WO2023042676A1 - 可変色粘着シートおよびその着色方法 - Google Patents

可変色粘着シートおよびその着色方法 Download PDF

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Publication number
WO2023042676A1
WO2023042676A1 PCT/JP2022/032983 JP2022032983W WO2023042676A1 WO 2023042676 A1 WO2023042676 A1 WO 2023042676A1 JP 2022032983 W JP2022032983 W JP 2022032983W WO 2023042676 A1 WO2023042676 A1 WO 2023042676A1
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WIPO (PCT)
Prior art keywords
adhesive sheet
color
sensitive adhesive
pressure
mass
Prior art date
Application number
PCT/JP2022/032983
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English (en)
French (fr)
Japanese (ja)
Inventor
大輔 水野
武史 仲野
Original Assignee
日東電工株式会社
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020247006254A priority Critical patent/KR20240058085A/ko
Priority to CN202280062304.3A priority patent/CN118076706A/zh
Publication of WO2023042676A1 publication Critical patent/WO2023042676A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/28—Pyronines ; Xanthon, thioxanthon, selenoxanthan, telluroxanthon dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation

Definitions

  • the present invention relates to a color-changeable pressure-sensitive adhesive sheet and its coloring method.
  • a display panel such as an organic EL panel has a laminated structure including a pixel panel and a cover glass.
  • a transparent adhesive sheet is used for bonding the elements included in the laminated structure.
  • Patent Document 1 describes a pressure-sensitive adhesive sheet provided with a colored portion containing a carbon black pigment.
  • adhesive sheets for display panel manufacturing are required to be able to form a plurality of colored portions with different shading levels according to the needs of the design and manufacturing process of the display panel.
  • the present invention provides a variable color pressure-sensitive adhesive sheet suitable for forming a plurality of colored portions with different shading levels, and a coloring method thereof.
  • the present invention [1] comprises a base polymer, a color-developing compound capable of reversibly changing between a color-developing state and a non-color-developing state by reaction with an acid, a thermal acid generator, a photoacid generator or and a photobase generator.
  • the configuration in which the color-changeable pressure-sensitive adhesive sheet contains a thermal acid generator is suitable for generating an acid from the thermal acid generator by heating and changing the color-developing compound from a non-coloring state to a coloring state by the acid.
  • the configuration in which the color-changeable pressure-sensitive adhesive sheet contains a photo-acid generator is suitable for generating an acid from the photo-acid generator upon irradiation with light and changing the color-developing compound from a non-color-developing state to a color-developing state by the acid.
  • the color-changeable pressure-sensitive adhesive sheet contains a photobase generator
  • a base is generated from the photobase generator by irradiation with light, and the acid is neutralized by the base to change the color-developing compound from a color-developing state to a non-color-developing state. suitable for change.
  • the color-changeable pressure-sensitive adhesive sheet contains a thermal acid generator and a photo-acid generator in addition to the color-forming compound
  • the color-changeable pressure-sensitive adhesive sheet is, for example, a color-changeable pressure-sensitive adhesive sheet is heated and colored as a whole, and then a part of the sheet is irradiated with light to darken the part, thereby forming a plurality of colored parts with different shading levels.
  • the color-changeable pressure-sensitive adhesive sheet contains a thermal acid generator and a photobase generator in addition to the color-forming compound
  • the color-changeable pressure-sensitive adhesive sheet (second type color-changeable pressure-sensitive adhesive sheet) is, for example, the color-changeable pressure-sensitive adhesive sheet as a whole. It is suitable for forming a plurality of colored portions with different shading levels by selectively heating and coloring a portion of the same sheet and then lightening the portion by irradiating the portion with light.
  • the present invention [2] comprises a base polymer, a color-forming compound capable of reversibly changing between a color-developed state and a non-color-developed state by reaction with an acid, a thermal acid generator residue, and a photoacid generator.
  • a color-changeable pressure-sensitive adhesive sheet containing a photobase generator is included.
  • the thermal acid generator generates acid and thermal acid generator residue by heating, and the color-developing compound reacts with the acid to develop color. That is, the color-changeable pressure-sensitive adhesive sheet containing the thermal acid generator residue and the color-developing compound has already undergone heating and is colored. Therefore, when the color-changeable pressure-sensitive adhesive sheet contains a photo-acid generator together with a color-forming compound and a thermal acid generator residue, the color-changeable pressure-sensitive adhesive sheet (the third type color-changeable pressure-sensitive adhesive sheet) can be partially irradiated with light. It is suitable for forming a plurality of colored portions with different shading levels by darkening the corresponding portion with .
  • the color-changeable pressure-sensitive adhesive sheet contains a photobase generator together with a color-developing compound and a thermal acid generator residue
  • the color-changeable pressure-sensitive adhesive sheet (fourth type color-changeable pressure-sensitive adhesive sheet) can be exposed to light by irradiating a portion of the sheet with light. By lightening the part, it is suitable for forming a plurality of colored parts with different light and shade levels.
  • the present invention [3] includes the color-changeable pressure-sensitive adhesive sheet according to [1] or [2] above, wherein the color-developing compound is a leuco dye.
  • a leuco dye has a high coloring property in a colored state, and is therefore preferable for ensuring the coloring property of the pressure-sensitive adhesive sheet.
  • the present invention [4] comprises a bonding step of bonding the first member and the second member via the color-changeable adhesive sheet according to [1] above, and heating the color-changeable adhesive sheet after the bonding step.
  • a method for coloring a color-changeable pressure-sensitive adhesive sheet comprising a coloring step of coloring and, after the coloring step, a discoloration step of discoloring a portion of the color-changeable pressure-sensitive adhesive sheet by irradiating the portion with light.
  • This method is suitable for forming a plurality of colored portions with different shading levels in the above-described first type color-changeable pressure-sensitive adhesive sheet attached to an adherend. This method is also suitable for forming a plurality of colored portions with different shading levels in the second type color-changeable pressure-sensitive adhesive sheet attached to an adherend.
  • the present invention [5] is a bonding step of bonding a first member and a second member via the color-changeable adhesive sheet according to [2] above; and a color changing step of changing the color of the portion by light irradiation.
  • This method is suitable for forming a plurality of colored portions with different shading levels in the above-described third type color-changeable pressure-sensitive adhesive sheet attached to an adherend. This method is also suitable for forming a plurality of colored portions with different shading levels in the above-described fourth type color-changeable pressure-sensitive adhesive sheet attached to an adherend.
  • the color-changeable pressure-sensitive adhesive sheet in the bonding step contains the photoacid generator, and in the discoloration step, a part of the color-changeable pressure-sensitive adhesive sheet is irradiated with light to darken the part.
  • the method for coloring the color-changeable pressure-sensitive adhesive sheet according to [4] or [5] above is included.
  • Such a coloring method is preferable for accurately forming a dark-colored portion on the color-changeable adhesive sheet by controlling the light irradiation area of the sheet.
  • the color-changeable pressure-sensitive adhesive sheet in the bonding step contains the photobase generator, and in the discoloration step, a part of the color-changeable pressure-sensitive adhesive sheet is lightly irradiated to lighten the color of the part.
  • the method for coloring the color-changeable pressure-sensitive adhesive sheet according to [4] or [5] is included.
  • Such a coloring method is preferable for accurately forming a light-colored portion on the color-changeable adhesive sheet by controlling the light irradiation area of the sheet.
  • FIG. 1 shows an example of how to use the color-changeable pressure-sensitive adhesive sheet shown in FIG. 2A shows the process of preparing the color-changeable adhesive sheet and the first member and the second member
  • FIG. 2B shows the process of bonding the members via the color-changeable adhesive sheet
  • FIG. 2C shows the color-changeable adhesive
  • FIG. 2D shows a step of heating and coloring the sheet
  • FIG. 2D shows a step of discoloring (darkening) a part of the color-changeable pressure-sensitive adhesive sheet by light irradiation.
