WO2021054374A1 - Pressure-sensitive adhesive sheet and method for producing member with pressure-sensitive adhesive sheet - Google Patents

Pressure-sensitive adhesive sheet and method for producing member with pressure-sensitive adhesive sheet Download PDF

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Publication number
WO2021054374A1
WO2021054374A1 PCT/JP2020/035131 JP2020035131W WO2021054374A1 WO 2021054374 A1 WO2021054374 A1 WO 2021054374A1 JP 2020035131 W JP2020035131 W JP 2020035131W WO 2021054374 A1 WO2021054374 A1 WO 2021054374A1
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Prior art keywords
pressure
sensitive adhesive
adhesive sheet
mass
color
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PCT/JP2020/035131
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French (fr)
Japanese (ja)
Inventor
武史 仲野
千尋 舟木
真由 尾▲崎▼
Original Assignee
日東電工株式会社
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Priority claimed from JP2020146094A external-priority patent/JP2021050330A/en
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN202080065732.2A priority Critical patent/CN114514298A/en
Priority to KR1020227008104A priority patent/KR20220062519A/en
Publication of WO2021054374A1 publication Critical patent/WO2021054374A1/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
    • 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
    • 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
    • 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]
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

  • the present invention relates to an adhesive sheet and a method for manufacturing a member with an adhesive sheet.
  • a highly reflective metal electrode layer is provided as one or both electrodes of a pair of electrodes for self-luminous emission of an organic EL element. .. External light reflection is likely to occur in an organic EL panel in which elements including such a metal electrode layer are arranged so as to form a display screen.
  • Patent Document 1 specifically describes that a pressure-sensitive adhesive sheet containing a carbon black pigment and a dye and colored is provided as the light absorption layer.
  • the presence or absence of foreign matter or air bubbles between the pressure-sensitive adhesive sheet and its adherend surface is inspected after bonding to a predetermined surface. It's hard to do.
  • the adhesive sheet In order to bond the adhesive sheet to an electronic component or an optical component, it is required that the presence or absence of foreign matter or air bubbles between the adhesive sheet and its adherend surface can be appropriately inspected after the bonding.
  • the adhesive sheet to be attached to an electronic component or an optical component is required not to cause metal corrosion on the adhesive sheet attached to the adherend or when there is a metal wiring in the vicinity thereof, for example.
  • the present invention provides a pressure-sensitive adhesive sheet suitable for reducing visible light transmission after being bonded to an adherend and also suitable for suppressing metal corrosion in the adherend, and a method for manufacturing a member with the pressure-sensitive adhesive sheet. To do.
  • the present invention [1] contains a base polymer, an acid generator, a color-developing compound that develops color by reaction with an acid, and a rust preventive agent of less than 100 parts by mass with respect to 100 parts by mass of the color-developing compound. Includes an adhesive sheet with an adhesive layer.
  • the present invention [2] includes the pressure-sensitive adhesive sheet according to the above [1], wherein the color-developing compound is a leuco dye.
  • the present invention [3] includes the pressure-sensitive adhesive sheet according to the above [1] or [2], wherein the rust preventive is a benzotriazole-based compound.
  • the present invention [4] includes the pressure-sensitive adhesive sheet according to any one of the above [1] to [3], wherein the base polymer is an acrylic polymer.
  • the present invention [5] includes the pressure-sensitive adhesive sheet according to any one of the above [1] to [4], wherein the haze of the pressure-sensitive adhesive layer is 3% or less.
  • the step of attaching the pressure-sensitive adhesive sheet according to any one of the above [1] to [5] to a member and applying an external stimulus to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet on the member includes a method for manufacturing a member with an adhesive sheet, which comprises a step of developing a color of the color-developing compound.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet contains both a color-developing compound that develops color by reaction with an acid and an acid generator. Such a configuration is suitable for lowering the visible light transmittance by generating an acid from an acid generator to develop a color-developing compound in the pressure-sensitive adhesive layer after being bonded to the adherend.
  • the adhesive layer contains a rust preventive.
  • the acid generated by the acid generator in the adhesive layer causes metal corrosion on the wiring. Is suitable for suppressing the occurrence of.
  • the content of the rust preventive in the pressure-sensitive adhesive layer is less than 100 parts by mass with respect to 100 parts by mass of the color-developing compound.
  • Such a configuration is suitable for suppressing the color development of the color-developing compound by the action of the rust preventive in the pressure-sensitive adhesive layer before bonding to the adherend, and therefore, visible light transmission of the pressure-sensitive adhesive layer. Suitable for reducing the sex after bonding the adherend.
  • the adhesive sheet as described above is suitable for reducing the visible light transmittance after being attached to the adherend, and is also suitable for suppressing metal corrosion in the adherend.
  • the metal corrosion of the wiring is suppressed while suppressing metal corrosion of the wiring. It is suitable for reducing the visible light transmittance of the adhesive sheet on the component at a desired timing.
  • FIG. 4A shows a step of preparing the first member
  • FIG. 4B shows a step of attaching the adhesive sheet to the first member
  • FIG. 4C shows a step of reducing the visible light transmittance of the adhesive sheet
  • 4D shows a step of sticking the second member to the adhesive sheet on the first member.
  • FIG. 1 is a schematic cross-sectional view of the pressure-sensitive adhesive sheet X according to the embodiment of the present invention.
  • the pressure-sensitive adhesive sheet X includes a pressure-sensitive adhesive layer 10.
  • the pressure-sensitive adhesive sheet X or the pressure-sensitive adhesive layer 10 has a sheet shape having a predetermined thickness, and has an upper surface and a lower surface extending in a direction (plane direction) orthogonal to the thickness direction.
  • the pressure-sensitive adhesive layer 10 is transparent (visible light transmissive) formed from a pressure-sensitive composition containing a base polymer, a color-developing compound that develops color by reaction with an acid, an acid generator, and a rust preventive. ) Is a pressure-sensitive adhesive layer.
  • the transparency of the pressure-sensitive adhesive layer 10 can be reduced ex post facto.
  • an acid is generated from the acid generator by an external stimulus applied at a desired timing, which will be described later, and the color-developing compound is developed by the acid to develop a highly transparent state. It can be changed to a low state (for example, it can be colored).
  • the base polymer is an adhesive component for developing adhesiveness in the adhesive layer 10.
  • the base polymer include polymers that exhibit rubber elasticity at room temperature, such as acrylic polymers, rubber-based polymers, polyester-based polymers, urethane-based polymers, polyether-based polymers, silicone-based polymers, polyamide-based polymers, and fluorine-based polymers. Can be mentioned. From the viewpoint of ensuring good transparency and adhesiveness 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 (meth) acrylic acid alkyl ester in a proportion of 50% by mass or more.
  • (Meta) acrylic acid shall mean acrylic acid and / or methacrylic acid.
  • Examples of the (meth) acrylic acid alkyl ester include a (meth) acrylic acid alkyl ester having a linear or branched 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 2 to 10 carbon atoms is preferably used, and butyl acrylate is more preferably used.
  • the ratio of the (meth) acrylic acid alkyl ester in the monomer component is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 70% by mass or more, from the viewpoint of appropriately expressing basic properties such as tackiness in the pressure-sensitive adhesive layer 10. Is 80% by mass or more, particularly preferably 90% by mass or more. The same ratio is, for example, 99% by mass or less.
  • the monomer component may contain one or more functional group-containing vinyl monomers copolymerizable with the (meth) acrylic acid alkyl ester.
  • the functional group-containing vinyl 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 ratio of the functional group-containing vinyl monomer in the monomer component is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass, from the viewpoint of ensuring the effect of using the functional group-containing vinyl monomer. % Or more.
  • the ratio is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 10% by mass or less.
  • Examples of the functional group-containing vinyl monomer include a carboxyl group-containing vinyl monomer, an acid anhydride vinyl monomer, a hydroxyl group-containing vinyl monomer, a sulfo group-containing vinyl monomer, a phosphoric acid group-containing vinyl monomer, a cyano group-containing vinyl monomer, and a glycidyl group-containing vinyl.
  • Monomers, aromatic vinyl monomers, vinyl ester monomers, and vinyl ether monomers can be mentioned.
  • the functional group-containing vinyl monomer may be used alone or in combination of two or more.
  • carboxyl group-containing vinyl monomer examples include acrylic acid, methacrylic acid, 2-carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid.
  • acid anhydride vinyl monomer examples include maleic anhydride and itaconic anhydride.
  • hydroxyl group-containing vinyl monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (. 4-Hydroxybutyl acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, and (4-Hydroxymethylcyclohexyl) methyl (meth) acrylate can be mentioned.
  • sulfo group-containing vinyl 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).
  • styrene sulfonic acid 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).
  • Acrylamide and (meth) acryloyloxynaphthalene sulfonic acid can be mentioned.
  • Examples of the phosphoric acid group-containing vinyl monomer include 2-hydroxyethylacryloyl phosphate.
  • Examples of the cyano group-containing vinyl monomer include acrylonitrile and methacrylonitrile.
  • Examples of the glycidyl group-containing vinyl monomer include glycidyl (meth) acrylate and -2-ethylglycidyl ether (meth) acrylate.
  • aromatic vinyl monomer examples include styrene, p-methylstyrene, o-methylstyrene, and ⁇ -methylstyrene.
  • Examples of the vinyl ester monomer include vinyl acetate and vinyl propionate.
  • Examples of the vinyl ether monomer include methyl vinyl ether and ethyl vinyl ether.
  • the monomer component preferably contains an acidic vinyl monomer having an anionic group.
  • the acidic vinyl monomer having an anionic group include the above-mentioned carboxyl group-containing vinyl monomer, sulfo group-containing vinyl monomer, and phosphoric acid group-containing vinyl monomer.
  • the proportion of the acidic vinyl monomer having an anionic group in the monomer component is preferably 1% by mass or more, more preferably 3% by mass or more.
  • the same ratio is, for example, 10% by mass or less, preferably 8% by mass or less.
  • the monomer component preferably contains substantially no basic vinyl monomer copolymerizable with the (meth) acrylic acid alkyl ester and having a lone electron pair.
  • the proportion of the basic vinyl monomer having a lone electron pair in the monomer component is, for example, 3% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0% by mass.
  • Examples of the basic vinyl monomer having an isolated electron pair include a heterocycle-containing basic vinyl monomer having nitrogen in the heterocycle, and specifically, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, and the like.
  • Examples thereof include vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholin, N-acryloylmorpholin, and N-vinylcaprolactam.
  • 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 a thermal polymerization initiator and a photopolymerization initiator can be used depending on the polymerization method.
  • 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-based polymerization initiator and a peroxide-based polymerization initiator.
  • examples of the azo-based 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, azobisisobutaleronitrile, 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'-dimethyleneisobutyramidine) dihydrochloride Can be mentioned.
  • the peroxide-based polymerization initiator include dibenzoyl peroxide, t-butyl permalate, and lauroyl peroxide.
  • the photopolymerization initiator examples include a benzoin ether type photopolymerization initiator, an acetophenone type photopolymerization initiator, an ⁇ -ketol type photopolymerization initiator, an aromatic sulfonyl chloride type photopolymerization initiator, and a photoactive oxime type photopolymerization initiator.
  • Agents benzoin-based photopolymerization initiators, benzyl-based photopolymerization initiators, benzophenone-based photopolymerization initiators, ketal-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators. Be done.
  • 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 for reacting with the cross-linking point to form a cross-linked structure include an isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, an oxazoline-based cross-linking agent, and an aziridine-based cross-linking agent.
  • examples thereof include a carbodiimide-based cross-linking agent and a metal chelate-based cross-linking agent.
  • the cross-linking agent may be used alone or in combination of two or more.
  • Examples of the isocyanate-based 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. Examples thereof include triisocyanate and polymethylene polyphenyl isocyanate.
  • examples of the isocyanate-based cross-linking agent include derivatives of these isocyanates (for example, isocyanurate-modified products and polyol-modified products).
  • examples of commercially available isocyanate-based 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 ().
  • Examples thereof include an isocyanurate form of hexamethylene diisocyanate (manufactured by Tosoh) and Takenate D110N (trimethylolpropane adduct form of xylylene diisocyanate, manufactured by Mitsui Chemicals).
  • epoxy-based 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 trimethyl propantri.
  • examples include glycidyl ether, diglycidyl aniline, diamine glycidyl amine, N, N, N', N'-tetraglycidyl-m-xylylene diamine, and 1,3-bis (N, N-diglycidyl aminomethyl) cyclohexane. ..
  • the amount of the cross-linking agent blended 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 crosslinked catalyst When a crosslinked structure is introduced into the base polymer, a crosslinked catalyst may be used to effectively proceed the crosslinking reaction.
  • the cross-linking catalyst include metal-based cross-linking catalysts such as tetra-n-butyl titanate, tetraisopropyl titanate, ferric nasem, butyl tin oxide, and dioctyl tin dilaurate.
  • 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.
  • the color-developing compound is a compound that changes from colorless (transparent) to colored (color-developed) by reaction with an acid, and is, for example, a leuco-based dye, p, p', p "-tris-dimethylaminotriphenylmethane, or the like.
  • Triarylmethane dyes diphenylmethane dyes such as 4,4-bis-dimethylaminophenylbenzhydrylbenzyl ether, fluorane dyes such as 3-diethylamino-6-methyl-7-chlorofluorane, 3-methylspirodi Spiropyran dyes such as naphthopyran and rhodamine dyes such as rhodamine-B-anilinolactum can be mentioned.
  • the color-developing compound may be used alone or in combination of two or more. From the viewpoint of ensuring good colorability in the pressure-sensitive adhesive layer 10, the pressure-sensitive composition preferably contains a leuco-based dye as a color-developing compound.
  • 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, and 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.
  • the acid generator examples include a photoacid generator that generates an acid when irradiated with active light and a thermoacid generator that generates an acid by heating.
  • a photoacid generator is used as the acid generator, the external stimulus for reducing the visible light transmittance of the pressure-sensitive adhesive layer 10 is irradiation with active light.
  • the type of active light as an external stimulus is determined by the type of photoacid generator (specifically, the wavelength of the active light that the photoacid generator generates acid).
  • the active light examples include ultraviolet rays, visible light, infrared rays, X-rays, ⁇ -rays, ⁇ -rays, and ⁇ -rays, and from the viewpoint of variety of equipment used and ease of handling, ultraviolet rays are preferable.
  • the external stimulus for reducing the visible light transmittance of the pressure-sensitive adhesive layer 10 is heating.
  • Examples of the photoacid generator include an onium compound that generates an acid by irradiation with ultraviolet rays.
  • 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.
  • the anion forming the onium salt for example, Cl -, Br -, I -, ZnCl 3 -, HSO 3 -, BF 4 -, PF 6 -, AsF 6 -, SbF 6 -, CH 3 SO 3 -, CF 3 SO 3 -, (C 6 F 5) 4 B -, (C 4 H 9) 4 B - , and the like.
  • the photoacid generator may be used alone or in combination of two or more.
  • the pressure-sensitive adhesive layer 10 preferably contains an onium salt composed of sulfonium and (C 6 F 5 ) 4 B ⁇ as an onium compound.
  • Examples of commercially available products of the photoacid generator for example, available from San-Apro Ltd. of CPI-310B (sulfonium and (C 6 F 5) 4 B - and onium salts) thereof.
  • thermoacid generator examples include aryl sulfonium salts and aryl iodonium salts.
  • 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, still more 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 10 parts by mass or less.
  • the amount of the acid generator 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, still more preferably 350 parts by mass or more, and more. For example, it is 1000 parts by mass or less, preferably 700 parts by mass or less, and more preferably 500 parts by mass or less. That is, the blending amount of the acid generator with respect to 2 parts by mass of the color-developing compound is, for example, 2 parts by mass or more, preferably 4 parts by mass or more, more preferably 6 parts by mass or more, still more preferably 7 parts by mass or more, and more. For example, it is 20 parts by mass or less, preferably 14 parts by mass or less, and more preferably 10 parts by mass or less.
  • rust preventive agent examples include triazole compounds, benzotriazole compounds, thiazole compounds, benzothiazole compounds, imidazole compounds, benzoimidazole compounds, azole compounds having hydroxyl groups, phosphorus compounds, amine compounds, and the like. And nitrite compounds.
  • the rust preventive may be used alone or in combination of two or more.
  • a benzotriazole-based compound is preferably used as the rust preventive material, and more preferably, a benzotriazole-based compound having a structure represented by the following formula (1) is used. ..
  • R is a substituent on the benzene ring, which is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, and a carboxyl group.
  • n in the formula (1) is an integer of 0 to 4, and n is 2 or more, n Rs may be the same as or different from each other.
  • the benzotriazole-based compound represented by the formula (1) include 1,2,3-benzotriazole, 5-methylbenzotriazole, 4-methylbenzotriazole, and carboxybenzotriazole.
