to CN201180044682.0A priority Critical patent/CN103108930B/en
Priority to KR1020137009611A priority patent/KR101494984B1/en
Priority to JP2012533934A priority patent/JP5854404B2/en
Publication of WO2012035958A1 publication Critical patent/WO2012035958A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • 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
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/208—Touch screens

Definitions

  • the present invention is characterized in that a photocurable transparent adhesive sheet obtained by curing a composition for a photocurable transparent adhesive sheet and a composition for a photocurable transparent adhesive sheet is used for laminating a transparent conductive film.
  • a transparent adhesive sheet for fixing a transparent conductive film, a transparent adhesive sheet for fixing a transparent conductive film, and a transparent adhesive sheet for fixing a transparent conductive film obtained by curing a composition for transparent adhesive sheet for fixing a transparent conductive film are transparent.
  • the present invention relates to a laminate that is bonded to a conductive layer surface of a conductive film.
  • the touch panel is a transparent base material for transparent optical substrates such as ITO (Indium Tin Oxide) and a transparent substrate, glass and a transparent protective sheet for protecting it, and a display device such as a liquid crystal display. It is the laminated body bonded together using the sheet
  • transparent optical substrates such as ITO (Indium Tin Oxide)
  • a display device such as a liquid crystal display. It is the laminated body bonded together using the sheet
  • touch panels There are two types of touch panels: a resistive touch panel that detects mainly the pressure at the time of input, and a capacitive touch panel that detects the input location by static electricity from the human body at the time of input.
  • the capacitive touch panel the conductive layer surface of the transparent conductive film is fixed so as to be in contact with the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive sheet. Therefore, there is a problem that when the pressure-sensitive adhesive layer is in contact with the conductive layer surface of the transparent conductive film, a metal oxidation reaction occurs due to the acid component contained in the pressure-sensitive adhesive, resulting in a decrease in the conductive function. For this reason, the adhesive sheet for fixing a transparent conductive film is required to have high metal corrosion prevention properties.
  • a pressure-sensitive adhesive sheet having metal corrosion prevention properties As a pressure-sensitive adhesive sheet having metal corrosion prevention properties, a pressure-sensitive adhesive sheet containing a metal corrosion inhibitor (for example, Patent Document 1) has been proposed. Moreover, the adhesive sheet (for example, patent document 2) which reduced the corrosivity with respect to a transparent conductive film by containing a specific amount of nitrogen atom containing components with respect to the acid component of an adhesive layer is proposed.
  • the pressure-sensitive adhesive sheet containing a metal corrosion inhibitor has a problem that the metal corrosion inhibitor is discolored in a durability test and optical properties are deteriorated.
  • the pressure-sensitive adhesive sheet containing a specific amount of a nitrogen atom-containing component has a problem that an increase in the electrical resistance value of ITO cannot be sufficiently suppressed due to the acid component contained in the pressure-sensitive adhesive layer.
  • the problem to be solved by the present invention is that the transparent adhesive sheet obtained by curing does not corrode the conductive layer even if it is directly bonded to the conductive layer surface of the transparent conductive film, and the cohesive force and transparency of the adhesive layer And it is providing the composition for photocurable transparent adhesive sheets which is excellent in punching workability. Furthermore, it is in providing this transparent adhesive sheet.
  • composition for sheets Comprising: The composition for photocurable transparent adhesive sheets whose carboxyl group monomer contained in a photopolymerizable monomer is below a predetermined amount is the composition for photocurable transparent adhesive sheets. It discovered that the transparency of the photocurable transparent adhesive sheet obtained by making it harden
  • the present invention is shown by the following (1) to (11).
  • the photopolymerizable monomer other than the (meth) acrylic acid ester having a hydroxyl group is a monofunctional alkyl (meth) acrylate and / or a cyclic alkyl (meth) acrylate.
  • a (meth) acryl group-containing polyolefin compound having a weight average molecular weight of 10,000 to 300,000 is a polyolefin polyol compound, a (meth) acrylate having a hydroxyl group, and two isocyanate groups in one molecule.
  • composition for a photocurable transparent adhesive sheet according to any one of (1) to (6) above, wherein the acid value is 0.5 mgKOH / g or less.
  • a photocurable transparent adhesive sheet obtained by curing the composition for a photocurable transparent adhesive sheet according to any one of (1) to (7) above is used for laminating a transparent conductive film.
  • a transparent adhesive sheet for fixing a transparent conductive film obtained by curing the composition for transparent adhesive sheet for fixing a transparent conductive film according to (8) above.
  • (11) A laminate characterized in that the transparent conductive sheet fixing transparent adhesive sheet according to (9) or (10) is adhered to a conductive layer surface of a transparent conductive film.
  • the composition for a photocurable transparent pressure-sensitive adhesive sheet of the present invention contains a high molecular weight (meth) acrylic group-containing polyolefin compound in the composition, and therefore is excellent in flexibility and moisture permeability of a pressure-sensitive adhesive sheet obtained by curing. Furthermore, since the composition contains only a small amount of carboxyl groups, corrosion of the conductive layer surface of the transparent conductive film due to the acid component of the transparent adhesive sheet obtained can be suppressed, and the composition has a hydroxyl group (meta) Since acrylic acid ester is contained, the cohesive force of the obtained adhesive sheet and the adhesiveness to a base material are excellent.
  • composition for a photocurable transparent adhesive sheet of the present invention comprises (A) a (meth) acrylic group-containing polyolefin compound having a weight average molecular weight of 10,000 to 300,000, and (B) a (meth) acrylic acid ester having a hydroxyl group. (C) A photopolymerizable monomer other than (meth) acrylic acid ester having a hydroxyl group, and (D) a photopolymerization initiator.
  • any polyolefin compound having a polyolefin skeleton and having a (meth) acryl group introduced therein can be used.
  • the polyolefin skeleton include polyethylene, polypropylene, ethylene / propylene copolymer, butadiene, isoprene, hydrogenated polybutadiene, hydrogenated polyisoprene, cycloolefin, and the like. Hydrogenated polybutadiene and hydrogenated polyisoprene skeleton are preferable in terms of light resistance, transparency (non-crystalline), and workability (liquid).
  • the (meth) acryl group means CH 2 ⁇ CH—CO— or CH 2 ⁇ C (CH 3 ) —CO—.
  • the method for introducing the (meth) acrylic group into the polyolefin is not particularly limited, but the polyolefin having a reactive hydroxyl group at the molecular end or the like is esterified with (meth) acrylic acid,
  • Examples of the method include (meth) acrylation by adding an isocyanate compound having two or more isocyanate groups in one molecule to a hydroxyl group of polyolefin and reacting the (meth) acrylate having an isocyanate group and a hydroxyl group.
  • (meth) acrylic group-containing polyolefin obtained by reacting a polyolefin polyol compound with an isocyanate compound having two or more isocyanate groups in one molecule and then urethanizing a (meth) acrylate having a hydroxyl group.
  • a compound is preferable at the point with the high cohesion force of the adhesive sheet obtained.
  • the polyolefin polyol compound has two or more hydroxyl groups in one molecule, but preferably has 2 to 4 hydroxyl groups. Further, the weight average molecular weight of the polyolefin polyol compound is preferably 5,000 to 30,000, more preferably 10,000 to 15,000. When the weight average molecular weight of the polyolefin polyol compound is lower than 5,000, the molecular weight of the resulting (meth) acryl group-containing polyolefin compound does not increase, and sufficient strength of the pressure-sensitive adhesive sheet tends not to be obtained. Moreover, when the weight average molecular weight of the polyolefin polyol compound is higher than 30,000, the molecular weight of the resulting (meth) acrylic group-containing polyolefin compound becomes too high and the handling tends to be difficult.
  • Examples of the compound having two or more isocyanate groups in one molecule include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate and hydrogenation thereof. And diisocyanate compounds such as products. Of these, isophorone diisocyanate is preferable from the viewpoint of light resistance and ease of reactivity control. These compounds having two or more isocyanate groups in one molecule can be used alone or in combination of two or more.
  • the amount of the isocyanate compound having two or more isocyanate groups in one molecule is preferably 8 to 35 parts by mass, more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the polyolefin polyol. More preferably, it is 11 to 25 parts by mass. If the amount of the isocyanate compound having two or more isocyanate groups in one molecule is less than 8 parts by mass, the resulting (meth) acrylic group-containing polyolefin compound becomes too high in molecular weight, making it difficult to handle. When the amount exceeds 35 parts by mass, the molecular weight of the resulting (meth) acrylic group-containing polyolefin compound becomes too low, so that the strength of the pressure-sensitive adhesive sheet tends to be insufficient.
  • Examples of the (meth) acrylate having a hydroxyl group to be reacted with an isocyanate group include hydroxyalkyl (meth) acrylate having an alkyl group having 2 to 7 carbon atoms, and specific examples thereof include 2- Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,3-butanediol (meth) acrylate, 1,4-butanediol (meth) acrylate, 1,6 -Hexanediol (meth) acrylate, 3-methylpentanediol (meth) acrylate, etc.
  • the amount of the (meth) acrylate having a hydroxyl group is preferably 3 to 18 parts by mass, more preferably 4 to 15 parts by mass with respect to 100 parts by mass of the polyolefin polyol. More preferably.
  • the amount of the (meth) acrylate having a hydroxyl group is less than 3 parts by mass, there may be an olefin compound having no (meth) acryl group, and the strength of the pressure-sensitive adhesive sheet is lowered, and the hydroxyl group is )
  • the amount of acrylate used exceeds 18 parts by mass, the pressure-sensitive adhesive sheet tends to be hardened because the amount of (meth) acrylic groups introduced into the olefin is too large.
  • the number of (meth) acrylic groups introduced in the (A) (meth) acrylic group-containing polyolefin compound of the present invention may be one or more (meth) acrylic groups per molecule, preferably 1 to 1 per molecule. Two.
  • the molecular weight of the (meth) acryl group-containing polyolefin compound is preferably 10,000 to 300,000, more preferably 20,000 to 200,000, and even more preferably 30,000 to 100,000. is there.
  • the weight average molecular weight is less than 10,000, the cohesive force of the obtained pressure-sensitive adhesive sheet is low, and thus the strength of the pressure-sensitive adhesive sheet may not be sufficient, which is not preferable.
  • the molecular weight is larger than 300,000, the viscosity of the photocurable transparent pressure-sensitive adhesive sheet composition becomes too high, and handling becomes difficult and workability is remarkably deteriorated.
  • the weight average molecular weight in the present invention is a value obtained by using a standard polystyrene calibration curve, measured at normal temperature under the following conditions using gel permeation chromatography (Shodex GPC-101 manufactured by Showa Denko KK). is there. Column: Showa Denko LF-804 Column temperature: 40 ° C Sample: 0.2 mass% copolymer solution in tetrahydrofuran Flow rate: 1 ml / min Eluent: Tetrahydrofuran detector: RI
  • the content of the (meth) acrylic group-containing polyolefin compound in the photocurable transparent adhesive sheet composition is preferably 10 to 50% by mass, and preferably 15 to 45% by mass in the composition. Is more preferable, and 20 to 40% by mass is even more preferable.
  • the content is less than 10% by mass, the resulting pressure-sensitive adhesive sheet becomes brittle, which is not preferable.
  • the amount is more than 50% by mass, the adhesive strength of the resulting adhesive sheet may be lowered, which is not preferable.
  • the (meth) acrylic acid ester having a hydroxyl group mentioned here preferably has no carboxyl group, and examples thereof include hydroxyalkyl (meth) acrylates having an alkyl group with 2 to 7 carbon atoms.
  • 2-hydroxyethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,3-butanediol (meth) acrylate, and 1,4-butanediol (Meth) acrylate, 1,6-hexanediol (meth) acrylate, 3-methylpentanediol (meth) acrylate and the like can be exemplified, and these can be used alone or in combination of two or more.
  • 2-hydroxyethyl acrylate is preferable from the viewpoint of the adhesive strength of the obtained adhesive sheet.
  • the content of the (B) hydroxyl group-containing (meth) acrylic acid ester is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, in the photocurable transparent adhesive sheet composition. More preferably, it is 10 to 20% by mass. If it is less than 1% by mass, the adhesiveness of the obtained pressure-sensitive adhesive sheet to the substrate is insufficient, which is not preferable. Moreover, when more than 30 mass%, the water resistance of an adhesive sheet worsens and is unpreferable.
  • a photopolymerizable monomer other than the (meth) acrylic acid ester having a hydroxyl group (hereinafter sometimes referred to as “(C) photopolymerizable monomer”) is a photopolymerizable monomer. Further, it refers to other than (meth) acrylic acid ester having a hydroxyl group, and a monomer not containing a carboxyl group (chemical formula: —COOH) is preferable.
  • the monomer is not particularly limited, and a monofunctional or polyfunctional photopolymerizable monomer having a vinyl group, a (meth) acryl group, or the like can be used alone or in combination of two or more.
  • a (meth) acrylate compound having a (meth) acryl group is preferable.
  • Alkoxyalkyl (meth) acrylates such as ethoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethoxyethyl (meth) acrylate, 2-ethoxyethoxyethyl (meth) acrylate, methoxy Fluorinated alkyl (meth) acrylates such as alkoxy (poly) alkylene glycol (meth) acrylates such as diethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, and octafluoropentyl (meth) acrylate , N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, etc.
  • (Meth) acrylate polyethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, hydroxypivalin Acid ester neopentyl glycol di (meth) acrylate, 1,3-bis (hydroxyethyl) -5,5-dimethylhydantoin di (meth) acrylate, ⁇ , ⁇ -di (meth) acrylbisdiethylene glycol phthalate, trimethylolpropane tri (Meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, poly Tylene glycol di (meth) acrylate, 1,4-butanediol di (meth)
  • Epoxy group-containing (meth) acrylate and the like Epoxy group-containing (meth) acrylate and the like.
  • the photopolymerizable monomer (C) of the present invention from the viewpoint of miscibility with the (meth) acrylic group-containing polyolefin compound, adhesiveness of the adhesive sheet, strength, light resistance, and heat resistance, monofunctional alkyl ( A (meth) acrylate or a cyclic alkyl (meth) acrylate is preferred.
  • the monofunctional or polyfunctional functional group here refers to a (meth) acrylic group.