  • FIG. 3 shows the process of preparing the color-changeable pressure-sensitive adhesive sheet and the first member and the second member
  • FIG. 4B shows the process of joining the members via the color-changeable pressure-sensitive adhesive sheet
  • FIG. 4C shows the color-changeable pressure-sensitive adhesive It represents a step of discoloring (deepening) a part of the sheet by light irradiation.
  • FIG. 5 shows a cross-sectional schematic diagram of one Embodiment of the color-changeable adhesive sheet of this invention.
  • 6A shows the process of preparing the color-changeable adhesive sheet and the first member and the second member
  • FIG. 6B shows the process of joining the members via the color-changeable adhesive sheet
  • FIG. 6C shows the color-changeable adhesive
  • FIG. 6D shows a step of heating and coloring the sheet
  • FIG. 6D shows a step of discoloring (lightening) a part of the color-changeable pressure-sensitive adhesive sheet by light irradiation.
  • FIG. 7 It is a cross-sectional schematic diagram of one Embodiment of the color-changeable adhesive sheet of this invention.
  • An example of how to use the color-changeable pressure-sensitive adhesive sheet shown in FIG. 7 is shown.
  • 8A shows the process of preparing the color-changeable pressure-sensitive adhesive sheet and the first member and the second member
  • FIG. 8B shows the process of joining the members via the color-changeable pressure-sensitive adhesive sheet
  • FIG. 8C shows the color-changeable pressure-sensitive adhesive It represents a step of discoloring (lightening) a part of the sheet by light irradiation.
  • FIG. 1 exemplarily shows a state in which release liners L1 and L2 are adhered to both sides of an adhesive sheet X.
  • the release liner L1 is arranged on one side of the adhesive sheet X in the thickness direction H.
  • the release liner L2 is arranged on the other side of the adhesive sheet X in the thickness direction H.
  • the adhesive sheet X is used, for example, as an adhesive sheet arranged on the image display side of a pixel panel in a display panel such as an organic EL panel (having a laminated structure including a pixel panel and a cover glass).
  • the adhesive sheet X is a sheet-like pressure-sensitive adhesive formed from the first adhesive composition.
  • Adhesive sheet X (first adhesive composition) contains a base polymer, a color-developing compound, a thermal acid generator, and a photoacid generator (first type color-changeable adhesive sheet).
  • the adhesive sheet X has transparency (visible light transmittance) in this embodiment.
  • the base polymer is an adhesive component that makes the adhesive sheet X exhibit adhesiveness.
  • the base polymer exhibits rubber elasticity in the room temperature range.
  • Base polymers include, for example, acrylic polymers, rubber polymers, polyester polymers, urethane polymers, polyether polymers, silicone polymers, polyamide polymers, and fluoropolymers. From the viewpoint of ensuring good transparency and adhesiveness in the pressure-sensitive adhesive sheet X, an acrylic polymer is preferably used as the base polymer.
  • An acrylic polymer is, for example, a copolymer of monomer components containing (meth)acrylic acid alkyl ester at a ratio of 50% by mass or more.
  • (Meth)acrylic acid means acrylic acid and/or methacrylic acid.
  • (Meth)acrylic acid alkyl esters include, for example, (meth)acrylic acid alkyl esters having a linear or branched alkyl group having 1 to 20 carbon atoms.
  • Examples of such (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylic acid.
  • the (meth)acrylic acid alkyl esters may be used alone, or two or more of them may be used in combination.
  • an acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms is preferably used, and more preferably having methyl methacrylate and an alkyl group having 2 to 12 carbon atoms.
  • a (meth)acrylic acid alkyl ester is used in combination, and more preferably, methyl methacrylate and 2-ethylhexyl acrylate are used in combination.
  • the ratio of the (meth)acrylic acid alkyl ester in the monomer component is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably It is 70% by mass or more. The same ratio is, for example, 99% by mass or less.
  • the monomer component may contain a copolymerizable monomer that can be copolymerized with the (meth)acrylic acid alkyl ester.
  • copolymerizable monomers include monomers having a polar group.
  • Polar group-containing monomers include, for example, hydroxyl group-containing monomers, nitrogen atom-containing ring-containing monomers, and carboxy group-containing monomers.
  • the polar group-containing monomer is useful for modifying the acrylic polymer, such as introducing cross-linking points into the acrylic polymer and securing the cohesive strength of the acrylic polymer.
  • the copolymerizable monomer preferably contains at least one selected from the group consisting of hydroxyl group-containing monomers, nitrogen atom-containing ring-containing monomers, and carboxy group-containing monomers. More preferably, the copolymerizable monomer includes a hydroxyl group-containing monomer and/or a monomer having a nitrogen atom-containing ring.
  • hydroxyl group-containing monomers examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth) ) 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.
  • 2-hydroxyethyl (meth)acrylate is preferably used, and 2-hydroxyethyl acrylate is more preferably used.
  • the ratio of the hydroxyl group-containing monomer in the monomer component is preferably 1% by mass or more, more preferably 3% by mass or more, from the viewpoint of introducing a crosslinked structure into the acrylic polymer and ensuring cohesive force in the pressure-sensitive adhesive sheet X. Preferably, it is 5% by mass or more. From the viewpoint of adjusting the polarity of the acrylic polymer, the same ratio is preferably 30% by mass or less, more preferably 20% by mass or less.
  • the polarity of the acrylic polymer is related to compatibility between various additive components in the pressure-sensitive adhesive sheet X and the acrylic polymer.
  • Examples of monomers having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-(meth)acryloyl-2-pyrrolidone, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-vinylmorpholine, N-vinyl -3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, N-vinylpyrazole, N-vinylisoxazole, N -vinylthiazole,
  • the ratio of the monomer having a nitrogen atom-containing ring in the monomer component is preferably 1% by mass or more, from the viewpoint of ensuring the cohesive force of the pressure-sensitive adhesive sheet X and ensuring the adhesion of the pressure-sensitive adhesive sheet X to the adherend. More preferably 3% by mass or more, still more preferably 5% by mass or more. The same proportion is preferably 30% by mass or less, more preferably 20% by mass or less, from the viewpoint of adjusting the glass transition temperature of the acrylic polymer and adjusting the polarity of the acrylic polymer.
  • Carboxy group-containing monomers include, for example, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
  • the ratio of the carboxy group-containing monomer in the monomer component is preferably from the viewpoint of introducing a crosslinked structure into the acrylic polymer, ensuring cohesive force in the pressure-sensitive adhesive sheet X, and ensuring adhesion of the pressure-sensitive adhesive sheet X to the adherend. It is 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more.
  • the ratio is preferably 30% by mass or less, more preferably 20% by mass or less, from the viewpoints of adjusting the glass transition temperature of the acrylic polymer and avoiding the risk of acid corrosion of the adherend.
  • the monomer component may contain other copolymerizable monomers.
  • copolymerizable monomers include, for example, acid anhydride monomers, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, epoxy group-containing monomers, cyano group-containing monomers, alkoxy group-containing monomers, and aromatic vinyl compounds. be done.
  • Anhydride monomers include, for example, maleic anhydride and itaconic anhydride.
  • sulfonic acid group-containing monomers examples include styrenesulfonic acid, allylsulfonic acid, sodium vinylsulfonate, 2-(meth)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid, sulfopropyl (meth) Acrylate, and (meth)acryloyloxynaphthalenesulfonic acid.
  • Phosphate group-containing monomers include, for example, 2-hydroxyethyl acryloyl phosphate.