  • the amount of the rust preventive compounded with respect to 100 parts by mass of the color-developing compound is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and further preferably 5 parts by mass from the viewpoint of ensuring the corrosion suppressing effect in the pressure-sensitive adhesive layer 10. It is more than a part. That is, the blending amount of the rust inhibitor with respect to 2 parts by mass of the color-developing compound is preferably 0.02 part by mass or more, more preferably 0.06 part by mass or more, and further preferably 0.1 part by mass or more.
  • the amount of the rust preventive compounded with respect to 100 parts by mass of the color-developing compound is preferably less than 100 parts by mass. It is 90 parts by mass or less, more preferably 85 parts by mass or less, further preferably 50 parts by mass or less, particularly preferably 30 parts by mass or less, and particularly preferably 10 parts by mass or less. That is, the amount of the rust preventive to be blended with respect to 2 parts by mass of the color-developing compound is preferably less than 2 parts by mass, preferably 1.8 parts by mass or less, more preferably 1.7 parts by mass or less, still more preferably 1 part by mass or less. , Especially preferably 0.6 parts by mass or less, and particularly preferably 0.2 parts by mass or less.
  • the blending amount of the rust inhibitor with respect to 100 parts by mass of the base polymer is preferably 0.02 parts by mass or more, more preferably 0.06 parts by mass or more, and further preferably 0.1 parts by mass or more.
  • the amount of the rust preventive compounded with respect to 100 parts by mass of the base polymer is preferably less than 2 parts by mass, more preferably 1.8 parts by mass or less, and further preferably 1.7 parts by mass or less.
  • the adhesive composition may contain other components if necessary.
  • Other components include, for example, silane coupling agents, tackifiers, plasticizers, softeners, antioxidants, fillers, antioxidants, surfactants, and antistatic agents.
  • the thickness of the pressure-sensitive adhesive layer 10 is, for example, 3 ⁇ m or more, preferably 10 ⁇ m or more, and 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 X, the thickness of the pressure-sensitive adhesive layer 10 is, for example, 100 ⁇ m or less, preferably 50 ⁇ m or less, and more preferably 30 ⁇ m or less.
  • the haze of the pressure-sensitive adhesive layer 10 is preferably 3% or less, more preferably 2% or less, further preferably 1% or less, still more preferably 0.8% or less, and particularly preferably 0.6% or less. Such a configuration is suitable for inspecting the presence or absence of foreign matter or air bubbles between the pressure-sensitive adhesive sheet X and its adherend surface after the pressure-sensitive adhesive sheet X is attached to a predetermined surface.
  • 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, for example, 80% or more, preferably 85% or more, more preferably. It is 90% or more, more preferably 92% or more.
  • Such a configuration is suitable for inspecting the presence or absence of foreign matter or air bubbles between the pressure-sensitive adhesive sheet X and its adherend surface after the pressure-sensitive adhesive sheet X is attached to a predetermined surface.
  • the average transmittance of the pressure-sensitive adhesive layer 10 at a wavelength of 400 to 700 nm after receiving the above-mentioned external stimulus is, for example, 70% or less, preferably 40% or less, more preferably 20% or less, still more preferably 17%. It is as follows. Such a configuration is suitable for preventing / suppressing the above-mentioned external light reflection on the adherend surface to which the adhesive sheet X is attached.
  • a pressure-sensitive adhesive composition containing various components for forming the pressure-sensitive adhesive layer 10 is applied onto a release film (first release film) to form a coating film, which is necessary from the coating film. It can be produced by drying and removing the solvent accordingly.
  • the release film examples include flexible plastic films such as polyethylene film, polypropylene film, polyethylene terephthalate film, and polyester film.
  • the thickness of the release film is, for example, 3 ⁇ m or more, and 200 ⁇ m or less, for example.
  • the surface of the release film is preferably subjected to a mold release treatment with a mold release agent such as silicone-based, fluorine-based, long-chain alkyl-based, or fatty acid amide-based, or a mold release treatment with silica powder.
  • 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 for removing the solvent is, for example, 50 ° C. to 200 ° C.
  • the drying time is, for example, 5 seconds to 20 minutes.
  • the cross-linking reaction involving the cross-linking agent in the sticky composition is promoted 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 undergone a surface release treatment, and the same film as described above can be used for the first release film.
  • the pressure-sensitive adhesive sheet X 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 X as needed when using the pressure-sensitive adhesive sheet X.
  • the adhesive sheet X may be a single-sided adhesive sheet with a base material having a base material 20 in addition to the pressure-sensitive adhesive layer 10.
  • the pressure-sensitive adhesive sheet X specifically includes the pressure-sensitive adhesive layer 10 and the base material 20 arranged on one side thereof, and preferably comes into contact with the base material 10 on one side thereof. It includes a pressure-sensitive adhesive layer 10 to be arranged.
  • Such an adhesive sheet X can be used as a reinforcing adhesive sheet for protecting the surface of a member and imparting impact resistance.
  • 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 base material 20 may be made of one kind of material or may be made of two or more kinds of materials.
  • the base material 20 may have a single-layer structure or a multi-layer structure.
  • the base material 20 may be a non-stretched film, a uniaxially stretched film, or a biaxially stretched film. From the viewpoint of achieving both transparency and mechanical strength of the base material 20, the plastic material for constructing 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, for example, 10% or less, preferably 5% or less, and more preferably 3% or less.
  • the haze of the base material 20 can be measured using a haze meter in accordance with JIS K7136 (2000).
  • the surface 11 on the pressure-sensitive adhesive layer 10 side of the base material 20 may be subjected to a physical treatment, a chemical treatment, or an undercoating 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 X, the thickness of the base material 20 is preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, and more preferably 100 ⁇ m or less.
  • the pressure-sensitive adhesive sheet X shown in FIG. 2 can be manufactured in the same manner as the above-mentioned manufacturing method except that the base material 20 is used instead of the first release film, for example.
  • the pressure-sensitive adhesive layer 10 of the pressure-sensitive adhesive sheet X contains both a color-developing compound that develops color by reaction with an acid and an acid generator.
  • Such a configuration is suitable for lowering the visible light transmittance by generating an acid from an acid generator to develop a color-developing compound in the pressure-sensitive adhesive layer 10 after being bonded to the adherend.
  • the adhesive sheet X after the adhesive sheet X is attached to a predetermined surface, foreign matter between the adhesive sheet X and the adherend surface in a state where the transparency (visible light transmission) of the adhesive sheet X is relatively high. It is possible to inspect the presence or absence of air bubbles and air bubbles, and after passing the inspection, apply an external stimulus to the pressure-sensitive adhesive layer 10 of the sheet to change the transparency of the sheet to a relatively low state.
  • the adhesive layer 10 contains a rust preventive as described above.
  • the acid generated by the acid generator in the pressure-sensitive adhesive layer 10 is applied to the wiring. Suitable for suppressing the occurrence of metal corrosion.
  • the content of the rust preventive in the pressure-sensitive adhesive layer 10 is less than 100 parts by mass with respect to 100 parts by mass of the color-developing compound, preferably 90 parts by mass or less, and more preferably 85 parts by mass. Below, it is more preferably 50 parts by mass or less, particularly preferably 30 parts by mass or less, and particularly preferably 10 parts by mass or less. Such a configuration is suitable for suppressing the color development of the color-developing compound by the action of the rust preventive agent in the pressure-sensitive adhesive layer 10 before bonding to the adherend.
  • a benzotriazole-based compound having active hydrogen when used as a rust preventive, the above configuration regarding the content of the rust preventive agent suppresses the color development of the chromogenic compound by the active hydrogen of the benzotriazole-based compound. Suitable.
  • a configuration suitable for suppressing the color development of the color-developing compound by the action of the rust preventive is suitable for reducing the visible light transmittance of the pressure-sensitive adhesive layer 10 after the adherend is attached.
  • the adhesive sheet X is suitable for reducing the visible light transmittance after being attached to the adherend, and is also suitable for suppressing metal corrosion in the adherend.
  • Such an adhesive sheet X can be suitably used as, for example, an external light reflection inhibitor to be assembled to an organic EL panel.
  • FIG. 3 is a schematic cross-sectional view of the member Y with the adhesive sheet.
  • the member Y with an adhesive sheet includes a member 31 (first member), a member 32 (second member), and an adhesive sheet X.
  • the member 31 is, for example, an optical device, an electronic device, or a component thereof.
  • the 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 adhesive sheet X is interposed between the members 31 and 32 to join them. Specifically, the pressure-sensitive adhesive sheet X is arranged so as to be in contact with one surface of the member 31 in the thickness direction, and the member 32 is arranged so as to be in contact with one side surface of the pressure-sensitive adhesive sheet X in the thickness direction.
  • FIG. 4 shows a method of manufacturing the member Y with the adhesive sheet.
  • This manufacturing method includes a preparation step, a first bonding step, and a transparency lowering step, and in the present embodiment, further includes a second bonding step.
  • the above-mentioned member 31 is prepared.
  • the adhesive sheet X is bonded to the member 31 as shown in FIG. 4B.
  • the presence or absence of foreign matter or air bubbles between the adhesive sheet adhering surface 31a of the member 31 and the adhesive sheet X is inspected.
  • an external stimulus is then applied to the pressure-sensitive adhesive layer 10 on the member 31 in the transparency lowering step, and as shown in FIG. 4C, the visible light transmission of the pressure-sensitive adhesive layer 10 is transmitted. Reduce the rate.
  • the pressure-sensitive adhesive layer 10 contains a photoacid generator as an acid generator
  • the external stimulus is irradiation with active light.
  • the active light is, for example, irradiated to the pressure-sensitive adhesive layer 10 of the pressure-sensitive adhesive sheet X from the side opposite to the member 31.
  • the pressure-sensitive adhesive layer 10 contains a thermoacid generator as the acid generator, the external stimulus is heating.
  • an acid is generated from the acid generator in the pressure-sensitive adhesive layer 10 by applying an external stimulus to the pressure-sensitive adhesive layer 10, and a color-developing compound is developed by the reaction with the acid.
  • the above-mentioned member 32 is bonded to the adhesive sheet X on the member 31.
  • the above-mentioned transparency reducing step may be carried out after the second bonding step instead of being carried out before such a second bonding step.
  • the member Y with the adhesive sheet can be manufactured as described above.
  • the above-mentioned adhesive sheet X is used. Therefore, in the manufacturing method, the same technical effect as described above is exhibited with respect to the pressure-sensitive adhesive sheet X.
  • Example 1 ⁇ Preparation of base polymer>
  • a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube, and a nitrogen gas introduction tube 95 parts by mass of butyl acrylate (BA), 5 parts by mass of acrylic acid (AA), and 2, as a polymerization initiator,
  • a mixture (reaction solution containing a monomer component) containing 0.2 parts by mass of 2'-azobisisobutyronitrile (AIBN) and 233 parts by mass of ethyl acetate as a solvent was mixed in a nitrogen atmosphere at 60 ° C. for 7 hours. Stirred below (polymerization reaction).
  • a polymer solution containing an acrylic polymer was obtained.
  • the weight average molecular weight (Mw) of the acrylic polymer in this polymer solution was 600,000.
  • the photoacid generator (trade name: CPI-310B, sulfonium and (C 6 F 5) 4 B - onium salts with, manufactured by SAN-APRO Ltd.) 7 parts by mass, color forming compounds 2 parts by mass of leuco dye (trade name "BLACK ND1", manufactured by Yamada Chemical Industry Co., Ltd.) and 1,2,3-benzotriazole (trade name "BT-120", manufactured by Johoku Chemical Industry Co., Ltd.) as a rust preventive. (Manufactured by) 0.1 parts by mass was added and mixed to obtain an adhesive composition.
  • Example 2 In the preparation of the adhesive composition, the amount of the rust inhibitor compounded is 0.05 parts by mass (Example 2), 0.5 parts by mass (Example 3), or 1 part by mass instead of 0.1 parts by mass.
  • Example 2 Each of the pressure-sensitive adhesive sheets of Examples 2 to 4 was produced in the same manner as the pressure-sensitive adhesive sheet of Example 1 except that the case of Example 4 was used.
  • Comparative Example 1 A pressure-sensitive adhesive sheet of Comparative Example 1 was prepared in the same manner as the pressure-sensitive adhesive sheet of Example 1 except that a rust preventive was not used in the preparation of the pressure-sensitive adhesive composition.
  • Comparative Example 2 The pressure-sensitive adhesive sheet of Comparative Example 2 was prepared in the same manner as the pressure-sensitive adhesive sheet of Example 1 except that the amount of the rust inhibitor compounded was 2 parts by mass instead of 0.1 parts by mass in the preparation of the pressure-sensitive adhesive composition. ..
  • the sample for this measurement was prepared as follows. First, the second release film was peeled off from the adhesive sheet. Next, the adhesive sheet was attached to the slide glass on the surface exposed by the peeling. In this bonding, a 2 kg hand roller was reciprocated once with respect to the adhesive sheet (with the first release film) on the slide glass. Next, the first release film was peeled off from the adhesive sheet on the slide glass.
  • the average transmittance at a wavelength of 400 to 700 nm was measured using a spectrophotometer U4100 manufactured by Hitachi High-Technologies Corporation (the first average in the state before UV irradiation). Transmittance measurement).
  • the measurement sample is arranged so that the adhesive sheet of the measurement sample is located on the light source side and the slide glass of the sample is located on the detector side.
  • Transmittance measurement was carried out.
  • the transmittance spectrum obtained by measuring only the slide glass under the same conditions was used as the baseline.
  • the measurement results (average transmittance at a wavelength of 400 to 700 nm before UV irradiation) are shown in Table 1.
  • the average transmittance at a wavelength of 400 to 700 nm after irradiation with ultraviolet rays (UV) was measured for each of the pressure-sensitive adhesive sheets of Examples 1 to 4 and Comparative Examples 1 and 2.
  • the sample for this measurement was prepared in the same manner as the sample for the first average transmittance measurement.
  • the measurement sample was irradiated with ultraviolet rays.
  • a UV-LED lamp was used as a light source, the irradiation wavelength was 365 nm, and the irradiation light amount was 8000 mJ / cm 2 .
  • the average transmittance at a wavelength of 400 to 700 nm was measured using a spectrophotometer U4100 manufactured by Hitachi High-Technologies Corporation (second average transmittance measurement in the state after UV irradiation). ).
  • the measurement conditions are the same as those for the first average transmittance measurement.
  • the measurement results are shown in Table 1.
  • ⁇ Haze> The haze was measured for each of the pressure-sensitive adhesive sheets of Examples 1 to 4 and Comparative Examples 1 and 2. Specifically, first, a sample for haze measurement was prepared in the same manner as the sample for average transmittance measurement described above. Next, with respect to the measurement sample, the haze was measured according to JIS K7136 (2000) using the haze meter "HM-150N" manufactured by Murakami Color Technology Research Institute. The measurement results are listed in Table 1.
  • the sample for color difference measurement (first sample for color difference measurement) was prepared as follows. First, the second release film was peeled off from the adhesive sheet. Next, an adhesive sheet was attached to an adherend with a Cu film on the surface exposed by the peeling (the adherend with a Cu film is a polyethylene terephthalate film having a Cu vapor-deposited film formed on the surface). ). In this bonding, a 2 kg hand roller was reciprocated once with respect to the adhesive sheet (with the first release film) on the adherend with the Cu film. Next, the first release film was peeled off from the adhesive sheet on the adherend with the Cu film.
  • the measurement sample was stored for 48 hours in a high temperature and high humidity environment.
  • the storage temperature is 60 ° C. and the storage humidity is 90% relative humidity.
  • L * a * b * L * , a * and b * in the color system was measured.
  • the tint at the time of the second color measurement became stronger than the tint at the time of the first color measurement.
  • the color difference ⁇ E * ab was obtained by the following formula (in the following formula, ⁇ L * is L * and the second in the first color measurement. is the difference between L * in the color measurement, .DELTA.a * is the difference between a * in a * and a second color measurement at the first color measurement, [Delta] b * is the first color The difference between b * in the measurement and b * in the second color measurement). It can be evaluated that the smaller the color difference in the first and second color measurements described above, the more the corrosion that induces discoloration on the metal surface (Cu film surface) is suppressed. Table 1 shows ⁇ E * ab obtained based on the measurement data of the first color measurement and the second color measurement on the adhesive sheet in the state before UV irradiation as the color difference ⁇ E 1.
