WO2013088889A1 - Production method for transparent double-sided adhesive sheet, and transparent double-sided adhesive sheet - Google Patents

Production method for transparent double-sided adhesive sheet, and transparent double-sided adhesive sheet Download PDF

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Publication number
WO2013088889A1
WO2013088889A1 PCT/JP2012/079345 JP2012079345W WO2013088889A1 WO 2013088889 A1 WO2013088889 A1 WO 2013088889A1 JP 2012079345 W JP2012079345 W JP 2012079345W WO 2013088889 A1 WO2013088889 A1 WO 2013088889A1
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Prior art keywords
meth
adhesive sheet
transparent double
sensitive adhesive
acrylate
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PCT/JP2012/079345
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French (fr)
Japanese (ja)
Inventor
中西　健一
伊藤　大悟
一博 佐々木
雄太 竹内
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昭和電工株式会社
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Priority to KR1020147019001A priority Critical patent/KR101619683B1/en
Priority to CN201280061981.XA priority patent/CN103987803B/en
Publication of WO2013088889A1 publication Critical patent/WO2013088889A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6204—Polymers of olefins
    • C08G18/6208—Hydrogenated polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape

Definitions

  • the present invention relates to a method for producing a transparent double-sided pressure-sensitive adhesive sheet obtained by curing a photocurable resin composition, a transparent double-sided pressure-sensitive adhesive sheet, a touch panel using the transparent double-sided pressure-sensitive adhesive sheet, and an image display device using the transparent double-sided pressure-sensitive adhesive sheet.
  • an image display device such as a liquid crystal display and an input device used in combination with the image display device such as a touch panel have been widely used in the fields of mobile phones and game machines.
  • transparent double-sided pressure-sensitive adhesive sheets are used for the purpose of bonding optical members.
  • ⁇ Double-sided pressure-sensitive adhesive sheets used for image display devices and touch panels are required not only to exhibit transparency and adhesiveness but also to fully exhibit the characteristics of pressure-sensitive adhesive sheets in various environments.
  • a double-sided pressure-sensitive adhesive sheet having properties that do not adversely affect the visibility and appearance retention of attached optical members and optical products at high temperatures, and a double-sided pressure-sensitive adhesive sheet with little change in storage elastic modulus due to temperature change are required. It has been.
  • a thick film of 100 ⁇ m or more is often used as a transparent double-sided pressure-sensitive adhesive sheet used for the purpose of bonding an optical member.
  • a transparent double-sided pressure-sensitive adhesive sheet having a thickness of 100 ⁇ m or more can be obtained by a method in which a polymer solution is applied onto a support such as a film, and then the solvent is heated to distill off. Has the problem of requiring a lot of energy and time.
  • a sheet having a film thickness of 100 ⁇ m or more can be easily obtained by applying a photocurable composition that does not use a solvent on a support and then producing a pressure-sensitive adhesive sheet by polymerization by light irradiation. I can do it.
  • polymerization by light irradiation has a problem in that it is difficult to set the amount of photopolymerization initiator and light irradiation conditions, and the productivity is not sufficiently increased. That is, if the amount of the photopolymerization initiator is increased in order to increase the productivity, the molecular weight decreases, so there is a problem that the storage elastic modulus at a high temperature decreases, and on the other hand, if the light irradiation time is shortened, the polymerization rate does not increase. There was a problem that the residual monomer increased.
  • a photopolymerizable acrylic pressure-sensitive adhesive composition layer is provided on one side of the film-like base material, and is not in contact with the film-like base material of the photopolymerizable acrylic pressure-sensitive adhesive composition layer.
  • a method of manufacturing a photopolymerizable acrylic pressure-sensitive adhesive sheet in which a cover film is bonded to one surface and polymerized by irradiation with ultraviolet rays is disclosed (for example, see Patent Document 1).
  • this method has a problem that the temperature control in the curing process for reducing the residual monomer is complicated.
  • the problem to be solved by the present invention is to provide a method for producing a transparent double-sided PSA sheet that obtains a thick film sheet with little change in storage modulus due to temperature change and low residual monomer, and further provides a transparent double-sided PSA sheet. It is.
  • the present inventors have made extensive studies and as a result, the resin layer of the photocurable resin composition on the light transmissive film (Y). Further, a light-transmitting film (Z) is laminated on the surface of the resin layer opposite to the surface in contact with the light-transmitting film (Y), and the laminated body obtained by the lamination has a low illuminance black
  • the manufacturing method of irradiating light and then irradiating active energy rays with high illuminance has found that there is little change in elastic modulus with temperature change, and that there are also few residual monomers, and the present invention has been completed based on this finding did.
  • the present invention is indicated by (I) to (VI) below.
  • (I) A method for producing a transparent double-sided pressure-sensitive adhesive sheet obtained by curing a photocurable resin composition, (1) applying a photocurable resin composition on the light transmissive film (Y) to form a resin layer having a thickness of 0.01 to 3 mm; (2) Laminating a light transmissive film (Z) on the formed resin layer; (3) irradiating the laminate obtained by lamination with black light at an irradiation dose of 10 to 300 mJ / cm 2 ; (4) a step of irradiating an active energy ray at a dose of 500 to 5000 mJ / cm 2 to the laminate irradiated with black light; About the transparent double-sided pressure-sensitive adhesive sheet in a state where both light-transmitting films are peeled off, (a) storage elastic modulus when dynamic viscoelasticity is measured under conditions of 40 ° C. and 1 Hz, and (b) conditions of 100 ° C. and 1 Hz The storage elastic modulus when dynamic viscoelasticity is measured with the formula (
  • the photocurable resin composition comprises (A) (meth) acrylic group-containing polyolefin compound 20 to 50% by mass, (B) (meth) acrylic monomer 49.8 to 79.8% by mass, and ( C) The method for producing a transparent double-sided pressure-sensitive adhesive sheet according to (I), comprising 0.2 to 5% by mass of a photopolymerization initiator.
  • (IV) (A) The (meth) acryl group-containing polyolefin compound has a hydrogenated polybutadiene skeleton or a hydrogenated polyisoprene skeleton, and (B) (meth) acrylic monomer is an alkyl (meth) acrylate and / or a cyclic alkyl (The method for producing a transparent double-sided pressure-sensitive adhesive sheet according to (II) or (III), comprising (meth) acrylate, wherein (C) the photopolymerization initiator comprises a carbonyl-based photopolymerization initiator.
  • the method for producing a transparent double-sided pressure-sensitive adhesive sheet of the present invention it is possible to obtain a transparent double-sided pressure-sensitive adhesive sheet with little change in elastic modulus due to temperature change and little residual monomer.
  • the transparent double-sided adhesive sheet obtained by the manufacturing method of this invention can be used for bonding of an optical member, and can be used suitably especially for bonding of a touch panel and an image display apparatus. Therefore, since this invention can obtain such a transparent double-sided adhesive sheet efficiently, its industrial use value is very high.
  • a method for producing a transparent double-sided PSA sheet obtained by curing the photocurable resin composition of the present invention (1) applying a photocurable resin composition on the light transmissive film (Y) to form a resin layer having a thickness of 0.01 to 3 mm; (2) Laminating a light transmissive film (Z) on the formed resin layer; (3) irradiating the laminate obtained by lamination with black light at an irradiation dose of 10 to 300 mJ / cm 2 ; (4) a step of irradiating an active energy ray at a dose of 500 to 5000 mJ / cm 2 to the laminate irradiated with black light;
  • About the transparent double-sided pressure-sensitive adhesive sheet in a state where both light-transmitting films are peeled off (a) storage elastic modulus when dynamic viscoelasticity is measured under conditions of 40 ° C. and 1 Hz, and (b) conditions of 100 ° C. and 1 Hz
  • the storage elastic modulus when dynamic viscoelasticity is measured with the formula (
  • step (1) A step of applying a photocurable resin composition on the light transmissive film (Y) of the present invention to form a resin layer having a thickness of 0.01 to 3 mm (hereinafter referred to as “step (1)”).
  • step (2) the light transmissive film used in the step of laminating the light transmissive film (Z) on the formed resin layer (hereinafter referred to as “step (2)”) is generally an adhesive tape.
  • the peeling film currently used for the adhesive sheet, a peeling sheet, or a separator can be used. Different light transmissive films may be used in the steps (1) and (2) of the present invention.
  • a polyester film such as polyethylene terephthalate (PET) or a polyolefin film such as a polypropylene film or a polyethylene film can be used.
  • PET polyethylene terephthalate
  • a polyolefin film such as a polypropylene film or a polyethylene film
  • the surface of the light transmissive film is preferably treated with a release agent such as a silicone release agent or a fluorine release agent.
  • the surface of the photocurable resin composition formed in the step (1) is light transmissive on the surface opposite to the surface on which the light transmissive film (Y) is laminated. Laminate the film (Z).
  • the thickness of the light-transmitting film can be appropriately selected according to the desired strength, flexibility, purpose of use, etc., and is not particularly limited, but is generally 10 to 300 ⁇ m, preferably 20 to 200 ⁇ m, more The thickness is preferably 30 to 150 ⁇ m.
  • light-transparent films having different thicknesses may be used. If the thickness of the light transmissive film is less than 10 ⁇ m, the film may be deformed by reaction heat generated in the process of curing the photocurable resin composition, which is not preferable. If the thickness of the light transmissive film is larger than 300 ⁇ m, the transmittance of black light and active energy rays may be deteriorated, which is not preferable.
  • the photocurable resin composition used in the present invention if it has an appropriate adhesive force when used as a transparent double-sided pressure-sensitive adhesive sheet, and has no problem in optical properties such as transparency and yellowing, particularly although not limited, it is preferable to use a photocurable resin composition containing (A) (meth) acrylic group-containing polyolefin compound, (B) (meth) acrylic monomer and (C) photopolymerization initiator.
  • any polyolefin compound having a polyolefin skeleton and having a (meth) acryl group introduced therein can be used.
  • Polyolefin skeletons that can be used for (meth) acrylic group-containing polyolefin compounds include skeletons derived from polyethylene, polypropylene, ethylene / propylene copolymers, butadiene, isoprene, hydrogenated polybutadiene, hydrogenated polyisoprene, cycloolefin, etc. Is mentioned.
  • the (A) (meth) acryl group-containing polyolefin compound preferably has a hydrogenated polybutadiene skeleton or a hydrogenated polyisoprene skeleton 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—.
  • (A) As a (meth) acryl group-containing polyolefin compound a compound having a polyolefin skeleton and an isocyanate group or a hydroxyl group is subjected to a urethanization reaction of a (meth) acrylate having a hydroxyl group or an isocyanate group, thereby producing a molecule in the molecule.
  • (A) (Meth) acrylic group-containing polyolefin compound obtained by introducing a (meth) acrylic group into is preferable from the viewpoint of adhesiveness and toughness.
  • (A) As a synthesis method of the (meth) acryl group-containing polyolefin compound the following two-step reaction can be exemplified.
  • the two-step reaction as the first example is as follows. First, a polyfunctional isocyanate compound having two or more isocyanate groups in one molecule (hereinafter sometimes referred to as “polyfunctional isocyanate compound”) with respect to the polyolefin polyol is used in a proportion in which the amount of isocyanate groups is larger than the amount of hydroxyl groups. By reacting, a urethane prepolymer having an isocyanate group is synthesized. At this time, the molecular weight can be adjusted by adjusting the ratio of the hydroxyl group equivalent of the polyolefin polyol and the isocyanate group equivalent of the polyfunctional isocyanate compound.
  • a (meth) acrylate having a hydroxyl group in the obtained urethane prepolymer a hydroxyalkyl (meth) acrylate or a (meth) acrylate monool derived from various polyols (with one hydroxyl group remaining, various polyols ( A (meth) acrylate group-containing polyolefin compound is obtained by reacting (meth) acrylate) and converting the remaining isocyanate group to a (meth) acryl group.
  • hydroxyalkyl (meth) acrylate examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,3-butanediol (meth) acrylate, Examples thereof include 1,4-butanediol (meth) acrylate, 1,6-hexanediol (meth) acrylate, 3-methylpentanediol (meth) acrylate and the like, and these can be used alone or in combination of two or more. Of these, 2-hydroxyethyl acrylate is preferred in terms of reactivity with isocyanate groups and photocurability.
  • the (meth) acryl group content can be adjusted by reacting the alkyl alcohol with an isocyanate group.
  • the saturated alcohol that can be used is not particularly limited, and one or more linear, branched, or alicyclic alkyl alcohols can be used.
  • the two-step reaction as the second example is as follows. First, a polyfunctional isocyanate compound is reacted with a polyolefin polyol at a ratio in which the hydroxyl group equivalent is larger than the isocyanate group equivalent to synthesize a polyurethane compound having a hydroxyl group with an extended chain length. At this time, the molecular weight can be adjusted by adjusting the ratio of the hydroxyl group equivalent of the polyolefin polyol and the isocyanate group equivalent of the polyfunctional isocyanate compound. At this time, the content of the (meth) acrylic group can be adjusted by adjusting the amount of the isocyanate group-containing (meth) acrylate to be reacted with the remaining hydroxyl group.