  • epoxy group-containing monomers examples include glycidyl (meth)acrylate, glycidyl (meth)acrylate ether, 2-ethylglycidyl (meth)acrylate ether, and allyl glycidyl ether.
  • Cyano group-containing monomers include, for example, acrylonitrile and methacrylonitrile.
  • alkoxy group-containing monomers examples include 2-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, (meth) butoxyethyl acrylate, ethoxypropyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, and methoxypolypropylene glycol (meth)acrylate.
  • Aromatic vinyl compounds include, for example, styrene, ⁇ -methylstyrene, and vinyltoluene. These copolymerizable monomers may be used alone, or two or more of them may be used in combination.
  • the acrylic polymer can be formed by polymerizing the above monomer components.
  • the polymerization method includes, for example, solution polymerization, bulk polymerization, and emulsion polymerization, preferably solution polymerization.
  • the polymerization initiator for example, a thermal polymerization initiator and a photopolymerization initiator are used.
  • the amount of the polymerization initiator to be 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 initiators include, for example, azo polymerization initiators and peroxide polymerization initiators.
  • azo polymerization initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis(2-methylpropionate)dimethyl, 4,4'-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis[2-(5-methyl-2- imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methylpropionamidine) disulfate, and 2,2'-azobis(N,N'-dimethyleneisobutyramidine) dihydrochloride mentioned.
  • Peroxide polymerization initiators include, for example, dibenzoyl peroxide, t-butyl permaleate, and lauroyl peroxid
  • photopolymerization initiators examples include benzoin ether-based photopolymerization initiators, acetophenone-based photopolymerization initiators, ⁇ -ketol-based photopolymerization initiators, aromatic sulfonyl chloride-based photopolymerization initiators, and photoactive oxime-based photopolymerization initiators.
  • 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.
  • the molecular weight of the base polymer can be adjusted by adjusting the type and amount of the polymerization initiator.
  • the weight-average molecular weight of the acrylic polymer is preferably 100,000 or more, more preferably 300,000 or more, and even more preferably 500,000 or more, from the viewpoint of securing the cohesive force of the adhesive sheet X.
  • the weight-average molecular weight is preferably 5 million or less, more preferably 3 million or less, still more preferably 2 million or less.
  • the weight average molecular weight of the acrylic polymer is calculated by measuring by gel permeation chromatography (GPC) and converting to polystyrene.
  • the glass transition temperature (Tg) of the acrylic polymer is preferably 0°C or lower, more preferably -10°C or lower, and even 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 following Fox formula can be used.
  • the Fox equation is a relational expression between the glass transition temperature Tg of a polymer and the glass transition temperature Tgi of a homopolymer of monomers 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.
  • Literature values can be used for the glass transition temperature of homopolymers.
  • the glass transition temperature of a homopolymer of a monomer can also be determined by the method specifically described in JP-A-2007-51271.
  • a color-forming compound is a compound that can reversibly change between a color-developing state and a non-color-developing state by reaction with an acid.
  • a color-forming compound in a non-color-forming state changes to a color-forming state by reaction with an acid.
  • the chromogenic compound in the chromogenic state is changed to the non-color-developing state by neutralizing the acid with a base.
  • Chromogenic compounds include, for example, leuco dyes, triarylmethane dyes, diphenylmethane dyes, fluorane dyes, spiropyran dyes, and rhodamine dyes.
  • the color-developing compounds may be used alone, or two or more of them may be used in combination.
  • Leuco dyes include, for example, 2'-anilino-6'-(N-ethyl-N-isopentylamino)-3'-methylspiro[phthalide-3,9'-[9H]xanthene], 3-dibutylamino- 6-methyl-7-anilinofluorane, 3-dipropylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-dimethylamino-6- Methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-xyridinofluorane, and 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole) -3-yl)-4-azaphthalide.
  • triarylmethane dyes examples include p,p′,p′′-tris-dimethylaminotriphenylmethane.
  • diphenylmethane dyes examples include 4,4-bis-dimethylaminophenylbenzhydrylbenzyl ether.
  • fluorane dyes examples include 3-diethylamino-6-methyl-7-chlorofluorane
  • examples of spiropyran dyes include 3-methylspirodinaphthopyran
  • examples of rhodamine dyes examples include: Examples include rhodamine-B-anilinolactam.
  • the color-developing compound is preferably a leuco dye, more preferably 2'-anilino-6'-(N-ethyl-N-isopentylamino). -3'-methylspiro[phthalido-3,9'-[9H]xanthene] is used.
  • the amount of the color-developing compound added to 100 parts by mass of the base polymer is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 1.5 parts by mass, from the viewpoint of ensuring the coloring property of the pressure-sensitive adhesive sheet X. or more, preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and even more preferably 5 parts by mass or less. Further, in the pressure-sensitive adhesive sheet X as the first type color-changeable pressure-sensitive adhesive sheet, even when all the thermal acid generators contained in the sheet at a predetermined concentration generate acid, a significant amount of the color-developing compound is non-color-developing. The color-developing compound is contained in the pressure-sensitive adhesive sheet X at the concentration that exists in the state (the same applies to the pressure-sensitive adhesive sheet X as the third type color-changeable pressure-sensitive adhesive sheet described later).
  • a thermal acid generator is a chemical species that generates acid when heated.
  • the acid generated from the thermal acid generator changes the color-developing compound in the non-color-developing state to the color-developing state.
  • Thermal acid generators include, for example, sulfonium salts and phosphonium salts that can be decomposed to generate an acid by heating. Examples of such thermal acid generators include salts of the following cations and anions.
  • Examples of cations include benzyl(4-hydroxyphenyl)methylsulfonium, (4-acetoxyphenyl)dimethylsulfonium, (4-hydroxyphenyl)dimethylsulfonium, (2-methylbenzyl)(4-hydroxyphenyl)methylsulfonium, ( 4-acetoxyphenyl)(2-methylbenzyl)methylsulfonium, (1-naphthylmethyl)(4-hydroxyphenyl)methylsulfonium, and benzyl(4-acetoxyphenyl)methylsulfonium.
  • Anions include tris(pentafluoroethyl)trifluorophosphate, hexafluorophosphate, tetrakis(pentafluorophenyl)borate, hexafluoroantimonate, p-toluenesulfonate, dodecylbenzenesulfonate, trifluoromethanesulfonate, and perfluorobutanesulfonate. is mentioned.
  • the thermal acid generator may be used alone, or two or more of them may be used in combination.
  • thermal acid generators include, for example, SANAID SI-45L, SANAID SI-60L, SANAID SI-80L, SANAID SI-100L, SANAID SI-110L, SANAID SI-150L, and SANAID manufactured by Sanshin Chemical Industry Co., Ltd.
  • thermal acid generators also include, for example, ADEKA's PP-33, CP-66 and CP-77. The thermal acid generator may be used alone, or two or more of them may be used in combination.
  • the thermal decomposition temperature (heating temperature for generating acid) of the thermal acid generator is preferably 80° C. or higher, more preferably 100° C. or higher, from the viewpoint of appropriate thermal decomposition of the thermal acid generator. It is preferably 120° C. or higher, more preferably 200° C. or lower, more preferably 180° C. or lower, and still more preferably 160° C. or lower.
  • the amount of the thermal acid generator compounded with respect to 100 parts by mass of the base polymer is preferably 0.1 parts by mass or more, more preferably 0.1 part by mass or more, from the viewpoint of ensuring the colorability of the colored portion 11 formed on the adhesive sheet X, which will be described later. It is 2 parts by mass or more, more preferably 0.3 parts by mass or more. From the viewpoint of ensuring a difference in the degree of coloring between the colored portions 11 and 12 formed on the adhesive sheet X, the amount of the thermal acid generator per 100 parts by mass of the base polymer is preferably 5 parts by mass or less, or more. It is preferably 3 parts by mass or less, more preferably 2 parts by mass or less.