  • the sample for color difference measurement was prepared as follows. First, the adhesive sheet was irradiated with ultraviolet rays. In the ultraviolet irradiation, a UV-LED lamp was used as a light source, the irradiation wavelength was 365 nm, and the irradiation light amount was 8000 mJ / cm 2 . Next, the second release film was peeled off from the adhesive sheet. Next, an adhesive sheet was attached to an adherend with a Cu film on the surface exposed by the peeling (the adherend with a Cu film is a polyethylene terephthalate film having a Cu vapor-deposited film formed on the surface). ). In this bonding, a 2 kg hand roller was reciprocated once with respect to the adhesive sheet (with the first release film) on the adherend with the Cu film. Next, the first release film was peeled off from the adhesive sheet on the adherend with the Cu film.
  • the adherend with a Cu film is a polyethylene terephthalate film having a Cu vapor-deposited film formed
  • Each of the pressure-sensitive adhesive sheets of Examples 1 to 4 (in the pressure-sensitive adhesive layer, a color-developing compound that develops color by the reaction of an acid generator and an acid, and a rust preventive agent, and the rust preventive agent content is a color-developing compound.
  • the average transmittance at a wavelength of 400 to 700 nm was 94.2% (Example 1) and 94.0% (Example 1) before being irradiated with ultraviolet rays. 2), 92.9% (Example 3) and 93.1% (Example 4), which are as high as 12.3% (Example 1) and 14.4% (Example 2) by being irradiated with ultraviolet rays. , 14.8% (Example 3) and 16.4% (Example 4). From this, it can be seen that each of the adhesive sheets of Examples 1 to 4 is suitable for reducing the visible light transmittance after being attached to the adherend.
  • the above-mentioned color difference ⁇ E 1 before the ultraviolet irradiation and the above-mentioned color difference ⁇ E 2 after the ultraviolet irradiation take a small value of 5 or less. (It can be evaluated that the smaller the color difference, the more the corrosion that induces discoloration on the metal surface is suppressed).
  • the color difference ⁇ E 1 before irradiation with ultraviolet rays is 18.6, and the color difference ⁇ E 1 after irradiation with ultraviolet rays is 1. 2 is 23.4, which is much higher than 5.
  • the average transmittance at a wavelength of 400 to 700 nm is 73. It was as low as 7%, and the color difference ⁇ E 2 in the state after ultraviolet irradiation was 7.3, which was significantly higher than 5.
  • the color-developing compound develops color due to the action of the rust preventive even before the irradiation with ultraviolet rays, and the rust preventive and the color-developing property in a high temperature and high humidity environment. It is considered that the color difference ⁇ E 2 is increased as the interaction with the compound is strengthened and the color development progresses. From these, it can be seen that each of the pressure-sensitive adhesive sheets of Examples 1 to 4 is suitable for suppressing metal corrosion in the adherend.
  • the adhesive sheet of the present invention is used as an adhesive sheet to be attached to the surface of various devices such as optical devices and electronic devices, for example.

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  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
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Abstract

This pressure-sensitive adhesive sheet (X) comprises a pressure-sensitive adhesive layer comprising a base polymer, an acid generator, a color-assuming compound, which assumes a color upon reaction with an acid, and a corrosion inhibitor. The amount of the corrosion inhibitor contained in the pressure-sensitive adhesive layer is less than 100 parts by mass per 100 parts by mass of the color-assuming compound. This method for producing a member with a pressure-sensitive adhesive sheet attached thereto comprises a step in which the pressure-sensitive adhesive sheet (X) is applied to a member and a step in which an external stimulus is given to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet (X) on the member to cause the color-assuming compound to assume a color.

Description

粘着シートおよび粘着シート付き部材の製造方法Manufacturing method of adhesive sheet and member with adhesive sheet
　本発明は、粘着シートおよび粘着シート付き部材の製造方法に関する。 The present invention relates to an adhesive sheet and a method for manufacturing a member with an adhesive sheet.
　ディスプレイ用パネルとして実用化されている有機エレクトロルミネッセンス（ＥＬ）パネルでは、有機ＥＬ素子を自己発光させるための一対の電極のうちの一方または両方の電極として、反射性の高い金属電極層が設けられる。そのような金属電極層を含む素子が表示画面を構成するように配列されている有機ＥＬパネルでは、外光反射が生じやすい。 In an organic electroluminescence (EL) panel that has been put into practical use as a display panel, a highly reflective metal electrode layer is provided as one or both electrodes of a pair of electrodes for self-luminous emission of an organic EL element. .. External light reflection is likely to occur in an organic EL panel in which elements including such a metal electrode layer are arranged so as to form a display screen.
　有機ＥＬパネルでの外光反射を防ぐための手法として、有機ＥＬパネルにおける有機ＥＬ素子の光出射側に、外光反射を抑制しうる程度の可視光吸収能を有する層（光吸収層）を設けることが提案されている。そのような技術は、例えば下記の特許文献１に記載されている。特許文献１には、具体的には、カーボンブラック顔料および染料を含有して着色している粘着シートを、前記の光吸収層として設けることが記載されている。 As a method for preventing external light reflection in the organic EL panel, a layer (light absorbing layer) having a visible light absorbing ability capable of suppressing external light reflection is provided on the light emitting side of the organic EL element in the organic EL panel. It is proposed to provide. Such a technique is described in, for example, Patent Document 1 below. Patent Document 1 specifically describes that a pressure-sensitive adhesive sheet containing a carbon black pigment and a dye and colored is provided as the light absorption layer.
特開２０１７－２０３８１０号公報JP-A-2017-203810
　しかしながら、含有成分によって予め着色されている粘着シートによると、例えば有機ＥＬパネルの製造過程において、所定表面に対する貼り合わせの後に当該粘着シートとその被着面との間における異物や気泡の有無を検査しにくい。電子部品や光学部品への粘着シートの貼り合わせには、貼り合わせの後に粘着シートとその被着面との間における異物や気泡の有無を適切に検査可能なことが求められる。 However, according to the pressure-sensitive adhesive sheet pre-colored with the contained components, for example, in the manufacturing process of an organic EL panel, the presence or absence of foreign matter or air bubbles between the pressure-sensitive adhesive sheet and its adherend surface is inspected after bonding to a predetermined surface. It's hard to do. In order to bond the adhesive sheet to an electronic component or an optical component, it is required that the presence or absence of foreign matter or air bubbles between the adhesive sheet and its adherend surface can be appropriately inspected after the bonding.
　一方、電子部品や光学部品に貼り合わせられる粘着シートには、その被着体における粘着シート貼着箇所やその近傍に例えば金属配線がある場合に当該配線に金属腐食を生じさせないことが求められる。 On the other hand, the adhesive sheet to be attached to an electronic component or an optical component is required not to cause metal corrosion on the adhesive sheet attached to the adherend or when there is a metal wiring in the vicinity thereof, for example.
　本発明は、被着体に貼り合わせた後に可視光透過性を低下させるのに適するとともに当該被着体における金属腐食を抑制するのに適した粘着シート、および粘着シート付き部材の製造方法を提供する。 The present invention provides a pressure-sensitive adhesive sheet suitable for reducing visible light transmission after being bonded to an adherend and also suitable for suppressing metal corrosion in the adherend, and a method for manufacturing a member with the pressure-sensitive adhesive sheet. To do.
　本発明［１］は、ベースポリマーと、酸発生剤と、酸との反応により発色する発色性化合物と、当該発色性化合物１００質量部に対して１００質量部未満の防錆剤とを含有する粘着剤層を備える粘着シートを含む。 The present invention [1] contains a base polymer, an acid generator, a color-developing compound that develops color by reaction with an acid, and a rust preventive agent of less than 100 parts by mass with respect to 100 parts by mass of the color-developing compound. Includes an adhesive sheet with an adhesive layer.
　本発明［２］は、前記発色性化合物がロイコ染料である、上記［１］に記載の粘着シートを含む。 The present invention [2] includes the pressure-sensitive adhesive sheet according to the above [1], wherein the color-developing compound is a leuco dye.
　本発明［３］は、前記防錆剤がベンゾトリアゾール系化合物である、上記［１］または［２］に記載の粘着シートを含む。 The present invention [3] includes the pressure-sensitive adhesive sheet according to the above [1] or [2], wherein the rust preventive is a benzotriazole-based compound.
　本発明［４］は、前記ベースポリマーがアクリルポリマーである、上記［１］から［３］のいずれか一つに記載の粘着シートを含む。 The present invention [4] includes the pressure-sensitive adhesive sheet according to any one of the above [1] to [3], wherein the base polymer is an acrylic polymer.
　本発明［５］は、前記粘着剤層のヘイズが３％以下である、上記［１］から［４］のいずれか一つに記載の粘着シートを含む。 The present invention [5] includes the pressure-sensitive adhesive sheet according to any one of the above [1] to [4], wherein the haze of the pressure-sensitive adhesive layer is 3% or less.
　本発明［６］は、上記［１］から［５］のいずれか一つに記載の粘着シートを部材に貼り合わせる工程と、前記部材上の前記粘着シートの前記粘着剤層に外部刺激を付与して前記発色性化合物を発色させる工程とを含む、粘着シート付き部材の製造方法を含む。 In the present invention [6], the step of attaching the pressure-sensitive adhesive sheet according to any one of the above [1] to [5] to a member and applying an external stimulus to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet on the member. The present invention includes a method for manufacturing a member with an adhesive sheet, which comprises a step of developing a color of the color-developing compound.
　粘着シートの粘着剤層は、酸との反応により発色する発色性化合物と酸発生剤とを共に含有する。このような構成は、被着体に貼り合わせた後の粘着剤層において、酸発生剤から酸を発生させて発色性化合物を発色させることによって、可視光透過性を低下させるのに適する。 The pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet contains both a color-developing compound that develops color by reaction with an acid and an acid generator. Such a configuration is suitable for lowering the visible light transmittance by generating an acid from an acid generator to develop a color-developing compound in the pressure-sensitive adhesive layer after being bonded to the adherend.
　また、粘着剤層は、防錆剤を含有する。このような構成は、粘着シートが貼り合わされた被着体の粘着シート貼着箇所やその近傍に金属配線がある場合に、粘着剤層内の酸発生剤が発生する酸によって当該配線に金属腐食が生ずるのを抑制するのに適する。 In addition, the adhesive layer contains a rust preventive. In such a configuration, when there is a metal wiring in or near the place where the adhesive sheet is attached to the adherend to which the adhesive sheet is attached, the acid generated by the acid generator in the adhesive layer causes metal corrosion on the wiring. Is suitable for suppressing the occurrence of.
　加えて、粘着剤層における防錆剤の含有量は、発色性化合物１００質量部に対して１００質量部未満である。このような構成は、被着体への貼り合わせの前の粘着剤層において、防錆剤の作用によって発色性化合物を発色させるのを抑制するのに適し、従って、粘着剤層の可視光透過性を被着体貼合せ後に低下させるのに適する。 In addition, the content of the rust preventive in the pressure-sensitive adhesive layer is less than 100 parts by mass with respect to 100 parts by mass of the color-developing compound. Such a configuration is suitable for suppressing the color development of the color-developing compound by the action of the rust preventive in the pressure-sensitive adhesive layer before bonding to the adherend, and therefore, visible light transmission of the pressure-sensitive adhesive layer. Suitable for reducing the sex after bonding the adherend.
　以上のような粘着シートは、被着体に貼り合わせた後に可視光透過性を低下させるのに適するとともに、当該被着体における金属腐食を抑制するのに適する。 The adhesive sheet as described above is suitable for reducing the visible light transmittance after being attached to the adherend, and is also suitable for suppressing metal corrosion in the adherend.
　また、このような粘着シートが用いられる粘着シート付き部材の製造方法は、部材における粘着シート貼合せ箇所やその近傍に例えば金属配線がある場合であっても当該配線の金属腐食を抑制しつつ、部品上の粘着シートの可視光透過性を所望のタイミングで低下させるのに適する。 Further, in the method of manufacturing a member with an adhesive sheet in which such an adhesive sheet is used, even if there is, for example, a metal wiring in or near the adhesive sheet bonding portion of the member, the metal corrosion of the wiring is suppressed while suppressing metal corrosion of the wiring. It is suitable for reducing the visible light transmittance of the adhesive sheet on the component at a desired timing.
本発明の粘着シートの一実施形態の断面模式図である。It is sectional drawing of one Embodiment of the adhesive sheet of this invention. 本発明の粘着シートの変形例（粘着シートが基材付き片面粘着シートである場合）の断面模式図である。It is sectional drawing of the modification of the adhesive sheet of this invention (when the adhesive sheet is a single-sided adhesive sheet with a base material). 粘着シート付き部材の断面模式図である。It is sectional drawing of the member with an adhesive sheet. 本発明の粘着シート付き部材の製造方法の一実施形態を示す。図４Ａは、第１部材を用意する工程を示し、図４Ｂは、第１部材に粘着シートを貼り合わせる工程を示し、図４Ｃは、粘着シートの可視光透過性を低下させる工程を示し、図４Ｄは、第１部材上の粘着シートに第２部材を貼り合わせる工程を示す。An embodiment of the method for manufacturing a member with an adhesive sheet of the present invention is shown. FIG. 4A shows a step of preparing the first member, FIG. 4B shows a step of attaching the adhesive sheet to the first member, and FIG. 4C shows a step of reducing the visible light transmittance of the adhesive sheet. 4D shows a step of sticking the second member to the adhesive sheet on the first member.
　図１は、本発明の一実施形態である粘着シートＸの断面模式図である。粘着シートＸは、粘着剤層１０を備える。粘着シートＸないし粘着剤層１０は、所定の厚みのシート形状を有し、厚み方向と直交する方向（面方向）に延びる上面および下面を有する。 FIG. 1 is a schematic cross-sectional view of the pressure-sensitive adhesive sheet X according to the embodiment of the present invention. The pressure-sensitive adhesive sheet X includes a pressure-sensitive adhesive layer 10. The pressure-sensitive adhesive sheet X or the pressure-sensitive adhesive layer 10 has a sheet shape having a predetermined thickness, and has an upper surface and a lower surface extending in a direction (plane direction) orthogonal to the thickness direction.
　粘着剤層１０は、ベースポリマーと、酸との反応により発色する発色性化合物と、酸発生剤と、防錆剤とを含有する粘着性組成物から形成された、透明性（可視光透過性）を有する感圧接着剤層である。また、粘着剤層１０の透明性は、事後的に低下させることが可能である。具体的には、粘着剤層１０においては、所望のタイミングで付与される後述の外部刺激によって酸発生剤から酸を発生させ、当該酸によって発色性化合物を発色させて、透明性が高い状態から低い状態へと変化させうる（例えば着色させうる）。 The pressure-sensitive adhesive layer 10 is transparent (visible light transmissive) formed from a pressure-sensitive composition containing a base polymer, a color-developing compound that develops color by reaction with an acid, an acid generator, and a rust preventive. ) Is a pressure-sensitive adhesive layer. In addition, the transparency of the pressure-sensitive adhesive layer 10 can be reduced ex post facto. Specifically, in the pressure-sensitive adhesive layer 10, an acid is generated from the acid generator by an external stimulus applied at a desired timing, which will be described later, and the color-developing compound is developed by the acid to develop a highly transparent state. It can be changed to a low state (for example, it can be colored).
　ベースポリマーは、粘着剤層１０において粘着性を発現させるための粘着成分である。ベースポリマーとしては、例えば、アクリルポリマー、ゴム系ポリマー、ポリエステル系ポリマー、ウレタン系ポリマー、ポリエーテル系ポリマー、シリコーン系ポリマー、ポリアミド系ポリマー、フッ素系ポリマー等の、室温域でゴム弾性を示すポリマーが挙げられる。粘着剤層１０における良好な透明性および粘着性を確保する観点から、ベースポリマーとしては、好ましくはアクリルポリマーが用いられる。 The base polymer is an adhesive component for developing adhesiveness in the adhesive layer 10. Examples of the base polymer include polymers that exhibit rubber elasticity at room temperature, such as acrylic polymers, rubber-based polymers, polyester-based polymers, urethane-based polymers, polyether-based polymers, silicone-based polymers, polyamide-based polymers, and fluorine-based polymers. Can be mentioned. From the viewpoint of ensuring good transparency and adhesiveness in the pressure-sensitive adhesive layer 10, an acrylic polymer is preferably used as the base polymer.
　粘着剤層１０におけるベースポリマーの含有割合は、粘着剤層１０でのベースポリマーの機能を適切に発現させる観点から、好ましくは５０質量％以上、より好ましくは６０質量％以上、さらに好ましくは７０質量％以上である。 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.
　アクリルポリマーは、例えば、（メタ）アクリル酸アルキルエステルを５０質量％以上の割合で含むモノマー成分を重合することにより得られるポリマーである。「（メタ）アクリル酸」とは、アクリル酸および／またはメタクリル酸をいうものとする。 The acrylic polymer is, for example, a polymer obtained by polymerizing a monomer component containing (meth) acrylic acid alkyl ester in a proportion of 50% by mass or more. "(Meta) acrylic acid" shall mean acrylic acid and / or methacrylic acid.