  • the content of the photopolymerizable monomer (C) is preferably 20 to 88% by mass, more preferably 20 to 70% by mass in the photocurable transparent adhesive sheet composition. More preferably, it is 40 to 69% by mass.
  • the adhesiveness of the obtained pressure-sensitive adhesive sheet to the substrate is insufficient, which is not preferable. Moreover, when more than 88 mass%, since the cohesion force of an adhesive sheet becomes low, an adhesive force becomes low and is unpreferable.
  • the carboxyl group-containing monomer such as acrylic acid or methacrylic acid contained in the photopolymerizable monomer (C) is 0.1% relative to the total amount of the photopolymerizable monomer (C). It is less than or equal to mass%, more preferably less than or equal to 0.05 mass%. More preferably, the photopolymerizable monomer (C) does not contain a carboxyl group-containing monomer. When the carboxyl group-containing monomer exceeds 0.1% by mass with respect to the total amount of the photopolymerizable monomer (C), it becomes difficult to suppress corrosion of the conductive layer surface of the transparent conductive film.
  • the theoretical glass transition temperature of the polymer comprising the (B) hydroxyl group-containing (meth) acrylic acid ester of the present invention and the photopolymerizable monomer (C) is 0 to 0 from the viewpoint of the strength and adhesive strength of the pressure-sensitive adhesive sheet. It is preferably 50 ° C., more preferably 5 to 45 ° C., and further preferably 10 to 40 ° C. When the temperature is lower than 0 ° C., the resulting pressure-sensitive adhesive sheet becomes too soft due to the influence of the (meth) acrylic group-containing polyolefin compound, so that the adhesive strength of the pressure-sensitive adhesive sheet is lowered, which is not preferable.
  • the theoretical glass transition temperature (Tg) is the following fox (FOX) based on the Tg of the homopolymer (homopolymer) of each monomer constituting the monomer raw material and the mass fraction (copolymerization ratio) of the monomer. It can be calculated from the equation (1).
  • T 1, T 2 ⁇ T n Is the glass transition temperature (absolute temperature) of the homopolymer of each monomer.
  • Tg of the homopolymer a value described in the “Adhesion Technology Handbook” of Nikkan Kogyo Shimbun Co., Ltd. or “Polymer Handbook” of Wiley-Interscience, which is a publicly known material, is adopted.
  • the Tg of a homopolymer of a monomer not described in the above-mentioned publicly known material the value obtained by the following method is adopted.
  • a test sample is prepared by casting and drying a homopolymer solution obtained by solution polymerization of a target monomer on a release liner.
  • differential scanning calorimetry was performed using a differential scanning calorimeter (DSC) at a rate of temperature increase of 10 ° C./min from ⁇ 80 ° C. to 280 ° C., and the endothermic start temperature due to glass transition. Is adopted as the Tg of the homopolymer.
  • Examples of the (D) photopolymerization initiator in the present invention include a carbonyl photopolymerization initiator, a sulfide photopolymerization initiator, a quinone photopolymerization initiator, an azo photopolymerization initiator, and a sulfochloride photopolymerization initiator. Thioxanthone photopolymerization initiator, peroxide photopolymerization initiator, and the like.
  • carbonyl photopolymerization initiator examples include benzophenone, benzyl, benzoin, ⁇ -bromoacetophenone, chloroacetone, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, p-dimethylamino.
  • Examples of the sulfide photopolymerization initiator include diphenyl disulfide, dibenzyl disulfide, tetraethylthiuram disulfide, tetramethylammonium monosulfide and the like.
  • Examples of the quinone photopolymerization initiator include benzoquinone and anthraquinone.
  • Examples of the azo photopolymerization initiator include azobisisobutyronitrile, 2,2′-azobispropane, hydrazine, and the like.
  • Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone and the like.
  • peroxide photopolymerization initiator examples include benzoyl peroxide and di-t-butyl peroxide.
  • photopolymerization initiators 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 is preferred from the viewpoint of solubility in the resulting composition for a photocurable transparent adhesive sheet. -ON is preferred.
  • photoinitiators are used individually or in combination of 2 or more types.
  • the content of the photopolymerization initiator is 0.2 to 5% by mass in the photocurable transparent adhesive sheet composition from the viewpoint of the balance between photocurability and the strength and adhesiveness of the resulting adhesive sheet. It is preferably 0.5 to 3% by mass, more preferably 0.8 to 2% by mass.
  • the content of the photopolymerization initiator is less than 0.2% by mass, the photocuring tends to be insufficient, and when it exceeds 5% by mass, the adhesiveness of the obtained pressure-sensitive adhesive sheet tends to decrease. There is not preferable.
  • the composition for a photocurable transparent pressure-sensitive adhesive sheet of the present invention is preferably 10 to 50% by mass of the component (A) and 1 to 30% by mass of the component (B) based on the total amount of the composition for the photocurable transparent pressure-sensitive adhesive sheet. %, (C) component 20 to 88% by mass, and (D) component 0.2 to 5% by mass. More preferably, the component (A) is 15 to 45% by mass, the component (B) is 5 to 25% by mass, and the component (C) is 20 to 70% by mass based on the total amount of the photocurable transparent adhesive sheet composition. And (D) component 0.2 to 5% by mass.
  • the component (A) is 20 to 40% by mass
  • the component (B) is 10 to 20% by mass
  • the component (C) is 40 to 69% by mass with respect to the total amount of the photocurable transparent adhesive sheet composition.
  • (D) component 0.5 to 3% by mass.
  • a tackifier resin may be added as necessary in order not to lower the transparency in order to improve the adhesive strength of the obtained pressure-sensitive adhesive sheet.
  • tackifying resins include rosin resins such as rosin and rosin esterified products; terpene resins such as diterpene polymers and ⁇ -pinene-phenol copolymers; aliphatic (C5) and aromatic ( Petroleum resin such as C9); styrene resin, phenol resin, xylene resin and the like.
  • an esterified product of hydrogenated rosin or disproportionated rosin with few unsaturated double bonds, aliphatic or aromatic petroleum resin, high Tg acrylic resin, or the like is preferable to add to the adhesive sheet.
  • addition amount of tackifying resin 100 mass parts of total amount of (A) component, (B) component, (C) component, and (D) component with respect to 100 mass parts of composition for photocurable transparent adhesive sheets 1 to 10 parts by mass is preferably added.
  • composition for a photocurable transparent pressure-sensitive adhesive sheet of the present invention may contain various known additives as long as the transparency is not impaired.
  • Additives include plasticizers, surface lubricants, leveling agents, softeners, antioxidants, antioxidants, light stabilizers, UV absorbers, polymerization inhibitors, benzotriazole-based light stabilizers, phosphate esters System and other flame retardants, and antistatic agents such as surfactants.
  • composition for a photocurable transparent adhesive sheet of the present invention may be made into a solution using an organic solvent for the purpose of adjusting the viscosity at the time of coating.
  • organic solvent examples include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, n-propanol and isopropanol. These organic solvents may be used alone or in combination of two or more.
  • the acid value of the composition for a photocurable transparent adhesive sheet of the present invention is preferably 0 to 0.5 mgKOH / g, more preferably 0 to 0.1 mgKOH / g, and further preferably 0 to 0.05 mgKOH / g. .
  • the acid value of the composition is a value measured according to JIS K0070. For example, measurement is performed as follows.
  • composition for transparent adhesive sheet for fixing transparent conductive film is a composition for pressure-sensitive adhesive sheets for fixing a transparent conductive film comprising the above-described composition for a photocurable transparent pressure-sensitive adhesive sheet.
  • any conductive layer may be used as long as it has a conductive layer on at least one surface layer.
  • the transparent conductive film provided by (1) is mentioned.
  • the conductive material deposited or coated in the conductive layer of the transparent conductive film is not particularly limited, and specific examples include indium tin oxide, indium oxide, tin oxide, zinc oxide, cadmium oxide, gallium oxide, and titanium oxide. It is done. Of these, indium tin oxide having excellent transparency and conductivity is preferably used.
  • the substrate on which the conductive material is deposited or coated is not particularly limited, and examples thereof include glass and resin films.
  • the transparent pressure-sensitive adhesive sheet for fixing a transparent conductive film of the present invention is a transparent pressure-sensitive adhesive sheet for fixing a transparent conductive film obtained by curing the above-described composition for fixing a transparent conductive film. It can be suitably bonded and the conductive layer is unlikely to corrode. Therefore, the laminated body which adhere
  • the adhesive layer consists of a single layer, multiple layers may be laminated
  • it is preferable that it is a double-sided adhesive sheet which does not have a base material but consists only of an adhesive layer from a viewpoint of ensuring transparency and shape followability.
  • the transparent adhesive sheet for fixing a transparent conductive film of the present invention is obtained by applying a transparent adhesive sheet composition for fixing a transparent conductive film to a release PET film, and irradiating the applied composition with ultraviolet rays using an ultraviolet irradiation device or the like. It can be obtained by photocuring.
  • the thickness of the transparent conductive film fixing pressure-sensitive adhesive sheet is preferably 5 to 500 ⁇ m, more preferably 10 to 300 ⁇ m. When the film thickness of the adhesive sheet for fixing a transparent conductive film becomes thinner than 5 ⁇ m, it becomes difficult to bond the adhesive sheet, and when it becomes thicker than 500 ⁇ m, it tends to be difficult to control the film thickness.
  • the pressure-sensitive adhesive sheet for fixing a transparent conductive film of the present invention preferably has a gel fraction determined by the following formula (3) of 80 to 100% when immersed in toluene at room temperature for 24 hours, More preferably, it is 100%.
  • the gel fraction of the pressure-sensitive adhesive sheet is lower than 80%, stringing or the like from the processed end face tends to occur during punching.
  • ⁇ (Meth) acrylic group-containing polyolefin compound (A-1)> A four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooling tube with a drying tube is mixed with isophorone diisocyanate 101.2 g and hydroxyl-terminated hydrogenated polybutadiene (manufactured by Nippon Soda Co., Ltd., product name: GI-3000, weight average molecular weight). 14,000) was charged at 84 ° C. and reacted at 60 ° C. When the residual isocyanate group became 1% or less, 53.9 g of 2-hydroxyethyl acrylate was charged and the temperature was raised to 70 ° C.
  • ⁇ (Meth) acrylic group-containing polyolefin compound (A-4)> A four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooling tube with a drying tube, 61.2 g of isophorone diisocyanate and hydrogenated polybutadiene having a hydroxyl group (Product name: GI-3000, manufactured by Nippon Soda Co., Ltd., weight average molecular weight) 14,000) was charged at 91 ° C. and reacted at 60 ° C. When the residual isocyanate group became 1% or less, 21.3 g of 2-hydroxyethyl acrylate was charged and the temperature was raised to 70 ° C. to carry out the reaction. However, it became high molecular weight and gelled during the reaction.
  • Examples 1 to 6, Comparative Examples 1 to 4 Each of the compositions shown in Table 1 was blended and mixed with a disper at room temperature to prepare a uniform photocurable transparent adhesive sheet composition.
  • the prepared composition for a photocurable transparent adhesive sheet is applied to a release PET film (100 mm ⁇ 100 mm ⁇ 100 ⁇ m) using an applicator so that the film thickness is 200 ⁇ m, and the upper surface is a release PET film having a thickness of 25 ⁇ m.
  • the pressure-sensitive adhesive sheet having a thickness of about 200 ⁇ m sandwiched between the release PET films was obtained by irradiating with UV rays and curing under the condition of 2 .
  • the composition for a photocurable transparent pressure-sensitive adhesive sheet containing the (meth) acryl group-containing polyolefin compound having a weight average molecular weight exceeding 300,000 The comparative example could not be prepared.
  • the adhesive sheet obtained above was cut to a size of 50 mm ⁇ 50 mm, the release PET film having a thickness of 25 ⁇ m was peeled off, and bonded to the indium tin oxide film surface of the 100 mm ⁇ 100 mm indium tin oxide-deposited PET film.
  • the electrical resistance value measuring device “Lorestar GP” manufactured by Mitsubishi Chemical Corporation was used at both ends of the bonded adhesive sheet, and the initial electrical resistance value (R 1 ) was measured.
  • the indium tin oxide-deposited PET film to which the adhesive sheet was bonded was left at 90 ° C. for 500 hours and left at 23 ° C. and 50% RH for 1 hour.
  • the resistance value (R 2 ) was measured.
  • the increase rate of the electric resistance value of the indium tin oxide film was calculated by the following formula (4).
  • the rate of increase in electrical resistance value was evaluated according to the following criteria. The results are shown in Table 1. ⁇ : Electrical resistance value increase rate of less than 5% ⁇ ; Electrical resistance value increase rate of 5 to less than 10% ⁇ : Electrical resistance value increase rate of 10% or more
  • the pressure-sensitive adhesive sheet obtained above was cut to a size of 25 ⁇ 100 mm, and after removing the 100 ⁇ m-thick release PET film from the release PET film existing on both sides of the pressure-sensitive adhesive sheet, the pressure-sensitive adhesive surface (measurement surface) was tested.
  • a 2 kg rubber roller (width: about 50 mm) was attached to the plate by reciprocating once to prepare a measurement sample.
  • a glass plate was used as a test plate.
  • the obtained measurement sample is left for 24 hours in an environment of 23 ° C.
  • Total light transmittance measurement The pressure-sensitive adhesive sheet obtained above was cut into a size of 30 mm ⁇ 30 mm, and the release PET film having a thickness of 25 ⁇ m was peeled off from the release PET film existing on both sides of the pressure-sensitive adhesive sheet, and then bonded to a glass plate for measurement. A sample was used. About the sample for a measurement, the total light transmittance (%) was measured using "HR-100 type" by Murakami Color Research Laboratory. The results are shown in Table 1.
  • the pressure-sensitive adhesive sheet was cut into a size of 20 mm ⁇ 40 mm to prepare a measurement sample. After this measurement sample was immersed in toluene at 23 ° C. for 24 hours, the measurement sample was taken out from toluene. Thereafter, the measurement sample was dried at 130 ° C. for 1 hour. Next, the weight of the measurement sample after drying was measured, and the gel fraction was calculated by the above-described formula (3). The results are shown in Table 1.
  • the composition for the photocurable transparent adhesive sheet of the present invention obtained in the examples is superior in the electrical resistance value increase rate, the total light transmittance, and the adhesive strength as compared with the comparative example.
  • composition for a photocurable transparent pressure-sensitive adhesive sheet of the present invention is useful as a pressure-sensitive adhesive sheet for fixing a transparent conductive film because it has high transparency, metal corrosion prevention and is excellent in adhesiveness. This is useful for fixing a transparent conductive film used in a touch panel of the type.

