WO2022054636A1 - Feuille adhésive à changement de couleur - Google Patents

Feuille adhésive à changement de couleur Download PDF

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Publication number
WO2022054636A1
WO2022054636A1 PCT/JP2021/031868 JP2021031868W WO2022054636A1 WO 2022054636 A1 WO2022054636 A1 WO 2022054636A1 JP 2021031868 W JP2021031868 W JP 2021031868W WO 2022054636 A1 WO2022054636 A1 WO 2022054636A1
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Prior art keywords
sensitive adhesive
pressure
meth
adhesive layer
adhesive sheet
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PCT/JP2021/031868
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English (en)
Japanese (ja)
Inventor
大輔 水野
武史 仲野
Original Assignee
日東電工株式会社
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Priority claimed from JP2021136862A external-priority patent/JP2022046422A/ja
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN202180061723.0A priority Critical patent/CN116075565A/zh
Priority to KR1020237007432A priority patent/KR20230062825A/ko
Publication of WO2022054636A1 publication Critical patent/WO2022054636A1/fr

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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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers

Definitions

  • the present invention relates to a variable color adhesive sheet.
  • a display panel such as an organic EL panel has a laminated structure including a pixel panel and a cover member.
  • a transparent adhesive sheet is used for bonding the elements included in the laminated structure.
  • Patent Document 1 specifically describes an adhesive sheet having a colored portion containing a carbon black pigment.
  • the present invention provides a variable color pressure-sensitive adhesive sheet capable of locally discoloring the pressure-sensitive adhesive layer after being attached to an adherend and suitable for suppressing bleeding of the discolored portion of the pressure-sensitive adhesive layer.
  • the present invention [1] is a variable color pressure-sensitive adhesive sheet provided with a color-changeable pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer comprises a colorant capable of developing a color by a first external stimulus, a base polymer, and a polymerizable compound. It contains a variable color pressure-sensitive adhesive sheet that is contained and can be cured by a second external stimulus different from the first external stimulus.
  • the present invention [2] includes the variable color pressure-sensitive adhesive sheet according to the above [1], wherein the pressure-sensitive adhesive layer further contains a photopolymerization initiator.
  • the variable according to the above [1] or [2], wherein the colorant is a compound that develops a color by reaction with an acid, and the pressure-sensitive adhesive layer further contains a photoacid generator. Includes color adhesive sheet.
  • the colorant is a compound that develops a color by reacting with an acid
  • the pressure-sensitive adhesive layer further contains a photoacid generator and a photopolymerization initiator, and the absorbance of the photoacid generator.
  • the content of the polymerizable compound in the pressure-sensitive adhesive layer is 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the base polymer, according to the above [1] to [4].
  • the variable color adhesive sheet according to any one of them is included.
  • the present invention [6] includes the variable color pressure-sensitive adhesive sheet according to any one of the above [1] to [5], wherein the pressure-sensitive adhesive layer has a thickness of 10 ⁇ m or more and 300 ⁇ m or less.
  • the present invention [7] includes the variable color pressure-sensitive adhesive sheet according to any one of the above [1] to [6], further comprising a base material arranged on one side in the thickness direction of the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive layer contains a colorant capable of developing a color by a first external stimulus as described above. Therefore, after the variable color pressure-sensitive adhesive sheet is attached to the adherend, the pressure-sensitive adhesive layer can be locally discolored by applying a first external stimulus to the portion to be discolored in the pressure-sensitive adhesive layer. With such a variable color pressure-sensitive adhesive sheet, the presence or absence of foreign matter and air bubbles between the sheet and the adherend can be inspected after the bonding and before the formation of the discolored portion of the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive layer contains a base polymer and a polymerizable compound as described above, and can be cured by a second external stimulus different from the first external stimulus.
  • a variable color pressure-sensitive adhesive sheet includes a portion to be discolored or a discolored portion in the pressure-sensitive adhesive layer while ensuring the softness (low elastic modulus) of the pressure-sensitive adhesive layer suitable for bonding to an adherend at the time of bonding. It is suitable for increasing the elastic modulus after laminating the region to be formed (for example, the entire pressure-sensitive adhesive layer).
  • Such a high elastic modulus of the pressure-sensitive adhesive layer is suitable for suppressing the diffusion of the colorant in the pressure-sensitive adhesive layer, and therefore, in the pressure-sensitive adhesive layer on which the discolored portion is formed, the bleeding of the discolored portion is suppressed. Suitable for.
  • FIG. 3A shows a process of preparing a variable color adhesive sheet and a member (adhesive body)
  • FIG. 3B shows a process of joining members to each other via a variable color adhesive sheet
  • FIG. 3C shows a variable color adhesive sheet.
  • 3D represents a step of forming a discolored portion in the pressure-sensitive adhesive layer of a variable-color pressure-sensitive adhesive sheet.
  • the pressure-sensitive adhesive sheet S as an embodiment of the variable-color pressure-sensitive adhesive sheet of the present invention includes the pressure-sensitive adhesive layer 10.
  • the adhesive sheet S has a sheet shape having a predetermined thickness and extends in a direction (plane direction) orthogonal to the thickness direction.
  • the adhesive sheet S is used, for example, as a transparent adhesive sheet arranged on the image display side of the pixel panel in a display panel such as an organic EL panel (having a laminated structure including a pixel panel and a cover member).
  • the pressure-sensitive adhesive layer 10 is a pressure-sensitive adhesive layer having transparency (visible light transmission) formed from the pressure-sensitive adhesive composition.
  • the tacky composition contains a base polymer, a polymerizable compound, a colorant capable of developing a color by a first external stimulus, and, in the present embodiment, a photopolymerization initiator.
  • the portion of the pressure-sensitive adhesive layer 10 that has been subjected to the first external stimulus which will be described later, can be discolored. That is, the transparency of the portion of the pressure-sensitive adhesive layer 10 that has been subjected to the first external stimulus can be reduced ex post facto. Further, the pressure-sensitive adhesive layer 10 can be cured by a second external stimulus described later, which is different from the first external stimulus.
  • the base polymer is an adhesive component for developing adhesiveness in the adhesive layer 10.
  • the base polymer exhibits rubber elasticity at room temperature.
  • examples of the base polymer include acrylic polymers, rubber polymers, polyester polymers, urethane polymers, polyether polymers, silicone polymers, polyamide polymers, and fluoropolymers. From the viewpoint of ensuring good transparency and tackiness in the pressure-sensitive adhesive layer 10, an acrylic polymer is preferably used as the base polymer.
  • the content ratio of the base polymer in the pressure-sensitive adhesive layer 10 is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass, from the viewpoint of appropriately expressing the function of the base polymer in the pressure-sensitive adhesive layer 10. % Or more.
  • the acrylic polymer is, for example, a polymer obtained by polymerizing a monomer component containing a (meth) acrylic acid alkyl ester in a proportion of 50% by mass or more.
  • (Meta) acrylic acid means acrylic acid and / or methacrylic acid.
  • Examples of the (meth) acrylic acid alkyl ester include linear or branched (meth) acrylic acid alkyl esters having an alkyl group having 1 to 20 carbon atoms.
  • Examples of such (meth) acrylic acid alkyl esters include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, n-butyl (meth) acrylic acid, and (meth) acrylic acid.
  • the (meth) acrylic acid alkyl ester may be used alone or in combination of two or more.