　（メタ）アクリル酸アルキルエステルとしては、例えば、直鎖状または分岐状の炭素数１～２０のアルキル基を有する（メタ）アクリル酸アルキルエステルが挙げられる。そのような（メタ）アクリル酸アルキルエステルとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓ－ブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸イソペンチル、（メタ）アクリル酸ネオペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ウンデシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸イソトリドデシル、（メタ）アクリル酸テトラデシル、（メタ）アクリル酸イソテトラデシル、（メタ）アクリル酸ペンタデシル、（メタ）アクリル酸ヘキサデシル、（メタ）アクリル酸ヘプタデシル、（メタ）アクリル酸オクタデシル、（メタ）アクリル酸イソオクタデシル、（メタ）アクリル酸ノナデシル、および（メタ）アクリル酸エイコシルが挙げられる。（メタ）アクリル酸アルキルエステルは、単独で用いられてもよいし、二種類以上が併用されてもよい。（メタ）アクリル酸アルキルエステルとしては、好ましくは、炭素数２～１０のアルキル基を有するアクリル酸アルキルエステルが用いられ、より好ましくはアクリル酸ブチルが用いられる。 Examples of the (meth) acrylic acid alkyl ester include a (meth) acrylic acid alkyl ester having a linear or branched 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. Isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, (meth) ) Hexyl acrylate, (meth) heptyl acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, ( Decyl acrylate, Isodecyl (meth) acrylate, Undecyl (meth) acrylate, Dodecyl (meth) acrylate, Isotridodecyl (meth) acrylate, Tetradecyl (meth) acrylate, Isotetra (meth) acrylate Decyl, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, isooctadecyl (meth) acrylate, nonadecil (meth) acrylate, and (meth) acrylic Acrylic acid acid is mentioned. The (meth) acrylic acid alkyl ester may be used alone or in combination of two or more. As the (meth) acrylic acid alkyl ester, an acrylic acid alkyl ester having an alkyl group having 2 to 10 carbon atoms is preferably used, and butyl acrylate is more preferably used.
　モノマー成分における（メタ）アクリル酸アルキルエステルの割合は、粘着剤層１０において粘着性等の基本特性を適切に発現させる観点から、好ましくは６０質量％以上、より好ましくは７０質量％以上、さらに好ましくは８０質量％以上、特に好ましくは９０質量％以上である。同割合は、例えば９９質量％以下である。 The ratio of the (meth) acrylic acid alkyl ester in the monomer component is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 70% by mass or more, from the viewpoint of appropriately expressing basic properties such as tackiness in the pressure-sensitive adhesive layer 10. Is 80% by mass or more, particularly preferably 90% by mass or more. The same ratio is, for example, 99% by mass or less.
　モノマー成分は、（メタ）アクリル酸アルキルエステルと共重合可能な１種または２種以上の官能基含有ビニルモノマーを含んでいてもよい。官能基含有ビニルモノマーは、アクリルポリマーへの架橋点の導入、アクリルポリマーの凝集力の確保など、アクリルポリマーの改質に役立つ。モノマー成分における官能基含有ビニルモノマーの割合は、官能基含有ビニルモノマーを用いることによる効果を確保する観点から、好ましくは０.１質量％以上、より好ましくは１質量％以上、さらに好ましくは３質量％以上である。同割合は、好ましくは４０質量％以下、より好ましくは３０質量％以下、さらに好ましくは２０質量％以下、特に好ましくは１０質量％以下である。 The monomer component may contain one or more functional group-containing vinyl monomers copolymerizable with the (meth) acrylic acid alkyl ester. The functional group-containing vinyl 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 ratio of the functional group-containing vinyl monomer in the monomer component is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass, from the viewpoint of ensuring the effect of using the functional group-containing vinyl monomer. % Or more. The ratio is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 10% by mass or less.
　官能基含有ビニルモノマーとしては、例えば、カルボキシル基含有ビニルモノマー、酸無水物ビニルモノマー、水酸基含有ビニルモノマー、スルホ基含有ビニルモノマー、リン酸基含有ビニルモノマー、シアノ基含有ビニルモノマー、グリシジル基含有ビニルモノマー、芳香族ビニルモノマー、ビニルエステルモノマー、およびビニルエーテルモノマーが挙げられる。官能基含有ビニルモノマーは、単独で用いられてもよいし、二種類以上が併用されてもよい。 Examples of the functional group-containing vinyl monomer include a carboxyl group-containing vinyl monomer, an acid anhydride vinyl monomer, a hydroxyl group-containing vinyl monomer, a sulfo group-containing vinyl monomer, a phosphoric acid group-containing vinyl monomer, a cyano group-containing vinyl monomer, and a glycidyl group-containing vinyl. Monomers, aromatic vinyl monomers, vinyl ester monomers, and vinyl ether monomers can be mentioned. The functional group-containing vinyl monomer may be used alone or in combination of two or more.
　カルボキシル基含有ビニルモノマーとしては、例えば、アクリル酸、メタクリル酸、（メタ）アクリル酸２－カルボキシエチル、（メタ）アクリル酸カルボキシペンチル、イタコン酸、マレイン酸、フマル酸、およびクロトン酸が挙げられる。 Examples of the carboxyl group-containing vinyl monomer include acrylic acid, methacrylic acid, 2-carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid.
　酸無水物ビニルモノマーとしては、例えば、無水マレイン酸および無水イタコン酸が挙げられる。 Examples of the acid anhydride vinyl monomer include maleic anhydride and itaconic anhydride.
　水酸基含有ビニルモノマーとしては、例えば、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸４－ヒドロキシブチル、（メタ）アクリル酸６－ヒドロキシヘキシル、（メタ）アクリル酸８－ヒドロキシオクチル、（メタ）アクリル酸１０－ヒドロキシデシル、（メタ）アクリル酸１２－ヒドロキシラウリル、および(４－ヒドロキシメチルシクロへキシル)メチル（メタ）アクリレートが挙げられる。 Examples of the hydroxyl group-containing vinyl monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (. 4-Hydroxybutyl acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, and (4-Hydroxymethylcyclohexyl) methyl (meth) acrylate can be mentioned.
　スルホ基含有ビニルモノマーとしては、例えば、スチレンスルホン酸、アリルスルホン酸、ビニルスルホン酸ナトリウム、２－（メタ）アクリルアミド－２－メチルプロパンスルホン酸、（メタ）アクリルアミドプロパンスルホン酸、スルホプロピル（メタ）アクリレート、および（メタ）アクリロイルオキシナフタレンスルホン酸が挙げられる。 Examples of the sulfo group-containing vinyl monomer 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). Acrylamide and (meth) acryloyloxynaphthalene sulfonic acid can be mentioned.
　リン酸基含有ビニルモノマーとしては、例えば、２－ヒドロキシエチルアクリロイルホスフェートが挙げられる。 Examples of the phosphoric acid group-containing vinyl monomer include 2-hydroxyethylacryloyl phosphate.
　シアノ基含有ビニルモノマーとしては、例えば、アクリロニトリルおよびメタクリロニトリルが挙げられる。 Examples of the cyano group-containing vinyl monomer include acrylonitrile and methacrylonitrile.
　グリシジル基含有ビニルモノマーとしては、例えば、（メタ）アクリル酸グリシジルおよび（メタ）アクリル酸－２－エチルグリシジルエーテルが挙げられる。 Examples of the glycidyl group-containing vinyl monomer include glycidyl (meth) acrylate and -2-ethylglycidyl ether (meth) acrylate.
　芳香族ビニルモノマーとしては、例えば、スチレン、ｐ－メチルスチレン、ｏ－メチルスチレン、およびα－メチルスチレンが挙げられる。 Examples of the aromatic vinyl monomer include styrene, p-methylstyrene, o-methylstyrene, and α-methylstyrene.
　ビニルエステルモノマーとしては、例えば、酢酸ビニルおよびプロピオン酸ビニルが挙げられる。 Examples of the vinyl ester monomer include vinyl acetate and vinyl propionate.
　ビニルエーテルモノマーとしては、例えば、メチルビニルエーテルおよびエチルビニルエーテルが挙げられる。 Examples of the vinyl ether monomer include methyl vinyl ether and ethyl vinyl ether.
　モノマー成分は、好ましくは、アニオン性基を有する酸性ビニルモノマーを含む。アニオン性基を有する酸性ビニルモノマーとしては、例えば、上述のカルボキシル基含有ビニルモノマー、スルホ基含有ビニルモノマー、およびリン酸基含有ビニルモノマーが挙げられる。モノマー成分が、アニオン性基を有する酸性ビニルモノマーを含む場合、当該モノマー成分から形成されるアクリルポリマーとともに粘着剤層１０中に含まれる酸発生剤から外部刺激に因って生じる強酸の乖離が、促進される傾向にある。そのため、粘着剤層１０中の発色性化合物の発色が強まる傾向にあり、また、粘着剤層１０の透明性低下状態が安定化する傾向にある。このような効果を得る観点からは、モノマー成分における、アニオン性基を有する酸性ビニルモノマーの割合は、好ましくは１質量％以上、より好ましくは３質量％以上である。また、同割合は、例えば１０質量％以下であり、好ましくは８質量％以下である。 The monomer component preferably contains an acidic vinyl monomer having an anionic group. Examples of the acidic vinyl monomer having an anionic group include the above-mentioned carboxyl group-containing vinyl monomer, sulfo group-containing vinyl monomer, and phosphoric acid group-containing vinyl monomer. When the monomer component contains an acidic vinyl monomer having an anionic group, the divergence of a strong acid caused by an external stimulus from the acid generator contained in the pressure-sensitive adhesive layer 10 together with the acrylic polymer formed from the monomer component It tends to be promoted. Therefore, the color development of the color-developing compound in the pressure-sensitive adhesive layer 10 tends to be strengthened, and the transparency-reduced state of the pressure-sensitive adhesive layer 10 tends to be stabilized. From the viewpoint of obtaining such an effect, the proportion of the acidic vinyl monomer having an anionic group in the monomer component is preferably 1% by mass or more, more preferably 3% by mass or more. The same ratio is, for example, 10% by mass or less, preferably 8% by mass or less.
　モノマー成分は、好ましくは、（メタ）アクリル酸アルキルエステルと共重合可能であって孤立電子対を有する塩基性ビニルモノマーを実質的に含まない。モノマー成分における、孤立電子対を有する塩基性ビニルモノマーの割合は、例えば３質量％以下、好ましくは１質量％以下、さらに好ましくは０．５質量％以下、とりわけ好ましくは０質量％である。モノマー成分が、孤立電子対を有する塩基性ビニルモノマーを実質的に含まない場合、粘着剤層１０の透明性低下状態が安定化する傾向にある。 The monomer component preferably contains substantially no basic vinyl monomer copolymerizable with the (meth) acrylic acid alkyl ester and having a lone electron pair. The proportion of the basic vinyl monomer having a lone electron pair in the monomer component is, for example, 3% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0% by mass. When the monomer component does not substantially contain the basic vinyl monomer having a lone electron pair, the transparent state of the pressure-sensitive adhesive layer 10 tends to be stabilized.
　孤立電子対を有する塩基性ビニルモノマーとしては、例えば、複素環に窒素を有する複素環含有塩基性ビニルモノマーが挙げられ、具体的には、Ｎ－ビニルピロリドン、メチルビニルピロリドン、ビニルピリジン、ビニルピペリドン、ビニルピリミジン、ビニルピペラジン、ビニルピラジン、ビニルピロール、ビニルイミダゾール、ビニルオキサゾール、ビニルモルホリン、Ｎ－アクリロイルモルホリン、およびＮ－ビニルカプロラクタムが挙げられる。 Examples of the basic vinyl monomer having an isolated electron pair include a heterocycle-containing basic vinyl monomer having nitrogen in the heterocycle, and specifically, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, and the like. Examples thereof include vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholin, N-acryloylmorpholin, and N-vinylcaprolactam.
　アクリルポリマーは、上述のモノマー成分を重合させることによって形成することができる。重合手法としては、例えば溶液重合、塊状重合、および乳化重合が挙げられ、好ましくは溶液重合が挙げられる。溶液重合では、例えば、モノマー成分と重合開始剤とを溶媒に配合して反応溶液を調製した後、その反応溶液を加熱する。そして、反応溶液中でのモノマー成分の重合反応を経ることによって、アクリルポリマーを含むアクリルポリマー溶液を得ることができる。重合開始剤としては、重合方法に応じて、熱重合開始剤および光重合開始剤を用いることができる。重合開始剤の使用量は、モノマー成分１００質量部に対して、例えば０．０５質量部以上であり、また、例えば１質量部以下である。 Acrylic polymer can be formed by polymerizing the above-mentioned monomer components. Examples of the polymerization method include solution polymerization, bulk polymerization, and emulsion polymerization, and solution polymerization is preferable. In 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. As the polymerization initiator, a thermal polymerization initiator and a photopolymerization initiator can be used depending on the polymerization method. 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.
　熱重合開始剤としては、例えば、アゾ系重合開始剤および過酸化物系重合開始剤が挙げられる。アゾ系重合開始剤としては、例えば、２,２'－アゾビスイソブチロニトリル、２,２'－アゾビス－２－メチルブチロニトリル、２,２'－アゾビス(２－メチルプロピオン酸)ジメチル、４,４'－アゾビス－４－シアノバレリアン酸、アゾビスイソバレロニトリル、２,２'－アゾビス(２－アミジノプロパン)ジヒドロクロライド、２,２'－アゾビス[２－(５－メチル－２－イミダゾリン－２－イル)プロパン]ジヒドロクロライド、２,２'－アゾビス(２－メチルプロピオンアミジン)二硫酸塩、および、２,２'－アゾビス(Ｎ,Ｎ'－ジメチレンイソブチルアミジン)ジヒドロクロライドが挙げられる。過酸化物系重合開始剤としては、例えば、ジベンゾイルペルオキシド、ｔ－ブチルペルマレエ－ト、および過酸化ラウロイルが挙げられる。 Examples of the thermal polymerization initiator include an azo-based polymerization initiator and a peroxide-based polymerization initiator. Examples of the azo-based 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, azobisisobutaleronitrile, 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'-dimethyleneisobutyramidine) dihydrochloride Can be mentioned. Examples of the peroxide-based polymerization initiator include dibenzoyl peroxide, t-butyl permalate, and lauroyl peroxide.
　光重合開始剤としては、例えば、ベンゾインエーテル系光重合開始剤、アセトフェノン系光重合開始剤、α－ケトール系光重合開始剤、芳香族スルホニルクロリド系光重合開始剤、光活性オキシム系光重合開始剤、ベンゾイン系光重合開始剤、ベンジル系光重合開始剤、ベンゾフェノン系光重合開始剤、ケタール系光重合開始剤、チオキサントン系光重合開始剤、および、アシルフォスフィンオキサイド系光重合開始剤が挙げられる。 Examples of the photopolymerization initiator include a benzoin ether type photopolymerization initiator, an acetophenone type photopolymerization initiator, an α-ketol type photopolymerization initiator, an aromatic sulfonyl chloride type photopolymerization initiator, and a photoactive oxime type photopolymerization initiator. Agents, benzoin-based photopolymerization initiators, benzyl-based photopolymerization initiators, benzophenone-based photopolymerization initiators, ketal-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators. Be done.
　アクリルポリマーの重量平均分子量は、粘着剤層１０における凝集力の確保の観点からは、好ましくは１０００００以上、より好ましくは３０００００以上、さらに好ましくは５０００００以上である。同重量平均分子量は、好ましくは５００００００以下、より好ましくは３００００００以下、さらに好ましくは２００００００以下である。アクリルポリマーの重量平均分子量は、ゲル・パーミエーション・クロマトグラフ（ＧＰＣ）によって測定してポリスチレン換算により算出される。 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.
　ベースポリマーのガラス転移温度（Ｔｇ）は、好ましくは０℃以下、より好ましくは－１０℃以下、さらに好ましくは－２０℃以下である。同ガラス転移温度は、例えば－８０℃以上である。 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.
　ポリマーのガラス転移温度（Ｔｇ）については、下記のＦｏｘの式に基づき求められるガラス転移温度（理論値）を用いることができる。Ｆｏｘの式は、ポリマーのガラス転移温度Ｔｇと、当該ポリマーを構成するモノマーのホモポリマーのガラス転移温度Ｔｇｉとの関係式である。下記のＦｏｘの式において、Ｔｇはポリマーのガラス転移温度（℃）を表し、Ｗｉは当該ポリマーを構成するモノマーｉの重量分率を表し、Ｔｇｉは、モノマーｉから形成されるホモポリマーのガラス転移温度（℃）を示す。ホモポリマーのガラス転移温度については文献値を用いることができ、例えば、「Polymer Handbook」（第４版，John Wiley & Sons, Inc., 1999年）および「新高分子文庫７ 塗料用合成樹脂入門」（北岡協三著，高分子刊行会，1995年）には、各種のホモポリマーのガラス転移温度が挙げられている。一方、モノマーのホモポリマーのガラス転移温度については、特開２００７－５１２７１号公報に具体的に記載されている手法によって求めることも可能である。 For 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. In the Fox formula below, Tg represents the glass transition temperature (° C.) of the polymer, Wi represents the weight fraction of the monomer i constituting the polymer, and 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.