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Abstract

The purpose of the present invention is to provide: a light-curing composition for use in a transparent pressure-sensitive adhesive sheet that is highly transparent and well suited to punching, has a strongly cohesive pressure-sensitive adhesive-agent layer, and does not corrode a conductive layer of a transparent conductive film even if bonded directly to the surface of said conductive layer; and a pressure-sensitive adhesive sheet. The present invention is a light-curing composition for use in a transparent pressure-sensitive adhesive sheet, said composition comprising: (A) a (meth)acryl-group-containing polyolefin compound that has a weight-average molecular weight of 10,000-300,000; (B) a (meth)acrylic acid ester that has a hydroxyl group; (C) photopolymerizable monomers other than (meth)acrylic acid esters having hydroxyl groups; and (D) a photopolymerization initiator. Said light-curing composition for use in a transparent pressure-sensitive adhesive sheet is characterized in that carboxyl-group-containing monomers constitute no more than 0.1% of the mass of the (C) photopolymerizable monomers.

Description

光硬化性透明粘着シート用組成物Composition for photocurable transparent adhesive sheet

　本発明は、光硬化性透明粘着シート用組成物、光硬化性透明粘着シート用組成物を硬化させて得られる光硬化性透明粘着シートが透明導電膜の貼り合せに使用されることを特徴とする透明導電膜固定用透明粘着シート用組成物、透明導電膜固定用透明粘着シート用組成物を硬化して得られる透明導電膜固定用透明粘着シート及び、透明導電膜固定用透明粘着シートが透明導電膜の導電層面に接着されていることを特徴とする積層体に関する。 The present invention is characterized in that a photocurable transparent adhesive sheet obtained by curing a composition for a photocurable transparent adhesive sheet and a composition for a photocurable transparent adhesive sheet is used for laminating a transparent conductive film. A transparent adhesive sheet for fixing a transparent conductive film, a transparent adhesive sheet for fixing a transparent conductive film, and a transparent adhesive sheet for fixing a transparent conductive film obtained by curing a composition for transparent adhesive sheet for fixing a transparent conductive film are transparent. The present invention relates to a laminate that is bonded to a conductive layer surface of a conductive film.

　近年、携帯電話、ゲーム機器などの分野にタッチパネルが搭載され始めている。タッチパネルは、ＩＴＯ（酸化インジウムスズ）などの透明導電膜を表層に有する透明基材やガラスとそれを保護する透明保護シート、さらには液晶ディスプレイなどの表示装置といった光学部材を、光学用の透明粘着シートを用いて貼り合せた積層体である。 In recent years, touch panels have begun to be installed in the fields of mobile phones and game machines. The touch panel is a transparent base material for transparent optical substrates such as ITO (Indium Tin Oxide) and a transparent substrate, glass and a transparent protective sheet for protecting it, and a display device such as a liquid crystal display. It is the laminated body bonded together using the sheet | seat.

　タッチパネルには、主に入力時の圧力で検知する抵抗膜方式のタッチパネルと、入力時の人体からの静電気で入力箇所を検知する静電容量方式のタッチパネルがある。静電容量方式のタッチパネルにおいては、透明導電膜の導電層面が、粘着シートの粘着剤層表面と接するように固定される。そのため、透明導電膜の導電層面に粘着剤層が接することで、粘着剤に含まれる酸成分によって金属の酸化反応が起こり、導電機能の低下が起こる問題がある。このため、透明導電膜固定用の粘着シートには高い金属腐食防止性が要求されている。 There are two types of touch panels: a resistive touch panel that detects mainly the pressure at the time of input, and a capacitive touch panel that detects the input location by static electricity from the human body at the time of input. In the capacitive touch panel, the conductive layer surface of the transparent conductive film is fixed so as to be in contact with the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive sheet. Therefore, there is a problem that when the pressure-sensitive adhesive layer is in contact with the conductive layer surface of the transparent conductive film, a metal oxidation reaction occurs due to the acid component contained in the pressure-sensitive adhesive, resulting in a decrease in the conductive function. For this reason, the adhesive sheet for fixing a transparent conductive film is required to have high metal corrosion prevention properties.

　金属腐食防止性を有する粘着シートとしては、金属腐食防止剤を含有する粘着シート（例えば、特許文献１）が提案されている。また、粘着剤層の酸成分に対して、特定量の窒素原子含有成分を含有させることで、透明導電膜に対する腐食性を低下させた粘着シート（例えば、特許文献２）が提案されている。 As a pressure-sensitive adhesive sheet having metal corrosion prevention properties, a pressure-sensitive adhesive sheet containing a metal corrosion inhibitor (for example, Patent Document 1) has been proposed. Moreover, the adhesive sheet (for example, patent document 2) which reduced the corrosivity with respect to a transparent conductive film by containing a specific amount of nitrogen atom containing components with respect to the acid component of an adhesive layer is proposed.

　しかしながら、金属腐食防止剤を含有する粘着シートは、金属腐食防止剤が耐久性試験で変色し、光学特性を低下させる等の問題があった。また、特定量の窒素原子含有成分を含有させた粘着シートは、粘着剤層に含まれる酸成分が原因で、ＩＴＯの電気抵抗値の上昇を十分に抑えられない問題があった。 However, the pressure-sensitive adhesive sheet containing a metal corrosion inhibitor has a problem that the metal corrosion inhibitor is discolored in a durability test and optical properties are deteriorated. In addition, the pressure-sensitive adhesive sheet containing a specific amount of a nitrogen atom-containing component has a problem that an increase in the electrical resistance value of ITO cannot be sufficiently suppressed due to the acid component contained in the pressure-sensitive adhesive layer.

特開２００６－４５３１５号公報JP 2006-45315 A 特開２０１０－１４４００２号公報JP 2010-144002 A

　本発明が解決しようとする課題は、硬化させて得られる透明粘着シートが、透明導電膜の導電層面に対して直接貼り合わせても導電層を腐食させず、粘着剤層の凝集力、透明性、及び打ち抜き加工性に優れる光硬化性透明粘着シート用組成物を提供することにある。さらには、該透明粘着シートを提供することにある。 The problem to be solved by the present invention is that the transparent adhesive sheet obtained by curing does not corrode the conductive layer even if it is directly bonded to the conductive layer surface of the transparent conductive film, and the cohesive force and transparency of the adhesive layer And it is providing the composition for photocurable transparent adhesive sheets which is excellent in punching workability. Furthermore, it is in providing this transparent adhesive sheet.

　本発明者らは、タッチパネル用光硬化性透明粘着シートが抱える前記の問題点を背景にして、鋭意検討を重ねた結果、高分子量の（メタ）アクリル基（化学式：－ＣＯＣＨ＝ＣＨ２　、－ＣＯＣ（ＣＨ３）＝ＣＨ２）含有ポリオレフィン化合物、ヒドロキシル基（化学式：－ＯＨ）を有する（メタ）アクリル酸エステル、光重合性単量体、及び光重合開始剤を配合した光硬化性透明粘着シート用組成物であって、光重合性単量体に含まれるカルボキシル基単量体が所定量以下である光硬化性透明粘着シート用組成物が、該光硬化性透明粘着シート用組成物を硬化させて得られる光硬化性透明粘着シートの透明性、粘着性、及び透明導電膜の金属腐食防止性が良好であることを見出し、この知見に基づいて本発明を完成した。 As a result of intensive studies against the problems of the photocurable transparent pressure-sensitive adhesive sheet for touch panels, the present inventors have studied high molecular weight (meth) acrylic groups (chemical formula: —COCH═CH 2 , — COC (CH 3 ) ═CH 2 ) -containing polyolefin compound, (meth) acrylic acid ester having a hydroxyl group (chemical formula: —OH), a photopolymerizable monomer, and a photocurable transparent adhesive containing a photopolymerization initiator It is a composition for sheets, Comprising: The composition for photocurable transparent adhesive sheets whose carboxyl group monomer contained in a photopolymerizable monomer is below a predetermined amount is the composition for photocurable transparent adhesive sheets. It discovered that the transparency of the photocurable transparent adhesive sheet obtained by making it harden | cure, adhesiveness, and the metal corrosion prevention property of a transparent conductive film were favorable, and completed this invention based on this knowledge.

　本発明は、以下（１）～（１１）で示される。 The present invention is shown by the following (1) to (11).

　（１）（Ａ）重量平均分子量が１万～３０万である（メタ）アクリル基含有ポリオレフィン化合物、（Ｂ）ヒドロキシル基を有する（メタ）アクリル酸エステル、（Ｃ）ヒドロキシル基を有する（メタ）アクリル酸エステル以外の光重合性単量体、及び（Ｄ）光重合開始剤を含有してなる光硬化性透明粘着シート用組成物であって、（Ｃ）ヒドロキシル基を有する（メタ）アクリル酸エステル以外の光重合性単量体に含まれるカルボキシル基含有単量体が（Ｃ）ヒドロキシル基を有する（メタ）アクリル酸エステル以外の光重合性単量体の全量に対して、０．１質量％以下であることを特徴とする光硬化性透明粘着シート用組成物。 (1) (A) (meth) acrylic group-containing polyolefin compound having a weight average molecular weight of 10,000 to 300,000, (B) (meth) acrylic acid ester having hydroxyl group, (C) (meth) having hydroxyl group A photopolymerizable monomer other than an acrylate ester, and (D) a photocurable transparent pressure-sensitive adhesive sheet composition containing a photopolymerization initiator, wherein (C) a (meth) acrylic acid having a hydroxyl group The carboxyl group-containing monomer contained in the photopolymerizable monomer other than the ester is (C) 0.1 mass relative to the total amount of the photopolymerizable monomer other than the (meth) acrylic acid ester having a hydroxyl group. % For a photocurable transparent adhesive sheet.

　（２）光硬化性透明粘着シート用組成物の全量に対して、（Ａ）重量平均分子量が１万～３０万である（メタ）アクリル基含有ポリオレフィン化合物１０～５０質量％、（Ｂ）ヒドロキシル基を有する（メタ）アクリル酸エステル１～３０質量％、（Ｃ）ヒドロキシル基を有する（メタ）アクリル酸エステル以外の光重合性単量体２０～８８質量％、及び（Ｄ）光重合開始剤０．２～５質量％を含有してなることを特徴とする（１）記載の光硬化性透明粘着シート用組成物。 (2) (M) (Meth) acrylic group-containing polyolefin compound having a weight average molecular weight of 10,000 to 300,000 with respect to the total amount of the photocurable transparent adhesive sheet composition, and (B) hydroxyl (Meth) acrylic acid ester having 1 to 30% by mass, (C) 20 to 88% by mass of photopolymerizable monomer other than (meth) acrylic acid ester having a hydroxyl group, and (D) a photopolymerization initiator The composition for a photocurable transparent pressure-sensitive adhesive sheet according to (1), comprising 0.2 to 5% by mass.

　（３）（Ｃ）ヒドロキシル基を有する（メタ）アクリル酸エステル以外の光重合性単量体がカルボキシル基含有単量体を含まないことを特徴とする上記（１）又は（２）に記載の光硬化性透明粘着シート用組成物。 (3) (C) The photopolymerizable monomer other than the (meth) acrylic acid ester having a hydroxyl group does not contain a carboxyl group-containing monomer, as described in (1) or (2) above The composition for photocurable transparent adhesive sheets.

　（４）（Ｂ）ヒドロキシル基を有する（メタ）アクリル酸エステル、及び（Ｃ）ヒドロキシル基を有する（メタ）アクリル酸エステル以外の光重合性単量体を重合して得られるポリマーの理論ガラス転移温度が０℃～５０℃であることを特徴とする上記（１）から（３）のいずれかに記載の光硬化性透明粘着シート用組成物。 (4) Theoretical glass transition of a polymer obtained by polymerizing (B) a (meth) acrylate having a hydroxyl group and (C) a photopolymerizable monomer other than a (meth) acrylate having a hydroxyl group The composition for a photocurable transparent pressure-sensitive adhesive sheet according to any one of (1) to (3) above, wherein the temperature is 0 ° C. to 50 ° C.

　（５）（Ｃ）ヒドロキシル基を有する（メタ）アクリル酸エステル以外の光重合性単量体が単官能アルキル（メタ）アクリレート、及び／又は環状アルキル（メタ）アクリレートであることを特徴とする上記（１）から（４）のいずれかに記載の光硬化性透明粘着シート用組成物。 (5) (C) The photopolymerizable monomer other than the (meth) acrylic acid ester having a hydroxyl group is a monofunctional alkyl (meth) acrylate and / or a cyclic alkyl (meth) acrylate. (1) The composition for photocurable transparent adhesive sheets in any one of (4).

　（６）（Ａ）重量平均分子量が１万～３０万である（メタ）アクリル基含有ポリオレフィン化合物が、ポリオレフィンポリオール化合物、ヒドロキシル基を有する（メタ）アクリレート、及び１分子中にイソシアネート基を２個以上有する化合物を反応させて得られる（メタ）アクリル基を有する化合物であることを特徴とする上記（１）から（５）のいずれかに記載の光硬化性透明粘着シート用組成物。 (6) (A) A (meth) acryl group-containing polyolefin compound having a weight average molecular weight of 10,000 to 300,000 is a polyolefin polyol compound, a (meth) acrylate having a hydroxyl group, and two isocyanate groups in one molecule. The composition for a photocurable transparent adhesive sheet according to any one of (1) to (5) above, which is a compound having a (meth) acrylic group obtained by reacting the compound having the above.

　（７）酸価が０．５ｍｇＫＯＨ／ｇ以下であることを特徴とする上記（１）から（６）のいずれかに記載の光硬化性透明粘着シート用組成物。 (7) The composition for a photocurable transparent adhesive sheet according to any one of (1) to (6) above, wherein the acid value is 0.5 mgKOH / g or less.