  • the isocyanate group-containing (meth) acrylate a commercially available compound may be used, or a hydroxyalkyl (meth) acrylate or (meth) acrylate monool derived from various polyols and a diisocyanate compound are reacted to form an isocyanate group at one end, What synthesized the isocyanate group containing (meth) acrylate which has a (meth) acryl group in the other terminal may be used.
  • the isocyanate group-containing (meth) acrylate include 2-isocyanatoethyl (meth) acrylate and 1,1-bis (acryloyloxymethyl) ethyl isocyanate. Of these, 2-isocyanatoethyl acrylate is preferred from the viewpoints of reactivity with hydroxyl groups and photocurability.
  • the two-step reaction in the above two examples is a reaction between a hydroxyl group and an isocyanate group, and a general urethane such as dibutyltin dilaurate or dibutyltin diethylhexoate in the presence of an organic solvent inert to the isocyanate group.
  • the reaction is usually carried out continuously at 30 to 100 ° C. for about 1 to 5 hours using the catalyst.
  • the amount of the urethanization catalyst used is usually 50 to 500 ppm based on the total mass of the raw materials used for the reaction.
  • the above polyolefin polyol preferably has a number average molecular weight of 500 to 5,000, more preferably 1,000 to 4,000.
  • the number average molecular weight is smaller than 500, the number of urethane bonds in the (A) (meth) acryl group-containing polyolefin compound is excessive, which may cause yellowing during curing, which is not preferable.
  • the number average molecular weight is greater than 5,000, the compatibility between the (meth) acrylic group-containing polyolefin compound and the (meth) acrylic acid ester is unfavorable.
  • the polyolefin polyol used in the present invention is preferably hydrogenated 1,2-polybutadiene diol or hydrogenated polyisoprene diol from the viewpoint of light resistance, transparency (non-crystalline) and workability (liquid).
  • Specific examples of commercially available hydrogenated 1,2-polybutadiene polyols that can be used include products manufactured by Nippon Soda Co., Ltd., product names: GI-1000, GI-2000, GI-3000 (number average molecular weights of about 1500 each). , About 2100, about 3000).
  • Specific examples of commercially available hydrogenated polyisoprene polyols include Idemitsu Kosan Co., Ltd. product name Epol (number average molecular weight of about 2500).
  • polyfunctional isocyanate compound examples include diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, and hydrogenated products thereof, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, And diisocyanate compounds such as tetramethylxylylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexyl diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and norbornane diisocyanate.
  • diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, and hydrogenated products thereof, hexamethylene diisocyanate, trimethylhe
  • isophorone diisocyanate or hydrogenated diphenylmethane diisocyanate is preferred 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 above (A) (meth) acryl group-containing polyolefin compound is made to have a high molecular weight by reacting a polyolefin polyol and a polyfunctional isocyanate compound, and then 50 to 100 mol% (meth ) It is preferable to introduce an acrylic group, and it is more preferable to introduce 70 to 100 mol% of a (meth) acrylic group.
  • the ratio of introducing the (meth) acrylic group is less than 50 mol%, there is a large change in storage elastic modulus depending on the temperature of the transparent double-sided PSA sheet that can be obtained by the presence of polyolefin polyol that cannot introduce the (meth) acrylic group. This is not preferable.
  • the content of the (A) (meth) acrylic group-containing polyolefin compound is preferably 20 to 50% by mass, more preferably 22 to 45% by mass in the photocurable resin composition, and more preferably 25 to More preferably, it is 40 mass%.
  • the content of the (A) (meth) acrylic group-containing polyolefin compound is less than 20% by mass, there is a possibility that a change in storage elastic modulus due to a temperature change of the obtained transparent double-sided PSA sheet is increased, which is not preferable.
  • the amount is more than 50% by mass, the compatibility with the (B) (meth) acrylic monomer may be deteriorated, which is not preferable.
  • the above (B) (meth) acrylic monomer means an acrylic monomer or methacrylic monomer having one or more (meth) acrylic groups in the molecule.
  • the (B) (meth) acrylic monomer that can be used is not particularly limited, and a monofunctional or polyfunctional photopolymerizable monomer having a (meth) acryl group may be used alone or in combination of two or more. Can be used.
  • (B) (meth) acrylic monomer examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and tert-butyl (meth).
  • Alkyl such as acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-hexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate (Meth) acrylate, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, norbornanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, disi Cycloalkyl (meth) acrylates such as lopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclodecane dimethylo
  • alkyl (meth) acrylates and cyclic alkyl (meth) acrylates are preferably used from the viewpoints of tackiness, reactivity, and transparency, and cyclohexyl acrylate and 2-ethylhexyl acrylate are particularly preferably used.
  • the content of the (B) (meth) acrylic monomer is preferably 49.8 to 79.8% by mass and more preferably 55 to 78% by mass in the photocurable resin composition. 60 to 75% by mass is more preferable.
  • the content of the (B) (meth) acrylic monomer is less than 49.8% by mass, the compatibility with the (A) (meth) acrylic group-containing polyolefin compound may be unfavorable.
  • the content of the (B) (meth) acrylic monomer is more than 79.8% by mass, the change in the storage elastic modulus depending on the temperature of the obtained transparent double-sided PSA sheet is unfavorable.
  • Examples of the (C) photopolymerization initiator include carbonyl photopolymerization initiator, sulfide photopolymerization initiator, quinone photopolymerization initiator, azo photopolymerization initiator, sulfochloride photopolymerization initiator, and thioxanthone. System photopolymerization initiator or peroxide photopolymerization initiator.
  • 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.
  • the peroxide photopolymerization initiator examples include benzoyl peroxide and di-t-butyl peroxide.
  • the photopolymerization initiator it is preferable to use a carbonyl-based photopolymerization initiator, and it is particularly preferable to use 1-hydroxycyclohexyl phenyl ketone from the viewpoint of solubility in the resulting photocurable resin composition. .
  • These (C) 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 resin composition in terms of the balance between photocurability and the strength and adhesiveness of the obtained transparent double-sided PSA sheet. It is preferably 0.5 to 3% by mass, more preferably 0.8 to 2% by mass.
  • content of a photoinitiator is less than 0.2 mass%, photocuring tends to become inadequate, and when it exceeds 5 mass%, the adhesiveness of the transparent double-sided adhesive sheet obtained will fall. It tends to be unfavorable.
  • a tackifier resin may be added as long as the transparency is not lowered in order to improve the adhesive strength of the obtained pressure-sensitive adhesive sheet.
  • tackifier 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 ( C9-based) and other petroleum resins, as well as styrene-based resins, phenol-based resins, xylene resins, and the like.
  • alicyclic tackifying resins with few unsaturated double bonds are preferred from the viewpoint of light resistance.
  • Specific alicyclic tackifier resins include rosin and rosin derivative hydrogenated resins, polyterpene resin hydrogenated resins, aromatic modified terpene resin hydrogenated resins, terpene phenol resin hydrogenated resins, coumarone and indene resins. Hydrogenated resin, alicyclic petroleum resin hydrogenated resin, aromatic petroleum resin hydrogenated resin, aliphatic aromatic copolymer petroleum resin hydrogenated resin, dicyclopentadiene petroleum resin hydrogenated resin And a hydrogenated resin of a dicyclopentadiene aromatic copolymer system and a hydrogenated resin of a low molecular weight polymer of styrene or substituted styrene.
  • the alicyclic tackifying resin can be used alone or in combination of two or more.
  • the addition amount of the tackifying resin is preferably 0 to 20 parts by mass, more preferably 0 to 15 parts by mass, and 0 to 10 parts by mass with respect to 100 parts by mass of the photocurable resin composition. More preferably. If the addition amount of the tackifying resin exceeds 20 parts by mass with respect to 100 parts by mass of the photocurable resin composition, the transparency of the obtained adhesive sheet tends to be too bad, which is not preferable.
  • the photocurable resin composition of the present invention may contain various known additives as long as the transparency is not impaired.
  • Additives include plasticizers, surface lubricants, softeners, antioxidants, anti-aging agents, light stabilizers, UV absorbers, polymerization inhibitors, light stabilizers such as benzotriazoles, phosphate esters, and others Flame retardants, and antistatic agents such as surfactants.
  • the thickness when the photocurable resin composition of the present invention is applied is in the range of 0.01 to 3 mm, more preferably 0.015 to 1 mm, and still more preferably 0.02 to 0.5 mm. It is. If the coating thickness is less than 0.01 mm, it is difficult to uniformly apply the film thickness, which may cause unevenness in the film thickness. When the thickness is larger than 3 mm, it is not preferable because it is difficult to transmit ultraviolet rays and the curability may be deteriorated.
  • the method of applying the photocurable resin composition on the light transmissive film (Y) is a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray coater, comma coater or direct coater. It does not restrict
  • step (3) there is (3) a step of irradiating the laminate obtained by laminating with black light at an irradiation dose of 10 to 300 mJ / cm 2 (hereinafter referred to as “step (3)”).
  • Black light is a lamp that emits only near-ultraviolet light having a wavelength of 300 to 400 nm.
  • the black light that can be used is not particularly limited as long as the light intensity at a wavelength of 365 nm is in the range of 0.20 to 10 mW / cm 2 , and a commercially available one can be used.
  • the light intensity at a wavelength of 365 nm is preferably 0.20 to 10 mW / cm 2 , and more preferably 0.5 to 5 mW / cm 2 .
  • the irradiation amount of black light is 10 to 300 mJ / cm 2 , the more preferable irradiation amount is 15 to 200 mJ / cm 2 , and the further preferable irradiation amount is 20 to 100 mJ / cm 2 .
  • the black light is irradiated at an angle substantially perpendicular to the plane on which the photocurable resin composition of the laminate obtained by lamination is applied.
  • the black light may be irradiated from one side or both sides of the laminate.
  • step (4) a step of irradiating the laminate irradiated with black light with active energy rays at an irradiation dose of 500 to 5000 mJ / cm 2 (hereinafter referred to as “step (4)”. ").
  • the active energy ray is a general term for an electron beam, an X-ray, an ultraviolet ray, a high-energy electron beam such as visible light in a low wavelength region, or an electromagnetic wave.
  • the active energy ray that can be used, those having a light intensity in the range of 20 to 500 mW / cm 2 at a wavelength of 365 nm are preferable, and a high pressure mercury lamp, a metal halide lamp and the like are exemplified as a light source.
  • the irradiation dose of the active energy ray in the range of 500 ⁇ 5000mJ / cm 2, more preferably in the range of 600 ⁇ 3000mJ / cm 2, more preferably in the range of 700 ⁇ 2000mJ / cm 2.
  • the irradiation amount of active energy rays is less than 500 mJ / cm 2 , the residual monomer of the obtained transparent double-sided PSA sheet increases.
  • an active energy ray is irradiated at an angle substantially perpendicular to the plane on which the photocurable resin composition is applied. Further, the active energy ray may be irradiated from one side or both sides of the laminate.
  • the transparent double-sided pressure-sensitive adhesive sheet obtained from the method for producing a transparent double-sided pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet layer obtained by curing a photocurable resin composition (that is, transparent in a state where both light-transmitting films are peeled off).
  • a photocurable resin composition that is, transparent in a state where both light-transmitting films are peeled off.
  • (Double-sided PSA sheet) (a) Storage elastic modulus when dynamic viscoelasticity is measured under conditions of 40 ° C. and 1 Hz and (b) Storage elastic modulus when dynamic viscoelasticity is measured under conditions of 100 ° C. and 1 Hz The rate is the formula (I): It satisfies.
  • the transparent double-sided PSA sheet preferably satisfies the condition 1 ⁇ (a) / (b) ⁇ 1.45, and more preferably satisfies the condition 1 ⁇ (a) / (b) ⁇ 1.4.
  • the transparent double-sided pressure-sensitive adhesive sheet is (a) / (b) ⁇ 1.5, the change in storage elastic modulus due to temperature change of the obtained transparent double-sided pressure-sensitive adhesive sheet is large.
  • the transparent double-sided PSA sheet may be altered, which is not preferable.
  • the light-transmitting film ( Y) forming a resin layer of the photocurable resin composition on the laminate, and laminating the light transmissive film (Z) on the surface of the resin layer opposite to the surface in contact with the light transmissive film (Y). It is necessary to harden the photocurable resin composition through the steps (3) and (4) with respect to the laminate obtained in (1).
  • the high-pressure mercury lamp and metal halide lamp which are the light sources of the active energy rays described above have high illuminance and include light having a wavelength of 400 nm or more, and thus heat the laminate.
  • the black light has a low illuminance and contains almost no light of 400 nm or more, so the laminate is not heated.
  • the photocurable resin composition is cured at low illuminance and low temperature by the step (3), a polymer having a high molecular weight and a high gel fraction can be obtained.
  • a transparent double-sided pressure-sensitive adhesive sheet with little decrease in storage modulus at high temperatures can be obtained. Furthermore, residual monomer can be reduced by performing the process (4) after the process (3).
  • the mass of the pressure-sensitive adhesive sheet layer obtained by curing the photocurable resin composition (that is, the transparent double-sided pressure-sensitive adhesive sheet in a state where both light-transmitting films are peeled off).