Ｆｏｘの式　　　１／（２７３＋Ｔｇ）＝Σ［Ｗｉ／（２７３＋Ｔｇｉ）］ Fox formula 1 / (273 + Tg) = Σ [Wi / (273 + Tgi)]
　粘着性組成物は、ベースポリマーへの架橋構造の導入の観点から、架橋剤を含有してもよい。ベースポリマーが架橋点を有する場合に当該架橋点と反応して架橋構造を形成するための架橋剤としては、例えば、イソシアネート系架橋剤、エポキシ系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、カルボジイミド系架橋剤、および金属キレート系架橋剤が挙げられる。架橋剤は、単独で用いられてもよいし、二種類以上が併用されてもよい。 The adhesive composition may contain a cross-linking agent from the viewpoint of introducing a cross-linked structure into the base polymer. When the base polymer has a cross-linking point, examples of the cross-linking agent for reacting with the cross-linking point to form a cross-linked structure include an isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, an oxazoline-based cross-linking agent, and an aziridine-based cross-linking agent. Examples thereof include a carbodiimide-based cross-linking agent and a metal chelate-based cross-linking agent. The cross-linking agent may be used alone or in combination of two or more.
　イソシアネート系架橋剤としては、例えば、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソシアネート、水添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、水添ジフェニルメタ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、ナフタリンジイソシアネート、トリフェニルメタントリイソシアネート、およびポリメチレンポリフェニルイソシアネートが挙げられる。また、イソシアネート系架橋剤としては、これらイソシアネートの誘導体（例えば、イソシアヌレート変性体およびポリオール変性体など）も挙げられる。イソシアネート系架橋剤の市販品としては、例えば、コロネートＬ（トリレンジイソシアネートのトリメチロールプロパンアダクト体，東ソー製）、コロネートＨＬ（へキサメチレンジイソシアネートのトリメチロールプロパンアダクト体，東ソー製）、コロネートＨＸ（ヘキサメチレンジイソシアネートのイソシアヌレート体，東ソー製）、およびタケネートＤ１１０Ｎ（キシリレンジイソシアネートのトリメチロールプロパンアダクト体，三井化学製）が挙げられる。 Examples of the isocyanate-based 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. Examples thereof include triisocyanate and polymethylene polyphenyl isocyanate. In addition, examples of the isocyanate-based cross-linking agent include derivatives of these isocyanates (for example, isocyanurate-modified products and polyol-modified products). Examples of commercially available isocyanate-based 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 (). Examples thereof include an isocyanurate form of hexamethylene diisocyanate (manufactured by Tosoh) and Takenate D110N (trimethylolpropane adduct form of xylylene diisocyanate, manufactured by Mitsui Chemicals).
　エポキシ系架橋剤としては、ビスフェノールＡ、エピクロルヒドリン型のエポキシ系樹脂、エチレングリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、１,６-ヘキサンジオールグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ジグリシジルアニリン、ジアミングリシジルアミン、Ｎ,Ｎ,Ｎ',Ｎ'-テトラグリシジル-ｍ-キシリレンジアミン、および１,３-ビス(Ｎ,Ｎ-ジグリシジルアミノメチル)シクロヘキサンが挙げられる。 Examples of the epoxy-based cross-linking agent 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 trimethyl propantri. Examples include glycidyl ether, diglycidyl aniline, diamine glycidyl amine, N, N, N', N'-tetraglycidyl-m-xylylene diamine, and 1,3-bis (N, N-diglycidyl aminomethyl) cyclohexane. ..
　架橋剤の配合量は、粘着剤層１０の凝集力を確保する観点からは、ベースポリマー１００質量部に対して、例えば０.０１質量部以上であり、好ましくは０.０５質量部以上、より好ましくは０.０７質量部以上である。粘着剤層１０において良好なタック性を確保する観点からは、ベースポリマー１００質量部に対する架橋剤の配合量は、例えば１０質量部以下であり、好ましくは５質量部以下、より好ましくは３質量部以下である。 From the viewpoint of ensuring the cohesive force of the pressure-sensitive adhesive layer 10, the amount of the cross-linking agent blended 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. From the viewpoint of ensuring good tackiness in the pressure-sensitive adhesive layer 10, 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.
　ベースポリマーに架橋構造が導入される場合、架橋反応を効果的に進行させるために架橋触媒が用いられてもよい。架橋触媒としては、例えば、テトラ－ｎ－ブチルチタネート、テトライソプロピルチタネート、ナーセム第二鉄、ブチルスズオキシド、ジオクチルスズジラウレートなどの金属系架橋触媒が挙げられる。架橋触媒の使用量は、ベースポリマー１００質量部に対して例えば０.０００１質量部以上であり、また、１質量部以下である。 When a crosslinked structure is introduced into the base polymer, a crosslinked catalyst may be used to effectively proceed the crosslinking reaction. Examples of the cross-linking catalyst include metal-based cross-linking catalysts such as tetra-n-butyl titanate, tetraisopropyl titanate, ferric nasem, butyl tin oxide, and dioctyl tin dilaurate. 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.
　発色性化合物は、酸との反応によって無色（透明）から有色に変化（発色）する化合物であって、例えば、ロイコ系色素、ｐ,ｐ',ｐ”－トリス－ジメチルアミノトリフェニルメタンなどのトリアリールメタン系色素、４,４－ビス－ジメチルアミノフェニルベンズヒドリルベンジルエーテルなどのジフェニルメタン系色素、３－ジエチルアミノ－６－メチル－７－クロロフルオランなどのフルオラン系色素、３-メチルスピロジナフトピランなどのスピロピラン系色素、および、ローダミン－Ｂ－アニリノラクタムなどのローダミン系色素が挙げられる。発色性化合物は、単独で用いられてもよいし、二種類以上が併用されてもよい。粘着剤層１０において良好な着色性を確保する観点からは、粘着性組成物は、好ましくは、発色性化合物としてロイコ系色素を含む。 The color-developing compound is a compound that changes from colorless (transparent) to colored (color-developed) by reaction with an acid, and is, for example, a leuco-based dye, p, p', p "-tris-dimethylaminotriphenylmethane, or the like. Triarylmethane dyes, diphenylmethane dyes such as 4,4-bis-dimethylaminophenylbenzhydrylbenzyl ether, fluorane dyes such as 3-diethylamino-6-methyl-7-chlorofluorane, 3-methylspirodi Spiropyran dyes such as naphthopyran and rhodamine dyes such as rhodamine-B-anilinolactum can be mentioned. The color-developing compound may be used alone or in combination of two or more. From the viewpoint of ensuring good colorability in the pressure-sensitive adhesive layer 10, the pressure-sensitive composition preferably contains a leuco-based dye as a color-developing compound.
　ベースポリマー１００質量部に対する発色性化合物の配合量は、好ましくは０.５質量部以上、より好ましくは１質量部以上である。同配合量は、好ましくは１０質量部以下、より好ましくは７質量部以下である。 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, and 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.
　酸発生剤としては、活性光線が照射されることによって酸を発生する光酸発生剤、および、加熱によって酸を発生する熱酸発生剤が挙げられる。酸発生剤として光酸発生剤が用いられる場合、粘着剤層１０の可視光透過性を低下させるための外部刺激は、活性光線の照射である。外部刺激としての活性光線の種類は、光酸発生剤の種類（具体的には、光酸発生剤が酸を発生する活性光線の波長）によって定まる。活性光線としては、例えば、紫外線、可視光、赤外線、Ｘ線、α線、β線、γ線が挙げられ、使用設備の多様性およびハンドリング容易性の観点からは、好ましくは紫外線が挙げられる。一方、酸発生剤として熱酸発生剤が用いられる場合、粘着剤層１０の可視光透過性を低下させるための外部刺激は、加熱である。 Examples of the acid generator include a photoacid generator that generates an acid when irradiated with active light and a thermoacid generator that generates an acid by heating. When a photoacid generator is used as the acid generator, the external stimulus for reducing the visible light transmittance of the pressure-sensitive adhesive layer 10 is irradiation with active light. The type of active light as an external stimulus is determined by the type of photoacid generator (specifically, the wavelength of the active light that the photoacid generator generates acid). Examples of the active light include ultraviolet rays, visible light, infrared rays, X-rays, α-rays, β-rays, and γ-rays, and from the viewpoint of variety of equipment used and ease of handling, ultraviolet rays are preferable. On the other hand, when a thermoacid generator is used as the acid generator, the external stimulus for reducing the visible light transmittance of the pressure-sensitive adhesive layer 10 is heating.
　光酸発生剤としては、例えば、紫外線の照射によって酸を発生するオニウム化合物が挙げられる。オニウム化合物は、例えば、オニウムカチオンとアニオンとのオニウム塩の形態で提供される。オニウムカチオンとしては、ヨードニウムおよびスルホニウムが挙げられる。オニウム塩をなすアニオンとしては、例えば、Ｃｌ－，Ｂｒ－，Ｉ－，ＺｎＣｌ３ －，ＨＳＯ３ －，ＢＦ４ －，ＰＦ６ －，ＡｓＦ６ －，ＳｂＦ６ －，ＣＨ３ＳＯ３ －，ＣＦ３ＳＯ３ －，(Ｃ６Ｆ５)４Ｂ－，(Ｃ４Ｈ９)４Ｂ－が挙げられる。光酸発生剤は、単独で用いられてもよいし、二種類以上が併用されてもよい。粘着剤層１０は、好ましくは、スルホニウムと(Ｃ６Ｆ５)４Ｂ－とからなるオニウム塩をオニウム化合物として含む。光酸発生剤の市販品としては、例えば、サンアプロ社製のＣＰＩ－３１０Ｂ（スルホニウムと(Ｃ６Ｆ５)４Ｂ－とのオニウム塩）が挙げられる。 Examples of the photoacid generator include an onium compound that generates an acid by irradiation with ultraviolet rays. 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. The anion forming the onium salt, for example, Cl -, Br -, I -, ZnCl 3 -, HSO 3 -, BF 4 -, PF 6 -, AsF 6 -, SbF 6 -, CH 3 SO 3 -, CF 3 SO 3 -, (C 6 F 5) 4 B -, (C 4 H 9) 4 B - , and the like. The photoacid generator may be used alone or in combination of two or more. The pressure-sensitive adhesive layer 10 preferably contains an onium salt composed of sulfonium and (C 6 F 5 ) 4 B − as an onium compound. Examples of commercially available products of the photoacid generator, for example, available from San-Apro Ltd. of CPI-310B (sulfonium and (C 6 F 5) 4 B - and onium salts) thereof.
　熱酸発生剤としては、例えば、アリールスルホニウム塩およびアリールヨードニウム塩が挙げられる。 Examples of the thermoacid generator include aryl sulfonium salts and aryl iodonium salts.
　ベースポリマー１００質量部に対する酸発生剤の配合量は、好ましくは１質量部以上、より好ましくは２質量部以上、さらに好ましくは５質量部以上、とりわけ好ましくは７質量部以上である。同配合量は、好ましくは２０質量部以下、より好ましくは１５質量部以下、さらに好ましくは１０質量部以下である。 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, still more 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 10 parts by mass or less.
　また、発色性化合物１００質量部に対する酸発生剤の配合量は、例えば１００質量部以上、好ましくは２００質量部以上、より好ましくは３００質量部以上、さらに好ましくは３５０質量部以上であり、また、例えば１０００質量部以下、好ましくは７００質量部以下、より好ましくは５００質量部以下である。すなわち、発色性化合物２質量部に対する酸発生剤の配合量は、例えば２質量部以上、好ましくは４質量部以上、より好ましくは６質量部以上、さらに好ましくは７質量部以上であり、また、例えば２０質量部以下、好ましくは１４質量部以下、より好ましくは１０質量部以下である。 The amount of the acid generator 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, still more preferably 350 parts by mass or more, and more. For example, it is 1000 parts by mass or less, preferably 700 parts by mass or less, and more preferably 500 parts by mass or less. That is, the blending amount of the acid generator with respect to 2 parts by mass of the color-developing compound is, for example, 2 parts by mass or more, preferably 4 parts by mass or more, more preferably 6 parts by mass or more, still more preferably 7 parts by mass or more, and more. For example, it is 20 parts by mass or less, preferably 14 parts by mass or less, and more preferably 10 parts by mass or less.
　防錆剤としては、例えば、トリアゾール系化合物、ベンゾトリアゾール系化合物、チアゾール系化合物、ベンゾチアゾール系化合物、イミダゾール系化合物、ベンゾイミダゾール系化合物、水酸基を有するアゾール系化合物、リン系化合物、アミン系化合物、および亜硝酸塩系化合物が挙げられる。防錆剤は、単独で用いられてもよいし、二種類以上が併用されてもよい。 Examples of the rust preventive agent include triazole compounds, benzotriazole compounds, thiazole compounds, benzothiazole compounds, imidazole compounds, benzoimidazole compounds, azole compounds having hydroxyl groups, phosphorus compounds, amine compounds, and the like. And nitrite compounds. The rust preventive may be used alone or in combination of two or more.
　被着体における金属腐食抑制の観点から、防錆材としては、好ましくはベンゾトリアゾール系化合物が用いられ、より好ましくは、下記式（１）で表される構造を有するベンゾトリアゾール系化合物が用いられる。 From the viewpoint of suppressing metal corrosion in the adherend, a benzotriazole-based compound is preferably used as the rust preventive material, and more preferably, a benzotriazole-based compound having a structure represented by the following formula (1) is used. ..
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　上記式（１）において、Ｒは、ベンゼン環上の置換基であって、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、炭素数６～１４のアリール基、カルボキシル基、炭素数２～６のカルボキシアルキル基、アミノ基、モノまたはジ－Ｃ１－１０アルキルアミノ基、アミノ－Ｃ１－６アルキル基、モノまたはジ－Ｃ１－１０アルキルアミノ－Ｃ１－６アルキル基、メルカプト基、炭素数１～６のアルコキシカルボニル基などの置換基から選択され得る。式（１）中のｎは０～４の整数であり、ｎが２以上である場合、ｎ個のＲは、互いに同一であってもよく、異なっていてもよい。式（１）で表わされるベンゾトリアゾール系化合物の好適例として、１，２，３－ベンゾトリアゾール、５－メチルベンゾトリアゾール、４－メチルベンゾトリアゾール、およびカルボキシベンゾトリアゾールが挙げられる。 In the above formula (1), R is a substituent on the benzene ring, which is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, and a carboxyl group. Carboxylalkyl group with 2-6 carbon atoms, amino group, mono or di-C 1-10 alkylamino group, amino-C 1-6 alkyl group, mono or di-C 1-10 alkyl amino-C 1-6 alkyl It can be selected from substituents such as groups, mercapto groups, alkoxycarbonyl groups with 1-6 carbon atoms. When n in the formula (1) is an integer of 0 to 4, and n is 2 or more, n Rs may be the same as or different from each other. Preferable examples of the benzotriazole-based compound represented by the formula (1) include 1,2,3-benzotriazole, 5-methylbenzotriazole, 4-methylbenzotriazole, and carboxybenzotriazole.