  • an acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms is preferably used, and more preferably, it has methyl acrylate and an alkyl group having 2 to 12 carbon atoms.
  • Acrylic acid alkyl ester is used in combination, and more preferably, methyl acrylate and 2-ethylhexyl acrylate are used in combination.
  • the ratio of the (meth) acrylic acid alkyl ester in the monomer component is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 60% by mass or more, from the viewpoint of appropriately expressing basic properties such as adhesiveness in the pressure-sensitive adhesive layer 10. Is 70% by mass or more. The same ratio is, for example, 99% by mass or less.
  • the monomer component may contain a copolymerizable monomer copolymerizable with the (meth) acrylic acid alkyl ester.
  • the copolymerizable monomer include a monomer having a polar group.
  • the polar group-containing monomer include a hydroxyl group-containing monomer, a monomer having a nitrogen atom-containing ring, and a carboxy group-containing monomer.
  • the polar group-containing monomer is useful for modifying the acrylic polymer, such as introducing a cross-linking point into the acrylic polymer and ensuring the cohesive force of the acrylic polymer.
  • the copolymerizable monomer preferably contains at least one selected from the group consisting of a hydroxyl group-containing monomer, a monomer having a nitrogen atom-containing ring, and a carboxy group-containing monomer. More preferably, the copolymerizable monomer comprises a hydroxyl group-containing monomer and / or a monomer having a nitrogen atom-containing ring.
  • Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth). ) 4-Hydroxybutyl acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, and ( Examples include 4-hydroxymethylcyclohexyl) methyl (meth) acrylate.
  • 2-hydroxyethyl (meth) acrylate is preferably used, and 2-hydroxyethyl acrylate is more preferably used.
  • the ratio of the hydroxyl group-containing monomer in the monomer component is preferably 1% by mass or more, more preferably 3% by mass or more, from the viewpoint of introducing a crosslinked structure into the acrylic polymer and ensuring the cohesive force in the pressure-sensitive adhesive layer 10. More preferably, it is 5% by mass or more. The same ratio is preferable from the viewpoint of adjusting the viscosity of the polymerization reaction solution during the polymerization of the acrylic polymer and adjusting the polarity of the acrylic polymer (related to the compatibility between various additive components in the pressure-sensitive adhesive layer 10 and the acrylic polymer). Is 30% by mass or less, more preferably 20% by mass or less.
  • Examples of the monomer having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, and N-vinylpyrazine.
  • N-vinyl-2-caprolactam N-vinyl-1,3-oxadin-2-one, N-vinyl-3,5-morpholindione
  • N-vinylpyrazole N-vinylisoxazole
  • N -Vinylthiazole N-vinylisothiazole
  • monomer having a nitrogen atom-containing ring N-vinyl-2-pyrrolidone is preferably used.
  • the ratio of the monomer having a nitrogen atom-containing ring in the monomer component is preferably 1% by mass from the viewpoint of ensuring the cohesive force in the pressure-sensitive adhesive layer 10 and the adhesion to the adherend in the pressure-sensitive adhesive layer 10. As mentioned above, it is more preferably 3% by mass or more, still more preferably 5% by mass or more. The same ratio is preferably 30 mass from the viewpoint of adjusting the glass transition temperature of the acrylic polymer and adjusting the polarity of the acrylic polymer (related to the compatibility between various additive components in the pressure-sensitive adhesive layer 10 and the acrylic polymer). % Or less, more preferably 20% by mass or less.
  • carboxy group-containing monomer examples include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
  • the ratio of the carboxy group-containing monomer in the monomer component is determined from the viewpoint of introducing a crosslinked structure into the acrylic polymer, ensuring the cohesive force in the pressure-sensitive adhesive layer 10, and ensuring the adhesion to the adherend in the pressure-sensitive adhesive layer 10. It is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more. The same ratio is preferably 30% by mass or less, more preferably 20% by mass or less, from the viewpoint of adjusting the glass transition temperature of the acrylic polymer and avoiding the risk of corrosion of the adherend by acid.
  • the monomer component may contain other copolymerizable monomers.
  • other copolymerizable monomers include acid anhydride monomers, sulfonic acid group-containing monomers, phosphate group-containing monomers, epoxy group-containing monomers, cyano group-containing monomers, amide group-containing monomers, monomers having a succinimide skeleton, and maleimides. , Itaconimides, alkoxy group-containing monomers, vinyl esters, vinyl ethers, and aromatic vinyl compounds.
  • Examples of the acid anhydride monomer include maleic anhydride and itaconic anhydride.
  • sulfonic acid group-containing monomer examples include styrene sulfonic acid, allyl sulfonic acid, sodium vinyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, and sulfopropyl (meth).
  • Examples of the phosphate group-containing monomer include 2-hydroxyethylacryloyl phosphate.
  • epoxy group-containing monomer examples include epoxy group-containing acrylates such as glycidyl (meth) acrylate and -2-ethyl glycidyl ether (meth) acrylate, allyl glycidyl ether, and glycidyl ether (meth) acrylate.
  • Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.
  • Examples of the amide group-containing monomer include N-vinylcarboxylic acid amides such as (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N-alkyl (meth) acrylamide, and N-vinylacetamide, and N-hydroxyalkyl.
  • Examples include (meth) acrylamide, N-alkoxyalkyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and N- (meth) acryloylmorpholin.
  • N, N-dialkyl (meth) acrylamide examples include N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, and N, N-diisopropyl ( Examples include meth) acrylamide, N, N-di (n-butyl) (meth) acrylamide, and N, N-di (t-butyl) (meth) acrylamide.
  • N-alkyl (meth) acrylamide examples include N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, and Nn-butyl (meth) acrylamide.
  • N-hydroxyalkyl (meth) acrylamide examples include N- (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, and N- (1-hydroxypropyl) (meth).
  • N- (3-hydroxypropyl) (meth) acrylamide N- (2-hydroxybutyl) (meth) acrylamide, N- (3-hydroxybutyl) (meth) acrylamide, and N- (4-hydroxybutyl) Examples include (meth) acrylamide.
  • N-alkoxyalkyl (meth) acrylamide include N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, and N-butoxymethyl (meth) acrylamide.
  • Examples of the monomer having a succinimide skeleton include N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, and N- (meth) acryloyl-8-oxyhexamethylene succinimide. Be done.
  • maleimides examples include N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, and N-phenylmaleimide.
  • Examples of the itaconimides include N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, and N-laurylitaconimide can be mentioned.
  • alkoxy group-containing monomer examples include (meth) acrylate alkoxyalkyls and (meth) acrylate alkoxyalkylene glycols.
  • examples of the (meth) acrylate alkoxyalkyls include (meth) acrylate 2-methoxyethyl, (meth) acrylate 3-methoxypropyl, (meth) acrylate 2-ethoxyethyl, and (meth) acrylate propoxyethyl. , Butoxyethyl (meth) acrylate, and ethoxypropyl (meth) acrylate.
  • examples of the (meth) acrylate alkoxyalkylene glycols include (meth) methoxyethylene glycol (meth) acrylate and methoxypolypropylene glycol (meth) acrylate.
  • vinyl esters examples include vinyl acetate and vinyl propionate.
  • vinyl ethers examples include methyl vinyl ether and ethyl vinyl ether.
  • aromatic vinyl compound examples include styrene, ⁇ -methylstyrene, and vinyltoluene.
  • olefins examples include ethylene, butadiene, isoprene, and isobutylene.
  • the copolymerizable monomer may be used alone or in combination of two or more.