  • the amount of the remaining monomer is preferably 1 to 500 wtppm, more preferably 1 to 400 wtppm, and still more preferably 1 to 300 wtppm.
  • the amount of the remaining monomer is more than 500 wtppm with respect to the mass of the pressure-sensitive adhesive sheet layer obtained by curing the photocurable resin composition, there is an odor problem, which is not preferable.
  • the transparent double-sided PSA sheet obtained by the method for producing a transparent double-sided PSA sheet of the present invention is an optical transparent double-sided PSA sheet used for optical applications. More specifically, it is used for applications for bonding optical members (for optical member bonding), optical product manufacturing applications, and the like. Although it will not specifically limit if it is a member which has an optical characteristic as an optical member, For example, the member used for an image display apparatus, a touchscreen, or these apparatuses is mentioned, For example, a polarizing plate, phase difference, etc. Plate, optical compensation film, brightness enhancement film, light guide plate, reflection film, antireflection film, transparent conductive film, design film, decorative film, surface protection film, prism, lens, color filter, transparent substrate, and these are laminated The member which has been mentioned.
  • the transparent double-sided pressure-sensitive adhesive sheet of the present invention is particularly preferably used for bonding members constituting a touch panel and an image display device.
  • the image display device include a liquid crystal display device, an organic EL (electroluminescence) display device, a PDP (plasma display panel), and electronic paper.
  • Examples 1 and 2 and Comparative Examples 1 to 4 Under the conditions shown in Table 1, the prepared photocurable resin composition was applied onto a 50 ⁇ m-thick release PET film (PET-O2-50-BU, manufactured by Mitsui Chemical Tosero Co., Ltd.) using an applicator.
  • PET-O2-50-BU manufactured by Mitsui Chemical Tosero Co., Ltd.
  • the storage elastic modulus was measured in a shear mode (1 Hz) using a dynamic viscoelasticity measuring device ARES manufactured by TI Instruments. A laminate of five transparent double-sided PSA sheets from which the peeled PET film had been removed was punched with a 7.9 mm ⁇ punching blade to obtain a test piece. Measured at a rate of temperature increase of 5 ° C./min in the measurement range of ⁇ 30 to 150 ° C., among these (a) storage elastic modulus at 40 ° C. and 1 Hz and (b) storage elastic modulus at 100 ° C. and 1 Hz (a) / (B) was calculated and shown in Table 1.
  • the measurement conditions are Column; ZB-5 Column temperature: 50 ° C. (maintained for 1 minute) ⁇ increased at 20 ° C./minute ⁇ 250 ° C. (maintained for 5 minutes when reaching 250 ° C.) Detector; FID
  • the transparent double-sided pressure-sensitive adhesive sheet production method of the example is superior to the comparative example in that the change in storage elastic modulus is small due to temperature change and the residual monomer is small. Recognize.
  • the method for producing a transparent double-sided pressure-sensitive adhesive sheet obtained by curing the photocurable resin composition of the present invention can provide a thick film sheet with little change in storage elastic modulus due to temperature change and little residual monomer.
  • the transparent double-sided PSA sheet that is useful as a method for producing a PSA sheet is suitably used for touch panels and image display devices.

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Abstract

Provided is a production method for a transparent double-sided adhesive sheet having little variation in the storage modulus therefor caused by temperature variation, and also having few residual monomers. The production method for the transparent double-sided adhesive sheet, whereby the transparent double-sided adhesive sheet having both sides of a light-permeable film peeled away fulfills prescribed conditions, is a production method for the transparent double-sided adhesive sheet obtained by curing a photo-curable resin composition, and has: a step (1) in which the photo-curable resin composition is coated upon a light-permeable film (Y), and a resin layer having a thickness of 0.01-3 mm is formed; a step (2) in which a light-permeable film (Z) is laminated on the formed resin layer; a step (3) in which a black light is irradiated at 10-300 mJ/cm2 on to a laminate obtained by laminating; and a step (4) in which active energy rays are irradiated at an irradiation amount of 500-5,000 mJ/cm2 on to the laminate having had the black light irradiated thereon.

Description

透明両面粘着シートの製造方法、透明両面粘着シートMethod for producing transparent double-sided pressure-sensitive adhesive sheet, transparent double-sided pressure-sensitive adhesive sheet
　本発明は、光硬化性樹脂組成物を硬化させて得られる透明両面粘着シートの製造方法、透明両面粘着シート、透明両面粘着シートを用いたタッチパネル及び透明両面粘着シートを用いた画像表示装置に関する。 The present invention relates to a method for producing a transparent double-sided pressure-sensitive adhesive sheet obtained by curing a photocurable resin composition, a transparent double-sided pressure-sensitive adhesive sheet, a touch panel using the transparent double-sided pressure-sensitive adhesive sheet, and an image display device using the transparent double-sided pressure-sensitive adhesive sheet.
　近年、携帯電話、ゲーム機器などの分野に液晶ディスプレイなどの画像表示装置や、タッチパネルなどの前記画像表示装置と組み合わせて用いられる入力装置が多く見られるようになってきた。これらの画像表示装置や入力装置には、光学部材を貼り合せる目的で透明両面粘着シートが使用されている。 In recent years, an image display device such as a liquid crystal display and an input device used in combination with the image display device such as a touch panel have been widely used in the fields of mobile phones and game machines. In these image display devices and input devices, transparent double-sided pressure-sensitive adhesive sheets are used for the purpose of bonding optical members.
　画像表示装置やタッチパネルに使用される両面粘着シートには、透明性、粘着性のみならず、粘着シートとしての特性を多様な環境下において十分に発揮することが要求される。例えば、高温下において、貼付した光学部材や光学製品などの視認性や外観の保持性に悪影響を及ぼさない性質を有する両面粘着シートや、温度変化によって貯蔵弾性率の変化が少ない両面粘着シートが求められている。 ¡Double-sided pressure-sensitive adhesive sheets used for image display devices and touch panels are required not only to exhibit transparency and adhesiveness but also to fully exhibit the characteristics of pressure-sensitive adhesive sheets in various environments. For example, a double-sided pressure-sensitive adhesive sheet having properties that do not adversely affect the visibility and appearance retention of attached optical members and optical products at high temperatures, and a double-sided pressure-sensitive adhesive sheet with little change in storage elastic modulus due to temperature change are required. It has been.
　また、光学部材を貼り合せる目的で使用される透明両面粘着シートには、１００μｍ以上の厚膜のシートを用いることも多くなってきている。１００μｍ以上の厚膜の透明両面粘着シートは、ポリマー溶液をフィルム等の支持体上に塗布し、その後溶剤を加熱留去する方法で得ることができるが、この場合、塗布溶剤留去の工程には大きなエネルギーと時間を要するという問題が有る。一方、溶剤を使用しない光硬化性組成物を支持体上に塗布した後、光照射により重合を行わせて粘着シートを製造する方法によっても、容易に膜厚が１００μｍ以上のシートを得ることが出来る。 Further, as a transparent double-sided pressure-sensitive adhesive sheet used for the purpose of bonding an optical member, a thick film of 100 μm or more is often used. A transparent double-sided pressure-sensitive adhesive sheet having a thickness of 100 μm or more can be obtained by a method in which a polymer solution is applied onto a support such as a film, and then the solvent is heated to distill off. Has the problem of requiring a lot of energy and time. On the other hand, a sheet having a film thickness of 100 μm or more can be easily obtained by applying a photocurable composition that does not use a solvent on a support and then producing a pressure-sensitive adhesive sheet by polymerization by light irradiation. I can do it.
　しかしながら、光照射による重合は、光重合開始剤の量及び光照射条件の設定等が難しく、生産性が充分に上がらないという問題点があった。すなわち生産性を上げるために光重合開始剤の量を多くすると分子量が小さくなるため、高温時の貯蔵弾性率が低下するという問題があり、一方、光照射時間を短縮すると重合率が上がらないため、残存モノマーが多くなるといった問題があった。 However, polymerization by light irradiation has a problem in that it is difficult to set the amount of photopolymerization initiator and light irradiation conditions, and the productivity is not sufficiently increased. That is, if the amount of the photopolymerization initiator is increased in order to increase the productivity, the molecular weight decreases, so there is a problem that the storage elastic modulus at a high temperature decreases, and on the other hand, if the light irradiation time is shortened, the polymerization rate does not increase. There was a problem that the residual monomer increased.
　この残存モノマーの問題に対して、フィルム状基材の片面に光重合性アクリル系粘着剤組成物層を設け、さらに光重合性アクリル系粘着剤組成物層のフィルム状基材と接していないもう一方の表面にカバーフィルムを貼り合わせ、紫外線を照射して重合させる光重合性アクリル系粘着シートを製造する方法が開示されている（例えば、特許文献１参照）。しかし、この方法では、残存モノマーを低減させるための硬化過程の温度コントロールが煩雑であるという問題があった。 For the problem of this residual monomer, a photopolymerizable acrylic pressure-sensitive adhesive composition layer is provided on one side of the film-like base material, and is not in contact with the film-like base material of the photopolymerizable acrylic pressure-sensitive adhesive composition layer. A method of manufacturing a photopolymerizable acrylic pressure-sensitive adhesive sheet in which a cover film is bonded to one surface and polymerized by irradiation with ultraviolet rays is disclosed (for example, see Patent Document 1). However, this method has a problem that the temperature control in the curing process for reducing the residual monomer is complicated.
　要するに、温度変化による貯蔵弾性率の変化が少なく、且つ残存モノマーが少ない、厚膜のシートを得る透明両面粘着シートの製造方法がないのが現状である。 In short, there is currently no method for producing a transparent double-sided PSA sheet that obtains a thick film sheet with little change in storage modulus due to temperature change and little residual monomer.
特開２００７－２１０４号公報JP 2007-2104 A
　本発明が解決しようとする課題は、温度変化による貯蔵弾性率の変化が少なく、且つ残存モノマーが少ない、厚膜のシートを得る透明両面粘着シートの製造方法、さらに透明両面粘着シートを提供することである。 The problem to be solved by the present invention is to provide a method for producing a transparent double-sided PSA sheet that obtains a thick film sheet with little change in storage modulus due to temperature change and low residual monomer, and further provides a transparent double-sided PSA sheet. It is.
　本発明者らは、透明両面粘着シートの製造方法が抱える前記の問題点を解決するために、鋭意検討を重ねた結果、光透過性フィルム（Ｙ）上に光硬化性樹脂組成物の樹脂層を形成し、さらに樹脂層の光透過性フィルム（Ｙ）と接している面とは反対側の面に光透過性フィルム（Ｚ）をラミネートし、ラミネートにより得られた積層体に低照度のブラックライトを照射し、次いで高照度の活性エネルギー線を照射する製造方法が、温度変化に伴う弾性率の変化が少ないこと、さらには残存モノマーが少ないことを見出し、この知見に基づいて本発明を完成した。 In order to solve the above-described problems of the method for producing a transparent double-sided PSA sheet, the present inventors have made extensive studies and as a result, the resin layer of the photocurable resin composition on the light transmissive film (Y). Further, a light-transmitting film (Z) is laminated on the surface of the resin layer opposite to the surface in contact with the light-transmitting film (Y), and the laminated body obtained by the lamination has a low illuminance black The manufacturing method of irradiating light and then irradiating active energy rays with high illuminance has found that there is little change in elastic modulus with temperature change, and that there are also few residual monomers, and the present invention has been completed based on this finding did.
　本発明は以下（Ｉ）～（ＶＩ）で示される。 The present invention is indicated by (I) to (VI) below.
　（Ｉ）光硬化性樹脂組成物を硬化させて得られる透明両面粘着シートの製造方法であって、
（１）光透過性フィルム（Ｙ）上に光硬化性樹脂組成物を塗工し、厚さ０．０１～３ｍｍの樹脂層を形成する工程と、
（２）形成した樹脂層に光透過性フィルム（Ｚ）をラミネートする工程と、
（３）ラミネートにより得られた積層体に、ブラックライトを１０～３００ｍＪ／ｃｍ２の照射量で照射する工程と、
（４）ブラックライトを照射した積層体に、活性エネルギー線を５００～５０００ｍＪ／ｃｍ２の照射量で照射する工程
とを有し、
両方の光透過性フィルムを剥離させた状態の透明両面粘着シートについて、（ａ）４０℃、１Ｈｚの条件で動的粘弾性を測定した際の貯蔵弾性率と（ｂ）１００℃、１Ｈｚの条件で動的粘弾性を測定した際の貯蔵弾性率が、式（イ）：
Figure JPOXMLDOC01-appb-M000002
 を満たす透明両面粘着シートの製造方法。 (I) A method for producing a transparent double-sided pressure-sensitive adhesive sheet obtained by curing a photocurable resin composition,
(1) applying a photocurable resin composition on the light transmissive film (Y) to form a resin layer having a thickness of 0.01 to 3 mm;
(2) Laminating a light transmissive film (Z) on the formed resin layer;
(3) irradiating the laminate obtained by lamination with black light at an irradiation dose of 10 to 300 mJ / cm 2 ;
(4) a step of irradiating an active energy ray at a dose of 500 to 5000 mJ / cm 2 to the laminate irradiated with black light;
About the transparent double-sided pressure-sensitive adhesive sheet in a state where both light-transmitting films are peeled off, (a) storage elastic modulus when dynamic viscoelasticity is measured under conditions of 40 ° C. and 1 Hz, and (b) conditions of 100 ° C. and 1 Hz The storage elastic modulus when dynamic viscoelasticity is measured with the formula (A):
Figure JPOXMLDOC01-appb-M000002
 The manufacturing method of the transparent double-sided adhesive sheet which satisfy | fills.