　発色性化合物１００質量部に対する防錆剤の配合量は、粘着剤層１０における腐食抑制効果を確保する観点からは、好ましくは１質量部以上、より好ましくは３質量部以上、さらに好ましくは５質量部以上である。すなわち、発色性化合物２質量部に対する防錆剤の配合量は、好ましくは０.０２質量部以上、より好ましくは０.０６質量部以上、さらに好ましくは０.１質量部以上である。また、粘着剤層１０において、防錆剤の作用によって発色性化合物を発色させるのを抑制する観点からは、発色性化合物１００質量部に対する防錆剤の配合量は、１００質量部未満、好ましくは９０質量部以下、より好ましくは８５質量部以下、さらに好ましくは５０質量部以下、特に好ましくは３０質量部以下、とりわけ好ましくは１０質量部以下である。すなわち、発色性化合物２質量部に対する防錆剤の配合量は、好ましくは２質量部未満、好ましくは１.８質量部以下、より好ましくは１.７質量部以下、さらに好ましくは１質量部以下、特に好ましくは０.６質量部以下、とりわけ好ましくは０.２質量部以下である。 The amount of the rust preventive compounded with respect to 100 parts by mass of the color-developing compound is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and further preferably 5 parts by mass from the viewpoint of ensuring the corrosion suppressing effect in the pressure-sensitive adhesive layer 10. It is more than a part. That is, the blending amount of the rust inhibitor with respect to 2 parts by mass of the color-developing compound is preferably 0.02 part by mass or more, more preferably 0.06 part by mass or more, and further preferably 0.1 part by mass or more. Further, from the viewpoint of suppressing the color development of the color-developing compound by the action of the rust preventive in the pressure-sensitive adhesive layer 10, the amount of the rust preventive compounded with respect to 100 parts by mass of the color-developing compound is preferably less than 100 parts by mass. It is 90 parts by mass or less, more preferably 85 parts by mass or less, further preferably 50 parts by mass or less, particularly preferably 30 parts by mass or less, and particularly preferably 10 parts by mass or less. That is, the amount of the rust preventive to be blended with respect to 2 parts by mass of the color-developing compound is preferably less than 2 parts by mass, preferably 1.8 parts by mass or less, more preferably 1.7 parts by mass or less, still more preferably 1 part by mass or less. , Especially preferably 0.6 parts by mass or less, and particularly preferably 0.2 parts by mass or less.
　ベースポリマー１００質量部に対する防錆剤の配合量は、好ましくは０.０２質量部以上、より好ましくは０.０６質量部以上、さらに好ましくは０.１質量部以上である。また、ベースポリマー１００質量部に対する防錆剤の配合量は、好ましくは２質量部未満、より好ましくは１.８質量部以下、さらに好ましくは１.７質量部以下である。 The blending amount of the rust inhibitor with respect to 100 parts by mass of the base polymer is preferably 0.02 parts by mass or more, more preferably 0.06 parts by mass or more, and further preferably 0.1 parts by mass or more. The amount of the rust preventive compounded with respect to 100 parts by mass of the base polymer is preferably less than 2 parts by mass, more preferably 1.8 parts by mass or less, and further preferably 1.7 parts by mass or less.
　粘着性組成物は、必要に応じて他の成分を含有してもよい。他の成分としては、例えば、シランカップリング剤、粘着性付与剤、可塑剤、軟化剤、劣化防止剤、充填剤、酸化防止剤、界面活性剤、および帯電防止剤が挙げられる。 The adhesive composition may contain other components if necessary. Other components include, for example, silane coupling agents, tackifiers, plasticizers, softeners, antioxidants, fillers, antioxidants, surfactants, and antistatic agents.
　粘着剤層１０の厚さは、被着体に対する充分な粘着性を確保する観点から、例えば３μｍ以上、好ましくは１０μｍ以上、より好ましくは１５μｍ以上である。粘着シートＸのハンドリング性の観点からは、粘着剤層１０の厚さは、例えば１００μｍ以下、好ましくは５０μｍ以下、より好ましくは３０μｍ以下である。 The thickness of the pressure-sensitive adhesive layer 10 is, for example, 3 μm or more, preferably 10 μm or more, and more preferably 15 μm or more, from the viewpoint of ensuring sufficient adhesiveness to the adherend. From the viewpoint of handleability of the pressure-sensitive adhesive sheet X, the thickness of the pressure-sensitive adhesive layer 10 is, for example, 100 μm or less, preferably 50 μm or less, and more preferably 30 μm or less.
　粘着剤層１０のヘイズは、好ましくは３％以下、より好ましくは２％以下、さらに好ましくは１％以下、ことさらに好ましくは０.８％以下、特に好ましくは０.６％以下である。このような構成は、粘着シートＸを所定表面に貼り合わせた後に粘着シートＸとその被着面との間における異物や気泡の有無を検査するのに適する。粘着剤層１０のヘイズは、ＪＩＳ Ｋ７１３６（２０００年）に準拠して、ヘイズメーターを使用して測定することができる。ヘイズメーターとしては、例えば、日本電色工業社製の「ＮＤＨ２０００」、および村上色彩技術研究所社製の「ＨＭ?１５０型」が挙げられる。 The haze of the pressure-sensitive adhesive layer 10 is preferably 3% or less, more preferably 2% or less, further preferably 1% or less, still more preferably 0.8% or less, and particularly preferably 0.6% or less. Such a configuration is suitable for inspecting the presence or absence of foreign matter or air bubbles between the pressure-sensitive adhesive sheet X and its adherend surface after the pressure-sensitive adhesive sheet X is attached to a predetermined surface. 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.
　粘着剤層１０の波長４００～７００ｎｍでの平均透過率（粘着剤層１０に上述の外部刺激を与える前の平均透過率）は、例えば８０％以上であり、好ましくは８５％以上、より好ましくは９０％以上、さらに好ましくは９２％以上である。このような構成は、粘着シートＸを所定表面に貼り合わせた後に粘着シートＸとその被着面との間における異物や気泡の有無を検査するのに適する。 The average transmittance of the pressure-sensitive adhesive layer 10 at a wavelength of 400 to 700 nm (the average transmittance before applying the above-mentioned external stimulus to the pressure-sensitive adhesive layer 10) is, for example, 80% or more, preferably 85% or more, more preferably. It is 90% or more, more preferably 92% or more. Such a configuration is suitable for inspecting the presence or absence of foreign matter or air bubbles between the pressure-sensitive adhesive sheet X and its adherend surface after the pressure-sensitive adhesive sheet X is attached to a predetermined surface.
　粘着剤層１０が上述の外部刺激を受けた後における波長４００～７００ｎｍでの平均透過率は、例えば７０％以下であり、好ましくは４０％以下、より好ましくは２０％以下、さらに好ましくは１７％以下である。このような構成は、粘着シートＸが貼り合わされた被着面での上述の外光反射を防止・抑制するのに適する。 The average transmittance of the pressure-sensitive adhesive layer 10 at a wavelength of 400 to 700 nm after receiving the above-mentioned external stimulus is, for example, 70% or less, preferably 40% or less, more preferably 20% or less, still more preferably 17%. It is as follows. Such a configuration is suitable for preventing / suppressing the above-mentioned external light reflection on the adherend surface to which the adhesive sheet X is attached.
　粘着シートＸは、例えば、粘着剤層１０を構成するための各種成分を含有する粘着性組成物を剥離フィルム（第１剥離フィルム）上に塗布して塗膜を形成し、塗膜から必要に応じて溶媒を乾燥除去することによって、製造することができる。 For the pressure-sensitive adhesive sheet X, for example, a pressure-sensitive adhesive composition containing various components for forming the pressure-sensitive adhesive layer 10 is applied onto a release film (first release film) to form a coating film, which is necessary from the coating film. It can be produced by drying and removing the solvent accordingly.
　剥離フィルムとしては、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリエチレンテレフタレートフィルム、ポリエステルフィルムなどの可撓性のプラスチックフィルムが挙げられる。剥離フィルムの厚さは、例えば３μｍ以上であり、また、例えば２００μｍ以下である。剥離フィルムの表面には、好ましくは、シリコーン系、フッ素系、長鎖アルキル系、脂肪酸アミド系などの離型剤による離型処理、または、シリカ粉による離型処理が施されている。 Examples of the release film include flexible plastic films such as polyethylene film, polypropylene film, polyethylene terephthalate film, and polyester film. The thickness of the release film is, for example, 3 μm or more, and 200 μm or less, for example. The surface of the release film is preferably subjected to a mold release treatment with a mold release agent such as silicone-based, fluorine-based, long-chain alkyl-based, or fatty acid amide-based, or a mold release treatment with silica powder.
　粘着性組成物の塗布方法としては、例えば、ロールコート、キスロールコート、グラビアコート、リバースコート、ロールブラッシュ、スプレーコート、ディップロールコート、バーコート、ナイフコート、エアーナイフコート、カーテンコート、リップコート、およびダイコートが挙げられる。溶媒除去のための乾燥温度は、例えば５０℃～２００℃である。その乾燥時間は、例えば５秒～２０分である。 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 for removing the solvent is, for example, 50 ° C. to 200 ° C. The drying time is, for example, 5 seconds to 20 minutes.
　用いる粘着性組成物が架橋剤を含む場合、上述の乾燥と同時に又はその後のエージングによって、粘着性組成物中の架橋剤が関与する架橋反応を進行させる。エージング条件は、架橋剤の種類によって適宜設定される。エージング温度は、例えば２０℃～１６０℃である。エージング時間は、例えば、１分から７日である。 When the tacky composition used contains a cross-linking agent, the cross-linking reaction involving the cross-linking agent in the sticky composition is promoted 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.
　また、エージングの前または後に、第１剥離フィルム上の粘着剤層１０の上に更に剥離フィルム（第２剥離フィルム）を積層してもよい。第２剥離フィルムは、表面離型処理が施された可撓性のプラスチックフィルムであり、第１剥離フィルムに関して上述したのと同様のものを用いることができる。 Further, before or after aging, 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 undergone a surface release treatment, and the same film as described above can be used for the first release film.
　以上のようにして、剥離フィルムによって粘着面が被覆保護された粘着シートＸを製造することができる。各剥離フィルムは、粘着シートＸを使用する際に必要に応じて粘着シートＸから剥がされる。 As described above, the pressure-sensitive adhesive sheet X 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 X as needed when using the pressure-sensitive adhesive sheet X.
　粘着シートＸは、図２に示すように、粘着剤層１０に加えて基材２０を備える基材付き片面粘着シートであってもよい。この場合、粘着シートＸは、具体的には、粘着剤層１０と、その一方面側に配置される基材２０とを備え、好ましくは、基材１０とのその一方面に接触するように配置される粘着剤層１０とを備える。このような粘着シートＸは、部材の表面保護や耐衝撃性付与などのための補強用の粘着シートとして使用することができる。 As shown in FIG. 2, the adhesive sheet X may be a single-sided adhesive sheet with a base material having a base material 20 in addition to the pressure-sensitive adhesive layer 10. In this case, the pressure-sensitive adhesive sheet X specifically includes the pressure-sensitive adhesive layer 10 and the base material 20 arranged on one side thereof, and preferably comes into contact with the base material 10 on one side thereof. It includes a pressure-sensitive adhesive layer 10 to be arranged. Such an adhesive sheet X can be used as a reinforcing adhesive sheet for protecting the surface of a member and imparting impact resistance.
　基材２０は、透明な支持体として機能する要素である。基材２０は、例えば、可撓性を有するプラスチックフィルムである。プラスチックフィルムの構成材料としては、例えば、ポリオレフィン、ポリエステル、ポリアミド、ポリイミド、ポリ塩化ビニル、ポリ塩化ビニリデン、セルロース、ポリスチレン、およびポリカーボネートが挙げられる。ポリオレフィンとしては、例えば、ポリエチレン、ポリプロピレン、ポリ－１－ブテン、ポリ－４－メチル－１－ペンテン、エチレン・プロピレン共重合体、エチレン・１－ブテン共重合体、エチレン・酢酸ビニル共重合体、エチレン・エチルアクリレート共重合体、およびエチレン・ビニルアルコール共重合体が挙げられる。ポリエステルとしては、例えば、ポリエチレンテレフタレート、ポリエチレンナフタレート、およびポリブチレンテレフタレートが挙げられる。ポリアミドとしては、例えば、ナイロン６、ナイロン６,６、および部分芳香族ポリアミドが挙げられる。基材２０は、一種類の材料からなってもよいし、二種類以上の材料からなってもよい。基材２０は、単層構造を有してもよいし、多層構造を有してもよい。基材２０は、無延伸フィルムであってもよいし、一軸延伸フィルムであってもよいし、二軸延伸フィルムであってもよい。基材２０において、その透明性と機械的強度とを両立させる観点からは、基材２０構成用のプラスチック材料は、好ましくはポリエステルであり、より好ましくはポリエチレンテレフタレートである。 The base material 20 is an element that functions as a transparent support. The base material 20 is, for example, a flexible plastic film. Examples of the constituent material of the plastic film include polyolefin, polyester, polyamide, polyimide, polyvinyl chloride, polyvinylidene chloride, cellulose, polystyrene, and polycarbonate. Examples of 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. Examples thereof include an ethylene / ethyl acrylate copolymer and an ethylene / vinyl alcohol copolymer. Examples of polyesters include polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate. Examples of the polyamide include nylon 6, nylon 6,6, and partially aromatic polyamide. The base material 20 may be made of one kind of material or may be made of two or more kinds of materials. The base material 20 may have a single-layer structure or a multi-layer structure. The base material 20 may be a non-stretched film, a uniaxially stretched film, or a biaxially stretched film. From the viewpoint of achieving both transparency and mechanical strength of the base material 20, the plastic material for constructing the base material 20 is preferably polyester, more preferably polyethylene terephthalate.
　基材２０は透明性を有する。基材２０のヘイズは、例えば１０％以下であり、好ましくは５％以下、より好ましくは３％以下である。基材２０のヘイズは、ＪＩＳ Ｋ７１３６（２０００年）に準拠して、ヘイズメーターを使用して測定することができる。 The base material 20 has transparency. The haze of the base material 20 is, for example, 10% or less, preferably 5% or less, and more preferably 3% or less. The haze of the base material 20 can be measured using a haze meter in accordance with JIS K7136 (2000).
　基材２０における粘着剤層１０側の面１１は、粘着剤層１０との密着性を高めるための物理的処理、化学的処理、または下塗り処理が施されていてもよい。物理的処理としては、例えば、コロナ処理およびプラズマ処理が挙げられる。化学的処理としては例えば酸処理およびアルカリ処理が挙げられる。 The surface 11 on the pressure-sensitive adhesive layer 10 side of the base material 20 may be subjected to a physical treatment, a chemical treatment, or an undercoating 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.
　基材２０の厚さは、基材２０が支持体として機能するための強度を確保する観点からは、好ましくは５μｍ以上、より好ましくは１０μｍ以上、より好ましくは２０μｍ以上である。また、粘着シートＸにおいて適度な可撓性を実現する観点からは、基材２０の厚さは、好ましくは２００μｍ以下、より好ましくは１５０μｍ以下、より好ましくは１００μｍ以下である。 The thickness of the base material 20 is preferably 5 μm or more, more preferably 10 μm or more, and more preferably 20 μm 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 X, the thickness of the base material 20 is preferably 200 μm or less, more preferably 150 μm or less, and more preferably 100 μm or less.
　図２に示す粘着シートＸは、例えば、第１剥離フィルムの代わりに基材２０を用いること以外は上述の製造方法と同様にして、製造することができる。 The pressure-sensitive adhesive sheet X shown in FIG. 2 can be manufactured in the same manner as the above-mentioned manufacturing method except that the base material 20 is used instead of the first release film, for example.
　粘着シートＸの粘着剤層１０は、上述のように、酸との反応により発色する発色性化合物と酸発生剤とを共に含有する。このような構成は、被着体に貼り合わせた後の粘着剤層１０において、酸発生剤から酸を発生させて発色性化合物を発色させることによって、可視光透過性を低下させるのに適する。例えば、粘着シートＸによると、粘着シートＸを所定表面に貼り合わせた後、粘着シートＸの透明性（可視光透過性）が相対的に高い状態で同シートと被着面との間における異物や気泡の有無を検査し、当該検査の通過の後、同シートの粘着剤層１０に外部刺激を与えて同シートの透明性を相対的に低い状態へと変化させることが可能である。 As described above, the pressure-sensitive adhesive layer 10 of the pressure-sensitive adhesive sheet X contains both a color-developing compound that develops color by reaction with an acid and an acid generator. Such a configuration is suitable for lowering the visible light transmittance by generating an acid from an acid generator to develop a color-developing compound in the pressure-sensitive adhesive layer 10 after being bonded to the adherend. For example, according to the adhesive sheet X, after the adhesive sheet X is attached to a predetermined surface, foreign matter between the adhesive sheet X and the adherend surface in a state where the transparency (visible light transmission) of the adhesive sheet X is relatively high. It is possible to inspect the presence or absence of air bubbles and air bubbles, and after passing the inspection, apply an external stimulus to the pressure-sensitive adhesive layer 10 of the sheet to change the transparency of the sheet to a relatively low state.
　また、粘着剤層１０は、上述のように、防錆剤を含有する。このような構成は、粘着シートＸが貼り合わされた被着体の粘着シート貼着箇所やその近傍に金属配線がある場合に、粘着剤層１０内の酸発生剤が発生する酸によって当該配線に金属腐食が生ずるのを抑制するのに適する。 Further, the adhesive layer 10 contains a rust preventive as described above. In such a configuration, when there is a metal wiring at or near the pressure-sensitive adhesive sheet-attached portion of the adherend to which the pressure-sensitive adhesive sheet X is bonded, the acid generated by the acid generator in the pressure-sensitive adhesive layer 10 is applied to the wiring. Suitable for suppressing the occurrence of metal corrosion.