  • Acrylic polymer can be formed by polymerizing the above-mentioned monomer components.
  • the polymerization method include solution polymerization, bulk polymerization, and emulsion polymerization, and solution polymerization is preferable.
  • solution polymerization for example, a monomer component and a polymerization initiator are mixed with a solvent to prepare a reaction solution, and then the reaction solution is heated. Then, an acrylic polymer solution containing an acrylic polymer can be obtained by undergoing a polymerization reaction of the monomer components in the reaction solution.
  • the polymerization initiator for example, a thermal polymerization initiator is used.
  • the amount of the polymerization initiator used is, for example, 0.05 parts by mass or more and, for example, 1 part by mass or less with respect to 100 parts by mass of the monomer component.
  • thermal polymerization initiator examples include an azo polymerization initiator and a peroxide polymerization initiator.
  • examples of the azo polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, and 2,2'-azobis (2-methylpropionic acid) dimethyl.
  • 4,4'-Azobis-4-cyanovaleric acid 4,4'-Azobis-4-cyanovaleric acid, azobisisobutyvaleronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (5-methyl-2-) Imidazoline-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, and 2,2'-azobis (N, N'-dimethyleneisobutyramidin) dihydrochloride Can be mentioned.
  • the peroxide polymerization initiator include dibenzoyl peroxide, t-butyl permaleate, and lauroyl peroxide.
  • the weight average molecular weight of the acrylic polymer is preferably 100,000 or more, more preferably 300,000 or more, still more preferably 500,000 or more, from the viewpoint of ensuring the cohesive force in the pressure-sensitive adhesive layer 10.
  • the weight average molecular weight is preferably 5,000,000 or less, more preferably 3,000,000 or less, still more preferably 2000000 or less.
  • the weight average molecular weight of the acrylic polymer is measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene.
  • the glass transition temperature (Tg) of the base polymer is preferably 0 ° C. or lower, more preferably ⁇ 10 ° C. or lower, still more preferably ⁇ 20 ° C. or lower.
  • the glass transition temperature is, for example, ⁇ 80 ° C. or higher.
  • the glass transition temperature (Tg) of the polymer the glass transition temperature (theoretical value) obtained based on the Fox formula below can be used.
  • the Fox formula is a relational expression between the glass transition temperature Tg of the polymer and the glass transition temperature Tgi of the homopolymer of the monomer constituting the polymer.
  • Tg represents the glass transition temperature (° C.) of the polymer
  • Wi represents the weight fraction of the monomer i constituting the polymer
  • Tgi represents the glass transition of the homopolymer formed from the monomer i. Indicates the temperature (° C).
  • Literature values can be used for the glass transition temperature of homopolymers, for example, "Polymer Handbook” (4th edition, John Wiley & Sons, Inc., 1999) and “New Polymer Bunko 7 Introduction to Synthetic Resins for Paints”. (Kyozo Kitaoka, Polymer Publications, 1995) lists the glass transition temperatures of various homopolymers. On the other hand, the glass transition temperature of the homopolymer of the monomer can also be obtained by the method specifically described in JP-A-2007-51271.
  • the adhesive composition may contain a cross-linking agent from the viewpoint of introducing a cross-linked structure into the base polymer.
  • a cross-linking agent examples include an isocyanate cross-linking agent, an epoxy cross-linking agent, an oxazoline cross-linking agent, an aziridine cross-linking agent, a carbodiimide cross-linking agent, and a metal chelate cross-linking agent.
  • the cross-linking agent may be used alone or in combination of two or more.
  • Examples of the isocyanate cross-linking agent include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalin diisocyanate, and triphenylmethane tri. Examples thereof include isocyanates and polymethylene polyphenyl isocyanates. Further, examples of the isocyanate cross-linking agent include derivatives of these isocyanates.
  • isocyanate derivative examples include isocyanurate-modified products and polyol-modified products.
  • isocyanate cross-linking agents include coronate L (trimethylolpropane adduct of tolylene diisocyanate, manufactured by Tosoh), coronate HL (trimethylolpropane adduct of hexamethylene diisocyanate, manufactured by Tosoh), and coronate HX (hexa).
  • Examples thereof include isocyanurate form of methylene diisocyanate (manufactured by Toso) and Takenate D110N (trimethylolpropane adduct form of xylylene diisocyanate, manufactured by Mitsui Kagaku).
  • epoxy cross-linking agent examples include bisphenol A, epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, and trimethylolpropane triglycidyl ether.
  • the blending amount of the cross-linking agent is, for example, 0.01 part by mass or more, preferably 0.05 part by mass or more, based on 100 parts by mass of the base polymer. It is preferably 0.07 parts by mass or more.
  • the blending amount of the cross-linking agent with respect to 100 parts by mass of the base polymer is, for example, 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 3 parts by mass. It is as follows.
  • a cross-linking catalyst may be used to effectively promote the cross-linking reaction.
  • the cross-linking catalyst include dibutyltin dilaurate, tetra-n-butyl titanate, tetraisopropyl titanate, ferric nasem, and butyltin oxide, and dibutyltin dilaurate is preferably used.
  • the amount of the cross-linking catalyst used is, for example, 0.0001 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of the base polymer.
  • a cross-linking inhibitor that can be removed ex post facto from the sticky composition may be added to the sticky composition.
  • dibutyltin dilaurate is used as the cross-linking catalyst
  • acetylacetone is preferably used as the cross-linking inhibitor. In this case, in the adhesive composition, acetylacetone coordinates with dibutyltin dilaurate, and the cross-linking reaction of the cross-linking agent with the veil polymer is suppressed.
  • acetylacetone can be volatilized and removed from the coating film by heating at a desired timing. This makes it possible to proceed with the cross-linking reaction of the cross-linking agent.
  • the blending amount of the cross-linking inhibitor is, for example, 100 parts by mass or more, preferably 1000 parts by mass or more with respect to 100 parts by mass of the cross-linking catalyst. Further, the blending amount is, for example, 5000 parts by mass or less.
  • the polymerizable compound is a compound having a polymerizable functional group.
  • the polymerizable functional group has an ethylenically unsaturated double bond.
  • Polymerizable functional groups include, for example, (meth) acryloyl groups, vinyl groups, and propenyl groups.
  • Examples of the polymerizable compound include a monomer having one polymerizable functional group (monofunctional monomer) and a monomer having a plurality of polymerizable functional groups (polyfunctional monomer).
  • a compound having a (meth) acryloyl group as a polymerizable functional group is used from the viewpoint of reactivity.
  • the (meth) acryloyl group means an acryloyl group and / or a methacryloyl group.
  • the polymerizable compound may be used alone or in combination of two or more.
  • Examples of the monofunctional monomer include ethyl (meth) acrylate, n-butyl (meth) acrylate, ter-butyl (meth) acrylate, isobutyl methacrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, and butoxydiethylene glycol (.
  • Meta acrylate, methoxypolyethylene glycol (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) Meta) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) Meta) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol
  • polyfunctional monomer examples include a bifunctional monomer, a trifunctional monomer, and a tetrafunctional or higher polyfunctional monomer.
  • bifunctional monomer examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethierlenglucol dimethacrylate, 1,6-hexanediol di (meth).
  • trifunctional monomer examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (acryloyloxyethyl) isocyanurate.
  • tetrafunctional or higher polyfunctional monomer examples include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, alkyl-modified dipentaerythritol pentaacrylate, and dipenta.