　（ＩＩ）前記光硬化性樹脂組成物が、（Ａ）（メタ）アクリル基含有ポリオレフィン化合物２０～５０質量％、（Ｂ）（メタ）アクリル系モノマー４９．８～７９．８質量％、及び（Ｃ）光重合開始剤０．２～５質量％を含む（Ｉ）記載の透明両面粘着シートの製造方法。 (II) The photocurable resin composition comprises (A) (meth) acrylic group-containing polyolefin compound 20 to 50% by mass, (B) (meth) acrylic monomer 49.8 to 79.8% by mass, and ( C) The method for producing a transparent double-sided pressure-sensitive adhesive sheet according to (I), comprising 0.2 to 5% by mass of a photopolymerization initiator.
　（ＩＩＩ）透明両面粘着シートの質量に対して、残存する（Ｂ）（メタ）アクリル系モノマーの量が１～５００ｗｔｐｐｍである（ＩＩ）に記載の透明両面粘着シートの製造方法。 (III) The method for producing a transparent double-sided pressure-sensitive adhesive sheet according to (II), wherein the amount of the remaining (B) (meth) acrylic monomer is 1 to 500 wtppm with respect to the mass of the transparent double-sided pressure-sensitive adhesive sheet.
　（ＩＶ）（Ａ）（メタ）アクリル基含有ポリオレフィン化合物が水添ポリブタジエン骨格又は水添ポリイソプレン骨格を有し、（Ｂ）（メタ）アクリル系モノマーがアルキル（メタ）アクリレート及び／又は環状アルキル（メタ）アクリレートを含み、（Ｃ）光重合開始剤がカルボニル系光重合開始剤を含む（ＩＩ）又は（ＩＩＩ）に記載の透明両面粘着シートの製造方法。 (IV) (A) The (meth) acryl group-containing polyolefin compound has a hydrogenated polybutadiene skeleton or a hydrogenated polyisoprene skeleton, and (B) (meth) acrylic monomer is an alkyl (meth) acrylate and / or a cyclic alkyl ( The method for producing a transparent double-sided pressure-sensitive adhesive sheet according to (II) or (III), comprising (meth) acrylate, wherein (C) the photopolymerization initiator comprises a carbonyl-based photopolymerization initiator.
　（Ｖ）活性エネルギー線が高圧水銀ランプ及び／又はメタルハライドランプを光源とするものである（Ｉ）～（ＩＶ）のいずれかに記載の透明両面粘着シートの製造方法。 (V) The method for producing a transparent double-sided pressure-sensitive adhesive sheet according to any one of (I) to (IV), wherein the active energy ray uses a high-pressure mercury lamp and / or a metal halide lamp as a light source.
　（ＶＩ）前記（Ｉ）～（Ｖ）のいずれかに記載の透明両面粘着シートの製造方法により得られる透明両面粘着シート。 (VI) A transparent double-sided pressure-sensitive adhesive sheet obtained by the method for producing a transparent double-sided pressure-sensitive adhesive sheet according to any one of (I) to (V).
　（ＶＩＩ）前記（ＶＩ）に記載の透明両面粘着シートを用いたタッチパネル。 (VII) A touch panel using the transparent double-sided pressure-sensitive adhesive sheet described in (VI) above.
　（ＶＩＩＩ）前記（ＶＩ）に記載の透明両面粘着シートを用いた画像表示装置。 (VIII) An image display device using the transparent double-sided pressure-sensitive adhesive sheet described in (VI).
　本発明の透明両面粘着シートの製造方法によれば、温度変化による弾性率の変化が少なく、さらに残存モノマーが少ない透明両面粘着シートを得ることが出来る。また、本発明の製造方法により得られる透明両面粘着シートは光学部材の貼り合せに用いることができ、特にタッチパネル、画像表示装置の貼り合わせに好適に用いることが出来る。したがって、本発明は、このような透明両面粘着シートを効率よく得ることができるため、その産業上の利用価値が極めて高いものである。 According to the method for producing a transparent double-sided pressure-sensitive adhesive sheet of the present invention, it is possible to obtain a transparent double-sided pressure-sensitive adhesive sheet with little change in elastic modulus due to temperature change and little residual monomer. Moreover, the transparent double-sided adhesive sheet obtained by the manufacturing method of this invention can be used for bonding of an optical member, and can be used suitably especially for bonding of a touch panel and an image display apparatus. Therefore, since this invention can obtain such a transparent double-sided adhesive sheet efficiently, its industrial use value is very high.
　以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
　本発明の光硬化性樹脂組成物を硬化させて得られる透明両面粘着シートの製造方法であって、
（１）光透過性フィルム（Ｙ）上に光硬化性樹脂組成物を塗工し、厚さ０．０１～３ｍｍの樹脂層を形成する工程と、
（２）形成した樹脂層に光透過性フィルム（Ｚ）をラミネートする工程と、
（３）ラミネートにより得られた積層体に、ブラックライトを１０～３００ｍＪ／ｃｍ２の照射量で照射する工程と、
（４）ブラックライトを照射した積層体に、活性エネルギー線を５００～５０００ｍＪ／ｃｍ２の照射量で照射する工程
とを有し、
両方の光透過性フィルムを剥離させた状態の透明両面粘着シートについて、（ａ）４０℃、１Ｈｚの条件で動的粘弾性を測定した際の貯蔵弾性率と（ｂ）１００℃、１Ｈｚの条件で動的粘弾性を測定した際の貯蔵弾性率が、式（イ）：
Figure JPOXMLDOC01-appb-M000003
 を満たす透明両面粘着シートの製造方法である。 A method for producing a transparent double-sided PSA sheet obtained by curing the photocurable resin composition of the present invention,
(1) applying a photocurable resin composition on the light transmissive film (Y) to form a resin layer having a thickness of 0.01 to 3 mm;
(2) Laminating a light transmissive film (Z) on the formed resin layer;
(3) irradiating the laminate obtained by lamination with black light at an irradiation dose of 10 to 300 mJ / cm 2 ;
(4) a step of irradiating an active energy ray at a dose of 500 to 5000 mJ / cm 2 to the laminate irradiated with black light;
About the transparent double-sided pressure-sensitive adhesive sheet in a state where both light-transmitting films are peeled off, (a) storage elastic modulus when dynamic viscoelasticity is measured under conditions of 40 ° C. and 1 Hz, and (b) conditions of 100 ° C. and 1 Hz The storage elastic modulus when dynamic viscoelasticity is measured with the formula (A):
Figure JPOXMLDOC01-appb-M000003
 It is a manufacturing method of the transparent double-sided adhesive sheet which satisfy | fills.
　本発明の（１）光透過性フィルム（Ｙ）上に光硬化性樹脂組成物を塗工し、厚さ０．０１～３ｍｍの樹脂層を形成する工程（以下、「（１）の工程」という）と、（２）形成した樹脂層に光透過性フィルム（Ｚ）をラミネートする工程（以下、「（２）の工程」という）に使用される光透過性フィルムは、一般的に粘着テープ又は粘着シートに使用されている剥離フィルム、剥離シート又はセパレーター等を用いることができる。本発明の（１）の工程と（２）の工程で、異なる光透過性フィルムを用いても良い。例えば、ポリエチレンテレフタレート（ＰＥＴ）等のポリエステルフィルム、ポリプロピレンフィルムやポリエチレンフィルム等のポリオレフィンフィルムなどを用いることができる。中でも、酸素を透過し難く、波長３００～４００ｎｍの光透過性、フィルム強度及び耐熱性の点からＰＥＴフィルムが特に好適に使用される。また、光透過性フィルムの表面は、シリコーン系離型剤やフッ素系離型剤などの離型剤により処理されたものが好ましい。さらに、光透過性フィルム（Ｙ）と光透過性フィルム（Ｚ）の剥離強度に差をつけることが好ましい。なお、（２）の工程では、（１）の工程において形成された光硬化性樹脂組成物の樹脂層の光透過性フィルム（Ｙ）が積層された面とは反対側の面に光透過性フィルム（Ｚ）をラミネートする。 (1) A step of applying a photocurable resin composition on the light transmissive film (Y) of the present invention to form a resin layer having a thickness of 0.01 to 3 mm (hereinafter referred to as “step (1)”). And (2) the light transmissive film used in the step of laminating the light transmissive film (Z) on the formed resin layer (hereinafter referred to as “step (2)”) is generally an adhesive tape. Or the peeling film currently used for the adhesive sheet, a peeling sheet, or a separator can be used. Different light transmissive films may be used in the steps (1) and (2) of the present invention. For example, a polyester film such as polyethylene terephthalate (PET) or a polyolefin film such as a polypropylene film or a polyethylene film can be used. Among these, a PET film is particularly preferably used from the viewpoints of light permeability at a wavelength of 300 to 400 nm, film strength, and heat resistance, which hardly transmits oxygen. The surface of the light transmissive film is preferably treated with a release agent such as a silicone release agent or a fluorine release agent. Furthermore, it is preferable to make a difference in the peel strength between the light transmissive film (Y) and the light transmissive film (Z). In the step (2), the surface of the photocurable resin composition formed in the step (1) is light transmissive on the surface opposite to the surface on which the light transmissive film (Y) is laminated. Laminate the film (Z).
　光透過性フィルムの厚さは、希望する強度や柔軟性、又は、使用目的などに応じて適宜に選択でき、特に限定されないが、一般的には、１０～３００μｍ、好ましくは２０～２００μｍ、より好ましくは３０～１５０μｍである。本発明の（１）の工程と（２）の工程で、異なる厚さの光過性フィルムを用いても良い。光透過性フィルムの厚さが１０μｍよりも小さくなると、光硬化性樹脂組成物が硬化する過程で発生する反応熱によりフィルムが変形する可能性があり好ましくない。光透過性フィルムの厚さが３００μｍよりも大きくなると、ブラックライトの光、及び活性エネルギー線の透過性が悪くなる可能性があり好ましくない。 The thickness of the light-transmitting film can be appropriately selected according to the desired strength, flexibility, purpose of use, etc., and is not particularly limited, but is generally 10 to 300 μm, preferably 20 to 200 μm, more The thickness is preferably 30 to 150 μm. In the steps (1) and (2) of the present invention, light-transparent films having different thicknesses may be used. If the thickness of the light transmissive film is less than 10 μm, the film may be deformed by reaction heat generated in the process of curing the photocurable resin composition, which is not preferable. If the thickness of the light transmissive film is larger than 300 μm, the transmittance of black light and active energy rays may be deteriorated, which is not preferable.
　本発明に使用される光硬化性樹脂組成物としては、透明両面粘着シートとして使用した際に適切な粘着力があり、透明性、黄変性等の光学特性に問題が無いものであれば、特に限定されないが、（Ａ）（メタ）アクリル基含有ポリオレフィン化合物、（Ｂ）（メタ）アクリル系モノマー及び（Ｃ）光重合開始剤を含む光硬化性樹脂組成物を用いることが好ましい。 As the photocurable resin composition used in the present invention, if it has an appropriate adhesive force when used as a transparent double-sided pressure-sensitive adhesive sheet, and has no problem in optical properties such as transparency and yellowing, particularly Although not limited, it is preferable to use a photocurable resin composition containing (A) (meth) acrylic group-containing polyolefin compound, (B) (meth) acrylic monomer and (C) photopolymerization initiator.
　（Ａ）（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あれば、使用することが出来る。（Ａ）（メタ）アクリル基含有ポリオレフィン化合物に使用でき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に由来する骨格が挙げられる。耐光性、透明性（非結晶性）及び作業性（液状）の点で、（Ａ）（メタ）アクリル基含有ポリオレフィン化合物は、水添ポリブタジエン骨格又は水添ポリイソプレン骨格を有することが好ましい。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。 As the (A) (meth) acryl group-containing polyolefin compound, any polyolefin compound having a polyolefin skeleton and having a (meth) acryl group introduced therein can be used. (A) Polyolefin skeletons that can be used for (meth) acrylic group-containing polyolefin compounds include skeletons derived from polyethylene, polypropylene, ethylene / propylene copolymers, butadiene, isoprene, hydrogenated polybutadiene, hydrogenated polyisoprene, cycloolefin, etc. Is mentioned. The (A) (meth) acryl group-containing polyolefin compound preferably has a hydrogenated polybutadiene skeleton or a hydrogenated polyisoprene skeleton 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—.