　（８）上記（１）から（７）のいずれかに記載の光硬化性透明粘着シート用組成物を硬化させて得られる光硬化性透明粘着シートが透明導電膜の貼り合せに使用されることを特徴とする透明導電膜固定用透明粘着シート用組成物。 (8) A photocurable transparent adhesive sheet obtained by curing the composition for a photocurable transparent adhesive sheet according to any one of (1) to (7) above is used for laminating a transparent conductive film. A composition for a transparent adhesive sheet for fixing a transparent conductive film.

　（９）上記（８）に記載の透明導電膜固定用透明粘着シート用組成物を硬化させて得られることを特徴とする透明導電膜固定用透明粘着シート。 (9) A transparent adhesive sheet for fixing a transparent conductive film, obtained by curing the composition for transparent adhesive sheet for fixing a transparent conductive film according to (8) above.

　（１０）ゲル分率が８０～１００％であることを特徴とする上記（９）に記載の透明導電膜固定用透明粘着シート。 (10) The transparent adhesive sheet for fixing a transparent conductive film according to (9), wherein the gel fraction is 80 to 100%.

　（１１）上記（９）又は（１０）に記載の透明導電膜固定用透明粘着シートが、透明導電膜の導電層面に接着されていることを特徴とする積層体。 (11) A laminate characterized in that the transparent conductive sheet fixing transparent adhesive sheet according to (9) or (10) is adhered to a conductive layer surface of a transparent conductive film.

　本発明の光硬化性透明粘着シート用組成物は、組成物中に高分子量の（メタ）アクリル基含有ポリオレフィン化合物が含まれるため、硬化させて得られる粘着シートの柔軟性、耐透湿性に優れており、さらに組成物中にカルボキシル基が微量しか含まれないため、得られる透明粘着シートの酸成分による透明導電膜の導電層面の腐食を抑制でき、組成物中にヒドロキシル基を有する（メタ）アクリル酸エステルが含まれるため、得られる粘着シートの凝集力と基材への密着性が優れている。 The composition for a photocurable transparent pressure-sensitive adhesive sheet of the present invention contains a high molecular weight (meth) acrylic group-containing polyolefin compound in the composition, and therefore is excellent in flexibility and moisture permeability of a pressure-sensitive adhesive sheet obtained by curing. Furthermore, since the composition contains only a small amount of carboxyl groups, corrosion of the conductive layer surface of the transparent conductive film due to the acid component of the transparent adhesive sheet obtained can be suppressed, and the composition has a hydroxyl group (meta) Since acrylic acid ester is contained, the cohesive force of the obtained adhesive sheet and the adhesiveness to a base material are excellent.

　以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.

［光硬化性透明粘着シート用組成物］
　本発明の光硬化性透明粘着シート用組成物は、（Ａ）重量平均分子量が１万～３０万である（メタ）アクリル基含有ポリオレフィン化合物、（Ｂ）ヒドロキシル基を有する（メタ）アクリル酸エステル、（Ｃ）ヒドロキシル基を有する（メタ）アクリル酸エステル以外の光重合性単量体、及び（Ｄ）光重合開始剤を含有してなる。 [Composition for photocurable transparent adhesive sheet]
The composition for a photocurable transparent adhesive sheet of the present invention comprises (A) a (meth) acrylic group-containing polyolefin compound having a weight average molecular weight of 10,000 to 300,000, and (B) a (meth) acrylic acid ester having a hydroxyl group. (C) A photopolymerizable monomer other than (meth) acrylic acid ester having a hydroxyl group, and (D) a photopolymerization initiator.

（（Ａ）（メタ）アクリル基含有ポリオレフィン化合物）
　（メタ）アクリル基含有ポリオレフィン化合物としては、ポリオレフィン骨格を有し、さらに（メタ）アクリル基が導入されているもので有れば使用することが出来る。ポリオレフィン骨格としては、ポリエチレン、ポリプロピレン、エチレン・プロピレン共重合体、ブタジエン、イソプレン、水添ポリブタジエン、水添ポリイソプレン、シクロオレフィン等の骨格が挙げられる。耐光性、透明性（非結晶性）、作業性（液状）の点で、水添ポリブタジエン、水添ポリイソプレン骨格が好ましい。なお、（メタ）アクリル基とはＣＨ２＝ＣＨ－ＣＯ－　または　ＣＨ２＝Ｃ（ＣＨ３）－ＣＯ－を意味する。 ((A) (Meth) acrylic group-containing polyolefin compound)
As the (meth) acryl group-containing polyolefin compound, any polyolefin compound having a polyolefin skeleton and having a (meth) acryl group introduced therein can be used. Examples of the polyolefin skeleton include polyethylene, polypropylene, ethylene / propylene copolymer, butadiene, isoprene, hydrogenated polybutadiene, hydrogenated polyisoprene, cycloolefin, and the like. Hydrogenated polybutadiene and hydrogenated polyisoprene skeleton are preferable in terms of light resistance, transparency (non-crystalline), and workability (liquid). The (meth) acryl group means CH 2 ═CH—CO— or CH 2 ═C (CH 3 ) —CO—.

　ポリオレフィンへの（メタ）アクリル基の導入方法は、特に限定されるものではないが、反応性の水酸基を分子末端等に有するポリオレフィンを（メタ）アクリル酸を用いてエステル化するか、または、まず、１分子中にイソシアネート基を２個以上有するイソシアネート化合物をポリオレフィンの水酸基に付加し、イソシアネート基とヒドロキシル基を有する（メタ）アクリレートを反応させることで（メタ）アクリル化する方法を例示できる。 The method for introducing the (meth) acrylic group into the polyolefin is not particularly limited, but the polyolefin having a reactive hydroxyl group at the molecular end or the like is esterified with (meth) acrylic acid, Examples of the method include (meth) acrylation by adding an isocyanate compound having two or more isocyanate groups in one molecule to a hydroxyl group of polyolefin and reacting the (meth) acrylate having an isocyanate group and a hydroxyl group.

　中でも、ポリオレフィンポリオール化合物に対して、１分子中にイソシアネート基を２個以上有するイソシアネート化合物を反応させ、次いでヒドロキシル基を有する（メタ）アクリレートをウレタン化反応させて得られる（メタ）アクリル基含有ポリオレフィン化合物は、得られる粘着シートの凝集力が高い点で好ましい。 Among them, (meth) acrylic group-containing polyolefin obtained by reacting a polyolefin polyol compound with an isocyanate compound having two or more isocyanate groups in one molecule and then urethanizing a (meth) acrylate having a hydroxyl group. A compound is preferable at the point with the high cohesion force of the adhesive sheet obtained.

　ポリオレフィンポリオール化合物は、１分子中に水酸基を２個以上有するものであるが、水酸基を２～４個有することが好ましい。また、ポリオレフィンポリオール化合物の重量平均分子量は、５，０００～３０，０００が好ましく、１０，０００～１５，０００がより好ましい。ポリオレフィンポリオール化合物の重量平均分子量が５，０００より低くなると、得られる（メタ）アクリル基含有ポリオレフィン化合物の分子量が高くならず、十分な粘着シートの強度が得られない傾向にある。また、ポリオレフィンポリオール化合物の重量平均分子量が３０，０００より高くなると、得られる（メタ）アクリル基含有ポリオレフィン化合物の分子量が高くなりすぎて、取り扱いが困難となる傾向にある。 The polyolefin polyol compound has two or more hydroxyl groups in one molecule, but preferably has 2 to 4 hydroxyl groups. Further, the weight average molecular weight of the polyolefin polyol compound is preferably 5,000 to 30,000, more preferably 10,000 to 15,000. When the weight average molecular weight of the polyolefin polyol compound is lower than 5,000, the molecular weight of the resulting (meth) acryl group-containing polyolefin compound does not increase, and sufficient strength of the pressure-sensitive adhesive sheet tends not to be obtained. Moreover, when the weight average molecular weight of the polyolefin polyol compound is higher than 30,000, the molecular weight of the resulting (meth) acrylic group-containing polyolefin compound becomes too high and the handling tends to be difficult.

　１分子中にイソシアネート基を２個以上有する化合物としては、例えば、トリレンジイソシアネート、キシ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、トリメチルヘキサメチレンジイソシアネート、テトラメチルキシリレンジイソシアネート、イソホロンジイソシアネート及びこれらの水素添加物等のジイソシアネート化合物が挙げられる。中でも、耐光性、反応性制御のしやすさの点から、イソホロンジイソシアネートが好ましい。これらの１分子中にイソシアネート基を２個以上有する化合物は、単独で又は２種類以上を組み合わせて使用できる。１分子中にイソシアネート基を２個以上有するイソシアネート化合物の使用量としては、ポリオレフィンポリオール１００質量部に対し、８～３５質量部であることが好ましく、１０～３０質量部であることがより好ましく、１１～２５質量部であることがさらに好ましい。１分子中にイソシアネート基を２個以上有するイソシアネート化合物の使用量が８質量部より少なくなると、得られる（メタ）アクリル基含有ポリオレフィン化合物の分子量が高くなりすぎるために取り扱い困難となり、イソシアネート化合物の使用量が３５質量部より多くなると、得られる（メタ）アクリル基含有ポリオレフィン化合物の分子量が低くなりすぎるために、粘着シートの強度が十分に得られない傾向にある。 Examples of the compound having two or more isocyanate groups in one molecule include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate and hydrogenation thereof. And diisocyanate compounds such as products. Of these, isophorone diisocyanate is preferable from the viewpoint of light resistance and ease of reactivity control. These compounds having two or more isocyanate groups in one molecule can be used alone or in combination of two or more. The amount of the isocyanate compound having two or more isocyanate groups in one molecule is preferably 8 to 35 parts by mass, more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the polyolefin polyol. More preferably, it is 11 to 25 parts by mass. If the amount of the isocyanate compound having two or more isocyanate groups in one molecule is less than 8 parts by mass, the resulting (meth) acrylic group-containing polyolefin compound becomes too high in molecular weight, making it difficult to handle. When the amount exceeds 35 parts by mass, the molecular weight of the resulting (meth) acrylic group-containing polyolefin compound becomes too low, so that the strength of the pressure-sensitive adhesive sheet tends to be insufficient.

　イソシアネート基と反応させる、ヒドロキシル基を有する（メタ）アクリレートとしては、例えば、アルキル基の炭素数が２～７であるヒドロキシアルキル（メタ）アクリレート等が挙げられ、これらの具体例としては、２－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、４－ヒドロキシブチル（メタ）アクリレート、１，３－ブタンジオール（メタ）アクリレート、１，４－ブタンジオール（メタ）アクリレート、１，６－ヘキサンジオール（メタ）アクリレート、３－メチルペンタンジオール（メタ）アクリレート等が例示でき、単独又は２種以上組み合わせて用いることができる。中でも、反応性の点で、２－ヒドロキシエチルアクリレート及び２－ヒドロキシエチルメタクリレートが好ましい。ヒドロキシル基を有する（メタ）アクリレートの使用量としては、ポリオレフィンポリオール１００質量部に対し、３～１８質量部であることが好ましく、４～１５質量部であることがより好ましく、５～１３質量部であることがさらに好ましい。ヒドロキシル基を有する（メタ）アクリレートの使用量が３質量部より少なくなると、（メタ）アクリル基を持たないオレフィン化合物が存在する可能性があり粘着シートの強度が低くなり、ヒドロキシル基を有する（メタ）アクリレートの使用量が１８質量部より多くなると、オレフィンに導入された（メタ）アクリル基の量が多くなりすぎるため粘着シートが固くなる傾向にある。 Examples of the (meth) acrylate having a hydroxyl group to be reacted with an isocyanate group include hydroxyalkyl (meth) acrylate having an alkyl group having 2 to 7 carbon atoms, and specific examples thereof include 2- Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,3-butanediol (meth) acrylate, 1,4-butanediol (meth) acrylate, 1,6 -Hexanediol (meth) acrylate, 3-methylpentanediol (meth) acrylate, etc. can be exemplified, and can be used alone or in combination of two or more. Of these, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferable in terms of reactivity. The amount of the (meth) acrylate having a hydroxyl group is preferably 3 to 18 parts by mass, more preferably 4 to 15 parts by mass with respect to 100 parts by mass of the polyolefin polyol. More preferably. When the amount of the (meth) acrylate having a hydroxyl group is less than 3 parts by mass, there may be an olefin compound having no (meth) acryl group, and the strength of the pressure-sensitive adhesive sheet is lowered, and the hydroxyl group is ) When the amount of acrylate used exceeds 18 parts by mass, the pressure-sensitive adhesive sheet tends to be hardened because the amount of (meth) acrylic groups introduced into the olefin is too large.

　本発明の（Ａ）（メタ）アクリル基含有ポリオレフィン化合物の（メタ）アクリル基の導入数としては、１分子中に（メタ）アクリル基が１個以上あれば良く、好ましくは１分子中１～２個である。 The number of (meth) acrylic groups introduced in the (A) (meth) acrylic group-containing polyolefin compound of the present invention may be one or more (meth) acrylic groups per molecule, preferably 1 to 1 per molecule. Two.