  • examples thereof include erythritol hexa (meth) acrylate, and isocyanuric acid EO-modified di and triacrylate.
  • the polymerizable compound is preferably a polyfunctional monomer, more preferably a trifunctional monomer or a tetrafunctional or higher polyfunctional monomer.
  • the trifunctional monomer for the polymerizable compound trimethylolpropane tri (meth) acrylate is preferably used, and trimethylolpropane triacrylate is more preferably used.
  • the tetrafunctional or higher functional monomer for the polymerizable compound dipentaerythritol hexa (meth) acrylate is preferably used, and more preferably dipentaerythritol hexaacrylate is used.
  • the amount of the polymerizable compound is preferably 5 parts by mass or more, more preferably 7 parts by mass or more with respect to 100 parts by mass of the base polymer. It is more preferably 9 parts by mass or more, and particularly preferably 10 parts by mass or more. From the viewpoint of ensuring sufficient adhesive strength in the cured pressure-sensitive adhesive layer 10, the blending amount of the polymerizable compound with respect to 100 parts by mass of the base polymer is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, still more preferably. Is 43 parts by mass or less.
  • the photopolymerization initiator initiates the polymerization reaction of the polymerizable compound.
  • the photopolymerization initiator include a benzoin ether photopolymerization initiator, an acetophenone photopolymerization initiator, an ⁇ -ketol photopolymerization initiator, an aromatic sulfonyl chloride photopolymerization initiator, a photoactive oxime photopolymerization initiator, and a benzoin photopolymerization initiator.
  • Examples thereof include an initiator, a benzyl photopolymerization initiator, a benzophenone photopolymerization initiator, a ketal photopolymerization initiator, a thioxanthone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator.
  • the colorant is preferably a compound (color-developing compound) that develops color by reaction with an acid. If the colorant is a color-developing compound, the tacky composition further contains an acid generator.
  • color-developing compound examples include leuco dye, triarylmethane dye, diphenylmethane dye, fluorane dye, spiropyran dye, and rhodamine dye.
  • the color-developing compound may be used alone or in combination of two or more.
  • leuco dyes examples include 2'-anilino-6'-(N-ethyl-N-isopentylamino) -3'-methylspiro [phthalide-3,9'-[9H] xanthene], 3-dibutylamino-.
  • Examples of the triarylmethane dye include p, p', p "-tris-dimethylaminotriphenylmethane.
  • Examples of the diphenylmethane dye include 4,4-bis-dimethylaminophenylbenzhydrylbenzyl ether.
  • Examples of the fluorane dye include 3-diethylamino-6-methyl-7-chlorofluorane.
  • Examples of the spiropyran dye include 3-methylspirodinaphthopyrane.
  • Examples of the rhodamine dye include 3-methylspirodinaphthopyrane.
  • Rhodamine-B-anilinolactum can be mentioned.
  • the color-developing compound is preferably a leuco dye, more preferably 2'-anilino-6'-(N-ethyl-N-isopentylamino)-.
  • 3'-Methylspiro [phthalide-3,9'-[9H] xanthene] is used.
  • the blending amount of the color-developing compound with respect to 100 parts by mass of the base polymer is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more.
  • the blending amount is preferably 10 parts by mass or less, more preferably 7 parts by mass or less.
  • a photoacid generator that generates an acid by being irradiated with active energy rays is preferably used.
  • the portion of the pressure-sensitive adhesive layer 10 that has been irradiated with the active energy ray as the first external stimulus can be discolored.
  • an acid is generated from the photoacid generator, and the color-developing compound is colored by the acid.
  • the portion of the pressure-sensitive adhesive layer 10 that has been irradiated with the active energy rays is colored, for example, in a dark color according to the color development of the color-developing compound.
  • the type of the active energy ray as the first external stimulus is determined by the type of the photoacid generator (specifically, the wavelength of the active energy ray in which the photoacid generator generates an acid).
  • the active energy ray include ultraviolet rays, visible light, infrared rays, X-rays, ⁇ rays, ⁇ rays, and ⁇ rays. From the viewpoint of variety of equipment used and ease of handling, the active energy ray preferably includes ultraviolet rays.
  • Examples of the photoacid generator include an onium compound that generates an acid by irradiation with ultraviolet rays (first external stimulus).
  • Onium compounds are provided, for example, in the form of onium salts of onium cations and anions.
  • Examples of onium cations include iodonium and sulfonium.
  • Examples of anions include Cl- , Br- , I- , ZnCl 3- , HSO 3- , BF 4- , PF 6- , AsF 6- , SbF 6- , CH 3 SO 3- , CF 3 SO 3- . , C 4 F 9 HSO 3- , (C 6 F 5 ) 4 B- , and (C 4 H 9 ) 4 B-.
  • the photoacid generator may be used alone or in combination of two or more.
  • the tacky composition preferably contains an onium salt (onium compound) composed of sulfonium and C 4 F 9 HSO 3- as a photoacid generator.
  • the blending amount of the acid generator with respect to 100 parts by mass of the base polymer is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 5 parts by mass or more, and particularly preferably 7 parts by mass or more.
  • the blending amount is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 12 parts by mass or less.
  • the blending amount of the acid generator with respect to 100 parts by mass of the color-developing compound is, for example, 100 parts by mass or more, preferably 200 parts by mass or more, more preferably 300 parts by mass or more, and further preferably 330 parts by mass or more.
  • the blending amount is preferably 1000 parts by mass or less, more preferably 700 parts by mass or less, and further preferably 500 parts by mass or less.
  • the adhesive composition may contain other components as needed.
  • Other components include, for example, silane coupling agents, tackifiers, plasticizers, softeners, antioxidants, surfactants, and antistatic agents.
  • the pressure-sensitive adhesive sheet S can be produced, for example, by applying the above-mentioned adhesive composition on a release film (first release film) to form a coating film, and then drying the coating film (in FIG. 1).
  • the adhesive sheet S is arranged on the release film L indicated by the virtual line).
  • Examples of the release film include a flexible plastic film.
  • Examples of the plastic film include polyethylene terephthalate film, polyethylene film, polypropylene film, and polyester film.
  • the thickness of the release film is, for example, 3 ⁇ m or more, and is, for example, 200 ⁇ m or less.
  • the surface of the release film is preferably mold-released.
  • Examples of the method of applying the adhesive composition include roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, and lip coat. , And die coat.
  • the drying temperature of the coating film is, for example, 50 ° C to 200 ° C.
  • the drying time is, for example, 5 seconds to 20 minutes.
  • the cross-linking reaction proceeds at the same time as the above-mentioned drying or by aging thereafter.
  • the aging conditions are appropriately set depending on the type of the cross-linking agent.
  • the aging temperature is, for example, 20 ° C to 160 ° C.
  • the aging time is, for example, 1 minute to 7 days.
  • a release film (second release film) may be further laminated on the pressure-sensitive adhesive layer 10 on the first release film.
  • the second release film is a flexible plastic film that has been subjected to a surface release treatment, and the same film as described above can be used for the first release film.
  • the pressure-sensitive adhesive sheet S whose adhesive surface is covered and protected by the release film can be manufactured.
  • Each release film is peeled off from the pressure-sensitive adhesive sheet S as needed when using the pressure-sensitive adhesive sheet S.