　（Ａ）（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及びイソシアネート基又はヒドロキシル基を有する化合物に対して、ヒドロキシル基又はイソシアネート基を有する（メタ）アクリレートをウレタン化反応させることにより、分子中に（メタ）アクリル基を導入して得られる（Ａ）（メタ）アクリル基含有ポリオレフィン化合物が、接着性及び靭性の点から好ましい。（Ａ）（メタ）アクリル基含有ポリオレフィン化合物の合成方法としては、以下のような２段階反応によるものを例示できる。 (A) As a (meth) acryl group-containing polyolefin compound, a compound having a polyolefin skeleton and an isocyanate group or a hydroxyl group is subjected to a urethanization reaction of a (meth) acrylate having a hydroxyl group or an isocyanate group, thereby producing a molecule in the molecule. (A) (Meth) acrylic group-containing polyolefin compound obtained by introducing a (meth) acrylic group into is preferable from the viewpoint of adhesiveness and toughness. (A) As a synthesis method of the (meth) acryl group-containing polyolefin compound, the following two-step reaction can be exemplified.
　１番目の例としての２段階反応は、以下の通りである。まず、ポリオレフィンポリオールに対して、１分子中にイソシアネート基を２個以上有する多官能イソシアネート化合物（以下、「多官能イソシアネート化合物」ということがある。）を、イソシアネート基量を水酸基量より多い割合で反応させて、イソシアネート基を有するウレタンプレポリマーを合成する。この時、ポリオレフィンポリオールの水酸基当量と多官能イソシアネート化合物のイソシアネート基当量の比を調整することで、分子量を調整することが可能である。次に、得られたウレタンプレポリマーにヒドロキシル基を有する（メタ）アクリレートとして、ヒドロキシアルキル（メタ）アクリレートや各種ポリオール由来の（メタ）アクリレートモノオール（１個の水酸基を残して、各種ポリオールを（メタ）アクリレート化したもの）を反応させて、残存するイソシアネート基を（メタ）アクリル基に転換することにより（Ａ）（メタ）アクリレート基含有ポリオレフィン化合物が得られる。ヒドロキシアルキル（メタ）アクリレートの具体例としては、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、イソシアネート基との反応性、光硬化性の点で、２－ヒドロキシエチルアクリレートが好ましい。この時、アルキルアルコールをイソシアネート基に反応させることで（メタ）アクリル基含有量を調整することが出来る。使用できる飽和アルコールとしては特に限定はなく、直鎖型、分岐型又は脂環型のアルキルアルコールを１種又は２種以上使用できる。 The two-step reaction as the first example is as follows. First, a polyfunctional isocyanate compound having two or more isocyanate groups in one molecule (hereinafter sometimes referred to as “polyfunctional isocyanate compound”) with respect to the polyolefin polyol is used in a proportion in which the amount of isocyanate groups is larger than the amount of hydroxyl groups. By reacting, a urethane prepolymer having an isocyanate group is synthesized. At this time, the molecular weight can be adjusted by adjusting the ratio of the hydroxyl group equivalent of the polyolefin polyol and the isocyanate group equivalent of the polyfunctional isocyanate compound. Next, as a (meth) acrylate having a hydroxyl group in the obtained urethane prepolymer, a hydroxyalkyl (meth) acrylate or a (meth) acrylate monool derived from various polyols (with one hydroxyl group remaining, various polyols ( A (meth) acrylate group-containing polyolefin compound is obtained by reacting (meth) acrylate) and converting the remaining isocyanate group to a (meth) acryl group. Specific examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,3-butanediol (meth) acrylate, Examples thereof include 1,4-butanediol (meth) acrylate, 1,6-hexanediol (meth) acrylate, 3-methylpentanediol (meth) acrylate and the like, and these can be used alone or in combination of two or more. Of these, 2-hydroxyethyl acrylate is preferred in terms of reactivity with isocyanate groups and photocurability. At this time, the (meth) acryl group content can be adjusted by reacting the alkyl alcohol with an isocyanate group. The saturated alcohol that can be used is not particularly limited, and one or more linear, branched, or alicyclic alkyl alcohols can be used.
　２番目の例としての２段階反応は以下の通りである。まず、ポリオレフィンポリオールに多官能イソシアネート化合物を、水酸基当量をイソシアネート基当量より多い割合で反応させて、鎖長延長した、水酸基を有するポリウレタン化合物を合成する。この時、ポリオレフィンポリオールの水酸基当量と多官能イソシアネート化合物のイソシアネート基当量の比を調整することで、分子量を調整することが可能である。この時、残存する水酸基に対して反応させるイソシアネート基含有（メタ）アクリレートの量を調整することで（メタ）アクリル基の含有量を調整することが出来る。イソシアネート基含有（メタ）アクリレートは、市販の化合物を使用しても良いし、ヒドロキシアルキル（メタ）アクリレートや各種ポリオール由来の（メタ）アクリレートモノオールとジイソシアネート化合物を反応させて片末端にイソシアネート基、もう一方の末端に（メタ）アクリル基を有するイソシアネート基含有（メタ）アクリレートを合成したものでも良い。イソシアネート基含有（メタ）アクリレートとしては、例えば、２－イソシアナトエチル（メタ）アクリレート、１，１－ビス（アクリロイルオキシメチル）エチルイソシアネート等があげられる。中でも、水酸基との反応性、及び光硬化性の点から、２－イソシアナトエチルアクリレートが好ましい。 The two-step reaction as the second example is as follows. First, a polyfunctional isocyanate compound is reacted with a polyolefin polyol at a ratio in which the hydroxyl group equivalent is larger than the isocyanate group equivalent to synthesize a polyurethane compound having a hydroxyl group with an extended chain length. At this time, the molecular weight can be adjusted by adjusting the ratio of the hydroxyl group equivalent of the polyolefin polyol and the isocyanate group equivalent of the polyfunctional isocyanate compound. At this time, the content of the (meth) acrylic group can be adjusted by adjusting the amount of the isocyanate group-containing (meth) acrylate to be reacted with the remaining hydroxyl group. As the isocyanate group-containing (meth) acrylate, a commercially available compound may be used, or a hydroxyalkyl (meth) acrylate or (meth) acrylate monool derived from various polyols and a diisocyanate compound are reacted to form an isocyanate group at one end, What synthesized the isocyanate group containing (meth) acrylate which has a (meth) acryl group in the other terminal may be used. Examples of the isocyanate group-containing (meth) acrylate include 2-isocyanatoethyl (meth) acrylate and 1,1-bis (acryloyloxymethyl) ethyl isocyanate. Of these, 2-isocyanatoethyl acrylate is preferred from the viewpoints of reactivity with hydroxyl groups and photocurability.
　上記２例の２段階反応は、いずれも、水酸基とイソシアネート基との反応であり、イソシアネート基に不活性な有機溶媒存在下、ジブチル錫ジラウレートやジブチル錫ジエチルヘキソエートのような一般的なウレタン化触媒を用いて、通常３０～１００℃、１～５時間程度継続して行われる。ウレタン化触媒の使用量は反応に供される原料の合計質量基準で、通常５０～５００ｐｐｍである。 The two-step reaction in the above two examples is a reaction between a hydroxyl group and an isocyanate group, and a general urethane such as dibutyltin dilaurate or dibutyltin diethylhexoate in the presence of an organic solvent inert to the isocyanate group. The reaction is usually carried out continuously at 30 to 100 ° C. for about 1 to 5 hours using the catalyst. The amount of the urethanization catalyst used is usually 50 to 500 ppm based on the total mass of the raw materials used for the reaction.
　上記のポリオレフィンポリオールとしては、数平均分子量で５００～５０００であることが好ましく、より好ましくは、１０００～４０００である。数平均分子量が５００より小さい場合には、（Ａ）（メタ）アクリル基含有ポリオレフィン化合物のウレタン結合が多くなりすぎるため、硬化時に黄変する可能性があり好ましくない。数平均分子量が５０００より大きい場合には、（メタ）アクリル基含ポリオレフィン化合物と（メタ）アクリル酸エステルとの相溶性が悪くなり好ましくない。本発明で用いられるポリオレフィンポリオールは、耐光性、透明性（非結晶性）及び作業性（液状）の点で水素添加１，２－ポリブタジエンジオール、水素添加ポリイソプレンジオールが好ましい。使用できる水素添加１，２－ポリブタジエンポリオールの市販品としては、具体的には、日本曹達株式会社製、製品名：ＧＩ‐１０００、ＧＩ‐２０００、ＧＩ‐３０００（数平均分子量は、それぞれ約１５００、約２１００、約３０００）を例示することが出来る。水素添加ポリイソプレンポリオールの市販品としては、具体的には、出光興産株式会社製、製品名エポール（数平均分子量は約２５００）を例示することが出来る。 The above polyolefin polyol preferably has a number average molecular weight of 500 to 5,000, more preferably 1,000 to 4,000. When the number average molecular weight is smaller than 500, the number of urethane bonds in the (A) (meth) acryl group-containing polyolefin compound is excessive, which may cause yellowing during curing, which is not preferable. When the number average molecular weight is greater than 5,000, the compatibility between the (meth) acrylic group-containing polyolefin compound and the (meth) acrylic acid ester is unfavorable. The polyolefin polyol used in the present invention is preferably hydrogenated 1,2-polybutadiene diol or hydrogenated polyisoprene diol from the viewpoint of light resistance, transparency (non-crystalline) and workability (liquid). Specific examples of commercially available hydrogenated 1,2-polybutadiene polyols that can be used include products manufactured by Nippon Soda Co., Ltd., product names: GI-1000, GI-2000, GI-3000 (number average molecular weights of about 1500 each). , About 2100, about 3000). Specific examples of commercially available hydrogenated polyisoprene polyols include Idemitsu Kosan Co., Ltd. product name Epol (number average molecular weight of about 2500).
　上記の多官能イソシアネート化合物としては、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、１，５－ナフチレ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、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、４，４’－ジシクロヘキシルジイソシアネート、１，３－ビス(イソシアナトメチル)シクロヘキサン、及びノルボルナンジイソシアネート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、又はジフェニルメタンジイソシアネートの水素添加物が好ましい。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。 Examples of the polyfunctional isocyanate compound include diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, and hydrogenated products thereof, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, And diisocyanate compounds such as tetramethylxylylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexyl diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and norbornane diisocyanate. Of these, isophorone diisocyanate or hydrogenated diphenylmethane diisocyanate is preferred 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.
　上記の（Ａ）（メタ）アクリル基含有ポリオレフィン化合物は、ポリオレフィンポリオールと多官能イソシアネート化合物を反応させることで、高分子量化させ、次いで残存する水酸基又はイソシアネート基に対して５０～１００ｍｏｌ％の（メタ）アクリル基を導入させることが好ましく、７０～１００ｍｏｌ％の（メタ）アクリル基を導入させることがより好ましい。（メタ）アクリル基を導入する割合が、５０ｍｏｌ％より少ない場合には、（メタ）アクリル基を導入できないポリオレフィンポリオールが存在することとなり得られる透明両面粘着シートの温度による貯蔵弾性率の変化が大きくなる可能性があり好ましくない。 The above (A) (meth) acryl group-containing polyolefin compound is made to have a high molecular weight by reacting a polyolefin polyol and a polyfunctional isocyanate compound, and then 50 to 100 mol% (meth ) It is preferable to introduce an acrylic group, and it is more preferable to introduce 70 to 100 mol% of a (meth) acrylic group. When the ratio of introducing the (meth) acrylic group is less than 50 mol%, there is a large change in storage elastic modulus depending on the temperature of the transparent double-sided PSA sheet that can be obtained by the presence of polyolefin polyol that cannot introduce the (meth) acrylic group. This is not preferable.
　上記（Ａ）（メタ）アクリル基含有ポリオレフィン化合物の含有量としては、光硬化性樹脂組成物中２０～５０質量％であることが好ましく、２２～４５質量％であることがより好ましく、２５～４０質量％であることがさらに好ましい。（Ａ）（メタ）アクリル基含有ポリオレフィン化合物の含有量が２０質量％より少ない場合には、得られる透明両面粘着シートの温度変化による貯蔵弾性率の変化が大きくなる可能性があり好ましくない。５０質量％より多い場合には、（Ｂ）（メタ）アクリル系モノマーとの相溶性が悪くなる可能性があり好ましくない。 The content of the (A) (meth) acrylic group-containing polyolefin compound is preferably 20 to 50% by mass, more preferably 22 to 45% by mass in the photocurable resin composition, and more preferably 25 to More preferably, it is 40 mass%. When the content of the (A) (meth) acrylic group-containing polyolefin compound is less than 20% by mass, there is a possibility that a change in storage elastic modulus due to a temperature change of the obtained transparent double-sided PSA sheet is increased, which is not preferable. When the amount is more than 50% by mass, the compatibility with the (B) (meth) acrylic monomer may be deteriorated, which is not preferable.
　上記（Ｂ）（メタ）アクリル系モノマーとは、分子中に一つ以上の（メタ）アクリル基を有するアクリル系モノマー又はメタクリル系モノマーを言う。使用できる（Ｂ）（メタ）アクリル系モノマーとしては、特に限定はなく、（メタ）アクリル基を有する、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。 The above (B) (meth) acrylic monomer means an acrylic monomer or methacrylic monomer having one or more (meth) acrylic groups in the molecule. The (B) (meth) acrylic monomer that can be used is not particularly limited, and a monofunctional or polyfunctional photopolymerizable monomer having a (meth) acryl group may be used alone or in combination of two or more. Can be used.