  • the amount of the thermal acid generator to be added to 100 parts by mass of the color-forming compound is preferably 5 parts by mass or more, more preferably 10 parts by mass, from the viewpoint of ensuring the colorability of the colored portion 11 formed on the pressure-sensitive adhesive sheet X, which will be described later. It is at least 15 parts by mass, more preferably at least 20 parts by mass.
  • the amount of the thermal acid generator to be blended with respect to 100 parts by mass of the color-developing compound is preferably 500 parts by mass or less, from the viewpoint of ensuring the difference in the degree of coloring between the colored portions 11 and 12 formed on the pressure-sensitive adhesive sheet X, which will be described later. More preferably 400 parts by mass or less, still more preferably 300 parts by mass or less.
  • a photoacid generator is a chemical species that generates acid when exposed to light.
  • the photoacid generator is excited by, for example, being irradiated with light of a predetermined wavelength or wavelength range to cause an acid generating reaction and generate acid.
  • the acid generation reaction is, for example, a decomposition reaction of the photoacid generator.
  • the wavelength of light that causes the acid generating reaction varies depending on the type of photoacid generator.
  • the photoacid generator does not substantially generate acid upon the heating described above to generate acid from the thermal acid generator.
  • the acid generated from the photoacid generator changes the color-developing compound in the non-color-developing state to the color-developing state.
  • photoacid generators include onium compounds that generate acid when irradiated with ultraviolet rays.
  • the onium compound is provided, for example, in the form of an onium salt of an onium cation and an anion.
  • Onium cations include, for example, sulfonium and iodonium.
  • Examples of anions include Cl ⁇ , Br ⁇ , I ⁇ , ZnCl 3 ⁇ , HSO 3 ⁇ , BF 4 ⁇ , PF 6 ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , CH 3 SO 3 ⁇ , CF 3 SO 3 ⁇ , C 4 F 9 HSO 3 ⁇ , (C 6 F 5 ) 4 B ⁇ , and (C 4 H 9 ) 4 B ⁇ .
  • the photoacid generators may be used alone, or two or more of them may be used in combination. Photoacid generators preferably include onium salts of sulfonium and (C 6 F 5 ) 4 B-- and onium salts of sulfonium and C 4 F 9 HSO 3 - .
  • photoacid generators include, for example, CPI-100, CPI-100P, CPI-101A, CPI-200K, CPI-210S, IK-1, IK-2, CPI-310B, and CPI manufactured by Sun-Apro. -410S.
  • Commercially available photoacid generators also include, for example, SP-056, SP-066, SP-130, SP-140, SP-150, SP-170, SP-171, and SP-172 manufactured by ADEKA. be done.
  • the blending amount of the photoacid generator with respect to 100 parts by mass of the base polymer is preferably 1 part by mass or more from the viewpoint of ensuring the colorability of the colored portion 12 (darker than the colored portion 11) formed on the adhesive sheet X, which will be described later. , 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 amount of the photoacid generator per 100 parts by mass of the base polymer is preferably 20 parts by mass or less, more preferably 15 parts by mass, from the viewpoint of compatibility between the base polymer and the photoacid generator in the pressure-sensitive adhesive composition. Below, more preferably 12 parts by mass or more.
  • the amount of the photoacid generator compounded with respect to 100 parts by mass of the color-developing compound is preferably 100 parts by mass or more, more preferably 150 parts by mass, from the viewpoint of ensuring the colorability of the colored portion 12 formed on the pressure-sensitive adhesive sheet X, which will be described later. Above, more preferably 200 parts by mass or more, particularly preferably 250 parts by mass or more.
  • the amount of the photoacid generator per 100 parts by mass of the color-forming compound is preferably 1000 parts by mass or less, more preferably 700 parts by mass, from the viewpoint of compatibility between the base polymer and the photoacid generator in the pressure-sensitive adhesive composition. parts or less, more preferably 500 parts by mass or less.
  • the amount of the photoacid generator to be mixed with 100 parts by mass of the thermal acid generator is, from the viewpoint of balancing the difference between the coloring property and the degree of coloring of the colored portions 11 and 12 formed on the pressure-sensitive adhesive sheet X, preferably 100 parts by mass or more, more preferably 500 parts by mass or more, still more preferably 1000 parts by mass or more; Particularly preferably, it is 2000 parts by mass or less.
  • the first pressure-sensitive adhesive composition may contain a cross-linking agent from the viewpoint of introducing a cross-linked structure into the base polymer.
  • Crosslinkers include, for example, isocyanate crosslinkers, epoxy crosslinkers, oxazoline crosslinkers, aziridine crosslinkers, carbodiimide crosslinkers, and metal chelate crosslinkers.
  • the cross-linking agents may be used alone, or two or more of them may be used in combination.
  • isocyanate cross-linking agents examples include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, isocyanates, and polymethylene polyphenyl isocyanates.
  • the isocyanate cross-linking agent also includes derivatives of these isocyanates.
  • isocyanate derivative examples include isocyanurate-modified products and polyol-modified products.
  • Commercially available isocyanate cross-linking agents include, for example, Coronate L (trimethylolpropane adduct of tolylene diisocyanate, manufactured by Tosoh Corporation), Coronate HL (trimethylolpropane adduct of hexamethylene diisocyanate, manufactured by Tosoh Corporation), and Coronate HX. (isocyanurate of hexamethylene diisocyanate, manufactured by Tosoh Corporation) and Takenate D110N (trimethylolpropane adduct of xylylene diisocyanate, manufactured by Mitsui Chemicals, Inc.).
  • Epoxy cross-linking agents include bisphenol A, epichlorohydrin type epoxy resin, ethylene glycol glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl.
  • Ether diglycidylaniline, diamineglycidylamine, N,N,N',N'-tetraglycidyl-m-xylylenediamine, and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane.
  • the amount of the cross-linking agent is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and still more preferably 100 parts by mass of the base polymer. is 0.07 parts by mass or more.
  • the amount of the cross-linking agent blended with respect to 100 parts by mass of the base polymer is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass. It is below the department.
  • a cross-linking catalyst When a cross-linked structure is introduced into the base polymer, a cross-linking catalyst may be used to effectively promote the cross-linking reaction.
  • Cross-linking catalysts include, for example, dibutyltin dilaurate, tetra-n-butyl titanate, tetraisopropyl titanate, Nasem ferric iron, and butyltin oxide, preferably dibutyltin dilaurate.
  • the amount of the cross-linking catalyst used is, for example, 0.0001 parts by mass or more and, for example, 1 part by mass or less with respect to 100 parts by mass of the base polymer.
  • a cross-linking inhibitor that can be subsequently removed from the first pressure-sensitive adhesive composition may be blended into the first pressure-sensitive adhesive composition.
  • dibutyltin dilaurate is used as the cross-linking catalyst
  • acetylacetone is preferably used as the cross-linking inhibitor.
  • acetylacetone is coordinated to dibutyltin dilaurate, and progress of the cross-linking reaction of the cross-linking agent to the base polymer is suppressed.
  • acetylacetone can be volatilized and removed from the coating film by heating at a desired timing. . This allows the cross-linking reaction of the cross-linking agent to proceed.
  • the amount of the cross-linking inhibitor is preferably 100 parts by mass or more, more preferably 1000 parts by mass or more, relative to 100 parts by mass of the cross-linking catalyst. Moreover, the compounding amount is, for example, 5000 parts by mass or less.
  • the first adhesive composition may contain other components as necessary.
  • Other ingredients include, for example, silane coupling agents, photosensitizers, tackifiers, plasticizers, softeners, antioxidants, surfactants, and antistatic agents.