　（Ａ）（メタ）アクリル基含有ポリオレフィン化合物の分子量は、重量平均分子量が１万～３０万であることが好ましく、より好ましくは２万～２０万であり、さらに好ましくは３万～１０万である。重量平均分子量が１万未満では、得られる粘着シートの凝集力が低くなることから粘着シートの強度が十分でない可能性があり好ましくない。また、分子量が３０万より大きい場合には、光硬化性透明粘着シート用組成物の粘度が高くなりすぎるために取り扱いが困難となり作業性が著しく悪くなり好ましくない。なお、本発明における重量平均分子量は、ゲルパーミエーションクロマトグラフィー（昭和電工株式会社製Ｓｈｏｄｅｘ　ＧＰＣ－１０１）を用いて、下記条件にて常温で測定し、標準ポリスチレン検量線を用いて求めた値である。
カラム：昭和電工製ＬＦ－８０４
カラム温度：４０℃
試料：共重合体の０．２質量％テトラヒドロフラン溶液
流量：１ｍｌ／分
溶離液：テトラヒドロフラン
検出器：ＲＩ (A) The molecular weight of the (meth) acryl group-containing polyolefin compound is preferably 10,000 to 300,000, more preferably 20,000 to 200,000, and even more preferably 30,000 to 100,000. is there. When the weight average molecular weight is less than 10,000, the cohesive force of the obtained pressure-sensitive adhesive sheet is low, and thus the strength of the pressure-sensitive adhesive sheet may not be sufficient, which is not preferable. On the other hand, when the molecular weight is larger than 300,000, the viscosity of the photocurable transparent pressure-sensitive adhesive sheet composition becomes too high, and handling becomes difficult and workability is remarkably deteriorated. The weight average molecular weight in the present invention is a value obtained by using a standard polystyrene calibration curve, measured at normal temperature under the following conditions using gel permeation chromatography (Shodex GPC-101 manufactured by Showa Denko KK). is there.
Column: Showa Denko LF-804
Column temperature: 40 ° C
Sample: 0.2 mass% copolymer solution in tetrahydrofuran Flow rate: 1 ml / min Eluent: Tetrahydrofuran detector: RI

　（Ａ）（メタ）アクリル基含有ポリオレフィン化合物の光硬化性透明粘着シート用組成物中の含有量としては、組成物中１０～５０質量％であることが好ましく、１５～４５質量％であることがより好ましく、２０～４０質量％であることがさらに好ましい。１０質量％より少ない場合には、得られる粘着シートが脆くなり好ましくない。５０質量％より多い場合には、得られる粘着シートの粘着力が低くなる可能性があり好ましくない。 (A) The content of the (meth) acrylic group-containing polyolefin compound in the photocurable transparent adhesive sheet composition is preferably 10 to 50% by mass, and preferably 15 to 45% by mass in the composition. Is more preferable, and 20 to 40% by mass is even more preferable. When the content is less than 10% by mass, the resulting pressure-sensitive adhesive sheet becomes brittle, which is not preferable. When the amount is more than 50% by mass, the adhesive strength of the resulting adhesive sheet may be lowered, which is not preferable.

（（Ｂ）ヒドロキシル基を有する（メタ）アクリル酸エステル）
　ここで言うヒドロキシル基を有する（メタ）アクリル酸エステルとは、カルボキシル基を有しないものが好ましく、例えば、アルキル基の炭素数が２～７であるヒドロキシアルキル（メタ）アクリレート等が挙げられ、これらの具体例としては、２－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、４－ヒドロキシブチル（メタ）アクリレート、１，３－ブタンジオール（メタ）アクリレート、１，４－ブタンジオール（メタ）アクリレート、１，６－ヘキサンジオール（メタ）アクリレート、３－メチルペンタンジオール（メタ）アクリレート等が例示でき、単独又は２種以上組み合わせて用いることができる。なかでも、得られる粘着シートの粘着力の点で、２－ヒドロキシエチルアクリレートが好ましい。（Ｂ）ヒドロキシル基を有する（メタ）アクリル酸エステルの含有量は、光硬化性透明粘着シート用組成物中に１～３０質量％含むことが好ましく、より好ましくは５～２５質量％であり、さらに好ましくは１０～２０質量％である。１質量％未満では、得られる粘着シートの基材への密着性が不十分となり好ましくない。また、３０質量％より多い場合には、粘着シートの耐水性が悪くなり好ましくない。 ((B) (Meth) acrylic acid ester having hydroxyl group)
The (meth) acrylic acid ester having a hydroxyl group mentioned here preferably has no carboxyl group, and examples thereof include hydroxyalkyl (meth) acrylates having an alkyl group with 2 to 7 carbon atoms. Specific examples of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,3-butanediol (meth) acrylate, and 1,4-butanediol (Meth) acrylate, 1,6-hexanediol (meth) acrylate, 3-methylpentanediol (meth) acrylate and the like can be exemplified, and these can be used alone or in combination of two or more. Of these, 2-hydroxyethyl acrylate is preferable from the viewpoint of the adhesive strength of the obtained adhesive sheet. The content of the (B) hydroxyl group-containing (meth) acrylic acid ester is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, in the photocurable transparent adhesive sheet composition. More preferably, it is 10 to 20% by mass. If it is less than 1% by mass, the adhesiveness of the obtained pressure-sensitive adhesive sheet to the substrate is insufficient, which is not preferable. Moreover, when more than 30 mass%, the water resistance of an adhesive sheet worsens and is unpreferable.

（（Ｃ）ヒドロキシル基を有する（メタ）アクリル酸エステル以外の光重合性単量体）
　（Ｃ）ヒドロキシル基を有する（メタ）アクリル酸エステル以外の光重合性単量体（以下、「（Ｃ）の光重合性単量体」ということがある。）は、光重合性単量体であって、ヒドロキシル基を有する（メタ）アクリル酸エステル以外のものを指し、カルボキシル基（化学式：－ＣＯＯＨ）を含有しない単量体が好ましい。当該単量体としては、特に限定はなくビニル基、（メタ）アクリル基等を有する、単官能性又は多官能性光重合性単量体を単独で又は２種類以上を組み合わせて使用できる。本発明の（Ｃ）の光重合性単量体としては、例えば、（メタ）アクリル基を有する（メタ）アクリレート化合物が好ましく、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、イソブチル（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－ヘキシル（メタ）アクリレート、ステアリル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート等のアルキル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ノルボルニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ノルボルナニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（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、ジシクロペンタニルオキシエチル（メタ）アクリレート、トリシクロデカンジメチロールジ（メタ）アクリレート等の環状アルキル（メタ）アクリレート等が挙げられる。エトキシエチル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、２－メトキシエトキシエチル（メタ）アクリレート、２－エトキシエトキシエチル（メタ）アクリレート等のアルコキシアルキル（メタ）アクリレート、メトキシジエチレングリコール（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、メトキシジプロピレングリコール（メタ）アクリレート等のアルコキシ（ポリ）アルキレングリコール（メタ）アクリレート、オクタフルオロペンチル（メタ）アクリレート等のフッ素化アルキル（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－ジエチルアミノエチル（メタ）アクリレート等のジアルキルアミノアルキル（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ヒドロキシピバリン酸エステルネオペンチルグリコールジ（メタ）アクリレート、１，３－ビス（ヒドロキシエチル）－５，５－ジメチルヒダントインジ（メタ）アクリレート、α，ω－ジ（メタ）アクリルビスジエチレングリコールフタレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、ジアクリロキシエチルフォスフェート、ジペンタエリスリトールトリヒドロキシ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート等の多官能性（メタ）アクリレート、アクリルアミド及びジメチルアクリルアミド、ジエチルアクリルアミド、（メタ）アクリロイルモルフォリン等のアクリルアミド誘導体、グリシジル（メタ）アクリレート等のエポキシ基含有（メタ）アクリレート等があげられる。本発明の（Ｃ）の光重合性単量体としては、（メタ）アクリル基含有ポリオレフィン化合物との混和性、粘着シートの粘着性、強度、耐光性、耐熱性の観点から、単官能アルキル（メタ）アクリレート、又は環状アルキル（メタ）アクリレートが好ましい。ここで言う単官能もしくは多官能の官能基とは、（メタ）アクリル基を指す。（Ｃ）の光重合性単量体の含有量は、光硬化性透明粘着シート用組成物中２０～８８質量％含むことが好ましく、より好ましくは２０～７０質量％である。さらに好ましくは、４０～６９質量％である。２０質量％未満では、得られる粘着シートの基材への密着性が不十分となり好ましくない。また、８８質量％より多い場合には、粘着シートの凝集力が低くなることから粘着力が低くなり好ましくない。 ((C) Photopolymerizable monomer other than (meth) acrylic acid ester having hydroxyl group)
(C) A photopolymerizable monomer other than the (meth) acrylic acid ester having a hydroxyl group (hereinafter sometimes referred to as “(C) photopolymerizable monomer”) is a photopolymerizable monomer. Further, it refers to other than (meth) acrylic acid ester having a hydroxyl group, and a monomer not containing a carboxyl group (chemical formula: —COOH) is preferable. The monomer is not particularly limited, and a monofunctional or polyfunctional photopolymerizable monomer having a vinyl group, a (meth) acryl group, or the like can be used alone or in combination of two or more. As the photopolymerizable monomer (C) of the present invention, for example, a (meth) acrylate compound having a (meth) acryl group is preferable. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (Meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-hexyl (meth) acrylate, stearyl Alkyl (meth) acrylates such as (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, norbornanyl (meth) ) Acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclodecane dimethylol di (meth) Examples thereof include cyclic alkyl (meth) acrylates such as acrylate. Alkoxyalkyl (meth) acrylates such as ethoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethoxyethyl (meth) acrylate, 2-ethoxyethoxyethyl (meth) acrylate, methoxy Fluorinated alkyl (meth) acrylates such as alkoxy (poly) alkylene glycol (meth) acrylates such as diethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, and octafluoropentyl (meth) acrylate , N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, etc. (Meth) acrylate, polyethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, hydroxypivalin Acid ester neopentyl glycol di (meth) acrylate, 1,3-bis (hydroxyethyl) -5,5-dimethylhydantoin di (meth) acrylate, α, ω-di (meth) acrylbisdiethylene glycol phthalate, trimethylolpropane tri (Meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, poly Tylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diacryloxyethyl phosphate, dipentaerythritol trihydroxy (meth) acrylate, tri Multifunctional (meth) acrylates such as methylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, acrylamide derivatives such as acrylamide and dimethylacrylamide, diethylacrylamide, (meth) acryloylmorpholine, glycidyl (meth) acrylate, etc. Epoxy group-containing (meth) acrylate and the like. As the photopolymerizable monomer (C) of the present invention, from the viewpoint of miscibility with the (meth) acrylic group-containing polyolefin compound, adhesiveness of the adhesive sheet, strength, light resistance, and heat resistance, monofunctional alkyl ( A (meth) acrylate or a cyclic alkyl (meth) acrylate is preferred. The monofunctional or polyfunctional functional group here refers to a (meth) acrylic group. The content of the photopolymerizable monomer (C) is preferably 20 to 88% by mass, more preferably 20 to 70% by mass in the photocurable transparent adhesive sheet composition. More preferably, it is 40 to 69% by mass. If it is less than 20% by mass, the adhesiveness of the obtained pressure-sensitive adhesive sheet to the substrate is insufficient, which is not preferable. Moreover, when more than 88 mass%, since the cohesion force of an adhesive sheet becomes low, an adhesive force becomes low and is unpreferable.

　本発明では、（Ｃ）の光重合性単量体に含まれるアクリル酸やメタクリル酸等のカルボキシル基含有単量体は、（Ｃ）の光重合性単量体の全量に対して０．１質量％以下であり、０．０５質量％以下であることがより好ましい。（Ｃ）の光重合性単量体は、カルボキシル基含有単量体を含まないことがさらに好ましい。カルボキシル基含有単量体が（Ｃ）の光重合性単量体の全量に対して０．１質量％を超えると、透明導電膜の導電層面の腐食の抑制が困難となる。 In the present invention, the carboxyl group-containing monomer such as acrylic acid or methacrylic acid contained in the photopolymerizable monomer (C) is 0.1% relative to the total amount of the photopolymerizable monomer (C). It is less than or equal to mass%, more preferably less than or equal to 0.05 mass%. More preferably, the photopolymerizable monomer (C) does not contain a carboxyl group-containing monomer. When the carboxyl group-containing monomer exceeds 0.1% by mass with respect to the total amount of the photopolymerizable monomer (C), it becomes difficult to suppress corrosion of the conductive layer surface of the transparent conductive film.

　本発明の（Ｂ）ヒドロキシル基を有する（メタ）アクリル酸エステル、及び（Ｃ）の光重合性単量体からなるポリマーの理論ガラス転移温度は、粘着シートの強度、接着力の観点から０～５０℃であることが好ましく、５～４５℃であることがより好ましく、１０～４０℃であることがさらに好ましい。０℃より低い場合には、得られる粘着シートが（メタ）アクリル基含有ポリオレフィン化合物の影響により柔らかくなりすぎるために粘着シートの接着力が低くなり好ましくない。また、５０℃より高い場合には、得られる粘着シートが硬くなりすぎ、十分な粘着性が得られないので好ましくない。ここで、理論ガラス転移温度（Ｔｇ）は、モノマー原料を構成する各モノマーの単独重合体（ホモポリマー）のＴｇおよび該モノマーの質量分率（共重合割合）に基づいて下記のフォックス（ＦＯＸ）の式（１）から算出することができる。

Figure JPOXMLDOC01-appb-M000001
The theoretical glass transition temperature of the polymer comprising the (B) hydroxyl group-containing (meth) acrylic acid ester of the present invention and the photopolymerizable monomer (C) is 0 to 0 from the viewpoint of the strength and adhesive strength of the pressure-sensitive adhesive sheet. It is preferably 50 ° C., more preferably 5 to 45 ° C., and further preferably 10 to 40 ° C. When the temperature is lower than 0 ° C., the resulting pressure-sensitive adhesive sheet becomes too soft due to the influence of the (meth) acrylic group-containing polyolefin compound, so that the adhesive strength of the pressure-sensitive adhesive sheet is lowered, which is not preferable. Moreover, when higher than 50 degreeC, since the adhesive sheet obtained becomes too hard and sufficient adhesiveness is not acquired, it is unpreferable. Here, the theoretical glass transition temperature (Tg) is the following fox (FOX) based on the Tg of the homopolymer (homopolymer) of each monomer constituting the monomer raw material and the mass fraction (copolymerization ratio) of the monomer. It can be calculated from the equation (1).
Figure JPOXMLDOC01-appb-M000001

　式（１）中のＷ１、Ｗ２・・・Ｗｎは各モノマーの質量分率（＝（各モノマーの配合量／モノマー全質量））であり、Ｔ１、Ｔ２・・・Ｔｎは、各モノマーのホモポリマーのガラス転移温度（絶対温度）である。ホモポリマーのＴｇとしては、公知資料である株式会社日刊工業新聞社の「粘着技術ハンドブック」またはＷｉｌｅｙ－Ｉｎｔｅｒｓｃｉｅｎｃｅの「ポリマーハンドブック（Ｐｏｌｙｍｅｒ　Ｈａｎｄｂｏｏｋ）」に記載の値を採用するものとする。上記公知資料に記載のないモノマーのホモポリマーのＴｇについては、以下の方法で求められた値を採用するものとする。すなわち、対象となるモノマーを溶液重合して得られたホモポリマー溶液を剥離ライナー上に流延乾燥させて試験サンプルを作製する。この試験サンプルにつき、示差走査熱量計（ＤＳＣ）を用いて、１０℃／分の昇温速度で－８０℃から２８０℃まで温度を変化させて示差走査熱量測定を行い、ガラス転移による吸熱開始温度を当該ホモポリマーのＴｇとして採用するものとする。 Is W 1, W 2 ··· W n is the mass fraction of each monomer in the formula (1) (= (amount / monomer total weight of each monomer)), T 1, T 2 ··· T n Is the glass transition temperature (absolute temperature) of the homopolymer of each monomer. As the Tg of the homopolymer, a value described in the “Adhesion Technology Handbook” of Nikkan Kogyo Shimbun Co., Ltd. or “Polymer Handbook” of Wiley-Interscience, which is a publicly known material, is adopted. For the Tg of a homopolymer of a monomer not described in the above-mentioned publicly known material, the value obtained by the following method is adopted. That is, a test sample is prepared by casting and drying a homopolymer solution obtained by solution polymerization of a target monomer on a release liner. For this test sample, differential scanning calorimetry was performed using a differential scanning calorimeter (DSC) at a rate of temperature increase of 10 ° C./min from −80 ° C. to 280 ° C., and the endothermic start temperature due to glass transition. Is adopted as the Tg of the homopolymer.