　具体的な（Ｂ）（メタ）アクリル系モノマーとしては、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、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、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、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、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）アクリレート等のヒドロキシル基含有（メタ）アクリレート、（メタ）アクリル酸、イタコン酸、無水マレイン酸等のカルボキシル基含有（メタ）アクリレートが上げられる。中でも、粘着性、反応性、透明性の観点から、アルキル（メタ）アクリレート、及び環状アルキル（メタ）アクリレートを用いることが好ましく、シクロヘキシルアクリレート及び２－エチルヘキシルアクリレートを用いることが特に好ましい。また、粘着性、反応性の観点から単官能性アクリルモノマーを２種以上組み合わせて用いることが好ましい。 Specific examples of the (B) (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and tert-butyl (meth). Alkyl such as acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-hexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate (Meth) acrylate, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, norbornanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, disi Cycloalkyl (meth) acrylates such as lopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, ethoxyethyl Alkoxyalkyl (meth) acrylates such as (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethoxyethyl (meth) acrylate, 2-ethoxyethoxyethyl (meth) acrylate, methoxydiethylene glycol ( Alkoxy (poly) alkylene glycols such as meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate Fluorinated alkyl (meth) acrylates such as (meth) acrylate and octafluoropentyl (meth) acrylate, dialkylaminoalkyl (meta) such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate ) 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, hydroxypivalic acid ester neo Pentyl glycol di (meth) acrylate, 1,3-bis (hydroxyethyl) -5,5-dimethylhydantoin di (meth) acrylate, α, ω-di (meth) acrylate Bisdiethylene glycol phthalate, trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, Polyfunctional (meth) acrylates such as 1,6-hexanediol di (meth) acrylate, diacryloxyethyl phosphate, dipentaerythritol trihydroxy (meth) acrylate, pentaerythritol tetra (meth) acrylate, acrylamide and dimethylacrylamide , Acrylamide derivatives such as diethylacrylamide, (meth) acryloylmorpholine, and epoxy group containing glycidyl (meth) acrylate (meta ) Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,3-butanediol (meth) acrylate, 1,4-butanediol (meth) Hydroxyl group-containing (meth) acrylates such as acrylate, 1,6-hexanediol (meth) acrylate, 3-methylpentanediol (meth) acrylate, carboxyl groups such as (meth) acrylic acid, itaconic acid, maleic anhydride ( (Meth) acrylate is raised. Of these, alkyl (meth) acrylates and cyclic alkyl (meth) acrylates are preferably used from the viewpoints of tackiness, reactivity, and transparency, and cyclohexyl acrylate and 2-ethylhexyl acrylate are particularly preferably used. In addition, it is preferable to use a combination of two or more monofunctional acrylic monomers from the viewpoint of adhesiveness and reactivity.
　上記（Ｂ）（メタ）アクリル系モノマーの含有量としては、光硬化性樹脂組成物中に４９．８～７９．８質量％であることが好ましく、５５～７８質量％であることがより好ましく、６０～７５質量％であることがさらに好ましい。（Ｂ）（メタ）アクリル系モノマーの含有量が４９．８質量％より少ない場合には、（Ａ）（メタ）アクリル基含有ポリオレフィン化合物との相溶性が悪くなる可能性があり好ましくない。（Ｂ）（メタ）アクリル系モノマーの含有量が７９．８質量％より多い場合には、得られる透明両面粘着シートの温度による貯蔵弾性率の変化が大きくなる可能性があり好ましくない。 The content of the (B) (meth) acrylic monomer is preferably 49.8 to 79.8% by mass and more preferably 55 to 78% by mass in the photocurable resin composition. 60 to 75% by mass is more preferable. When the content of the (B) (meth) acrylic monomer is less than 49.8% by mass, the compatibility with the (A) (meth) acrylic group-containing polyolefin compound may be unfavorable. When the content of the (B) (meth) acrylic monomer is more than 79.8% by mass, the change in the storage elastic modulus depending on the temperature of the obtained transparent double-sided PSA sheet is unfavorable.
　上記（Ｃ）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又は過酸化物系光重合開始剤等が挙げられる。 Examples of the (C) photopolymerization initiator include carbonyl photopolymerization initiator, sulfide photopolymerization initiator, quinone photopolymerization initiator, azo photopolymerization initiator, sulfochloride photopolymerization initiator, and thioxanthone. System photopolymerization initiator or peroxide photopolymerization initiator.
　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又は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、過酸化ベンゾイル又はジ－ｔ－ブチルペルオキシド等が挙げられる。（Ｃ）光重合開始剤としては、得られる光硬化性樹脂組成物中における溶解性の点から、カルボニル系光重合開始剤を用いることが好ましく、１－ヒドロキシシクロヘキシルフェニルケトンを用いることが特に好ましい。これらの（Ｃ）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. (C) As the photopolymerization initiator, it is preferable to use a carbonyl-based photopolymerization initiator, and it is particularly preferable to use 1-hydroxycyclohexyl phenyl ketone from the viewpoint of solubility in the resulting photocurable resin composition. . These (C) photoinitiators are used individually or in combination of 2 or more types.
　（Ｃ）光重合開始剤の含有量は、光硬化性及び得られる透明両面粘着シートの強度と粘着性のバランスの点から、光硬化性樹脂組成物中に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。（Ｃ）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透明両面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。 (C) The content of the photopolymerization initiator is 0.2 to 5% by mass in the photocurable resin composition in terms of the balance between photocurability and the strength and adhesiveness of the obtained transparent double-sided PSA sheet. It is preferably 0.5 to 3% by mass, more preferably 0.8 to 2% by mass. (C) When content of a photoinitiator is less than 0.2 mass%, photocuring tends to become inadequate, and when it exceeds 5 mass%, the adhesiveness of the transparent double-sided adhesive sheet obtained will fall. It tends to be unfavorable.
　本発明の光硬化性樹脂組成物には、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。中でも耐光性の点から不飽和二重結合が少ない脂環型粘着付与樹脂が好ましい。具体的な脂環型粘着付与樹脂としては、ロジンおよびロジン誘導体の水素添加樹脂、ポリテルペン樹脂の水素添加樹脂、芳香族変性テルペン樹脂の水素添加樹脂、テルペンフェノール樹脂の水素添加樹脂、クマロン・インデン樹脂の水素添加物、脂環族系石油樹脂の水素添加樹脂、芳香族系石油樹脂の水素添加樹脂、脂肪族芳香族共重合系石油樹脂の水素添加樹脂、ジシクロペンタジエン系石油樹脂の水素添加樹脂、ジシクロペンタジエン芳香族共重合系の水素添加樹脂、スチレンまたは置換スチレンの低分子量重合体の水素添加樹脂が例示される。脂環型粘着付与樹脂は、単独で又は２種類以上を組み合わせて使用できる。粘着付与樹脂の添加量としては、光硬化性樹脂組成物１００質量部に対して、０～２０質量部であることが好ましく、０～１５質量部であることがより好ましく、０～１０質量部であることがさらに好ましい。粘着付与樹脂の添加量が光硬化性樹脂組成物１００質量部に対して、２０質量部を超えると得られる粘着シートの透明性が悪くなりすぎる傾向にあり好ましくない。 In the photocurable resin composition of the present invention, if necessary, a tackifier resin may be added as long as the transparency is not lowered in order to improve the adhesive strength of the obtained pressure-sensitive adhesive sheet. Examples of tackifier 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 ( C9-based) and other petroleum resins, as well as styrene-based resins, phenol-based resins, xylene resins, and the like. Of these, alicyclic tackifying resins with few unsaturated double bonds are preferred from the viewpoint of light resistance. Specific alicyclic tackifier resins include rosin and rosin derivative hydrogenated resins, polyterpene resin hydrogenated resins, aromatic modified terpene resin hydrogenated resins, terpene phenol resin hydrogenated resins, coumarone and indene resins. Hydrogenated resin, alicyclic petroleum resin hydrogenated resin, aromatic petroleum resin hydrogenated resin, aliphatic aromatic copolymer petroleum resin hydrogenated resin, dicyclopentadiene petroleum resin hydrogenated resin And a hydrogenated resin of a dicyclopentadiene aromatic copolymer system and a hydrogenated resin of a low molecular weight polymer of styrene or substituted styrene. The alicyclic tackifying resin can be used alone or in combination of two or more. The addition amount of the tackifying resin is preferably 0 to 20 parts by mass, more preferably 0 to 15 parts by mass, and 0 to 10 parts by mass with respect to 100 parts by mass of the photocurable resin composition. More preferably. If the addition amount of the tackifying resin exceeds 20 parts by mass with respect to 100 parts by mass of the photocurable resin composition, the transparency of the obtained adhesive sheet tends to be too bad, which is not preferable.
　また、本発明の光硬化性樹脂組成物には、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、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 photocurable resin composition of the present invention may contain various known additives as long as the transparency is not impaired. Additives include plasticizers, surface lubricants, softeners, antioxidants, anti-aging agents, light stabilizers, UV absorbers, polymerization inhibitors, light stabilizers such as benzotriazoles, phosphate esters, and others Flame retardants, and antistatic agents such as surfactants.
　本発明の光硬化性樹脂組成物を塗工した際の厚さは０．０１～３ｍｍの範囲であり、より好ましくは０．０１５～１ｍｍであり、さらに好ましくは、０．０２～０．５ｍｍである。塗工する厚さが０．０１ｍｍより小さくなると、膜厚を均一に塗布することが難しく、膜厚にムラが生じる可能性があり好ましくない。厚さが３ｍｍより大きい場合には、紫外線の透過が困難になり硬化性が悪くなる可能性があり好ましくない。光硬化性樹脂組成物を光透過性フィルム（Ｙ）上に塗布する方法はグラビヤロールコーター、リバースロールコーター、キスロールコーター、ディップロールコーター、バーコーター、ナイフコーター、スプレーコーター、コンマコーター又はダイレクトコーターなど特に制限されず、公知の方法を用いることができる。 The thickness when the photocurable resin composition of the present invention is applied is in the range of 0.01 to 3 mm, more preferably 0.015 to 1 mm, and still more preferably 0.02 to 0.5 mm. It is. If the coating thickness is less than 0.01 mm, it is difficult to uniformly apply the film thickness, which may cause unevenness in the film thickness. When the thickness is larger than 3 mm, it is not preferable because it is difficult to transmit ultraviolet rays and the curability may be deteriorated. The method of applying the photocurable resin composition on the light transmissive film (Y) is a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray coater, comma coater or direct coater. It does not restrict | limit in particular, A well-known method can be used.
　光透過性フィルム（Ｙ）上に光硬化性樹脂組成物を塗工して形成された樹脂層に、光透過性フィルム（Ｚ）をラミネートする方法としては、ローラーを用いる方法など公知の方法を用いることができる。 As a method of laminating the light transmissive film (Z) on the resin layer formed by coating the light curable resin composition on the light transmissive film (Y), a known method such as a method using a roller is used. Can be used.
　本発明では、（３）ラミネートにより得られた積層体に、ブラックライトを１０～３００ｍＪ／ｃｍ２の照射量で照射する工程（以下、「（３）の工程」という）を有する。ブラックライトとは、波長が３００～４００ｎｍの近紫外の光だけを放出するランプのことである。使用できるブラックライトとしては、波長３６５ｎｍにおける光強度が０．２０～１０ｍＷ／ｃｍ２の範囲のものであれば、特に限定はなく、市販のものを用いることが出来る。波長３６５ｎｍにおける光強度が０．２０～１０ｍＷ／ｃｍ２であることが好ましく、０．５～５ｍＷ／ｃｍ２であることがより好ましい。光強度が０．２０ｍＷ／ｃｍ２より小さい場合には、照射時間が長くなりすぎるため、生産性が悪くなる可能性があり好ましくない。１０ｍＷ／ｃｍ２より大きい場合には、得られる透明両面粘着シートの温度変化による貯蔵弾性率の変化が大きくなる可能性があり好ましくない。ブラックライトの照射量は、１０～３００ｍＪ／ｃｍ２であり、より好ましい照射量は、１５～２００ｍＪ／ｃｍ２であり、さらに好ましい照射量は、２０～１００ｍＪ／ｃｍ２である。ブラックライトの照射量が、１０ｍＪ／ｃｍ２より小さい場合には、得られる透明両面粘着シートの温度による貯蔵弾性率の変化が大きくなる。ブラックライトの照射量が、３００ｍＪ／ｃｍ２より大きい場合には、照射時間が長くなりすぎるため、生産性が悪くなる。本発明では、ラミネートにより得られた積層体の光硬化性樹脂組成物が塗工されている平面に対して、略垂直な角度で、ブラックライトが照射されることが好ましい。また、ブラックライトの照射は、積層体の片面から、又は両面からのどちらでも構わない。 In the present invention, there is (3) a step of irradiating the laminate obtained by laminating with black light at an irradiation dose of 10 to 300 mJ / cm 2 (hereinafter referred to as “step (3)”). Black light is a lamp that emits only near-ultraviolet light having a wavelength of 300 to 400 nm. The black light that can be used is not particularly limited as long as the light intensity at a wavelength of 365 nm is in the range of 0.20 to 10 mW / cm 2 , and a commercially available one can be used. The light intensity at a wavelength of 365 nm is preferably 0.20 to 10 mW / cm 2 , and more preferably 0.5 to 5 mW / cm 2 . When the light intensity is less than 0.20 mW / cm 2 , the irradiation time becomes too long, so that productivity may be deteriorated. When it is larger than 10 mW / cm 2, the change in storage elastic modulus due to temperature change of the obtained transparent double-sided PSA sheet is likely to be large, which is not preferable. The irradiation amount of black light is 10 to 300 mJ / cm 2 , the more preferable irradiation amount is 15 to 200 mJ / cm 2 , and the further preferable irradiation amount is 20 to 100 mJ / cm 2 . When the irradiation amount of black light is smaller than 10 mJ / cm 2 , the change in storage elastic modulus depending on the temperature of the obtained transparent double-sided PSA sheet becomes large. When the irradiation amount of the black light is larger than 300 mJ / cm 2 , the irradiation time becomes too long, so that the productivity is deteriorated. In the present invention, it is preferable that the black light is irradiated at an angle substantially perpendicular to the plane on which the photocurable resin composition of the laminate obtained by lamination is applied. The black light may be irradiated from one side or both sides of the laminate.