  • the first pressure-sensitive adhesive composition does not substantially contain the photobase generator described below.
  • the amount of the photobase generator compounded with respect to 100 parts by mass of the base polymer is preferably 0.01 parts by mass or less, more preferably 0.005 parts by mass or less, and particularly preferably 0 parts.
  • the pressure-sensitive adhesive sheet X is prepared by, for example, preparing the above-described first pressure-sensitive adhesive composition in a varnish state further containing a solvent, applying the composition on the release liner L1 to form a coating film, and then forming the coating film. It can be produced by drying. Solvents for varnish preparation include, for example, ethyl acetate and toluene.
  • the drying temperature of the coating film of the first pressure-sensitive adhesive composition is lower than the thermal decomposition temperature of the thermal acid generator used, for example, 85° C. to 155° C., from the viewpoint of suppressing the coloring of the pressure-sensitive adhesive sheet X by heating. .
  • Examples of the release liner L1 include a flexible plastic film.
  • Examples of the plastic film include polyethylene terephthalate film, polyethylene film, polypropylene film, and polyester film.
  • the thickness of the release liner L1 is, for example, 3 ⁇ m or more and, for example, 200 ⁇ m or less.
  • the surface of the release liner L1 is preferably release-treated.
  • the cross-linking reaction proceeds simultaneously with the above-described drying or by subsequent aging.
  • Aging conditions are appropriately set according to the type of cross-linking agent.
  • the aging temperature is, for example, 20° C. to 80° C.
  • the aging time is, for example, 1 minute to 7 days.
  • the aging temperature is lower than the thermal decomposition temperature of the thermal acid generator used from the viewpoint of suppressing the coloration of the adhesive sheet X during aging.
  • a release liner L2 may be further laminated on the adhesive sheet X on the release liner L1 (Fig. 1 exemplarily shows the case where the release liner L2 is laminated).
  • the release liner L2 is preferably a flexible plastic film with surface release treatment.
  • Release liner L2 includes, for example, the plastic films described above for release liner L1.
  • the adhesive sheet X whose adhesive surface is covered and protected by the release liners L1 and L2 can be manufactured.
  • the release liners L1 and L2 are peeled off from the adhesive sheet X at necessary timings when the adhesive sheet X is used.
  • the thickness of the adhesive sheet X is preferably 10 ⁇ m or more, more preferably 15 ⁇ m or more, from the viewpoint of ensuring sufficient adhesion to the adherend. From the viewpoint of handleability of the adhesive sheet X, the thickness of the adhesive sheet X is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, even more preferably 100 ⁇ m or less, and particularly preferably 50 ⁇ m or less.
  • the adhesive sheet X exhibits an adhesive force to the glass plate of, for example, 1 N/25 mm or more. Yes, and for example less than 50N/25mm.
  • the average transmittance of the adhesive sheet X at a wavelength of 400 to 700 nm is preferably 90% or more, more preferably 95% or more, and still more preferably 97% or more. , particularly preferably 99% or more. Such a configuration is preferable for inspecting the presence or absence of foreign matter and air bubbles between the adhesive sheet X and the adherend after bonding the adhesive sheet X to the adherend.
  • the first average transmittance is, for example, 100% or less.
  • the average transmittance at a wavelength of 400 to 700 nm can be measured by the method described later with regard to the examples described later (the same applies to the average transmittance described later).
  • the average transmittance (second average transmittance) of the adhesive sheet X at a wavelength of 400 to 700 nm after heating the adhesive sheet X at 153 ° C. for 3 minutes is preferably 85% or less, more preferably It is 80% or less, more preferably 75% or less, particularly preferably 70% or less.
  • the second average transmittance is preferably 40% or higher, more preferably 50% or higher, still more preferably 60% or higher, and particularly preferably 65% or higher. Such a configuration is preferable from the viewpoint of ensuring a difference in degree of coloring between colored portions 11 and 12 formed on the adhesive sheet X, which will be described later.
  • the average transmittance (third average transmittance) of the adhesive sheet X at a wavelength of 400 to 700 nm after the adhesive sheet X is irradiated with light is preferably 40% or less, more preferably 30%. Below, more preferably 20% or less, particularly preferably 15% or less. Such a configuration is preferable for ensuring the deep color of the colored portion 12 (darker than the colored portion 11) formed on the adhesive sheet X. Also, the third average transmittance is, for example, 1% or more in the present embodiment.
  • a UV-LED lamp with a wavelength of 365 nm in a Quark Technology UV-LED irradiation device (model number “QEL-350-RU6W-CW-MY”) is used as a light source, and the wavelength is in the range of 320 to 390 nm. is 8000 mJ/cm 2 (the same applies to the light irradiation described later regarding the measurement of the average transmittance T 2 ).
  • the difference ⁇ T (
  • ) between the second average transmittance (T 1 ) and the third average transmittance (T 2 ) is preferably 30% or more, more preferably 40%. % or more, more preferably 50% or more, particularly preferably 60% or more. Such a configuration is preferable for ensuring the contrast between the colored portions 11 and 12.
  • FIG. Further, the difference ⁇ T is, for example, 95% or less in this embodiment.
  • the ratio (T 2 /T 1 ) of the third average transmittance (T 2 ) to the second average transmittance (T 1 ) is preferably 0.5 or less, more preferably 0.3 or less, More preferably, it is 0.2 or less. Such a configuration is preferable for ensuring the contrast between the colored portions 11 and 12.
  • FIG. Also, the ratio (T 2 /T 1 ) is, for example, 0.1 or more in this embodiment.
  • This method is a coloring method for a color-changeable pressure-sensitive adhesive sheet for joining members, and includes a preparing step, a joining step, a coloring step, and a discoloring step.
  • the adhesive sheet X, the first member 21, and the second member 22 are prepared.
  • the first member 21 is, for example, a display panel such as an organic EL panel.
  • the first member 21 may be other electronic devices and optical devices.
  • the second member 22 is, for example, a transparent base material.
  • Transparent substrates include transparent plastic substrates and transparent glass substrates. The same applies to the first member 21 and the second member 22 which will be described later.
  • the first member 21 and the second member 22 are bonded via the adhesive sheet X.
  • the laminated body W is obtained.
  • the adhesive sheet X is arranged so as to contact one surface of the first member 21 in the thickness direction H, and the second member 22 contacts one surface of the adhesive sheet X in the thickness direction H.
  • the pressure-sensitive adhesive sheet X in the bonding step in the present embodiment contains a color-developing compound in a non-color-developing state, a thermal acid generator, and a photoacid generator (first type variable color adhesive sheet).
  • the presence or absence of foreign matter and air bubbles between the members 21 and 22 and the adhesive sheet X is inspected as necessary. If unacceptable foreign matter or air bubbles are detected as a result of the inspection, the members 21 and 22 are separated from each other, and a new adhesive sheet X can be used to repeat the joining process.
  • the adhesive sheet X in the laminate W is heated to color the adhesive sheet X, as shown in FIG. 2C.
  • the heating temperature is equal to or higher than the thermal decomposition temperature of the thermal acid generator, and is, for example, 130° C. to 180° C. depending on the thermal acid generator used.
  • the thermal acid generator is thermally decomposed to generate acid, and some color-developing compounds change from a non-color-developing state to a color-developing state by reaction with the acid (other The chromogenic compound remains in a non-chromogenic state).
  • the adhesive sheet X is colored (in FIG. 2C, the entire adhesive sheet X is illustrated as a colored portion 11).
  • the adhesive sheet X in the laminate W is irradiated with light to form a colored portion 12 on the adhesive sheet X, as shown in FIG. 2D.
  • the adhesive sheet X is irradiated with light of a predetermined wavelength from the transparent second member 22 side through a mask pattern (not shown) for masking a predetermined area of the adhesive sheet X.