  • the thickness of the pressure-sensitive adhesive layer 10 is preferably 10 ⁇ m or more, more preferably 15 ⁇ m or more, from the viewpoint of ensuring sufficient adhesiveness to the adherend. From the viewpoint of handleability of the pressure-sensitive adhesive sheet S, the thickness of the pressure-sensitive adhesive layer 10 is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, still more preferably 100 ⁇ m or less, and particularly preferably 50 ⁇ m or less.
  • the haze of the pressure-sensitive adhesive layer 10 is preferably 3% or less, more preferably 2% or less, and more preferably 1% or less. Such a configuration is suitable for inspecting the presence or absence of foreign matter and air bubbles between the pressure-sensitive adhesive sheet S and the adherend after the pressure-sensitive adhesive sheet S is attached to the adherend.
  • the haze of the pressure-sensitive adhesive layer 10 can be measured using a haze meter in accordance with JIS K7136 (2000). Examples of the haze meter include "NDH2000" manufactured by Nippon Denshoku Kogyo Co., Ltd. and "HM-150 type” manufactured by Murakami Color Technology Research Institute.
  • the average transmittance of the pressure-sensitive adhesive layer 10 at a wavelength of 400 to 700 nm is preferably 80% or more, more preferably 85% or more. More preferably, it is 90% or more.
  • Such a configuration is suitable for inspecting the presence or absence of foreign matter and air bubbles between the pressure-sensitive adhesive sheet S and the adherend after the pressure-sensitive adhesive sheet S is attached to the adherend.
  • the adhesive force exhibited by the adhesive sheet S on the stainless steel plate in a peeling test under the peeling conditions of 23 ° C., a peeling angle of 180 ° and a peeling speed of 300 mm / min after being bonded to the glass plate is, for example, 1 N / 25 mm or more. It is, for example, 50 N / 25 mm or less.
  • the shear storage elastic modulus (first shear storage elastic modulus) at 25 ° C., which is shown by the dynamic viscoelasticity measurement of the pressure-sensitive adhesive layer 10 (before curing) under the conditions of a frequency of 1 Hz and a heating rate of 5 ° C./min, is determined. It is preferably 0.1 ⁇ 10 5 Pa or more, more preferably 0.2 ⁇ 10 5 Pa or more, and further preferably 0.3 ⁇ 10 5 Pa or more.
  • the first shear storage elastic modulus is preferably 10 ⁇ 10 5 Pa or less, more preferably 5 ⁇ 10 5 Pa or less, and further preferably 3 ⁇ 10 5 Pa or less.
  • the pressure-sensitive adhesive layer 10 of the pressure-sensitive adhesive sheet S preferably has a wavelength region in which the ratio of the absorbance Y of the photopolymerization initiator to the absorbance X of the photoacid generator is 2 or more within a wavelength range of 300 nm or more and 500 nm or less.
  • the ratio is preferably 3 or more, more preferably 10 or more, still more preferably 50 or more, and particularly preferably 100 or more.
  • the same ratio is, for example, 1 million or less.
  • the pressure-sensitive adhesive sheet S may be a single-sided pressure-sensitive adhesive sheet with a base material, which comprises a base material 20 in addition to the pressure-sensitive adhesive layer 10.
  • the pressure-sensitive adhesive sheet S specifically includes a pressure-sensitive adhesive layer 10 and a base material 20 arranged on one side in the thickness direction thereof.
  • the substrate 20 contacts one side of the pressure-sensitive adhesive layer 10 in the thickness direction.
  • the base material 20 is an element that functions as a transparent support.
  • the base material 20 is, for example, a flexible plastic film.
  • the constituent material of the plastic film include polyolefin, polyester, polyamide, polyimide, polyvinyl chloride, polyvinylidene chloride, cellulose, polystyrene, and polycarbonate.
  • the polyolefin include polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / vinyl acetate copolymer, and the like.
  • the plastic material of the base material 20 is preferably polyester, more preferably polyethylene terephthalate.
  • the base material 20 has transparency.
  • the haze of the base material 20 is preferably 3% or less, more preferably 2% or less, still more preferably 1% or less.
  • the haze of the base material 20 can be measured using a haze meter in accordance with JIS K7136 (2000).
  • the surface of the base material 20 on the pressure-sensitive adhesive layer 10 side may be subjected to a physical treatment, a chemical treatment, or an undercoat treatment for enhancing the adhesion to the pressure-sensitive adhesive layer 10.
  • Physical treatments include, for example, corona treatment and plasma treatment.
  • Examples of the chemical treatment include acid treatment and alkali treatment.
  • the thickness of the base material 20 is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and more preferably 20 ⁇ m or more from the viewpoint of ensuring the strength for the base material 20 to function as a support. Further, from the viewpoint of realizing appropriate flexibility in the pressure-sensitive adhesive sheet S, the thickness of the base material 20 is preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, still more preferably 100 ⁇ m or less.
  • the pressure-sensitive adhesive sheet S shown in FIG. 2 can be manufactured by the same method as the above-mentioned pressure-sensitive adhesive sheet manufacturing method except that the base material 20 is used instead of the first release film, for example.
  • FIGS. 3A to 3D show an example of how to use the adhesive sheet S.
  • the method includes a preparation step, a joining step, a curing step, and a discolored portion forming step.
  • the adhesive sheet S, the first member 31, and the second member 32 are prepared.
  • the first member 31 is, for example, a display panel such as an organic EL panel.
  • the first member 31 may be another electronic device or an optical device.
  • the second member 32 is, for example, a transparent base material. Examples of the transparent base material include a transparent plastic base material and a transparent glass base material.
  • the first member 31 and the second member 32 are joined via the adhesive sheet S.
  • the laminated body Z is obtained.
  • the adhesive sheet S is arranged so as to be in contact with one surface in the thickness direction of the first member 31, and the second member 32 is arranged so as to be in contact with one surface in the thickness direction of the adhesive sheet S. Will be done.
  • a second external stimulus is applied to the pressure-sensitive adhesive layer 10 in the laminate Z (in the case where the above inspection is performed, the laminate Z that has passed the inspection) to provide a pressure-sensitive adhesive.
  • the layer 10 is cured.
  • the second external stimulus is irradiation with active energy rays.
  • This active energy ray is applied to the pressure-sensitive adhesive layer 10 from the side of the transparent second member 32.
  • the light source for irradiating the active energy ray in this step include an ultraviolet LED light, a high-pressure mercury lamp, and a metal halide lamp.
  • a wavelength cut filter for cutting a part of the wavelength region in the active energy ray emitted from the light source may be used as needed.
  • the wavelength range of the active energy ray as the second external stimulus is different from that of the active energy ray as the first external stimulus.
  • the active energy ray as the second external stimulus has a wavelength that does not substantially generate an acid in the acid generator.
  • the lower limit of the wavelength range of the active energy ray is preferably 365 nm, more preferably 370 nm, still more preferably 375 nm, still more preferably 380 nm, still more preferably 385 nm, still more preferably 390 nm, and particularly preferably 395 nm.
  • a photopolymerization initiator that initiates the polymerization reaction of the polymerizable compound by being irradiated with active energy rays having such a wavelength is blended in the pressure-sensitive adhesive layer 10.
  • the polymerization reaction of the polymerizable compound is started by the photopolymerization initiator, and the polymerization reaction proceeds.
  • the elastic modulus of the pressure-sensitive adhesive layer 10 increases.