　本発明では、（３）の工程の後、（４）ブラックライトを照射した積層体に、活性エネルギー線を５００～５０００ｍＪ／ｃｍ２の照射量で照射する工程（以下、「（４）の工程」という）を有する。活性エネルギー線とは、電子線、Ｘ線、紫外線、低波長領域の可視光等エネルギーの高い電子線若しくは電磁波の総称である。使用できる活性エネルギー線としては、波長３６５ｎｍにおける光強度が２０～５００ｍＷ／ｃｍ２の範囲のものが好ましく、高圧水銀ランプ、メタルハライドランプ等が光源として例示される。活性エネルギー線の照射量としては、５００～５０００ｍＪ／ｃｍ２の範囲であり、より好ましくは、６００～３０００ｍＪ／ｃｍ２の範囲であり、さらに好ましくは、７００～２０００ｍＪ／ｃｍ２の範囲である。活性エネルギー線の照射量が５００ｍＪ／ｃｍ２より少ない場合には、得られる透明両面粘着シートの残存モノマーが多くなる。活性エネルギー線の照射量が５０００ｍＪ／ｃｍ２より多い場合には、照射時間が長くなりすぎるため、生産性が悪くなる。本発明では、光硬化性樹脂組成物が塗工されている平面に対して、略垂直な角度で、活性エネルギー線が照射されることが好ましい。また、活性エネルギー線の照射は、積層体の片面から、又は両面からのどちらでも構わない。 In the present invention, after the step (3), (4) a step of irradiating the laminate irradiated with black light with active energy rays at an irradiation dose of 500 to 5000 mJ / cm 2 (hereinafter referred to as “step (4)”. "). The active energy ray is a general term for an electron beam, an X-ray, an ultraviolet ray, a high-energy electron beam such as visible light in a low wavelength region, or an electromagnetic wave. As the active energy ray that can be used, those having a light intensity in the range of 20 to 500 mW / cm 2 at a wavelength of 365 nm are preferable, and a high pressure mercury lamp, a metal halide lamp and the like are exemplified as a light source. The irradiation dose of the active energy ray, in the range of 500 ~ 5000mJ / cm 2, more preferably in the range of 600 ~ 3000mJ / cm 2, more preferably in the range of 700 ~ 2000mJ / cm 2. When the irradiation amount of active energy rays is less than 500 mJ / cm 2 , the residual monomer of the obtained transparent double-sided PSA sheet increases. When the irradiation amount of the active energy ray is more than 5000 mJ / cm 2 , the irradiation time becomes too long, so that the productivity is deteriorated. In this invention, it is preferable that an active energy ray is irradiated at an angle substantially perpendicular to the plane on which the photocurable resin composition is applied. Further, the active energy ray may be irradiated from one side or both sides of the laminate.
　本発明の透明両面粘着シートの製造方法より得られる透明両面粘着シートは、光硬化性樹脂組成物を硬化させて得られる粘着シート層（つまり、両方の光透過性フィルムを剥離させた状態の透明両面粘着シート）について、（ａ）４０℃、１Ｈｚの条件で動的粘弾性を測定した際の貯蔵弾性率と（ｂ）１００℃、１Ｈｚの条件で動的粘弾性を測定した際の貯蔵弾性率が、式（イ）：
Figure JPOXMLDOC01-appb-M000004
 を満たすものである。透明両面粘着シートは、１＜（ａ）／（ｂ）＜１．４５の条件を満たすことが好ましく、１＜（ａ）／（ｂ）＜１．４の条件を満たすことがより好ましい。透明両面粘着シートが（ａ）／（ｂ）≧１．５の場合には、得られる透明両面粘着シートの温度変化による貯蔵弾性率の変化が大きいことから、高温時の粘着剤の凝集力が低くなり、１≧（ａ）／（ｂ）の場合には、透明両面粘着シートが変質している可能性があることから好ましくない。 The transparent double-sided pressure-sensitive adhesive sheet obtained from the method for producing a transparent double-sided pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet layer obtained by curing a photocurable resin composition (that is, transparent in a state where both light-transmitting films are peeled off). (Double-sided PSA sheet) (a) Storage elastic modulus when dynamic viscoelasticity is measured under conditions of 40 ° C. and 1 Hz and (b) Storage elastic modulus when dynamic viscoelasticity is measured under conditions of 100 ° C. and 1 Hz The rate is the formula (I):
Figure JPOXMLDOC01-appb-M000004
 It satisfies. The transparent double-sided PSA sheet preferably satisfies the condition 1 <(a) / (b) <1.45, and more preferably satisfies the condition 1 <(a) / (b) <1.4. When the transparent double-sided pressure-sensitive adhesive sheet is (a) / (b) ≧ 1.5, the change in storage elastic modulus due to temperature change of the obtained transparent double-sided pressure-sensitive adhesive sheet is large. In the case of 1 ≧ (a) / (b), the transparent double-sided PSA sheet may be altered, which is not preferable.
　本発明の透明両面粘着シートの動的粘弾性を測定した際の貯蔵弾性率が、式（イ）を満たすためには、（１）の工程及び（２）の工程により、光透過性フィルム（Ｙ）上に光硬化性樹脂組成物の樹脂層を形成し、樹脂層の光透過性フィルム（Ｙ）と接している面とは反対側の面に光透過性フィルム（Ｚ）をラミネートすることで得られた積層体に対して、（３）の工程及び（４）の工程を経て、光硬化性樹脂組成物を硬化させることが必要である。上で述べた、活性エネルギー線の光源である高圧水銀ランプ、メタルハライドランプは、照度が高く、波長が４００ｎｍ以上の光も含まれるため、積層体を加熱してしまう。一方、ブラックライトは、照度が低く、４００ｎｍ以上の光がほとんど含まれないので、積層体は加熱されない。（４）の工程に先立って、（３）の工程により、光硬化性樹脂組成物を低照度、低温で硬化させれば、高分子量でゲル分率の高いポリマーを得ることができ、その結果、高温での貯蔵弾性率の低下が少ない透明両面粘着シートを得ることができる。さらに、（３）の工程の後に（４）の工程を行うことで残存モノマーを少なくすることができる。 In order for the storage elastic modulus at the time of measuring the dynamic viscoelasticity of the transparent double-sided PSA sheet of the present invention to satisfy the formula (A), the light-transmitting film ( Y) forming a resin layer of the photocurable resin composition on the laminate, and laminating the light transmissive film (Z) on the surface of the resin layer opposite to the surface in contact with the light transmissive film (Y). It is necessary to harden the photocurable resin composition through the steps (3) and (4) with respect to the laminate obtained in (1). The high-pressure mercury lamp and metal halide lamp which are the light sources of the active energy rays described above have high illuminance and include light having a wavelength of 400 nm or more, and thus heat the laminate. On the other hand, the black light has a low illuminance and contains almost no light of 400 nm or more, so the laminate is not heated. Prior to the step (4), if the photocurable resin composition is cured at low illuminance and low temperature by the step (3), a polymer having a high molecular weight and a high gel fraction can be obtained. A transparent double-sided pressure-sensitive adhesive sheet with little decrease in storage modulus at high temperatures can be obtained. Furthermore, residual monomer can be reduced by performing the process (4) after the process (3).
　本発明の透明両面粘着シートの製造方法では、前記光硬化性樹脂組成物を硬化させて得られる粘着シート層（つまり、両方の光透過性フィルムを剥離させた状態の透明両面粘着シート）の質量に対して、残存したモノマー量（例えば、（メタ）アクリル系モノマーの量）が１～５００ｗｔｐｐｍであることが好ましく、より好ましくは、１～４００ｗｔｐｐｍであり、さらに好ましくは、１～３００ｗｔｐｐｍである。前記光硬化性樹脂組成物を硬化させて得られる粘着シート層の質量に対して、残存したモノマー量が５００ｗｔｐｐｍより多い場合には、臭気の問題があり好ましくない。 In the method for producing a transparent double-sided pressure-sensitive adhesive sheet of the present invention, the mass of the pressure-sensitive adhesive sheet layer obtained by curing the photocurable resin composition (that is, the transparent double-sided pressure-sensitive adhesive sheet in a state where both light-transmitting films are peeled off). In contrast, the amount of the remaining monomer (for example, the amount of the (meth) acrylic monomer) is preferably 1 to 500 wtppm, more preferably 1 to 400 wtppm, and still more preferably 1 to 300 wtppm. When the amount of the remaining monomer is more than 500 wtppm with respect to the mass of the pressure-sensitive adhesive sheet layer obtained by curing the photocurable resin composition, there is an odor problem, which is not preferable.
　本発明の透明両面粘着シートの製造方法により得られる透明両面粘着シートは、光学用途に用いられる光学用透明両面粘着シートである。より具体的には、光学部材を貼り合わせる用途（光学部材貼り合わせ用）や光学製品の製造用途などに用いられる。光学部材としては、光学的特性を有する部材であれば、特に限定されないが、例えば、画像表示装置、タッチパネルを構成する部材又はこれらの機器に用いられる部材が挙げられ、例えば、偏光板、位相差板、光学補償フィルム、輝度向上フィルム、導光板、反射フィルム、反射防止フィルム、透明導電フィルム、意匠フィルム、装飾フィルム、表面保護フィルム、プリズム、レンズ、カラーフィルター、透明基板、さらにはこれらが積層されている部材が挙げられる。 The transparent double-sided PSA sheet obtained by the method for producing a transparent double-sided PSA sheet of the present invention is an optical transparent double-sided PSA sheet used for optical applications. More specifically, it is used for applications for bonding optical members (for optical member bonding), optical product manufacturing applications, and the like. Although it will not specifically limit if it is a member which has an optical characteristic as an optical member, For example, the member used for an image display apparatus, a touchscreen, or these apparatuses is mentioned, For example, a polarizing plate, phase difference, etc. Plate, optical compensation film, brightness enhancement film, light guide plate, reflection film, antireflection film, transparent conductive film, design film, decorative film, surface protection film, prism, lens, color filter, transparent substrate, and these are laminated The member which has been mentioned.
　本発明の透明両面粘着シートは、とりわけ、タッチパネル、画像表示装置を構成する部材の貼り合せに用いられることが好ましい。なお、画像表示装置としては、液晶表示装置、有機ＥＬ（エレクトロルミネッセンス）表示装置、ＰＤＰ（プラズマディスプレイパネル）、電子ペーパーなどが挙げられる。 The transparent double-sided pressure-sensitive adhesive sheet of the present invention is particularly preferably used for bonding members constituting a touch panel and an image display device. Examples of the image display device include a liquid crystal display device, an organic EL (electroluminescence) display device, a PDP (plasma display panel), and electronic paper.
　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.
（参考例）光硬化性樹脂組成物の作製
　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１４モル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、水酸基価２５ｍｇＫＯＨ／ｇ）を１５モル仕込み、６０℃で反応させた。残存イソシアネート基が０．１モル％以下となった時点で、２－イソシアネートエチルアクリレート２モルを仕込み、７０℃まで昇温して２時間反応をさせ、ＩＲ測定（赤外分光光度計、パーキンエルマー社製）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、（Ａ）（メタ）アクリル基含有ポリオレフィン化合物（重量平均分子量７０，０００）を得た。 (Reference Example) Production of photocurable resin composition A four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooling tube with a drying tube was charged with 14 mol of isophorone diisocyanate and hydroxyl-terminated hydrogenated polybutadiene (manufactured by Nippon Soda Co., Ltd.). Product name: GI-3000, hydroxyl value 25 mg KOH / g) was charged at 15 mol and reacted at 60 ° C. When the residual isocyanate group became 0.1 mol% or less, 2 mol of 2-isocyanatoethyl acrylate was added, the temperature was raised to 70 ° C., the reaction was performed for 2 hours, and IR measurement (infrared spectrophotometer, Perkin Elmer) After confirming that the isocyanate group had disappeared by the company), the reaction was terminated, and (A) (meth) acryl group-containing polyolefin compound (weight average molecular weight 70,000) was obtained.