  • a mask pattern not shown
  • Examples of light sources for light irradiation in this process include ultraviolet LED lamps, high-pressure mercury lamps, and metal halide lamps.
  • a wavelength cut filter for cutting a part of the wavelength region of the light emitted from the light source may be used as necessary.
  • the light source and wavelength cut filter in the color change process are the same for other coloring methods described later.
  • an acid generation reaction of the photoacid generator is induced in the portion of the pressure-sensitive adhesive sheet X irradiated with light to generate an acid, and the reaction with the acid converts the non-color-developing compound into a color-developing state. Change.
  • the light-irradiated portion of the adhesive sheet X darkens. That is, the colored portion 12 having a darker color than the colored portion 11 is formed on the adhesive sheet X. As shown in FIG.
  • the colored portions 11 and 12 with different shading levels can be formed on the adhesive sheet X that joins the members.
  • the above configuration in which the pressure-sensitive adhesive sheet X contains a thermal acid generator is suitable for generating an acid from the thermal acid generator by heating, and changing the color-developing compound from a non-coloring state to a color-developing state by the acid.
  • the above structure in which the pressure-sensitive adhesive sheet X contains a photoacid generator is suitable for generating an acid from the photoacid generator by light irradiation, and changing the color-developing compound from a non-coloring state to a color-developing state by the acid.
  • the above-described configuration in which the pressure-sensitive adhesive sheet X contains a thermal acid generator and a photoacid generator in addition to the color-developing compound is obtained by heating the pressure-sensitive adhesive sheet X as a whole to color it as shown in FIG. As shown in 2D, by irradiating a portion of the sheet with light to darken the portion, it is suitable for forming colored portions 11 and 12 having different light and shade levels.
  • the colored portions 11 and 12 having different shading levels can impart a design property to the pressure-sensitive adhesive sheet X, and also provide light-shielding properties or anti-reflection properties to necessary portions. can be granted.
  • the first-stage coloring (FIG. 2C) as the initial coloring and the second-stage coloring (FIG. 2D) are due to the coloring state of the same type of coloring compound. Therefore, the hues of the first stage coloring and the second stage coloring are the same or substantially the same.
  • the pressure-sensitive adhesive sheet X described above does not require any adjustment to match the hues of the coloring in the first stage and the coloring in the second stage.
  • the adhesive sheet X also has such technical advantages.
  • the coated film of the first pressure-sensitive adhesive composition is dried at a temperature equal to or higher than the thermal decomposition temperature of the thermal acid generator to produce a colored pressure-sensitive adhesive sheet X' (shown in FIG. 3). can be manufactured.
  • the thermal acid generator is thermally decomposed to generate an acid, and the reaction with the acid causes a reaction.
  • Some color-forming compounds change from a non-color-forming state to a color-forming state (other color-forming compounds remain in a non-color-forming state).
  • Thermal decomposition of the thermal acid generator produces acid and thermal acid generator residue.
  • Such a pressure-sensitive adhesive sheet X' contains a base polymer, a color-developing compound, a thermal acid generator residue, and a photoacid generator (third type color-changeable pressure-sensitive adhesive sheet).
  • the thermal acid generator residue includes the cations described above with respect to the thermal acid generator or decomposition products thereof.
  • the second average transmittance of the adhesive sheet X' at a wavelength of 400 to 700 nm (the average transmittance of the adhesive sheet X' before light irradiation) is the same as the second average transmittance of the adhesive sheet X described above.
  • the third average transmittance of the adhesive sheet X′ at a wavelength of 400 to 700 nm after the adhesive sheet X′ is irradiated with light is the same as the third average transmittance of the adhesive sheet X described above.
  • the difference ⁇ T (
  • the ratio (T 2 /T 1 ) of the third average transmittance (T 2 ) to the second average transmittance (T 1 ) in the adhesive sheet X' is the ratio (T 2 / T 1 ) described above for the adhesive sheet X is similar to
  • This method is a method of coloring a variable color pressure-sensitive adhesive sheet for joining members, and includes a preparation step, a joining step, and a color changing step.
  • the adhesive sheet X', the first member 21, and the second member 22 are prepared.
  • the first member 21 and the second member 22 are joined via the adhesive sheet X'.
  • a laminated body W' is obtained.
  • the adhesive sheet X' is arranged so as to be in contact with one surface of the first member 21 in the thickness direction H, and the second member 22 is arranged to contact one side of the adhesive sheet X' in the thickness direction H. placed in contact with each other.
  • the pressure-sensitive adhesive sheet X′ in the bonding step in the present embodiment contains a coloring compound in a coloring state, a thermal acid generator residue, and a photoacid generator (third type variable color adhesive sheet).
  • the adhesive sheet X' in the laminate W' is irradiated with light to form a colored portion 12 on the adhesive sheet X'.
  • the adhesive sheet X' is irradiated with light of a predetermined wavelength through a mask pattern (not shown) for masking a predetermined area of the adhesive sheet X'. do.
  • the portion of the adhesive sheet X' not masked with the mask pattern is discolored.
  • the portion of the pressure-sensitive adhesive sheet X′ irradiated with light causes an acid generation reaction of the photoacid generator to generate an acid, and the reaction with the acid converts the non-color-developing compound into a color-developing state. change to As a result, the light-irradiated portion of the adhesive sheet X' is darkened. That is, the colored portion 12 darker than the colored portion 11 is formed on the adhesive sheet X'.
  • the colored portions 11 and 12 having different shading levels can be formed on the adhesive sheet X' that joins the members.
  • the thermal acid generator generates acid and thermal acid generator residue by heating, and the color-forming compound reacts with the acid to develop color. That is, the pressure-sensitive adhesive sheet X' containing the thermal acid generator residue and the color-developing compound has already been heated and colored as described above. Therefore, in the above-described configuration in which the pressure-sensitive adhesive sheet X' contains the photo-acid generator together with the color-forming compound and the residue of the thermal acid generator, as shown in FIG. Therefore, it is suitable for forming colored portions 11 and 12 having different light and shade levels. In such a pressure-sensitive adhesive sheet X', the colored portions 11 and 12 having different shading levels can impart design properties to the pressure-sensitive adhesive sheet X', and can impart light-shielding properties or anti-reflection properties to necessary portions.
  • the initial coloring (Fig. 4A) and the subsequent coloring (Fig. 4C) are due to the coloring state of the same type of coloring compound, so the hue of both coloring are the same or substantially the same.
  • the pressure-sensitive adhesive sheet X' described above does not require any adjustment to match the hues of the two colors. Adhesive sheet X' also has such technical advantages.
  • FIG. 5 shows a pressure-sensitive adhesive sheet X as a second embodiment of the color-changeable pressure-sensitive adhesive sheet of the present invention (FIG. 5 exemplarily shows a state in which release liners L1 and L2 are attached to both sides of the pressure-sensitive adhesive sheet X). ).
  • the pressure-sensitive adhesive sheet X as the second embodiment is a sheet-like pressure-sensitive adhesive formed from the second pressure-sensitive adhesive composition.
  • Adhesive sheet X (second adhesive composition) contains a base polymer, a color-developing compound, a thermal acid generator, and a photobase generator (second type color-changeable adhesive sheet).
  • the pressure-sensitive adhesive sheet X as the second embodiment contains a photobase generator instead of a photoacid generator, the amount of the thermal acid generator, and the second and third average transmittance at a wavelength of 400 to 700 nm. is different from the adhesive sheet X as the first embodiment.
  • the adhesive sheet X as the second embodiment is the same as the adhesive sheet X as the first embodiment.
  • a photobase generator is a chemical species that generates a base upon being irradiated with light.
  • the photobase generator is excited by, for example, being irradiated with light of a predetermined wavelength or wavelength range to cause a base generating reaction to generate a base.