  • the pressure-sensitive adhesive layer 10 has a wavelength region (wavelength region R) in which the ratio of the absorbance Y of the photopolymerization initiator to the absorbance X of the photoacid generator is 2 or more within the range of a wavelength of 300 nm or more and 500 nm or less. It is preferable to have it in.
  • the ratio (Y / X) in the wavelength region R is preferably 3 or more, more preferably 10 or more, and further preferably 100 or more.
  • at least a part of the wavelength of the active energy ray irradiated as the second external stimulus is in the wavelength region R. More preferably, all the wavelengths of the active energy rays irradiated as the second external stimulus are in the wavelength region R.
  • Such a configuration in which an active energy ray having a wavelength within the wavelength region is given to the pressure-sensitive adhesive layer 10 as a second external stimulus cures the pressure-sensitive adhesive layer 10 while suppressing discoloration in the pressure-sensitive adhesive layer 10 in the curing step.
  • the ratio of the absorbance Y of the photopolymerization initiator to the absorbance X of the photoacid generator is larger. preferable.
  • the shear storage elastic modulus (second shear storage elastic modulus) at 25 ° C. which is shown by the dynamic viscoelasticity measurement of the pressure-sensitive adhesive layer 10 after curing under the conditions of a frequency of 1 Hz and a heating rate of 5 ° C./min, is preferable. Is 0.2 ⁇ 10 5 Pa or more, more preferably 2 ⁇ 10 5 Pa or more, and further preferably 5 ⁇ 10 5 Pa or more.
  • the second shear storage elastic modulus is preferably 100 ⁇ 10 5 Pa or less, more preferably 50 ⁇ 10 5 Pa or less, and further preferably 25 ⁇ 10 5 Pa or less.
  • the ratio of the second shear storage elastic modulus to the first shear storage elastic modulus is preferably 2 or more, more preferably 5 or more, still more preferably 10 or more.
  • the ratio is preferably 300 or less, more preferably 250 or less, still more preferably 100 or less, still more preferably 50 or less, and particularly preferably 30 or less.
  • the pressure-sensitive adhesive layer 10 in the laminated body Z is given a first external stimulus to form the discoloration portion 11 in the pressure-sensitive adhesive layer 10.
  • a first external stimulus to the pressure-sensitive adhesive layer 10 from the side of the transparent second member 32 via a mask pattern (not shown) for masking a predetermined region in the pressure-sensitive adhesive layer 10. Irradiate the active energy ray (first active energy ray). As a result, the portion of the pressure-sensitive adhesive layer 10 that is not masked by the mask pattern is discolored.
  • Examples of the light source for irradiating the active energy ray in this step include an ultraviolet LED light, a high-pressure mercury lamp, and a metal halide lamp. Further, in the activation energy ray irradiation in this step, a wavelength cut filter for cutting a part of the wavelength region in the active energy ray emitted from the light source may be used as needed.
  • the wavelength range of the first active energy ray is different from that of the above-mentioned active energy ray (second active energy ray) as the second external stimulus.
  • the wavelength range of the first active energy ray preferably includes at least a range smaller than the wavelength range of the second active energy ray (wavelength range on the short wavelength side) (the wavelength range of the first active energy ray is the second active energy. It may include a range that overlaps with the wavelength range of the line).
  • the first active energy ray has a lower limit in the wavelength range, or when the lower limit is set in the wavelength range of the first active energy ray by using, for example, a wavelength cut filter, the lower limit of the wavelength range of the first active energy ray is set.
  • the first active energy ray may contain light having a wavelength of less than 300 nm.
  • Light sources of such light include, for example, high pressure mercury lamps and metal halide lamps.
  • the upper limit of the wavelength range of the first active energy ray is It is preferably 400 nm, more preferably 395 nm, still more preferably 390 nm, even more preferably 385 nm, still more preferably 380 nm, still more preferably 375 nm, and particularly preferably 370 nm.
  • a photoacid generator that generates an acid by being irradiated with active energy rays having such a wavelength is blended in the pressure-sensitive adhesive layer 10.
  • an acid is generated from the photoacid generator at the portion of the pressure-sensitive adhesive layer 10 that has been irradiated with the first active energy ray, and the color-developing compound is developed by the reaction with the acid.
  • the discolored portion 11 is formed on the pressure-sensitive adhesive layer 10.
  • Such a discolored portion forming step may be carried out before the curing step.
  • the adhesive sheet S can be used for joining between members.
  • the metal is provided by providing the discolored portion 11 in a pattern shape corresponding to (that is, facing) the metal wiring formed on the pixel panel included in the panel. External light reflection in wiring can be suppressed.
  • the pressure-sensitive adhesive layer 10 contains a colorant capable of developing a color by a first external stimulus, as described above. Therefore, after the pressure-sensitive adhesive sheet S is attached to the adherend (members 31, 32 in the present embodiment), the pressure-sensitive adhesive layer 10 is locally applied by applying a first external stimulus to the portion to be discolored in the pressure-sensitive adhesive layer 10. It can be discolored.
  • the pressure-sensitive adhesive sheet S capable of forming the discolored portion 11 on the pressure-sensitive adhesive layer 10 after being bonded to the adherend the pressure-sensitive adhesive sheet S and the adherend are formed after the bonding and before the discolored portion 11 of the pressure-sensitive adhesive layer 10 is formed. The presence or absence of foreign matter and air bubbles can be inspected between.
  • the pressure-sensitive adhesive layer 10 contains a base polymer and a polymerizable compound as described above, and can be cured by a second external stimulus different from the first external stimulus.
  • a pressure-sensitive adhesive sheet S ensures the softness (low elastic modulus) of the pressure-sensitive adhesive layer 10 suitable for bonding to an adherend at the time of bonding, and at the time of bonding, the discolored portion or the discolored portion 11 in the pressure-sensitive adhesive layer 10. It is suitable for increasing the elastic modulus after laminating the region including (for example, the entire pressure-sensitive adhesive layer 10).
  • Such a high elastic modulus of the pressure-sensitive adhesive layer 10 is suitable for suppressing the diffusion of the colorant in the pressure-sensitive adhesive layer 10, and is therefore suitable for suppressing the bleeding of the discolored portion 11 of the pressure-sensitive adhesive layer 10.
  • the second shear storage elastic modulus of the adhesive layer 10 after curing is preferably 0.2 ⁇ 10 5 Pa or more, more preferably 2 ⁇ 10 5 Pa or more, and further preferably 5 ⁇ 10 5 Pa. That is all.
  • Such a configuration is suitable for suppressing bleeding of the discolored portion 11 formed on the pressure-sensitive adhesive layer 10.
  • the ratio of the second shear storage elastic modulus to the first shear storage elastic modulus of the pressure-sensitive adhesive layer 10 before curing is preferably 2 or more, more preferably 5 or more, still more preferably 10 or more, and further. It is preferably 100 or less, more preferably 50 or less, still more preferably 30 or less.
  • Such a configuration is suitable for balancing the bonding force of the pressure-sensitive adhesive sheet S (adhesive layer 10) in the above-mentioned bonding step with the suppression of bleeding of the discolored portion 11.
  • the present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples.
  • the specific numerical values such as the compounding amount (content), the physical property value, the parameter, etc. described below are the compounding amounts corresponding to them described in the above-mentioned "form for carrying out the invention” (forms for carrying out the invention). It can be replaced with an upper limit (numerical value defined as “less than or equal to” or “less than”) or a lower limit (numerical value defined as "greater than or equal to” or “greater than or equal to”) such as content), physical property value, and parameter.