　その後、得られた（Ａ）（メタ）アクリル基含有ポリオレフィン化合物３０質量部に対して、シクロヘキシルアクリレート３０質量部、２－エチルヘキシルアクリレート４０質量部、（Ｃ）光重合開始剤イルガキュアー１８４（ＢＡＳＦ社製）１質量部を配合し、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樹脂組成物を調製した。 Thereafter, 30 parts by mass of the (A) (meth) acrylic group-containing polyolefin compound obtained, 30 parts by mass of cyclohexyl acrylate, 40 parts by mass of 2-ethylhexyl acrylate, (C) photopolymerization initiator Irgacure 184 (BASF Corporation) (Product made) 1 mass part was mix | blended and the uniform photocurable resin composition was prepared by mixing using a disper at room temperature.
実施例１及び２、比較例１～４
　表１に示す各条件で、調製した光硬化性樹脂組成物を、アプリケーターを用いて５０μｍ厚の剥離ＰＥＴフィルム（三井化学東セロ株式会社製、ＰＥＴ－Ｏ２－５０－ＢＵ）上に塗布し、上面を５０μｍ厚の剥離ＰＥＴフィルム（三井化学東セロ株式会社製、ＰＥＴ－ＯＶ－５０－ＢＵ）で、ゴムローラーを用いてラミネートした後、ブラックライト（東芝ライテック株式会社製、商品名：ＦＨＦ３２ＢＬＢ－Ｔ、波長３６５ｎｍにおける光強度が０．５ｍＷ／ｃｍ２）を照射し、その後にメタルハライドランプ（アイグラフィックス株式会社製、商品名：Ｍ０４－Ｌ４１、波長３６５ｎｍにおける光強度が７０ｍＷ／ｃｍ２）を照射して、光硬化性樹脂組成物の硬化を行ない、透明両面粘着シートを得た。 Examples 1 and 2 and Comparative Examples 1 to 4
Under the conditions shown in Table 1, the prepared photocurable resin composition was applied onto a 50 μm-thick release PET film (PET-O2-50-BU, manufactured by Mitsui Chemical Tosero Co., Ltd.) using an applicator. Was laminated with a rubber roller using a peeled PET film (Mitsui Chemicals Tosero Co., Ltd., PET-OV-50-BU) having a thickness of 50 μm, and then black light (manufactured by Toshiba Lighting & Technology Co., Ltd., trade name: FHF32BLB-T, Irradiate with a light intensity at a wavelength of 365 nm of 0.5 mW / cm 2 , and then irradiate a metal halide lamp (product name: M04-L41, manufactured by Eye Graphics Co., Ltd., light intensity at a wavelength of 365 nm of 70 mW / cm 2 ). Then, the photocurable resin composition was cured to obtain a transparent double-sided PSA sheet.
（貯蔵弾性率の測定）
　貯蔵弾性率の測定は、ティ・エイ・インスツルメント社製、動的粘弾性測定装置ＡＲＥＳを用いて剪断モード（１Ｈｚ）にて行った。剥離ＰＥＴフィルムを除去した透明両面粘着シートを５枚積層したものを、７．９ｍｍφの抜き刃で打ち抜いて試験片とした。－３０～１５０℃の測定範囲で昇温速度５℃／分で測定を行い、このうち（ａ）４０℃、１Ｈｚにおける貯蔵弾性率と（ｂ）１００℃、１Ｈｚにおける貯蔵弾性率から（ａ）／（ｂ）を計算し、表１に示す。 (Measurement of storage modulus)
The storage elastic modulus was measured in a shear mode (1 Hz) using a dynamic viscoelasticity measuring device ARES manufactured by TI Instruments. A laminate of five transparent double-sided PSA sheets from which the peeled PET film had been removed was punched with a 7.9 mmφ punching blade to obtain a test piece. Measured at a rate of temperature increase of 5 ° C./min in the measurement range of −30 to 150 ° C., among these (a) storage elastic modulus at 40 ° C. and 1 Hz and (b) storage elastic modulus at 100 ° C. and 1 Hz (a) / (B) was calculated and shown in Table 1.
（残存モノマーの測定）
　粘着シート層（両方の光透過性フィルムを剥離させた状態の透明両面粘着シート）の固形分０．５ｇにおける残存モノマー量の定量は、ガスクロマトグラフィーにより行なった。結果を表１に示す。 (Measurement of residual monomer)
The amount of residual monomer at a solid content of 0.5 g of the pressure-sensitive adhesive sheet layer (transparent double-sided pressure-sensitive adhesive sheet with both light-transmitting films peeled) was quantified by gas chromatography. The results are shown in Table 1.
（ガスクロマトグラフィー測定）
　剥離ＰＥＴフィルムを剥離した透明両面粘着シート約０．５ｇにテトラヒドロフラン５０ｍｌを添加した後、室温（２３℃）で３日間放置して粘着剤（または粘着剤層）中のモノマーを抽出した。このモノマーを抽出したテトラヒドロフラン１μＬをガスクロマトグラフィー（島津製作所株式会社製、ＧＣ－２０１０　ＳＨＩＭＡＤＺＵ）に注入して分析を行った。結果を表１に示す。 (Gas chromatography measurement)
After adding 50 ml of tetrahydrofuran to about 0.5 g of the transparent double-sided pressure-sensitive adhesive sheet from which the peeled PET film was peeled, the monomer in the pressure-sensitive adhesive (or pressure-sensitive adhesive layer) was extracted by leaving it at room temperature (23 ° C.) for 3 days. 1 μL of tetrahydrofuran extracted from this monomer was injected into a gas chromatography (Shimadzu Corporation, GC-2010 SHIMADZU) for analysis. The results are shown in Table 1.
　測定条件は、
　カラム；ＺＢ－５
　カラム温度；５０℃（１分間維持）→２０℃／分で上昇→２５０℃（２５０℃に到達すると５分間維持）
　検出器；ＦＩＤ The measurement conditions are
Column; ZB-5
Column temperature: 50 ° C. (maintained for 1 minute) → increased at 20 ° C./minute → 250 ° C. (maintained for 5 minutes when reaching 250 ° C.)
Detector; FID
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表１の結果から明らかなように、実施例の透明両面粘着シートの製造方法は、比較例と比べて、温度変化によって貯蔵弾性率の変化が少なく、且つ、残存モノマーが少なく優れていることがわかる。 As is clear from the results in Table 1, the transparent double-sided pressure-sensitive adhesive sheet production method of the example is superior to the comparative example in that the change in storage elastic modulus is small due to temperature change and the residual monomer is small. Recognize.
　本発明の光硬化性樹脂組成物を硬化させて得られる透明両面粘着シートの製造方法は、温度変化によって貯蔵弾性率の変化が少なく、且つ残存モノマーが少ない、厚膜のシートを得ることが出来、粘着シートの製造方法として有用であり、当該製造方法により得られる透明両面粘着シートは、タッチパネル、画像表示装置に好適に使用される。 The method for producing a transparent double-sided pressure-sensitive adhesive sheet obtained by curing the photocurable resin composition of the present invention can provide a thick film sheet with little change in storage elastic modulus due to temperature change and little residual monomer. The transparent double-sided PSA sheet that is useful as a method for producing a PSA sheet is suitably used for touch panels and image display devices.

Claims (8)

  1. 光硬化性樹脂組成物を硬化させて得られる透明両面粘着シートの製造方法であって、
    （１）光透過性フィルム（Ｙ）上に光硬化性樹脂組成物を塗工し、厚さ０．０１～３ｍｍの樹脂層を形成する工程と、
    （２）形成した樹脂層に光透過性フィルム（Ｚ）をラミネートする工程と、
    （３）ラミネートにより得られた積層体に、ブラックライトを１０～３００ｍＪ／ｃｍ２の照射量で照射する工程と、
    （４）ブラックライトを照射した積層体に、活性エネルギー線を５００～５０００ｍＪ／ｃｍ２の照射量で照射する工程
    とを有し、
    両方の光透過性フィルムを剥離させた状態の透明両面粘着シートについて、（ａ）４０℃、１Ｈｚの条件で動的粘弾性を測定した際の貯蔵弾性率と（ｂ）１００℃、１Ｈｚの条件で動的粘弾性を測定した際の貯蔵弾性率が、式（イ）：
    Figure JPOXMLDOC01-appb-M000001
     を満たす透明両面粘着シートの製造方法。     A method for producing a transparent double-sided PSA sheet obtained by curing a photocurable resin composition,
    (1) applying a photocurable resin composition on the light transmissive film (Y) to form a resin layer having a thickness of 0.01 to 3 mm;
    (2) Laminating a light transmissive film (Z) on the formed resin layer;
    (3) irradiating the laminate obtained by lamination with black light at an irradiation dose of 10 to 300 mJ / cm 2 ;
    (4) a step of irradiating an active energy ray at a dose of 500 to 5000 mJ / cm 2 to the laminate irradiated with black light;
    About the transparent double-sided pressure-sensitive adhesive sheet in a state where both light-transmitting films are peeled off, (a) storage elastic modulus when dynamic viscoelasticity is measured under conditions of 40 ° C. and 1 Hz, and (b) conditions of 100 ° C. and 1 Hz The storage elastic modulus when dynamic viscoelasticity is measured with the formula (A):
    Figure JPOXMLDOC01-appb-M000001
     The manufacturing method of the transparent double-sided adhesive sheet which satisfy | fills.
  2. 光硬化性樹脂組成物が、（Ａ）（メタ）アクリル基含有ポリオレフィン化合物２０～５０質量％、（Ｂ）（メタ）アクリル系モノマー４９．８～７９．８質量％、及び（Ｃ）光重合開始剤０．２～５質量％を含む請求項１記載の透明両面粘着シートの製造方法。 The photocurable resin composition comprises (A) (meth) acrylic group-containing polyolefin compound 20 to 50% by mass, (B) (meth) acrylic monomer 49.8 to 79.8% by mass, and (C) photopolymerization. The method for producing a transparent double-sided pressure-sensitive adhesive sheet according to claim 1, comprising 0.2 to 5% by mass of an initiator.
  3. 透明両面粘着シートの質量に対して、残存する（Ｂ）（メタ）アクリル系モノマーの量が１～５００ｗｔｐｐｍである請求項２に記載の透明両面粘着シートの製造方法。 The method for producing a transparent double-sided pressure-sensitive adhesive sheet according to claim 2, wherein the amount of the remaining (B) (meth) acrylic monomer is 1 to 500 wtppm with respect to the mass of the transparent double-sided pressure-sensitive adhesive sheet.
  4. （Ａ）（メタ）アクリル基含有ポリオレフィン化合物が水添ポリブタジエン骨格又は水添ポリイソプレン骨格を有し、（Ｂ）（メタ）アクリル系モノマーがアルキル（メタ）アクリレート及び／又は環状アルキル（メタ）アクリレートを含み、（Ｃ）光重合開始剤がカルボニル系光重合開始剤を含む請求項２又は３に記載の透明両面粘着シートの製造方法。 (A) (meth) acryl group-containing polyolefin compound has hydrogenated polybutadiene skeleton or hydrogenated polyisoprene skeleton, and (B) (meth) acrylic monomer is alkyl (meth) acrylate and / or cyclic alkyl (meth) acrylate The method for producing a transparent double-sided pressure-sensitive adhesive sheet according to claim 2 or 3, wherein (C) the photopolymerization initiator contains a carbonyl-based photopolymerization initiator.
  5. 活性エネルギー線が高圧水銀ランプ及び／又はメタルハライドランプを光源とするものである請求項１～４のいずれかに記載の透明両面粘着シートの製造方法。 The method for producing a transparent double-sided pressure-sensitive adhesive sheet according to any one of claims 1 to 4, wherein the active energy ray is a high-pressure mercury lamp and / or a metal halide lamp as a light source.
  6. 請求項１～５のいずれかに記載の透明両面粘着シートの製造方法により得られる透明両面粘着シート。 A transparent double-sided pressure-sensitive adhesive sheet obtained by the method for producing a transparent double-sided pressure-sensitive adhesive sheet according to any one of claims 1 to 5.
  7. 請求項６に記載の透明両面粘着シートを用いたタッチパネル。 A touch panel using the transparent double-sided pressure-sensitive adhesive sheet according to claim 6.
  8. 請求項６に記載の透明両面粘着シートを用いた画像表示装置。 An image display device using the transparent double-sided pressure-sensitive adhesive sheet according to claim 6.
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WO2015111584A1 (en) * 2014-01-22 2015-07-30 旭硝子株式会社 Curable resin composition, and layered body and image display device using curable resin composition
KR20160113313A (en) 2014-03-17 2016-09-28 케이제이 케미칼즈 가부시키가이샤 Urethane oligomer and active energy ray curable resin composition containing same
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