  • a base generation reaction is, for example, a decomposition reaction of a photobase generator.
  • the wavelength of light that causes the base generation reaction varies depending on the type of photobase generator.
  • the photobase generator does not substantially generate base upon the above-described heating for acid generation from the thermal acid generator.
  • the base generated from the photobase generator neutralizes the acid to change the color-developing compound into a non-color-developing state.
  • photobase generators examples include ⁇ -aminoacetophenone compounds, oxime ester compounds, and compounds having biguanide-type cations.
  • Biguanide-type cations include, for example, alkylbiguanidiniums, cycloalkylbiguanidiniums, and cycloalkyl-alkylbiguanidiniums.
  • examples of the anion paired with the biguanide-type cation in the photobase active agent include borate anions.
  • Photobase generators also include compounds having a substituent as a base generator.
  • Substituent groups that are base generators include, for example, acyloxyimino groups, N-formylated aromatic amino groups, N-acylated aromatic amino groups, nitrobenzylcarbamate groups, and alkoxybenzylcarbamate groups.
  • the photobase generators may be used alone, or two or more of them may be used in combination.
  • Examples of commercially available photobase generators include WPBG-018 (9-anthramethyl N,N'-diethylcarbamate) and WPBG-027 ((E)-1-[3-(2- hydroxyphenyl)-2-propenoyl]piperidine), WPBG-082 (Guanidium 2-(3-benzoylphenyl)propionate), WPBG-140 (1-(anthraquinon-2-yl)ethylimidazole carboxylate), WPBG-266 ( 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidium 2-(3-benzoylphenyl)propionate), WPBG-300 (1,2-dicyclohexyl-4,4,5,5-tetramethylbiguani n-butyltriphenylborate), and WPBG-345 (1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidinium tetraki
  • the amount of the photobase generator compounded with respect to 100 parts by mass of the base polymer is preferably 1 part by mass or more, from the viewpoint of ensuring the lightness of the colored portion 11 (lighter than the colored portion 12) formed on the adhesive sheet X, which will be described later. It is 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 amount of the photobase generator compounded with respect to 100 parts by mass of the base polymer is preferably 20 parts by mass or less, more preferably 15 parts by mass, from the viewpoint of compatibility between the base polymer and the photobase generator in the pressure-sensitive adhesive composition. Below, more preferably 12 parts by mass or more.
  • the amount of the photobase generator compounded with respect to 100 parts by mass of the color-forming compound is preferably 100 parts by mass or more, more preferably 150 parts by mass, from the viewpoint of ensuring the light color of the colored portion 11 formed on the pressure-sensitive adhesive sheet X, which will be described later. Above, more preferably 200 parts by mass or more, particularly preferably 250 parts by mass or more.
  • the amount of the photobase generator per 100 parts by mass of the color-forming compound is preferably 1000 parts by mass or less, more preferably 700 parts by mass, from the viewpoint of compatibility between the base polymer and the photobase generator in the pressure-sensitive adhesive composition. parts or less, more preferably 500 parts by mass or less.
  • the amount of the photobase generator to be blended with respect to 100 parts by mass of the thermal acid generator is, from the viewpoint of balancing the difference between the coloring property and the degree of coloring of the colored portions 11 and 12 formed on the pressure-sensitive adhesive sheet X, preferably 10 parts by mass or more, more preferably 100 parts by mass or more, still more preferably 500 parts by mass or more, particularly preferably 1000 parts by mass or more, and preferably 3000 parts by mass or less, more preferably 2000 parts by mass or less; More preferably, it is 1700 mass parts or less.
  • the average transmittance (second average transmittance) of the adhesive sheet X at a wavelength of 400 to 700 nm after heating the adhesive sheet X at 153 ° C. for 3 minutes is preferably 75% or less, more preferably It is 71% or less, more preferably 65% or less, particularly preferably 60% or less.
  • the average transmittance T1 is, for example, 1% or more in this embodiment.
  • the average transmittance (third average transmittance) of the adhesive sheet X at a wavelength of 400 to 700 nm after the adhesive sheet X is irradiated with light is preferably 80% or more, more preferably 85%. above, more preferably 90% or more, particularly preferably 95% or more.
  • Such a configuration is preferable from the viewpoint of ensuring a difference in degree of coloring between the colored portions 11 and 12 formed on the adhesive sheet X.
  • the average transmittance T2 is, for example, 99% or less in this embodiment.
  • the difference ⁇ T (
  • ) between the second average transmittance (T 1 ) and the third average transmittance (T 2 ) is preferably 15% or more, more preferably 20%. % or more, more preferably 25% or more, and particularly preferably 30% or more. Such a configuration is preferable for ensuring the contrast between the colored portions 11 and 12.
  • FIG. Further, the difference ⁇ T is, for example, 90% or less in this embodiment.
  • the ratio (T 2 /T 1 ) of the third average transmittance (T 2 ) to the second average transmittance (T 1 ) is preferably 1.2 or more, more preferably 1.3 or more, More preferably, it is 1.4 or more. Such a configuration is preferable for ensuring the contrast between the colored portions 11 and 12.
  • FIG. Also, the ratio (T 2 /T 1 ) is, for example, 5 or less in this embodiment.
  • the pressure-sensitive adhesive sheet X as the second embodiment is prepared by, for example, preparing the second pressure-sensitive adhesive composition in a varnish state further containing a solvent, and then coating the composition on the release liner L1 to form a coating film, It can be produced by drying the coating film.
  • the drying temperature of the coating film of the second pressure-sensitive adhesive composition is lower than the thermal decomposition temperature of the thermal acid generator used, for example, 85° C. to 155° C., from the viewpoint of suppressing the coloring of the pressure-sensitive adhesive sheet X by heating. .
  • This method is a coloring method for a color-changeable pressure-sensitive adhesive sheet for joining members, and includes a preparing step, a joining step, a coloring step, and a discoloring step.
  • the adhesive sheet X, the first member 21, and the second member 22 are prepared.
  • the first member 21 and the second member 22 are bonded via the adhesive sheet X.
  • the laminated body W is obtained.
  • the adhesive sheet X is arranged so as to contact one surface of the first member 21 in the thickness direction H, and the second member 22 contacts one surface of the adhesive sheet X in the thickness direction H.
  • the pressure-sensitive adhesive sheet X in the bonding step in the present embodiment contains a color-developing compound in a non-color-developing state, a thermal acid generator, and a photobase generator (second type variable color adhesive sheet).
  • the presence or absence of foreign matter and air bubbles between the members 21 and 22 and the adhesive sheet X is inspected as necessary. If unacceptable foreign matter or air bubbles are detected as a result of the inspection, the members 21 and 22 are separated from each other, and a new adhesive sheet X can be used to repeat the joining process.
  • the adhesive sheet X in the laminate W is heated to color the adhesive sheet X, as shown in FIG. 6C.
  • the heating temperature is equal to or higher than the thermal decomposition temperature of the thermal acid generator, and is, for example, 130° C. to 180° C. depending on the thermal acid generator used.
  • the adhesive sheet X in this step, thermal decomposition of the thermal acid generator is induced to generate acid, and the reaction with the acid causes the color-developing compound to change from a non-color-developing state to a color-developing state.
  • the adhesive sheet X is colored (in FIG. 6C, the entire adhesive sheet X is illustrated as a colored portion 11).
  • the adhesive sheet X in the laminate W is irradiated with light to form a colored portion 12 on the adhesive sheet X, as shown in FIG. 6D.
  • the adhesive sheet X is irradiated with light of a predetermined wavelength from the transparent second member 22 side through a mask pattern (not shown) for masking a predetermined area of the adhesive sheet X.