  • Example 1 ⁇ Preparation of base polymer> In a reaction vessel equipped with a stirrer, a thermometer, a reflux cooler, and a nitrogen gas introduction tube, 63 parts by mass of 2-ethylhexyl acrylate (2EHA), 9 parts by mass of methyl methacrylate (MMA), and 2-acrylic acid. 13 parts by mass of hydroxyethyl (HEA), 15 parts by mass of N-vinyl-2-pyrrolidone (NVP), and 0.2 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator. The mixture containing 233 parts by mass of ethyl acetate as a solvent was stirred at 60 ° C. for 7 hours under a nitrogen atmosphere (polymerization reaction). As a result, a polymer solution containing an acrylic polymer was obtained. The weight average molecular weight (Mw) of the acrylic polymer in this polymer solution was 1.2 million.
  • Mw weight average molecular
  • DPHA dipentaerythritol hexaacrylate
  • Polymerization initiator (trade name "Omnirad 819", bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, manufactured by IGM Resins BV) 0.1 part by mass and leuco dye as a color-developing compound (trade name "" S-205 “, 2'-anilino-6'-(N-ethyl-N-isopentylamino) -3'-methylspiro [phthalide-3,9'-[9H] xanthene], manufactured by Yamada Chemical Industry Co., Ltd.) 2 .2 parts by mass, photoacid generator (trade name "Sp-056", onium salt of sulfonium and C4 F 9 HSO 3- , manufactured by ADEKA), 7.8 parts by mass, and isocyanate cross-linking as a cross-linking agent.
  • photoacid generator (trade name "Sp-056", onium salt of sulfonium and C4 F 9 HSO 3- , manufactured
  • ⁇ Formation of adhesive layer> An adhesive composition was applied by a fountain roll onto a 38 ⁇ m-thick polyethylene terephthalate film (base film) whose surface had been mold-released to form a coating film. The coating was then dried by heating at 132 ° C. for 3 minutes. As a result, a pressure-sensitive adhesive layer having a thickness of 25 ⁇ m was formed on the base film. Next, a mold release-treated surface of a separator (a polyethylene terephthalate film having a thickness of 38 ⁇ m whose one side was mold-released) was attached to the pressure-sensitive adhesive layer on the base film. Then, it was aged at 60 ° C. for 24 hours to allow the cross-linking reaction in the pressure-sensitive adhesive layer to proceed.
  • a separator a polyethylene terephthalate film having a thickness of 38 ⁇ m whose one side was mold-released
  • the adhesive sheet of Example 1 was produced.
  • the composition of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet of Example 1 is shown in Table 1 in units of mass (the same applies to Examples and Comparative Examples described later).
  • each component was blended in the blending amount shown in Table 1 in the preparation of the tacky composition.
  • TMPTA trimethylolpropane triacrylate
  • each component was blended in the blending amounts shown in Table 1 (the polymerizable compound and the photopolymerization initiator were not blended).
  • the adhesive sheet was attached to eagle glass (thickness 0.55 mm, manufactured by Matsunami Glass Co., Ltd.) to prepare a measurement sample (first measurement sample).
  • the average transmittance at a wavelength of 400 to 700 nm was measured using a spectrophotometer U4150 manufactured by Hitachi High-Technologies Corporation (first transmittance measurement).
  • the total light transmittance of the measurement sample at a wavelength of 400 to 700 nm was measured at a pitch of 1 nm.
  • the transmittance spectrum obtained by measuring only the eagle glass under the same conditions was used as the baseline.
  • the measured average transmittance T1 (average transmittance at a wavelength of 400 to 700 nm before UV irradiation) of the pressure-sensitive adhesive layer is shown in Table 1.
  • the sample was irradiated with ultraviolet rays.
  • the pressure-sensitive adhesive sheet (adhesive layer) in the sample was irradiated with ultraviolet rays from the eagle glass side through the same glass in an environment of 23 ° C. and a relative humidity of 50% (the pressure-sensitive adhesive by the UV irradiation).
  • the leuco dye in the layer was reacted with the photoacid generator).
  • a UV-LED lamp having a wavelength of 365 nm in a UV-LED irradiation device (model number "QEL-350-RU6W-CW-MY") manufactured by Quark Technology Co., Ltd. is used as a light source, and the integrated irradiation amount is 8000 mJ / cm. It was set to 2 (integrated irradiation light amount in the wavelength range of 320 to 390 nm). As described above, a measurement sample (second measurement sample) was prepared.
  • the average transmittance at a wavelength of 400 to 700 nm was measured using a spectrophotometer U4150 manufactured by Hitachi High-Technologies Corporation (second transmittance measurement). Regarding the specific measurement method and conditions, the second transmittance measurement is the same as the first transmittance measurement described above.
  • the measured average transmittance T2 (average transmittance at a wavelength of 400 to 700 nm after UV irradiation) of the pressure-sensitive adhesive layer is shown in Table 1. Table 1 also shows the ratio of the average transmittance T2 to the above-mentioned average transmittance T1.
  • Shear storage elastic modulus of adhesive layer (before hardening treatment)> The shear storage elastic modulus of the pressure-sensitive adhesive layer of each of the pressure-sensitive adhesive sheets of Examples 1 to 5 and Comparative Example 1 was examined by dynamic viscoelasticity measurement (first measurement).
  • the sample for the first measurement was prepared as follows. First, 60 pressure-sensitive adhesive layers (thickness 25 ⁇ m) were laminated for each pressure-sensitive adhesive layer to be measured to obtain a laminated pressure-sensitive adhesive layer (thickness 1.5 mm). Next, a columnar pellet (thickness 1.5 mm, diameter 7.9 mm) as a first measurement sample was obtained by punching the laminated pressure-sensitive adhesive layer.
  • a dynamic viscoelasticity measuring device (trade name "ARES", manufactured by Leometric Co., Ltd.) was used for the dynamic viscoelasticity measurement. Specifically, after fixing the measurement sample to the jig of the parallel plate having a diameter of 7.9 mm, the dynamic viscoelasticity measurement was carried out by the above-mentioned apparatus. In this measurement, the measurement mode was the shear mode, the measurement temperature range was ⁇ 70 ° C. to 250 ° C., the temperature rise rate was 5 ° C./min, and the frequency was 1 Hz. Table 1 shows the shear storage elastic modulus E1 of the pressure-sensitive adhesive layer (before the curing treatment) at 25 ° C.
  • the sample for the second measurement (cylindrical pellet obtained by punching the laminated pressure-sensitive adhesive layer with a thickness of 1.5 mm) was irradiated with ultraviolet rays (curing treatment) on each of the 60 pressure-sensitive adhesive layers before stacking. Except for the above, it was prepared in the same manner as the first measurement sample. In the curing treatment, specifically, each pressure-sensitive adhesive layer before laminating was irradiated with ultraviolet rays in an environment of 23 ° C. and a relative humidity of 50%.
  • a UV-LED lamp having a wavelength of 405 nm in a UV-LED irradiation device (model number "QEL-350-RU6W-CW-MY") manufactured by Quark Technology Co., Ltd. is used as a light source, and the integrated irradiation amount is 2000 mJ / cm. It was set to 2 (integrated irradiation light amount in the wavelength range of 395 to 445 nm).