　加えて、粘着剤層１０における防錆剤の含有量は、上述のように、発色性化合物１００質量部に対して１００質量部未満であり、好ましくは９０質量部以下、より好ましくは８５質量部以下、さらに好ましくは５０質量部以下、特に好ましくは３０質量部以下、とりわけ好ましくは１０質量部以下である。このような構成は、被着体への貼り合わせの前の粘着剤層１０において、防錆剤の作用によって発色性化合物を発色させるのを抑制するのに適する。例えば、活性水素を有するベンゾトリアゾール系化合物が防錆剤として用いられる場合、防錆剤の含有量に関する上記構成は、ベンゾトリアゾール系化合物の活性水素によって発色性化合物を発色させるのを抑制するのに適する。防錆剤の作用によって発色性化合物を発色させるのを抑制するのに適する構成は、粘着剤層１０の可視光透過性を被着体貼合せ後に低下させるのに適する。 In addition, as described above, the content of the rust preventive in the pressure-sensitive adhesive layer 10 is less than 100 parts by mass with respect to 100 parts by mass of the color-developing compound, preferably 90 parts by mass or less, and more preferably 85 parts by mass. Below, it is more preferably 50 parts by mass or less, particularly preferably 30 parts by mass or less, and particularly preferably 10 parts by mass or less. Such a configuration is suitable for suppressing the color development of the color-developing compound by the action of the rust preventive agent in the pressure-sensitive adhesive layer 10 before bonding to the adherend. For example, when a benzotriazole-based compound having active hydrogen is used as a rust preventive, the above configuration regarding the content of the rust preventive agent suppresses the color development of the chromogenic compound by the active hydrogen of the benzotriazole-based compound. Suitable. A configuration suitable for suppressing the color development of the color-developing compound by the action of the rust preventive is suitable for reducing the visible light transmittance of the pressure-sensitive adhesive layer 10 after the adherend is attached.
　以上のように、粘着シートＸは、被着体に貼り合わせた後に可視光透過性を低下させるのに適するとともに、当該被着体における金属腐食を抑制するのに適する。このような粘着シートＸは、例えば、有機ＥＬパネルに組み付けられる外光反射防止材として好適に使用することが可能である。 As described above, the adhesive sheet X is suitable for reducing the visible light transmittance after being attached to the adherend, and is also suitable for suppressing metal corrosion in the adherend. Such an adhesive sheet X can be suitably used as, for example, an external light reflection inhibitor to be assembled to an organic EL panel.
　図３は、粘着シート付き部材Ｙの断面模式図である。粘着シート付き部材Ｙは、部材３１（第１部材）と、部材３２（第２部材）と、粘着シートＸとを備える。 FIG. 3 is a schematic cross-sectional view of the member Y with the adhesive sheet. The member Y with an adhesive sheet includes a member 31 (first member), a member 32 (second member), and an adhesive sheet X.
　部材３１は、例えば、光学デバイス、電子デバイス、または、それらの構成部品である。部材３２は、例えば、透明基材である。透明基材としては、透明プラスチック基材および透明ガラス基材が挙げられる。粘着シートＸは、部材３１,３２間に介在してこれらを接合している。具体的には、粘着シートＸは、部材３１の厚さ方向一方面に接触するように配置され、部材３２は、その粘着シートＸの厚さ方向一方面に接触するように配置されている。 The member 31 is, for example, an optical device, an electronic device, or a component thereof. The 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 adhesive sheet X is interposed between the members 31 and 32 to join them. Specifically, the pressure-sensitive adhesive sheet X is arranged so as to be in contact with one surface of the member 31 in the thickness direction, and the member 32 is arranged so as to be in contact with one side surface of the pressure-sensitive adhesive sheet X in the thickness direction.
　図４は、粘着シート付き部材Ｙの製造方法を示す。この製造方法は、用意工程と、第１貼合せ工程と、透明性低下工程とを含み、本実施形態では第２貼合せ工程を更に含む。 FIG. 4 shows a method of manufacturing the member Y with the adhesive sheet. This manufacturing method includes a preparation step, a first bonding step, and a transparency lowering step, and in the present embodiment, further includes a second bonding step.
　用意工程では、図４Ａに示すように、上述の部材３１を用意する。 In the preparation step, as shown in FIG. 4A, the above-mentioned member 31 is prepared.
　第１貼合せ工程では、図４Ｂに示すように、部材３１に対して粘着シートＸを貼り合わせる。 In the first bonding step, the adhesive sheet X is bonded to the member 31 as shown in FIG. 4B.
　第１貼合せ工程の後、必要に応じて、部材３１における粘着シート被着面３１ａと粘着シートＸとの間における異物や気泡の有無を検査する。 After the first bonding step, if necessary, the presence or absence of foreign matter or air bubbles between the adhesive sheet adhering surface 31a of the member 31 and the adhesive sheet X is inspected.
　検査を通過した貼合わせ体においては、次に、透明性低下工程にて、部材３１上の粘着剤層１０に外部刺激を与えて、図４Ｃに示すように、粘着剤層１０の可視光透過率を低下させる。粘着剤層１０が酸発生剤として光酸発生剤を含む場合、外部刺激は活性光線照射である。活性光線は、例えば、粘着シートＸの粘着剤層１０に対して部材３１とは反対の側から照射される。粘着剤層１０が酸発生剤として熱酸発生剤を含む場合、外部刺激は加熱である。本工程では、粘着剤層１０への外部刺激の付与により、粘着剤層１０において、酸発生剤から酸が発生し、当該酸との反応によって発色性化合物が発色する。 In the bonded body that has passed the inspection, an external stimulus is then applied to the pressure-sensitive adhesive layer 10 on the member 31 in the transparency lowering step, and as shown in FIG. 4C, the visible light transmission of the pressure-sensitive adhesive layer 10 is transmitted. Reduce the rate. When the pressure-sensitive adhesive layer 10 contains a photoacid generator as an acid generator, the external stimulus is irradiation with active light. The active light is, for example, irradiated to the pressure-sensitive adhesive layer 10 of the pressure-sensitive adhesive sheet X from the side opposite to the member 31. When the pressure-sensitive adhesive layer 10 contains a thermoacid generator as the acid generator, the external stimulus is heating. In this step, an acid is generated from the acid generator in the pressure-sensitive adhesive layer 10 by applying an external stimulus to the pressure-sensitive adhesive layer 10, and a color-developing compound is developed by the reaction with the acid.
　次に、第２貼合せ工程では、図４Ｃに示すように、部材３１上の粘着シートＸに上述の部材３２を貼り合わせる。上述の透明性低下工程は、このような第２貼合せ工程の前に実施する代わりに、第２貼合せ工程の後に実施してもよい。 Next, in the second bonding step, as shown in FIG. 4C, the above-mentioned member 32 is bonded to the adhesive sheet X on the member 31. The above-mentioned transparency reducing step may be carried out after the second bonding step instead of being carried out before such a second bonding step.
　例えば以上のようにして、粘着シート付き部材Ｙを製造することができる。 For example, the member Y with the adhesive sheet can be manufactured as described above.
　以上のような、粘着シート付き部材の製造方法では、上述の粘着シートＸが用いられる。したがって、当該製造方法においては、粘着シートＸに関して上述したのと同様の技術的効果が奏される。 In the method for manufacturing a member with an adhesive sheet as described above, the above-mentioned adhesive sheet X is used. Therefore, in the manufacturing method, the same technical effect as described above is exhibited with respect to the pressure-sensitive adhesive sheet X.
〔実施例１〕
〈ベースポリマーの調製〉
　撹拌機、温度計、還流冷却管、および窒素ガス導入管を備える反応容器内で、アクリル酸ブチル（ＢＡ）９５質量部と、アクリル酸（ＡＡ）５質量部と、重合開始剤としての２,２'－アゾビスイソブチロニトリル（ＡＩＢＮ）０.２質量部と、溶媒としての酢酸エチル２３３質量部とを含む混合物（モノマー成分を含有する反応溶液）を、６０℃で７時間、窒素雰囲気下で撹拌した（重合反応）。これにより、アクリルポリマーを含有するポリマー溶液を得た。このポリマー溶液中のアクリルポリマーの重量平均分子量（Ｍｗ）は６０００００であった。 [Example 1]
<Preparation of base polymer>
In a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube, and a nitrogen gas introduction tube, 95 parts by mass of butyl acrylate (BA), 5 parts by mass of acrylic acid (AA), and 2, as a polymerization initiator, A mixture (reaction solution containing a monomer component) containing 0.2 parts by mass of 2'-azobisisobutyronitrile (AIBN) and 233 parts by mass of ethyl acetate as a solvent was mixed in a nitrogen atmosphere at 60 ° C. for 7 hours. Stirred below (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 600,000.
〈粘着性組成物の調製〉
　アクリルポリマーを含有する上述のポリマー溶液に、アクリルポリマー１００質量部あたり、エポキシ系架橋剤（商品名「テトラッドＣ」，１,３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン，三菱ガス化学社製）０.０７５質量部と、光酸発生剤（商品名：ＣＰＩ－３１０Ｂ，スルホニウムと(Ｃ６Ｆ５)４Ｂ－とのオニウム塩，サンアプロ社製）７質量部と、発色性化合物としてのロイコ系色素（商品名「ＢＬＡＣＫ ＮＤ１」，山田化学工業社製）２質量部と、防錆剤としての１,２,３－ベンゾトリアゾール（商品名「ＢＴ－１２０」，城北化学工業社製）０.１質量部とを加えて混合して、粘着性組成物を得た。 <Preparation of adhesive composition>
In the above-mentioned polymer solution containing an acrylic polymer, an epoxy-based cross-linking agent (trade name "Tetrad C", 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, Mitsubishi Gas Chemicals) per 100 parts by mass of the acrylic polymer. Company, Ltd.) and 0.075 parts by mass, the photoacid generator (trade name: CPI-310B, sulfonium and (C 6 F 5) 4 B - onium salts with, manufactured by SAN-APRO Ltd.) 7 parts by mass, color forming compounds 2 parts by mass of leuco dye (trade name "BLACK ND1", manufactured by Yamada Chemical Industry Co., Ltd.) and 1,2,3-benzotriazole (trade name "BT-120", manufactured by Johoku Chemical Industry Co., Ltd.) as a rust preventive. (Manufactured by) 0.1 parts by mass was added and mixed to obtain an adhesive composition.
〈粘着シートの作製〉
　表面が離型処理されている厚さ５０μｍのポリエチレンテレフタレートフィルム（第１剥離フィルム）上に、ファウンテンロールを使用して粘着性組成物を塗布して塗膜を形成した。次に、この塗膜を１３０℃で１分間加熱乾燥し、第１剥離フィルム上に厚さ２５μｍの粘着剤層を形成した。次に、第１剥離フィルム上の粘着剤層に、一方面が離型処理されている厚さ２５μｍのポリエチレンテレフタレートフィルム（第２剥離フィルム）の離型処理面を貼り合わせた。その後、２５℃で４日間、エージングし、粘着剤層中の架橋反応を進行させた。以上のようにして、実施例１の粘着シートを作製した。粘着シートの粘着剤層の組成を表１に掲げる（表１において、組成を表す各数値の単位は「質量部」である）。 <Making an adhesive sheet>
An adhesive composition was applied to a polyethylene terephthalate film (first release film) having a thickness of 50 μm and whose surface had been mold-released using a fountain roll to form a coating film. Next, this coating film was heated and dried at 130 ° C. for 1 minute to form an adhesive layer having a thickness of 25 μm on the first release film. Next, the release-treated surface of a 25 μm-thick polyethylene terephthalate film (second release film) whose one surface was release-treated was attached to the pressure-sensitive adhesive layer on the first release film. Then, it was aged at 25 ° C. for 4 days to allow the cross-linking reaction in the pressure-sensitive adhesive layer to proceed. As described above, the pressure-sensitive adhesive sheet of Example 1 was produced. The composition of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is listed in Table 1 (in Table 1, the unit of each numerical value representing the composition is "part by mass").
〔実施例２～４〕
　粘着性組成物の調製において、防錆剤の配合量を、０.１質量部に代えて０.０５質量部（実施例２）、０.５質量部（実施例３）、または１質量部（実施例４）としたこと以外は実施例１の粘着シートと同様にして、実施例２～４の各粘着シートを作製した。 [Examples 2 to 4]
In the preparation of the adhesive composition, the amount of the rust inhibitor compounded is 0.05 parts by mass (Example 2), 0.5 parts by mass (Example 3), or 1 part by mass instead of 0.1 parts by mass. Each of the pressure-sensitive adhesive sheets of Examples 2 to 4 was produced in the same manner as the pressure-sensitive adhesive sheet of Example 1 except that the case of Example 4 was used.
〔比較例１〕
　粘着性組成物の調製において防錆剤を用いなかったこと以外は実施例１の粘着シートと同様にして、比較例１の粘着シートを作製した。 [Comparative Example 1]
A pressure-sensitive adhesive sheet of Comparative Example 1 was prepared in the same manner as the pressure-sensitive adhesive sheet of Example 1 except that a rust preventive was not used in the preparation of the pressure-sensitive adhesive composition.
〔比較例２〕
　粘着性組成物の調製において防錆剤の配合量を０.１質量部に代えて２質量部としたこと以外は実施例１の粘着シートと同様にして、比較例２の粘着シートを作製した。 [Comparative Example 2]
The pressure-sensitive adhesive sheet of Comparative Example 2 was prepared in the same manner as the pressure-sensitive adhesive sheet of Example 1 except that the amount of the rust inhibitor compounded was 2 parts by mass instead of 0.1 parts by mass in the preparation of the pressure-sensitive adhesive composition. ..
＜平均透過率＞
　実施例１～４および比較例１,２の各粘着シートについて、波長４００～７００ｎｍでの平均透過率を測定した。 <Average transmittance>
For each of the pressure-sensitive adhesive sheets of Examples 1 to 4 and Comparative Examples 1 and 2, the average transmittance at a wavelength of 400 to 700 nm was measured.
　本測定用のサンプルは、次のようにして作製した。まず、粘着シートから第２剥離フィルムを剥離した。次に、当該剥離によって露出した側の面にて粘着シートをスライドガラスに対して貼り合わせた。この貼り合わせでは、スライドガラス上の粘着シート（第１剥離フィルムを伴う）に対して、２ｋｇのハンドローラを１往復させた。次に、スライドガラス上の粘着シートから第１剥離フィルムを剥離した。 The sample for this measurement was prepared as follows. First, the second release film was peeled off from the adhesive sheet. Next, the adhesive sheet was attached to the slide glass on the surface exposed by the peeling. In this bonding, a 2 kg hand roller was reciprocated once with respect to the adhesive sheet (with the first release film) on the slide glass. Next, the first release film was peeled off from the adhesive sheet on the slide glass.
　このようにして作製した測定用サンプルについて、日立ハイテクノロジーズ社製の分光光度計Ｕ４１００を使用して、波長４００～７００ｎｍでの平均透過率を測定した（ＵＶ照射前の状態での第１の平均透過率測定）。本測定では、光源とディテクターを備える透過率測定装置内において、測定用サンプルの粘着シートが光源側に位置し且つ同サンプルのスライドガラスがディテクター側に位置するように測定用サンプルを配置した状態で、透過率測定を実施した。また、本測定では、スライドガラスのみについて同一条件で測定して得られた透過率スペクトルをベースラインとして用いた。測定結果（ＵＶ照射前の波長４００～７００ｎｍでの平均透過率）を、表１に掲げる。 With respect to the measurement sample thus prepared, the average transmittance at a wavelength of 400 to 700 nm was measured using a spectrophotometer U4100 manufactured by Hitachi High-Technologies Corporation (the first average in the state before UV irradiation). Transmittance measurement). In this measurement, in a transmittance measuring device equipped with a light source and a detector, the measurement sample is arranged so that the adhesive sheet of the measurement sample is located on the light source side and the slide glass of the sample is located on the detector side. , Transmittance measurement was carried out. Moreover, in this measurement, the transmittance spectrum obtained by measuring only the slide glass under the same conditions was used as the baseline. The measurement results (average transmittance at a wavelength of 400 to 700 nm before UV irradiation) are shown in Table 1.