（（Ｄ）光重合開始剤）
　本発明における（Ｄ）光重合開始剤としては、例えば、カルボニル系光重合開始剤、スルフィド系光重合開始剤、キノン系光重合開始剤、アゾ系光重合開始剤、スルホクロリド系光重合開始剤、チオキサントン系光重合開始剤、過酸化物系光重合開始剤等が挙げられる。 ((D) Photopolymerization initiator)
Examples of the (D) photopolymerization initiator in the present invention include a carbonyl photopolymerization initiator, a sulfide photopolymerization initiator, a quinone photopolymerization initiator, an azo photopolymerization initiator, and a sulfochloride photopolymerization initiator. Thioxanthone photopolymerization initiator, peroxide photopolymerization initiator, and the like.

　カルボニル系光重合開始剤としては、例えば、ベンゾフェノン、ベンジル、ベンゾイン、ω－ブロモアセトフェノン、クロロアセトン、アセトフェノン、２，２－ジエトキシアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、ｐ－ジメチルアミノアセトフェノン、ｐ－ジメチルアミノプロピオフェノン、２－クロロベンゾフェノン、ｐ，ｐ′－ジクロロベンゾフェノン、ｐ，ｐ′－ビスジエチルアミノベンゾフェノン、ミヒラーケトン、ベンゾインメチルエーテル、ベンゾインイソブチルエーテル、ベンゾイン－ｎ－ブチルエーテル、ベンジルメチルケタール、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－イソプロピルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、メチルベンゾイルホルメート、２，２－ジエトキシアセトフェノン、４－Ｎ，Ｎ′－ジメチルアセトフェノン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン等が挙げられる。 Examples of the carbonyl photopolymerization initiator include benzophenone, benzyl, benzoin, ω-bromoacetophenone, chloroacetone, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, p-dimethylamino. Acetophenone, p-dimethylaminopropiophenone, 2-chlorobenzophenone, p, p'-dichlorobenzophenone, p, p'-bisdiethylaminobenzophenone, Michler's ketone, benzoin methyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, benzylmethyl Ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- (4-isopropylphenyl) -2 Hydroxy-2-methylpropan-1-one, methylbenzoylformate, 2,2-diethoxyacetophenone, 4-N, N'-dimethylacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholinopropan-1-one and the like.

　スルフィド系光重合開始剤としては、例えば、ジフェニルジスルフィド、ジベンジルジスルフィド、テトラエチルチウラムジスルフィド、テトラメチルアンモニウムモノスルフィド等が挙げられる。キノン系光重合開始剤としては、例えば、ベンゾキノン、アントラキノン等が挙げられる。アゾ系光重合開始剤としては、例えば、アゾビスイソブチロニトリル、２，２′－アゾビスプロパン、ヒドラジン等が挙げられる。チオキサントン系光重合開始剤としては、例えば、チオキサントン、２－クロロチオキサントン、２－メチルチオキサントン等が挙げられる。過酸化物系光重合開始剤としては、例えば、過酸化ベンゾイル、ジ－ｔ－ブチルペルオキシド等が挙げられる。これらの光重合開始剤の中では、得られる光硬化性透明粘着シート用組成物における溶解性の点から、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オンが好ましい。これらの光重合開始剤は、単独で又は２種類以上を組み合わせて使用される。 Examples of the sulfide photopolymerization initiator include diphenyl disulfide, dibenzyl disulfide, tetraethylthiuram disulfide, tetramethylammonium monosulfide and the like. Examples of the quinone photopolymerization initiator include benzoquinone and anthraquinone. Examples of the azo photopolymerization initiator include azobisisobutyronitrile, 2,2′-azobispropane, hydrazine, and the like. Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone and the like. Examples of the peroxide photopolymerization initiator include benzoyl peroxide and di-t-butyl peroxide. Among these photopolymerization initiators, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 is preferred from the viewpoint of solubility in the resulting composition for a photocurable transparent adhesive sheet. -ON is preferred. These photoinitiators are used individually or in combination of 2 or more types.

　（Ｄ）光重合開始剤の含有量は、光硬化性及び得られる粘着シートの強度、粘着性のバランスの点から、光硬化性透明粘着シート用組成物中に０．２～５質量％であることが好ましく、０．５～３質量％であることがより好ましく、０．８～２質量％であることがさらに好ましい。（Ｄ）光重合開始剤の含有量が０．２質量％未満であると、光硬化が不十分となる傾向にあり、５質量％を超えると得られる粘着シートの粘着性が低下する傾向にあり好ましくない。 (D) The content of the photopolymerization initiator is 0.2 to 5% by mass in the photocurable transparent adhesive sheet composition from the viewpoint of the balance between photocurability and the strength and adhesiveness of the resulting adhesive sheet. It is preferably 0.5 to 3% by mass, more preferably 0.8 to 2% by mass. (D) When the content of the photopolymerization initiator is less than 0.2% by mass, the photocuring tends to be insufficient, and when it exceeds 5% by mass, the adhesiveness of the obtained pressure-sensitive adhesive sheet tends to decrease. There is not preferable.

　本発明の光硬化性透明粘着シート用組成物は、好ましくは、光硬化性透明粘着シート用組成物の全量に対して、（Ａ）成分１０～５０質量％、（Ｂ）成分１～３０質量％、（Ｃ）成分２０～８８質量％、及び（Ｄ）成分０．２～５質量％を含有してなる。そして、より好ましくは、光硬化性透明粘着シート用組成物の全量に対して、（Ａ）成分１５～４５質量％、（Ｂ）成分５～２５質量％、（Ｃ）成分２０～７０質量％、及び（Ｄ）成分０．２～５質量％を含有してなる。そして、更に好ましくは、光硬化性透明粘着シート用組成物の全量に対して、（Ａ）成分２０～４０質量％、（Ｂ）成分１０～２０質量％、（Ｃ）成分４０～６９質量％、及び（Ｄ）成分０．５～３質量％を含有してなる。 The composition for a photocurable transparent pressure-sensitive adhesive sheet of the present invention is preferably 10 to 50% by mass of the component (A) and 1 to 30% by mass of the component (B) based on the total amount of the composition for the photocurable transparent pressure-sensitive adhesive sheet. %, (C) component 20 to 88% by mass, and (D) component 0.2 to 5% by mass. More preferably, the component (A) is 15 to 45% by mass, the component (B) is 5 to 25% by mass, and the component (C) is 20 to 70% by mass based on the total amount of the photocurable transparent adhesive sheet composition. And (D) component 0.2 to 5% by mass. More preferably, the component (A) is 20 to 40% by mass, the component (B) is 10 to 20% by mass, and the component (C) is 40 to 69% by mass with respect to the total amount of the photocurable transparent adhesive sheet composition. And (D) component 0.5 to 3% by mass.

　本発明の光硬化性透明粘着シート用組成物には、必要に応じて、得られる粘着シートの接着力を向上させるため、透明性を低下させない範囲で粘着付与樹脂を添加しても良い。粘着付与樹脂の例としては、ロジンやロジンのエステル化物等のロジン系樹脂；ジテルペン重合体やα－ピネン－フェノール共重合体等のテルペン系樹脂；脂肪族系（Ｃ５系）や芳香族系（Ｃ９系）等の石油樹脂；その他、スチレン系樹脂、フェノール系樹脂、キシレン樹脂等が挙げられる。耐光性の点から不飽和二重結合が少ない水添ロジンや不均化ロジンのエステル化物や、脂肪族や芳香族系石油樹脂、高Ｔｇアクリル樹脂等を粘着シートに添加することが好ましい。粘着付与樹脂の添加量としては、光硬化性透明粘着シート用組成物１００質量部に対して（（Ａ）成分、（Ｂ）成分、（Ｃ）成分及び（Ｄ）成分の合計量１００質量部に対して）、１～１０質量部を添加することが好ましい。 In the composition for a photocurable transparent pressure-sensitive adhesive sheet of the present invention, a tackifier resin may be added as necessary in order not to lower the transparency in order to improve the adhesive strength of the obtained pressure-sensitive adhesive sheet. Examples of tackifying resins include rosin resins such as rosin and rosin esterified products; terpene resins such as diterpene polymers and α-pinene-phenol copolymers; aliphatic (C5) and aromatic ( Petroleum resin such as C9); styrene resin, phenol resin, xylene resin and the like. From the viewpoint of light resistance, it is preferable to add an esterified product of hydrogenated rosin or disproportionated rosin with few unsaturated double bonds, aliphatic or aromatic petroleum resin, high Tg acrylic resin, or the like to the adhesive sheet. As addition amount of tackifying resin, 100 mass parts of total amount of (A) component, (B) component, (C) component, and (D) component with respect to 100 mass parts of composition for photocurable transparent adhesive sheets 1 to 10 parts by mass is preferably added.

　また、本発明の光硬化性透明粘着シート用組成物には、必要に応じて、透明性を損なわない範囲で、公知の各種添加剤を含んでいてもよい。添加剤としては、可塑剤、表面潤滑剤、レベリング剤、軟化剤、酸化防止剤、老化防止剤、光安定剤、紫外線吸収剤、重合禁止剤、ベンゾトリアゾール系等の光安定剤、リン酸エステル系およびその他の難燃剤、界面活性剤のような帯電防止剤などが挙げられる。 In addition, the composition for a photocurable transparent pressure-sensitive adhesive sheet of the present invention may contain various known additives as long as the transparency is not impaired. Additives include plasticizers, surface lubricants, leveling agents, softeners, antioxidants, antioxidants, light stabilizers, UV absorbers, polymerization inhibitors, benzotriazole-based light stabilizers, phosphate esters System and other flame retardants, and antistatic agents such as surfactants.

　また、本発明の光硬化性透明粘着シート用組成物は、塗工時の粘度調整を目的として有機溶媒を用いて溶液としてもよい。用いられる有機溶媒としては、たとえば、メチルエチルケトン、アセトン、酢酸エチル、テトラヒドロフラン、ジオキサン、シクロヘキサノン、ｎ－へキサン、トルエン、キシレン、ｎ－プロパノール、イソプロパノールなどが挙げられる。これらの有機溶媒は単独で使用してもよく、また２種以上を混合してもよい。 Further, the composition for a photocurable transparent adhesive sheet of the present invention may be made into a solution using an organic solvent for the purpose of adjusting the viscosity at the time of coating. Examples of the organic solvent used include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, n-propanol and isopropanol. These organic solvents may be used alone or in combination of two or more.

　本発明の光硬化性透明粘着シート用組成物の酸価は、好ましくは０～０．５ｍｇＫＯＨ／ｇ、より好ましくは０～０．１ｍｇＫＯＨ／ｇ、さらに好ましくは０～０．０５ｍｇＫＯＨ／ｇである。酸価が０．５ｍｇＫＯＨ／ｇより高いと、透明導電膜の導電層面の腐食の抑制が困難となる。なお、組成物の酸価はＪＩＳ　Ｋ００７０に準拠して測定した値である。例えば、以下のように測定する。 The acid value of the composition for a photocurable transparent adhesive sheet of the present invention is preferably 0 to 0.5 mgKOH / g, more preferably 0 to 0.1 mgKOH / g, and further preferably 0 to 0.05 mgKOH / g. . When the acid value is higher than 0.5 mgKOH / g, it becomes difficult to suppress corrosion of the conductive layer surface of the transparent conductive film. The acid value of the composition is a value measured according to JIS K0070. For example, measurement is performed as follows.

　精密天秤で１００ｍｌ三角フラスコに試料約２ｇ程度を精秤し、これにエタノール／ジエチルエーテル＝１／１（重量比）の混合溶媒１０ｍｌを加えて溶解する。更に、この容器に指示薬としてフェノールフタレインエタノール溶液を１～３滴添加し、試料が均一になるまで充分に攪拌する。これを、０．１Ｎ水酸化カリウム－エタノール溶液で滴定し、指示薬のうすい紅色が３０秒間続いたときを、中和の終点とする。その結果から下記の計算式（２）を用いて得た値を、組成物の酸価とする。

Figure JPOXMLDOC01-appb-M000002
　　Ｂ：０．１Ｎ水酸化カリウム－エタノール溶液の使用量（ｍｌ）
　　ｆ：０．１Ｎ水酸化カリウム－エタノール溶液のファクター
　　Ｓ：試料の採取量（ｇ） About 2 g of a sample is precisely weighed in a 100 ml Erlenmeyer flask with a precision balance, and 10 ml of a mixed solvent of ethanol / diethyl ether = 1/1 (weight ratio) is added to dissolve it. Further, add 1 to 3 drops of a phenolphthalein ethanol solution as an indicator to the container and stir well until the sample is uniform. This is titrated with a 0.1N potassium hydroxide-ethanol solution, and the end point of neutralization is when the light red color of the indicator lasts for 30 seconds. The value obtained from the result using the following formula (2) is defined as the acid value of the composition.
Figure JPOXMLDOC01-appb-M000002
 B: Amount of 0.1N potassium hydroxide-ethanol solution used (ml)
f: Factor of 0.1N potassium hydroxide-ethanol solution S: Amount of sample collected (g)

（透明導電膜固定用透明粘着シート用組成物）
　本発明の透明導電膜固定用粘着シート用組成物は、上記の光硬化性透明粘着シート用組成物からなる透明導電膜固定用粘着シート用組成物である。 (Composition for transparent adhesive sheet for fixing transparent conductive film)
The composition for pressure-sensitive adhesive sheets for fixing a transparent conductive film of the present invention is a composition for pressure-sensitive adhesive sheets for fixing a transparent conductive film comprising the above-described composition for a photocurable transparent pressure-sensitive adhesive sheet.