  • Table 1 shows the shear storage modulus E2 of the pressure-sensitive adhesive layer (after the curing treatment) at 25 ° C., 65 ° C., and 85 ° C.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet was irradiated with ultraviolet rays in an environment of 23 ° C. and a relative humidity of 50% (the pressure-sensitive adhesive layer of each of the pressure-sensitive adhesive sheets of Examples 1 to 5 was cured by the UV irradiation).
  • a UV-LED lamp having a wavelength of 405 nm in a UV-LED irradiation device (model number "QEL-350-RU6W-CW-MY”) manufactured by Quark Technology Co., Ltd. is used as a light source, and an adhesive is applied through the base film.
  • the layer was irradiated with ultraviolet rays, and the integrated irradiation light amount was set to 2000 mJ / cm 2 (integrated irradiation light amount in the wavelength range of 395 to 445 nm). Same as UV irradiation conditions).
  • a linear discolored portion was formed on the pressure-sensitive adhesive layer by irradiating the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet with ultraviolet rays through a photomask having a linear opening.
  • the photomask is formed from a dry film photoresist arranged on the surface of the pressure-sensitive adhesive sheet on the base film side, and the line width of the opening of the photomask is about 250 to 280 ⁇ m (the line width of the opening is the photomask). Different for each).
  • a UV-LED lamp with a wavelength of 365 nm in a UV-LED irradiation device (model number "QEL-350-RU6W-CW-MY" manufactured by Quark Technology Co., Ltd.
  • the pressure-sensitive adhesive layer was irradiated with ultraviolet rays, and the integrated irradiation light amount was set to 2000 mJ / cm 2 (the integrated irradiation light amount in the wavelength range of 320 to 390 nm).
  • the line width of the linear discolored portion formed on the adhesive layer was measured (measurement of the initial line width). Specifically, first, the linear discolored portion formed on the adhesive layer is observed with a digital microscope (trade name "VHX-900", manufactured by KEYENCE), and a part of the discolored portion and its vicinity are observed. The area to be included was photographed at a magnification of 50 times. Next, the captured image was binarized by image analysis software. Next, in the image after the binarization process, the line width (W1) of the linear discolored portion was measured.
  • the pressure-sensitive adhesive sheet having the linear discolored portion formed on the pressure-sensitive adhesive layer was heat-treated at 85 ° C. for 120 hours (first durability test).
  • the specific measurement method is the same as the measurement method described above for the measurement of the initial line width.
  • the line width W1 of the linear discolored portion before the first durability test, the line width W2 of the linear discolored portion after the first durability test, and the rate of increase of the line width W2 with respect to the line width W1 (W2 / W1). Is shown in Table 1.
  • the pressure-sensitive adhesive layers of the pressure-sensitive adhesive sheets of Examples 1 to 5 and Comparative Example 1 were formed in the same manner as described above except that the second durability test was performed instead of the first durability test. The degree of suppression of bleeding in the linear discolored part was investigated.
  • the second durability test the pressure-sensitive adhesive sheet having the linear discolored portion formed on the pressure-sensitive adhesive layer was heat-treated at 65 ° C. and 90% relative humidity for 120 hours.
  • the line width W1 of the linear discolored portion before the second durability test, the line width W3 of the linear discolored portion after the second durability test, and the rate of increase of the line width W3 with respect to the line width W1 (W3 / W1). Is shown in Table 1.
  • the rate of increase in the line width (W2 / W1) of the linearly discolored portion after the first durability test was smaller in each of the pressure-sensitive adhesive sheets of Examples 1 to 5 than that of the pressure-sensitive adhesive sheet of Comparative Example 1.
  • the rate of increase in the line width (W3 / W1) of the linearly discolored portion after the second durability test was also smaller in each of the pressure-sensitive adhesive sheets of Examples 1 to 5 than that of the pressure-sensitive adhesive sheet of Comparative Example 1. That is, in each of the pressure-sensitive adhesive sheets of Examples 1 to 5, bleeding of the discolored portion of the pressure-sensitive adhesive layer was suppressed as compared with the pressure-sensitive adhesive sheet of Comparative Example 1.
  • variable color adhesive sheet of the present invention is used, for example, in the process of manufacturing a display panel for bonding elements included in a laminated structure of a display panel.
  • Adhesive sheet (variable color adhesive sheet) 10 Adhesive layer 11 Discolored part 20 Base material 31 First member 32 Second member

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La feuille adhésive (S) selon la présente invention est une feuille adhésive à changement de couleur comprenant une couche adhésive (10) pouvant changer de couleur. La couche adhésive (10) comprend un agent colorant pouvant produire une couleur par l'intermédiaire d'une première stimulation externe, un polymère de base et un composé polymérisable, et est durcissable par l'intermédiaire d'une seconde stimulation externe différente de la première stimulation externe.
PCT/JP2021/031868 2020-09-10 2021-08-31 Feuille adhésive à changement de couleur WO2022054636A1 (fr)

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JP7343728B1 (ja) 2023-06-07 2023-09-12 デクセリアルズ株式会社 光硬化型接着組成物、硬化物、接続構造体及び接続構造体の製造方法

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JPS62153377A (ja) * 1985-12-27 1987-07-08 F S K Kk ウェハダイシング用粘着シート
JPH11140388A (ja) * 1997-09-08 1999-05-25 Sekisui Chem Co Ltd 硬化型粘接着シート
JP2004175978A (ja) * 2002-11-28 2004-06-24 Nitto Denko Corp 粘着剤組成物、粘着剤層、その形成方法および粘着シート
JP2006243018A (ja) * 2005-02-28 2006-09-14 Sekisui Chem Co Ltd 液晶表示素子用遮光シール剤、上下導通材料、及び、液晶表示素子
US20160381821A1 (en) * 2015-04-15 2016-12-29 Boe Technology Group Co., Ltd. Display panel, fabrication method thereof and display device
WO2019065375A1 (fr) * 2017-09-28 2019-04-04 日東電工株式会社 Film renforcé
WO2020189390A1 (fr) * 2019-03-15 2020-09-24 日東電工株式会社 Composition d'agent adhésif, couche d'agent adhésif et feuille adhésive

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JP2017203810A (ja) 2016-05-09 2017-11-16 日本化薬株式会社 有機エレクトロルミネッセンスディスプレイ用カラーフィルタに含有される光吸収層、及びそれを用いたシート

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JPS62153377A (ja) * 1985-12-27 1987-07-08 F S K Kk ウェハダイシング用粘着シート
JPH11140388A (ja) * 1997-09-08 1999-05-25 Sekisui Chem Co Ltd 硬化型粘接着シート
JP2004175978A (ja) * 2002-11-28 2004-06-24 Nitto Denko Corp 粘着剤組成物、粘着剤層、その形成方法および粘着シート
JP2006243018A (ja) * 2005-02-28 2006-09-14 Sekisui Chem Co Ltd 液晶表示素子用遮光シール剤、上下導通材料、及び、液晶表示素子
US20160381821A1 (en) * 2015-04-15 2016-12-29 Boe Technology Group Co., Ltd. Display panel, fabrication method thereof and display device
WO2019065375A1 (fr) * 2017-09-28 2019-04-04 日東電工株式会社 Film renforcé
WO2020189390A1 (fr) * 2019-03-15 2020-09-24 日東電工株式会社 Composition d'agent adhésif, couche d'agent adhésif et feuille adhésive

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7343728B1 (ja) 2023-06-07 2023-09-12 デクセリアルズ株式会社 光硬化型接着組成物、硬化物、接続構造体及び接続構造体の製造方法

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