　また、実施例１～４および比較例１,２の各粘着シートについて、紫外線（ＵＶ）照射後における波長４００～７００ｎｍでの平均透過率を測定した。本測定用のサンプルは、第１の平均透過率測定用のサンプルと同様にして作製した。当該測定用サンプルに対しては、紫外線を照射した。紫外線照射においては、光源としてＵＶ－ＬＥＤランプを使用し、照射波長を３６５ｎｍとし、照射光量を８０００ｍＪ/ｃｍ２とした。そして、本測定用サンプルについて、日立ハイテクノロジーズ社製の分光光度計Ｕ４１００を使用して、波長４００～７００ｎｍでの平均透過率を測定した（ＵＶ照射後の状態での第２の平均透過率測定）。測定条件は、第１の平均透過率測定と同じである。その測定結果（ＵＶ照射後の波長４００～７００ｎｍでの平均透過率）を、表１に掲げる。 In addition, the average transmittance at a wavelength of 400 to 700 nm after irradiation with ultraviolet rays (UV) was measured for each of the pressure-sensitive adhesive sheets of Examples 1 to 4 and Comparative Examples 1 and 2. The sample for this measurement was prepared in the same manner as the sample for the first average transmittance measurement. The measurement sample was irradiated with ultraviolet rays. In the ultraviolet irradiation, a UV-LED lamp was used as a light source, the irradiation wavelength was 365 nm, and the irradiation light amount was 8000 mJ / cm 2 . Then, for this measurement sample, the average transmittance at a wavelength of 400 to 700 nm was measured using a spectrophotometer U4100 manufactured by Hitachi High-Technologies Corporation (second average transmittance measurement in the state after UV irradiation). ). The measurement conditions are the same as those for the first average transmittance measurement. The measurement results (average transmittance at a wavelength of 400 to 700 nm after UV irradiation) are shown in Table 1.
＜ヘイズ＞
　実施例１～４および比較例１,２の各粘着シートについて、ヘイズを測定した。具体的には、まず、上述の平均透過率測定用のサンプルと同様にして、ヘイズ測定用のサンプルを作製した。次に、測定用サンプルについて、村上色彩技術研究所社製のヘイズメーター「ＨＭ－１５０Ｎ」を使用して、ＪＩＳ Ｋ７１３６（２０００年）に準拠してヘイズを測定した。測定結果を表１に掲げる。 <Haze>
The haze was measured for each of the pressure-sensitive adhesive sheets of Examples 1 to 4 and Comparative Examples 1 and 2. Specifically, first, a sample for haze measurement was prepared in the same manner as the sample for average transmittance measurement described above. Next, with respect to the measurement sample, the haze was measured according to JIS K7136 (2000) using the haze meter "HM-150N" manufactured by Murakami Color Technology Research Institute. The measurement results are listed in Table 1.
＜色差＞
　実施例１～４および比較例１,２の各粘着シートについて、紫外線照射前の状態で金属表面に及ぼす変色作用を、粘着シートが貼着される金属表面における色差をもって調べた。 <Color difference>
For each of the pressure-sensitive adhesive sheets of Examples 1 to 4 and Comparative Examples 1 and 2, the discoloration effect on the metal surface before irradiation with ultraviolet rays was examined by the color difference on the metal surface to which the pressure-sensitive adhesive sheet was attached.
　色差測定用のサンプル（第１の色差測定用サンプル）は、次のようにして作製した。まず、粘着シートから第２剥離フィルムを剥離した。次に、当該剥離によって露出した側の面にて粘着シートをＣｕ膜付被着体に貼り合わせた（Ｃｕ膜付被着体は、Ｃｕ蒸着膜が表面に形成されているポリエチレンテレフタレートフィルムである）。この貼り合わせでは、Ｃｕ膜付被着体上の粘着シート（第１剥離フィルムを伴う）に対して、２ｋｇのハンドローラを１往復させた。次に、Ｃｕ膜付被着体上の粘着シートから第１剥離フィルムを剥離した。 The sample for color difference measurement (first sample for color difference measurement) was prepared as follows. First, the second release film was peeled off from the adhesive sheet. Next, an adhesive sheet was attached to an adherend with a Cu film on the surface exposed by the peeling (the adherend with a Cu film is a polyethylene terephthalate film having a Cu vapor-deposited film formed on the surface). ). In this bonding, a 2 kg hand roller was reciprocated once with respect to the adhesive sheet (with the first release film) on the adherend with the Cu film. Next, the first release film was peeled off from the adhesive sheet on the adherend with the Cu film.
　このようにして作製された色差測定用サンプルについて、続いて、日立ハイテクノロジーズ社製の分光光度計Ｕ４１００を使用して、Ｌ＊ａ＊ｂ＊表色系におけるＬ＊、ａ＊およびｂ＊の各値を測定した（第１の色測定）。 With respect to the color difference measurement sample thus prepared, subsequently, using a spectrophotometer U4100 manufactured by Hitachi High-Technologies Corporation, L * a * b * in the color system of L * , a * and b * Each value was measured (first color measurement).
　この後、測定用サンプルを、高温・高湿環境下にて４８時間保管した。保管温度は６０℃であり、保管湿度は相対湿度９０％である。そして、このような高温・高湿環境を経た測定用サンプルについて、日立ハイテクノロジーズ社製の分光光度計Ｕ４１００を使用して、Ｌ＊ａ＊ｂ＊表色系におけるＬ＊、ａ＊およびｂ＊の各値を測定した（第２の色測定）。いずれの測定用サンプルにおいても、第２の色測定時の色味は、第１の色測定時の色味よりも強くなった。 After that, the measurement sample was stored for 48 hours in a high temperature and high humidity environment. The storage temperature is 60 ° C. and the storage humidity is 90% relative humidity. Then, for the measurement sample that has undergone such a high temperature and high humidity environment, using a spectrophotometer U4100 manufactured by Hitachi High-Technologies Corporation, L * a * b * L * , a * and b * in the color system. Each value of (second color measurement) was measured. In each of the measurement samples, the tint at the time of the second color measurement became stronger than the tint at the time of the first color measurement.
　そして、第１の色測定および第２の色測定の測定データに基づき、下記式によって色差ΔＥ＊ ａｂを求めた（下記式において、ΔＬ＊は、第１の色測定でのＬ＊と第２の色測定でのＬ＊との差であり、Δａ＊は、第１の色測定でのａ＊と第２の色測定でのａ＊との差であり、Δｂ＊は、第１の色測定でのｂ＊と第２の色測定でのｂ＊との差である）。上述の第１および第２の色測定における色差が小さいほど、金属表面（Ｃｕ膜表面）において変色を誘発する腐食が抑制されていると評価することができる。ＵＶ照射前の状態の粘着シートにおける第１の色測定および第２の色測定の測定データに基づき求められたΔＥ＊ ａｂを、色差ΔＥ１として表１に掲げる。 Then, based on the measurement data of the first color measurement and the second color measurement, the color difference ΔE * ab was obtained by the following formula (in the following formula, ΔL * is L * and the second in the first color measurement. is the difference between L * in the color measurement, .DELTA.a * is the difference between a * in a * and a second color measurement at the first color measurement, [Delta] b * is the first color The difference between b * in the measurement and b * in the second color measurement). It can be evaluated that the smaller the color difference in the first and second color measurements described above, the more the corrosion that induces discoloration on the metal surface (Cu film surface) is suppressed. Table 1 shows ΔE * ab obtained based on the measurement data of the first color measurement and the second color measurement on the adhesive sheet in the state before UV irradiation as the color difference ΔE 1.
　ΔＥ＊ ａｂ＝［(ΔＬ＊)２＋(Δａ＊)２＋(Δｂ＊)２］１／２ ΔE * ab = [(ΔL * ) 2 + (Δa * ) 2 + (Δb * ) 2 ] 1/2
　また、実施例１～４および比較例１,２の各粘着シートについて、紫外線照射後の状態で金属表面に及ぼす変色作用を、粘着シートが貼着される金属表面における色差をもって調べた。 Further, for each of the pressure-sensitive adhesive sheets of Examples 1 to 4 and Comparative Examples 1 and 2, the discoloration effect on the metal surface after irradiation with ultraviolet rays was examined by the color difference on the metal surface to which the pressure-sensitive adhesive sheet is attached.
　色差測定用のサンプル（第２の色差測定用サンプル）は、次のようにして作製した。まず、粘着シートに対して紫外線を照射した。紫外線照射においては、光源としてＵＶ－ＬＥＤランプを使用し、照射波長を３６５ｎｍとし、照射光量を８０００ｍＪ/ｃｍ２とした。次に、粘着シートから第２剥離フィルムを剥離した。次に、当該剥離によって露出した側の面にて粘着シートをＣｕ膜付被着体に貼り合わせた（Ｃｕ膜付被着体は、Ｃｕ蒸着膜が表面に形成されているポリエチレンテレフタレートフィルムである）。この貼り合わせでは、Ｃｕ膜付被着体上の粘着シート（第１剥離フィルムを伴う）に対して、２ｋｇのハンドローラを１往復させた。次に、Ｃｕ膜付被着体上の粘着シートから第１剥離フィルムを剥離した。 The sample for color difference measurement (second color difference measurement sample) was prepared as follows. First, the adhesive sheet was irradiated with ultraviolet rays. In the ultraviolet irradiation, a UV-LED lamp was used as a light source, the irradiation wavelength was 365 nm, and the irradiation light amount was 8000 mJ / cm 2 . Next, the second release film was peeled off from the adhesive sheet. Next, an adhesive sheet was attached to an adherend with a Cu film on the surface exposed by the peeling (the adherend with a Cu film is a polyethylene terephthalate film having a Cu vapor-deposited film formed on the surface). ). In this bonding, a 2 kg hand roller was reciprocated once with respect to the adhesive sheet (with the first release film) on the adherend with the Cu film. Next, the first release film was peeled off from the adhesive sheet on the adherend with the Cu film.
　このようにして作製された第２の色差測定用サンプルを上述の第１の色差測定用サンプルの代わりに用いたこと以外は、第１の色差測定用サンプルについての上述の第１の色測定、高温・高湿環境下での保管、および第２の色測定を行った。第２の色差測定用サンプルにおける第１の色測定および第２の色測定の測定データに基づき求められたΔＥ＊ ａｂを、ＵＶ照射後の状態での粘着シートについての色差ΔＥ２として表１に掲げる。 The above-mentioned first color measurement for the first color difference measurement sample, except that the second color difference measurement sample thus prepared is used in place of the above-mentioned first color difference measurement sample. Storage in a high temperature and high humidity environment and a second color measurement were performed. Table 1 shows ΔE * ab obtained based on the measurement data of the first color measurement and the second color measurement in the second color difference measurement sample as the color difference ΔE 2 for the adhesive sheet in the state after UV irradiation. Raise.
〔評価〕
　実施例１～４の各粘着シート（粘着剤層において、酸発生剤と、酸との反応により発色する発色性化合物と、防錆剤とを含み、且つ、防錆剤含有量が発色性化合物含有量に対して質量基準で当量未満である）では、波長４００～７００ｎｍでの平均透過率は、紫外線照射を受ける前には９４.２％（実施例１）、９４.０％（実施例２）、９２.９％（実施例３）および９３.１％（実施例４）と高く、紫外線照射を受けることによって１２.３％（実施例１）、１４.４％（実施例２）、１４.８％（実施例３）および１６.４％（実施例４）に低下する。このことから、実施例１～４の各粘着シートは、被着体に貼り合わせた後に可視光透過性を低下させるのに適することが分かる。 [Evaluation]
Each of the pressure-sensitive adhesive sheets of Examples 1 to 4 (in the pressure-sensitive adhesive layer, a color-developing compound that develops color by the reaction of an acid generator and an acid, and a rust preventive agent, and the rust preventive agent content is a color-developing compound. The average transmittance at a wavelength of 400 to 700 nm was 94.2% (Example 1) and 94.0% (Example 1) before being irradiated with ultraviolet rays. 2), 92.9% (Example 3) and 93.1% (Example 4), which are as high as 12.3% (Example 1) and 14.4% (Example 2) by being irradiated with ultraviolet rays. , 14.8% (Example 3) and 16.4% (Example 4). From this, it can be seen that each of the adhesive sheets of Examples 1 to 4 is suitable for reducing the visible light transmittance after being attached to the adherend.
　また、実施例１～４の各粘着シートでは、紫外線照射前の状態での上述の色差ΔＥ１についても、紫外線照射後の状態での上述の色差ΔＥ２についても、５以下の小さな値をとる（色差が小さいほど、金属表面において変色を誘発する腐食が抑制されていると評価することができる）。これに対し、粘着剤層に防錆剤を含まない比較例１の粘着シートでは、紫外線照射前の状態での色差ΔＥ１が１８.６であり、且つ、紫外線照射後の状態での色差ΔＥ２が２３.４であり、いずれも５を大きく上回る。また、発色性化合物に対して質量基準で同量の防錆剤を粘着剤層に含む比較例２の粘着シートでは、紫外線照射を受ける前の状態で波長４００～７００ｎｍの平均透過率が７３.７％と低く、且つ、紫外線照射後の状態での色差ΔＥ２が７.３であって５を有意に上回った。比較例２の粘着シートによると、紫外線照射前であっても、防錆剤の作用によって発色性化合物が発色するものと考えられ、また、高温・高湿環境下での防錆剤と発色性化合物との相互作用が強まり、発色が進行することによって色差ΔＥ２が上昇しているものと考えられる。これらから、実施例１～４の各粘着シートは、被着体における金属腐食を抑制するのに適することが分かる。 Further, in each of the adhesive sheets of Examples 1 to 4, the above-mentioned color difference ΔE 1 before the ultraviolet irradiation and the above-mentioned color difference ΔE 2 after the ultraviolet irradiation take a small value of 5 or less. (It can be evaluated that the smaller the color difference, the more the corrosion that induces discoloration on the metal surface is suppressed). On the other hand, in the pressure-sensitive adhesive sheet of Comparative Example 1 in which the pressure-sensitive adhesive layer does not contain a rust preventive, the color difference ΔE 1 before irradiation with ultraviolet rays is 18.6, and the color difference ΔE 1 after irradiation with ultraviolet rays is 1. 2 is 23.4, which is much higher than 5. Further, in the pressure-sensitive adhesive sheet of Comparative Example 2 in which the pressure-sensitive adhesive layer contains the same amount of rust preventive as the color-developing compound on a mass basis, the average transmittance at a wavelength of 400 to 700 nm is 73. It was as low as 7%, and the color difference ΔE 2 in the state after ultraviolet irradiation was 7.3, which was significantly higher than 5. According to the adhesive sheet of Comparative Example 2, it is considered that the color-developing compound develops color due to the action of the rust preventive even before the irradiation with ultraviolet rays, and the rust preventive and the color-developing property in a high temperature and high humidity environment. It is considered that the color difference ΔE 2 is increased as the interaction with the compound is strengthened and the color development progresses. From these, it can be seen that each of the pressure-sensitive adhesive sheets of Examples 1 to 4 is suitable for suppressing metal corrosion in the adherend.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　本発明の粘着シートは、例えば、光学デバイスや電子デバイスなど各種デバイスの表面に貼り合わせられる粘着シートとして用いられる。 The adhesive sheet of the present invention is used as an adhesive sheet to be attached to the surface of various devices such as optical devices and electronic devices, for example.
Ｘ　　　　　粘着シート
Ｙ　　　　　粘着シート付き部材
１０　　　　粘着剤層
２０　　　　基材
３１，３２　部材
３１ａ　　　粘着シート被着面 X Adhesive sheet Y Member with adhesive sheet 10 Adhesive layer 20 Base materials 31, 32 Member 31a Adhesive sheet Adhesive surface

Claims (6)

  1. 　ベースポリマーと、酸発生剤と、酸との反応により発色する発色性化合物と、当該発色性化合物１００質量部に対して１００質量部未満の防錆剤とを含有する粘着剤層を備えることを特徴とする、粘着シート。 A pressure-sensitive adhesive layer containing a base polymer, an acid generator, a color-developing compound that develops color by a reaction with an acid, and a rust preventive agent of less than 100 parts by mass with respect to 100 parts by mass of the color-developing compound is provided. Adhesive sheet as a feature.
  2. 　前記発色性化合物がロイコ染料であることを特徴とする、請求項１に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 1, wherein the color-developing compound is a leuco dye.
  3. 　前記防錆剤がベンゾトリアゾール系化合物であることを特徴とする、請求項１に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 1, wherein the rust preventive is a benzotriazole-based compound.
  4. 　前記ベースポリマーがアクリルポリマーであることを特徴とする、請求項１に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 1, wherein the base polymer is an acrylic polymer.
  5. 　前記粘着剤層のヘイズが３％以下であることを特徴とする、請求項１に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 1, wherein the haze of the pressure-sensitive adhesive layer is 3% or less.
  6. 　請求項１に記載の粘着シートを部材に貼り合わせる工程と、
    　前記部材上の前記粘着シートの前記粘着剤層に外部刺激を付与して前記発色性化合物を発色させる工程と、を含むことを特徴とする、粘着シート付き部材の製造方法。
          The step of attaching the adhesive sheet according to claim 1 to the member, and
    A method for producing a member with a pressure-sensitive adhesive sheet, which comprises a step of applying an external stimulus to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet on the member to develop a color of the color-developing compound.
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