　本発明の透明導電膜固定用粘着シート用組成物が使用される透明導電膜としては、少なくとも片面の表層に導電層を有するものであればよく、透明基材の表層に導電物質が蒸着やコーティングにより設けられた透明導電膜を挙げられる。透明導電膜の導電層において蒸着やコーティングされる導電物質は、特に限定されないが、具体的には、酸化インジウムスズ、酸化インジウム、酸化スズ、酸化亜鉛、酸化カドミウム、酸化ガリウム、酸化チタンなどが挙げられる。なかでも、透明性、導電性に優れる酸化インジウムスズが好適に用いられる。透明導電膜において、導電物質が蒸着またはコーティングされる基材としては、特に限定されるものではないが、ガラス、樹脂フィルムなどが挙げられる。 As the transparent conductive film in which the composition for fixing a transparent conductive film of the present invention is used, any conductive layer may be used as long as it has a conductive layer on at least one surface layer. The transparent conductive film provided by (1) is mentioned. The conductive material deposited or coated in the conductive layer of the transparent conductive film is not particularly limited, and specific examples include indium tin oxide, indium oxide, tin oxide, zinc oxide, cadmium oxide, gallium oxide, and titanium oxide. It is done. Of these, indium tin oxide having excellent transparency and conductivity is preferably used. In the transparent conductive film, the substrate on which the conductive material is deposited or coated is not particularly limited, and examples thereof include glass and resin films.

（透明導電膜固定用透明粘着シート）
　本発明の透明導電膜固定用透明粘着シートは、上記の透明導電膜固定用透明粘着シート用組成物を硬化させてなる透明導電膜固定用透明粘着シートであって、透明導電膜の導電層面と好適に接着でき、かつ導電層の腐食が生じ難いものである。したがって、透明導電膜固定用透明粘着シートを透明導電膜の導電層面と接着させた積層体はタッチパネルとして好適に用いることができる。また、本発明の透明導電膜固定用透明粘着シートは、基材を有するものであっても、基材を有さず粘着剤層のみからなる両面粘着シートであってもよい。また、粘着剤層は単一層からなるものであっても複数層が積層されていてもよい。なかでも、透明性の確保や、形状追従性の観点からは、基材を有さず、粘着剤層のみからなる両面粘着シートであることが好ましい。 (Transparent adhesive sheet for fixing transparent conductive film)
The transparent pressure-sensitive adhesive sheet for fixing a transparent conductive film of the present invention is a transparent pressure-sensitive adhesive sheet for fixing a transparent conductive film obtained by curing the above-described composition for fixing a transparent conductive film. It can be suitably bonded and the conductive layer is unlikely to corrode. Therefore, the laminated body which adhere | attached the transparent adhesive sheet for transparent conductive film adhesion with the conductive layer surface of a transparent conductive film can be used suitably as a touch panel. Further, the transparent adhesive sheet for fixing a transparent conductive film of the present invention may have a base material, or may be a double-sided pressure-sensitive adhesive sheet having only a pressure-sensitive adhesive layer without having a base material. Moreover, even if the adhesive layer consists of a single layer, multiple layers may be laminated | stacked. Especially, it is preferable that it is a double-sided adhesive sheet which does not have a base material but consists only of an adhesive layer from a viewpoint of ensuring transparency and shape followability.

　本発明の透明導電膜固定用透明粘着シートは、離型ＰＥＴフィルムに透明導電膜固定用透明粘着シート用組成物を塗布し、塗布した組成物に紫外線照射装置等を用いて紫外線を照射して光硬化させることで、得ることができる。透明導電膜固定用粘着シートの膜厚は、５～５００μｍとすることが好ましく、１０～３００μｍとすることがより好ましい。透明導電膜固定用粘着シートの膜厚が５μｍより薄くなると、粘着シートの貼り合わせが困難となり、５００μｍより厚くなると、膜厚の制御が困難となる傾向にある。 The transparent adhesive sheet for fixing a transparent conductive film of the present invention is obtained by applying a transparent adhesive sheet composition for fixing a transparent conductive film to a release PET film, and irradiating the applied composition with ultraviolet rays using an ultraviolet irradiation device or the like. It can be obtained by photocuring. The thickness of the transparent conductive film fixing pressure-sensitive adhesive sheet is preferably 5 to 500 μm, more preferably 10 to 300 μm. When the film thickness of the adhesive sheet for fixing a transparent conductive film becomes thinner than 5 μm, it becomes difficult to bond the adhesive sheet, and when it becomes thicker than 500 μm, it tends to be difficult to control the film thickness.

　本発明の透明導電膜固定用粘着シートは、トルエン中に室温下で２４時間浸漬した際の下記の式（３）で求められるゲル分率が、８０～１００％であることが好ましく、９０～１００％であることがより好ましい。粘着シートのゲル分率が８０％より低い場合には、打ち抜き加工時に加工端面からの糸引きなどが発生しやすくなる傾向にある。

Figure JPOXMLDOC01-appb-M000003
The pressure-sensitive adhesive sheet for fixing a transparent conductive film of the present invention preferably has a gel fraction determined by the following formula (3) of 80 to 100% when immersed in toluene at room temperature for 24 hours, More preferably, it is 100%. When the gel fraction of the pressure-sensitive adhesive sheet is lower than 80%, stringing or the like from the processed end face tends to occur during punching.
Figure JPOXMLDOC01-appb-M000003

　以下に実施例、及び比較例により本発明をより具体的に説明するが、本発明は、これらの例によってなんら限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these examples.

＜（メタ）アクリル基含有ポリオレフィン化合物（Ａ－１）＞
　温度計、撹拌器、滴下ロート、乾燥管付き冷却管を備えた四つ口フラスコにイソホロンジイソシアネート１０１．２ｇ及び水酸基末端水素添加ポリブタジエン（日本曹達株式会社製、製品名：ＧＩ‐３０００、重量平均分子量　１４，０００）を８４４．３ｇ仕込み、６０℃で反応させ、残存イソシアネート基が１％以下となった時点で、２－ヒドロキシエチルアクリレート５３．９ｇを仕込み７０℃まで昇温して２時間反応をさせ、ＩＲ測定によりイソシアネート基が消失したことを確認した後、反応を終了し、（メタ）アクリル基含有ポリオレフィン化合物（Ａ－１）（重量平均分子量５０，０００）を得た。 <(Meth) acrylic group-containing polyolefin compound (A-1)>
A four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooling tube with a drying tube is mixed with isophorone diisocyanate 101.2 g and hydroxyl-terminated hydrogenated polybutadiene (manufactured by Nippon Soda Co., Ltd., product name: GI-3000, weight average molecular weight). 14,000) was charged at 84 ° C. and reacted at 60 ° C. When the residual isocyanate group became 1% or less, 53.9 g of 2-hydroxyethyl acrylate was charged and the temperature was raised to 70 ° C. and reacted for 2 hours. After confirming the disappearance of the isocyanate group by IR measurement, the reaction was terminated to obtain a (meth) acryl group-containing polyolefin compound (A-1) (weight average molecular weight 50,000).

＜（メタ）アクリル基含有ポリオレフィン化合物（Ａ－２）＞
　温度計、撹拌器、滴下ロート、乾燥管付き冷却管を備えた四つ口フラスコにイソホロンジイソシアネート１５２．９ｇ及び水酸基末端水素添加ポリイソプレン（出光興産株式会社製、製品名：エポール、重量平均分子量１２，０００）を７６４．５ｇ仕込み、６０℃で反応させる。残存イソシアネート基が１％以下となった時点で、２－ヒドロキシエチルアクリレート８１．７ｇを仕込み、７０℃まで昇温して２時間反応をさせ、ＩＲ測定によりイソシアネート基が消失したことを確認した後、反応を終了し、（メタ）アクリル基含有ポリオレフィン化合物（Ａ－２）（重量平均分子量５５，０００）を得た。 <(Meth) acrylic group-containing polyolefin compound (A-2)>
A four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooling tube with a drying tube was charged with 152.9 g of isophorone diisocyanate and polyisoprene with hydroxyl group-terminated hydrogen (product name: Epol, weight average molecular weight 12). , 000) is charged at 76 ° C and reacted at 60 ° C. When the residual isocyanate group became 1% or less, 81.7 g of 2-hydroxyethyl acrylate was added, the temperature was raised to 70 ° C., the reaction was conducted for 2 hours, and after confirming the disappearance of the isocyanate group by IR measurement The reaction was completed to obtain a (meth) acryl group-containing polyolefin compound (A-2) (weight average molecular weight 55,000).

＜（メタ）アクリル基含有ポリオレフィン化合物（Ａ－３）＞
　温度計、撹拌器、滴下ロート、乾燥管付き冷却管を備えた四つ口フラスコにイソホロンジイソシアネート２４６．１ｇ及び水酸基末端水素添加ポリブタジエン（日本曹達株式会社製、製品名：ＧＩ‐１０００、重量平均分子量　３，０００）を６１８．５ｇ仕込み、６０℃で反応させ、残存イソシアネート基が１％以下となった時点で、２－ヒドロキシエチルアクリレート１３５．０ｇを仕込み７０℃まで昇温して２時間反応をさせ、ＩＲ測定によりイソシアネート基が消失したことを確認した後、反応を終了し、（メタ）アクリル基含有ポリオレフィン化合物（Ａ－３）（重量平均分子量５，０００）を得た。 <(Meth) acrylic group-containing polyolefin compound (A-3)>
A four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooling tube with a drying tube was mixed with 246.1 g of isophorone diisocyanate and polybutadiene with hydroxyl group-terminated hydrogenated product (product name: GI-1000, manufactured by Nippon Soda Co., Ltd., weight average molecular weight) 3,000) was allowed to react at 60 ° C., and when the remaining isocyanate groups became 1% or less, 135.0 g of 2-hydroxyethyl acrylate was charged and the temperature was raised to 70 ° C., followed by reaction for 2 hours. After confirming disappearance of the isocyanate group by IR measurement, the reaction was terminated to obtain a (meth) acryl group-containing polyolefin compound (A-3) (weight average molecular weight 5,000).

＜（メタ）アクリル基含有ポリオレフィン化合物（Ａ－４）＞
　温度計、撹拌器、滴下ロート、乾燥管付き冷却管を備えた四つ口フラスコにイソホロンジイソシアネート６１．２ｇ及び水酸基末端水素添加ポリブタジエン（日本曹達株式会社製、製品名：ＧＩ‐３０００、重量平均分子量　１４，０００）を９１７．１ｇ仕込み、６０℃で反応させ、残存イソシアネート基が１％以下となった時点で、２－ヒドロキシエチルアクリレート２１．３ｇを仕込み７０℃まで昇温して反応を行なったが、高分子量化し反応途中でゲル化してしまった。 <(Meth) acrylic group-containing polyolefin compound (A-4)>
A four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooling tube with a drying tube, 61.2 g of isophorone diisocyanate and hydrogenated polybutadiene having a hydroxyl group (Product name: GI-3000, manufactured by Nippon Soda Co., Ltd., weight average molecular weight) 14,000) was charged at 91 ° C. and reacted at 60 ° C. When the residual isocyanate group became 1% or less, 21.3 g of 2-hydroxyethyl acrylate was charged and the temperature was raised to 70 ° C. to carry out the reaction. However, it became high molecular weight and gelled during the reaction.

（実施例１～６、比較例１～４）
　表１に示す組成でそれぞれ配合し、室温下でディスパーを用いて混合することで均一な光硬化性透明粘着シート用組成物を調製した。調製した光硬化性透明粘着シート用組成物を、アプリケーターを用い、膜厚が２００μｍとなるように離型ＰＥＴフィルム（１００ｍｍ×１００ｍｍ×１００μｍ）に塗布し、上面を２５μｍ厚の離型ＰＥＴフィルムで覆った後、紫外線照射装置（日本電池株式会社製、ＵＶ照射装置４ｋｗ×１、出力：１６０Ｗ／ｃｍ、メタルハライドランプ）を用い、照射距離１２ｃｍ、ランプ移動速度２０ｍ／ｍｉｎ、照射量約５００ｍＪ／ｃｍ２の条件で紫外線を照射して硬化させ、離型ＰＥＴフィルムに挟まれた膜厚が約２００μｍの粘着シートを得た。なお、（メタ）アクリル基含有ポリオレフィン化合物（Ａ－４）はゲル化してしまったため、重量平均分子量が３０万を超える（メタ）アクリル基含有ポリオレフィン化合物を含有する光硬化性透明粘着シート用組成物の比較例は調製することができなかった。 (Examples 1 to 6, Comparative Examples 1 to 4)
Each of the compositions shown in Table 1 was blended and mixed with a disper at room temperature to prepare a uniform photocurable transparent adhesive sheet composition. The prepared composition for a photocurable transparent adhesive sheet is applied to a release PET film (100 mm × 100 mm × 100 μm) using an applicator so that the film thickness is 200 μm, and the upper surface is a release PET film having a thickness of 25 μm. After covering, using an ultraviolet irradiation device (manufactured by Nippon Battery Co., Ltd., UV irradiation device 4 kw × 1, output: 160 W / cm, metal halide lamp), irradiation distance 12 cm, lamp moving speed 20 m / min, irradiation amount about 500 mJ / cm The pressure-sensitive adhesive sheet having a thickness of about 200 μm sandwiched between the release PET films was obtained by irradiating with UV rays and curing under the condition of 2 . In addition, since the (meth) acryl group-containing polyolefin compound (A-4) was gelled, the composition for a photocurable transparent pressure-sensitive adhesive sheet containing the (meth) acryl group-containing polyolefin compound having a weight average molecular weight exceeding 300,000 The comparative example could not be prepared.

（理論ガラス転移温度の算定）
　実施例及び比較例について、用いた（Ｂ）ヒドロキシル基を有する（メタ）アクリル酸エステル及び（Ｃ）の光重合性単量体からなるポリマーの理論ガラス転移温度を、上記式（１）から算出した。結果を表１に示す。 (Calculation of theoretical glass transition temperature)
About the Example and the comparative example, the theoretical glass transition temperature of the polymer which consists of the (B) hydroxyl group-containing (meth) acrylic acid ester and the photopolymerizable monomer (C) used was calculated from the above formula (1). did. The results are shown in Table 1.

（酸価）
　実施例及び比較例の光硬化性透明粘着シート用組成物の酸価を、上記の方法を用いて、式（２）により算出した。結果を表１に示す。 (Acid value)
The acid value of the composition for photocurable transparent adhesive sheets of an Example and a comparative example was computed by Formula (2) using said method. The results are shown in Table 1.

（酸化インジウムスズ膜の電気抵抗値測定）
　上で得られた粘着シートを５０ｍｍ×５０ｍｍの大きさに切り取り、２５μｍ厚の離型ＰＥＴフィルムを剥がし、１００ｍｍ×１００ｍｍの酸化インジウムスズ蒸着ＰＥＴフィルムの酸化インジウムスズ膜面に貼り合わせた。貼り合せた粘着シートの両端に電気抵抗値測定機　三菱化学株式会社製「ロレスターＧＰ」を使用し、初期の電気抵抗値（Ｒ１）を測定した。粘着シートを貼り合わせた酸化インジウムスズ蒸着ＰＥＴフィルムを６０℃、）９０％ＲＨ条件下に５００時間放置し、２３℃、５０％ＲＨ条件下に１時間放置した後、初期と同じ箇所での電気抵抗値（Ｒ２）を測定した。酸化インジウムスズ膜の電気抵抗値上昇率は下記の式（４）で算出した。

Figure JPOXMLDOC01-appb-M000004
(Measurement of electrical resistance of indium tin oxide film)
The adhesive sheet obtained above was cut to a size of 50 mm × 50 mm, the release PET film having a thickness of 25 μm was peeled off, and bonded to the indium tin oxide film surface of the 100 mm × 100 mm indium tin oxide-deposited PET film. The electrical resistance value measuring device “Lorestar GP” manufactured by Mitsubishi Chemical Corporation was used at both ends of the bonded adhesive sheet, and the initial electrical resistance value (R 1 ) was measured. The indium tin oxide-deposited PET film to which the adhesive sheet was bonded was left at 90 ° C. for 500 hours and left at 23 ° C. and 50% RH for 1 hour. The resistance value (R 2 ) was measured. The increase rate of the electric resistance value of the indium tin oxide film was calculated by the following formula (4).
Figure JPOXMLDOC01-appb-M000004

　電気抵抗値上昇率の評価は、下記の基準で行なった。結果を表１に示す。
○；電気抵抗値上昇率５％未満
△；電気抵抗値上昇率５～１０％未満
×；電気抵抗値上昇率１０％以上 The rate of increase in electrical resistance value was evaluated according to the following criteria. The results are shown in Table 1.
○: Electrical resistance value increase rate of less than 5% △; Electrical resistance value increase rate of 5 to less than 10% ×: Electrical resistance value increase rate of 10% or more

（粘着シートの粘着力測定）
　上で得られた粘着シートを２５×１００ｍｍの大きさに切り取り、粘着シートの両面に存在する離型ＰＥＴフィルムのうち１００μｍ厚の離型ＰＥＴフィルムを剥がした後、粘着面（測定面）を試験板に２ｋｇのゴムローラー（幅：約５０ｍｍ）を１往復させることにより貼付し、測定用サンプルを作製した。試験板としてガラス板を用いた。得られた測定用サンプルについて、２３℃、湿度５０％の環境下で２４時間放置し、ＪＩＳ　Ｚ０２３７に準じて、剥離速度３００ｍｍ／分で１８０°方向の引張試験を行い、粘着シートのガラス板に対する粘着力（Ｎ／２５ｍｍ）を測定した。得られた測定値を粘着力とした。結果を表１に示す。 (Measurement of adhesive strength of adhesive sheet)
The pressure-sensitive adhesive sheet obtained above was cut to a size of 25 × 100 mm, and after removing the 100 μm-thick release PET film from the release PET film existing on both sides of the pressure-sensitive adhesive sheet, the pressure-sensitive adhesive surface (measurement surface) was tested. A 2 kg rubber roller (width: about 50 mm) was attached to the plate by reciprocating once to prepare a measurement sample. A glass plate was used as a test plate. The obtained measurement sample is left for 24 hours in an environment of 23 ° C. and 50% humidity, and subjected to a tensile test in the 180 ° direction at a peeling rate of 300 mm / min in accordance with JIS Z0237, to the glass sheet of the pressure-sensitive adhesive sheet. The adhesive strength (N / 25 mm) was measured. The obtained measured value was defined as adhesive strength. The results are shown in Table 1.

（全光線透過率測定）
　上で得られた粘着シートを３０ｍｍ×３０ｍｍの大きさに切り取り、粘着シートの両面に存在する離型ＰＥＴフィルムのうち２５μｍ厚の離型ＰＥＴフィルムを剥がし、ガラス板に貼り合わせたものを測定用サンプルとした。測定用サンプルについて、株式会社村上色彩技術研究所製「ＨＲ－１００型」を使用し、全光線透過率（％）を測定した。結果を表１に示す。 (Total light transmittance measurement)
The pressure-sensitive adhesive sheet obtained above was cut into a size of 30 mm × 30 mm, and the release PET film having a thickness of 25 μm was peeled off from the release PET film existing on both sides of the pressure-sensitive adhesive sheet, and then bonded to a glass plate for measurement. A sample was used. About the sample for a measurement, the total light transmittance (%) was measured using "HR-100 type" by Murakami Color Research Laboratory. The results are shown in Table 1.

（ゲル分率）
　粘着シートを２０ｍｍ×４０ｍｍの大きさに切り取り、測定用サンプルを作製した。この測定用サンプルをトルエン中に２３℃で２４時間浸漬した後、測定用サンプルをトルエンから取り出した。その後、測定用サンプルを１３０℃で１時間乾燥した。次に、乾燥後の測定用サンプルの重量を測定し、上述した式（３）によりゲル分率を算出した。結果を表１に示す。 (Gel fraction)
The pressure-sensitive adhesive sheet was cut into a size of 20 mm × 40 mm to prepare a measurement sample. After this measurement sample was immersed in toluene at 23 ° C. for 24 hours, the measurement sample was taken out from toluene. Thereafter, the measurement sample was dried at 130 ° C. for 1 hour. Next, the weight of the measurement sample after drying was measured, and the gel fraction was calculated by the above-described formula (3). The results are shown in Table 1.

Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005

　表１の結果から明らかなように、実施例で得られた本発明の光硬化性透明粘着シート用組成物は、比較例と比べて電気抵抗値上昇率、全光線透過率、粘着力に優れていることがわかる。 As is clear from the results in Table 1, the composition for the photocurable transparent adhesive sheet of the present invention obtained in the examples is superior in the electrical resistance value increase rate, the total light transmittance, and the adhesive strength as compared with the comparative example. You can see that

　本発明の光硬化性透明粘着シート用組成物は、高い透明性、金属腐食防止性を有し、且つ粘着性に優れることから透明導電膜固定用の粘着シートとして有用であり、特に静電容量方式のタッチパネルに使用される透明導電膜の固定用に有用である。 The composition for a photocurable transparent pressure-sensitive adhesive sheet of the present invention is useful as a pressure-sensitive adhesive sheet for fixing a transparent conductive film because it has high transparency, metal corrosion prevention and is excellent in adhesiveness. This is useful for fixing a transparent conductive film used in a touch panel of the type.

Claims (11)

（Ａ）重量平均分子量が１万～３０万である（メタ）アクリル基含有ポリオレフィン化合物、（Ｂ）ヒドロキシル基を有する（メタ）アクリル酸エステル、（Ｃ）ヒドロキシル基を有する（メタ）アクリル酸エステル以外の光重合性単量体、及び（Ｄ）光重合開始剤を含有してなる光硬化性透明粘着シート用組成物であって、（Ｃ）ヒドロキシル基を有する（メタ）アクリル酸エステル以外の光重合性単量体に含まれるカルボキシル基含有単量体が（Ｃ）ヒドロキシル基を有する（メタ）アクリル酸エステル以外の光重合性単量体の全量に対して、０．１質量％以下であることを特徴とする光硬化性透明粘着シート用組成物。 (A) (meth) acryl group-containing polyolefin compound having a weight average molecular weight of 10,000 to 300,000, (B) (meth) acrylate ester having hydroxyl group, (C) (meth) acrylate ester having hydroxyl group It is a photocurable transparent pressure-sensitive adhesive sheet composition comprising a photopolymerizable monomer other than (D) and a photopolymerization initiator, and (C) a (meth) acrylic acid ester having a hydroxyl group. The carboxyl group-containing monomer contained in the photopolymerizable monomer is (C) 0.1% by mass or less based on the total amount of the photopolymerizable monomer other than the (meth) acrylic acid ester having a hydroxyl group. A composition for a photocurable transparent pressure-sensitive adhesive sheet. 光硬化性透明粘着シート用組成物の全量に対して、（Ａ）重量平均分子量が１万～３０万である（メタ）アクリル基含有ポリオレフィン化合物１０～５０質量％、（Ｂ）ヒドロキシル基を有する（メタ）アクリル酸エステル１～３０質量％、（Ｃ）ヒドロキシル基を有する（メタ）アクリル酸エステル以外の光重合性単量体２０～８８質量％、及び（Ｄ）光重合開始剤０．２～５質量％を含有してなることを特徴とする請求項１記載の光硬化性透明粘着シート用組成物。 (A) 10-50 mass% of (meth) acryl group-containing polyolefin compound having a weight average molecular weight of 10,000 to 300,000, and (B) a hydroxyl group, based on the total amount of the photocurable transparent adhesive sheet composition 1 to 30% by mass of (meth) acrylate ester, (C) 20 to 88% by mass of photopolymerizable monomer other than (meth) acrylate ester having a hydroxyl group, and (D) a photopolymerization initiator 0.2 The composition for a photocurable transparent pressure-sensitive adhesive sheet according to claim 1, wherein the composition contains -5% by mass. （Ｃ）ヒドロキシル基を有する（メタ）アクリル酸エステル以外の光重合性単量体がカルボキシル基含有単量体を含まないことを特徴とする請求項１又は２記載の光硬化性透明粘着シート用組成物。 (C) The photopolymerizable monomer other than the (meth) acrylic acid ester having a hydroxyl group does not contain a carboxyl group-containing monomer. 3. The photocurable transparent adhesive sheet according to claim 1 or 2, Composition. （Ｂ）ヒドロキシル基を有する（メタ）アクリル酸エステル、及び（Ｃ）ヒドロキシル基を有する（メタ）アクリル酸エステル以外の光重合性単量体を重合して得られるポリマーの理論ガラス転移温度が０℃～５０℃であることを特徴とする請求項１～３のいずれかに記載の光硬化性透明粘着シート用組成物。 The theoretical glass transition temperature of a polymer obtained by polymerizing a photopolymerizable monomer other than (B) a hydroxyl group-containing (meth) acrylate ester and (C) a hydroxyl group-containing (meth) acrylate ester is 0. The composition for a photocurable transparent adhesive sheet according to any one of claims 1 to 3, wherein the composition is at 50 ° C to 50 ° C. （Ｃ）ヒドロキシル基を有する（メタ）アクリル酸エステル以外の光重合性単量体が単官能アルキル（メタ）アクリレート、及び／又は環状アルキル（メタ）アクリレートであることを特徴とする請求項１～４のいずれかに記載の光硬化性透明粘着シート用組成物 (C) The photopolymerizable monomer other than the (meth) acrylic acid ester having a hydroxyl group is a monofunctional alkyl (meth) acrylate and / or a cyclic alkyl (meth) acrylate. The composition for photocurable transparent adhesive sheets in any one of 4 （Ａ）重量平均分子量が１万～３０万である（メタ）アクリル基含有ポリオレフィン化合物が、ポリオレフィンポリオール化合物、ヒドロキシル基を有する（メタ）アクリレート、及び１分子中にイソシアネート基を２個以上有する化合物を反応させて得られる（メタ）アクリル基を有する化合物であることを特徴とする請求項１～５のいずれかに記載の光硬化性透明粘着シート用組成物。 (A) A (meth) acryl group-containing polyolefin compound having a weight average molecular weight of 10,000 to 300,000 is a polyolefin polyol compound, a (meth) acrylate having a hydroxyl group, and a compound having two or more isocyanate groups in one molecule 6. The composition for a photocurable transparent pressure-sensitive adhesive sheet according to claim 1, which is a compound having a (meth) acrylic group obtained by reacting the above. 酸価が０．５ｍｇＫＯＨ／ｇ以下であることを特徴とする請求項１～６のいずれかに記載の光硬化性透明粘着シート用組成物。 The composition for a photocurable transparent adhesive sheet according to any one of claims 1 to 6, wherein the acid value is 0.5 mgKOH / g or less. 請求項１～７のいずれか記載の光硬化性透明粘着シート用組成物を硬化させて得られる光硬化性透明粘着シートが透明導電膜の貼り合せに使用されることを特徴とする透明導電膜固定用透明粘着シート用組成物。 A transparent conductive film characterized in that a photocurable transparent adhesive sheet obtained by curing the composition for a photocurable transparent adhesive sheet according to any one of claims 1 to 7 is used for laminating a transparent conductive film. Composition for fixing transparent adhesive sheet. 請求項８記載の透明導電膜固定用透明粘着シート用組成物を硬化させて得られることを特徴とする透明導電膜固定用透明粘着シート。 A transparent adhesive sheet for fixing a transparent conductive film obtained by curing the composition for transparent adhesive sheet for fixing a transparent conductive film according to claim 8. ゲル分率が８０～１００％であることを特徴とする請求項９記載の透明導電膜固定用透明粘着シート。 The transparent adhesive sheet for fixing a transparent conductive film according to claim 9, wherein the gel fraction is 80 to 100%. 請求項９又は１０記載の透明導電膜固定用透明粘着シートが、透明導電膜の導電層面に接着されていることを特徴とする積層体。 A laminated body, wherein the transparent adhesive sheet for fixing a transparent conductive film according to claim 9 or 10 is adhered to a conductive layer surface of the transparent conductive film.
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