  • a mask pattern not shown
  • an acid generation reaction of the photobase generator is induced in the portion of the pressure-sensitive adhesive sheet X irradiated with light to generate a base.
  • the color-developing state is changed to a non-color-developing state (in the light-irradiated portion, other color-developing compounds remain in a color-developing state).
  • the light-irradiated portion of the adhesive sheet X is lightened. That is, the colored portion 12 lighter in color than the colored portion 11 is formed on the adhesive sheet X. As shown in FIG.
  • the colored portions 11 and 12 with different shading levels can be formed on the adhesive sheet X that joins the members.
  • the above configuration in which the pressure-sensitive adhesive sheet X contains a thermal acid generator is suitable for generating an acid from the thermal acid generator by heating, and changing the color-developing compound from a non-coloring state to a color-developing state by the acid.
  • a base is generated from the photobase generator by light irradiation, and the base neutralizes the acid to change the color-developing compound from a color-developing state to a non-color-developing state.
  • the above-described configuration in which the pressure-sensitive adhesive sheet X contains the thermal acid generator and the photobase generator in addition to the color-developing compound is obtained by heating the entire pressure-sensitive adhesive sheet X to color it as shown in FIG. As shown in 6D, by irradiating a portion of the sheet with light to lighten the portion, it is suitable for forming colored portions 11 and 12 having different light and shade levels.
  • the colored portions 11 and 12 having different shading levels can impart design properties to the adhesive sheet X, and can impart light shielding properties or antireflection properties to necessary portions.
  • the coated film of the second pressure-sensitive adhesive composition is dried at a temperature equal to or higher than the thermal decomposition temperature of the thermal acid generator to produce a colored pressure-sensitive adhesive sheet X'. (shown in FIG. 7) can be produced.
  • thermal decomposition of the thermal acid generator is induced to generate an acid, which reacts with the acid to develop color.
  • the polar compound changes from a non-colored state to a colored state.
  • Thermal decomposition of the thermal acid generator produces acid and thermal acid generator residue.
  • Such a pressure-sensitive adhesive sheet X' contains a base polymer, a color-developing compound, a thermal acid generator residue, and a photobase generator (fourth type color-changeable pressure-sensitive adhesive sheet).
  • the thermal acid generator residue includes the cations described above with respect to the thermal acid generator or decomposition products thereof.
  • the second average transmittance of the adhesive sheet X' at a wavelength of 400 to 700 nm (the average transmittance of the adhesive sheet X' before light irradiation) is the same as the second average transmittance described above for the adhesive sheet X as the second embodiment. It is the same.
  • the third average transmittance at a wavelength of 400 to 700 nm of the adhesive sheet X′ after the adhesive sheet X′ is irradiated with light is the same as the third average transmittance described above with respect to the adhesive sheet X as the second embodiment. is.
  • the difference ⁇ T (
  • the ratio (T 2 /T 1 ) of the third average transmittance (T 2 ) to the second average transmittance ( T 1 ) in the adhesive sheet X′ is the ratio ( T 2 /T 1 ).
  • This method is a method of coloring a variable color pressure-sensitive adhesive sheet for joining members, and includes a preparation step, a joining step, and a color changing step.
  • the adhesive sheet X', the first member 21, and the second member 22 are prepared.
  • the first member 21 and the second member 22 are bonded via the adhesive sheet X'.
  • a laminated body W' is obtained.
  • the adhesive sheet X' is arranged so as to be in contact with one surface of the first member 21 in the thickness direction H, and the second member 22 is arranged to contact one side of the adhesive sheet X' in the thickness direction H. placed in contact with each other.
  • the pressure-sensitive adhesive sheet X′ in the bonding step in the present embodiment contains a coloring compound in a coloring state, a thermal acid generator residue, and a photobase generator (fourth type variable color adhesive sheet).
  • the adhesive sheet X' in the laminate W' is irradiated with light to form the colored portion 12 on the adhesive sheet X'.
  • the adhesive sheet X' is irradiated with light of a predetermined wavelength through a mask pattern (not shown) for masking a predetermined area of the adhesive sheet X'. do.
  • the portion of the adhesive sheet X' not masked with the mask pattern is discolored.
  • a base generation reaction is induced by the photobase generator to generate a base. is changed from a coloring state to a non-coloring state (the chromogenic compound remains in the coloring state in the portion not irradiated with light).
  • the light-irradiated portion of the adhesive sheet X' is lightened. That is, the colored portion 12 lighter in color than the colored portion 11 is formed on the adhesive sheet X'.
  • the colored portions 11 and 12 having different shading levels can be formed on the adhesive sheet X' that joins the members.
  • the thermal acid generator generates acid and thermal acid generator residue by heating, and the color-forming compound reacts with the acid to develop color. That is, the pressure-sensitive adhesive sheet X' containing the thermal acid generator residue and the color-developing compound has already been heated and colored as described above. Therefore, the above-described configuration in which the pressure-sensitive adhesive sheet X′ contains the photobase generator together with the color-forming compound and the residue of the thermal acid generator causes light irradiation of a part of the sheet to lighten the color of the part, as shown in FIG. 8C. Therefore, it is suitable for forming colored portions 11 and 12 having different shading levels. In such a pressure-sensitive adhesive sheet X', the colored portions 11 and 12 having different shading levels can impart design properties to the pressure-sensitive adhesive sheet X', and can impart light-shielding properties or anti-reflection properties to necessary portions.
  • the weight average molecular weight (Mw) of acrylic polymer P1 was about 1,200,000.
  • a pressure-sensitive adhesive composition is applied onto the release-treated surface of a 38 ⁇ m-thick first film (product name “Diafoil MRF #38”, polyethylene terephthalate film, manufactured by Mitsubishi Plastics, Inc.), one side of which is release-treated, to form a coating film. formed.
  • the coating was then dried by heating at 152°C for 3 minutes. As a result, an adhesive sheet having a thickness of 25 ⁇ m was formed on the first film.
  • the acid generated from the thermal acid generator by the heating reacted with the leuco dye, and the adhesive sheet was colored.
  • a release-treated surface of a 38 ⁇ m-thick second film product name “Diafoil MRE #38”, polyethylene terephthalate film, manufactured by Mitsubishi Plastics Co., Ltd.
  • a release-treated surface of a 38 ⁇ m-thick second film product name “Diafoil MRE #38”, polyethylene terephthalate film, manufactured by Mitsubishi Plastics Co., Ltd.
  • the composition of the pressure-sensitive adhesive sheet of Example 1 is shown in Table 1 in units of parts by mass (the same applies to Examples and Comparative Examples described later).
  • Example 2 The pressure-sensitive adhesive sheet of Example 1, except that 7 parts by mass of a photobase generator (product name "WPBG-018", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used in place of the photoacid generator in the preparation of the pressure-sensitive adhesive composition.
  • a pressure-sensitive adhesive sheet of Example 2 was prepared in the same manner as above.
  • Example 3 The pressure-sensitive adhesive sheet of Example 1, except that 7 parts by mass of a photobase generator (product name "WPBG-345", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used in place of the photoacid generator in the preparation of the pressure-sensitive adhesive composition.
  • a pressure-sensitive adhesive sheet of Example 3 was prepared in the same manner as above.
  • 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 no thermal acid generator was used in the preparation of the pressure-sensitive adhesive composition.
  • Comparative Example 2 A pressure-sensitive adhesive sheet of Comparative Example 2 was prepared in the same manner as the pressure-sensitive adhesive sheet of Example 1 except for the following. In the preparation of the pressure-sensitive adhesive composition, 7 parts by mass of a photobase generator (product name “WPBG-018”, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used instead of the photoacid generator, and no thermal acid generator was used. rice field.
  • a photobase generator product name “WPBG-018”, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • a pressure-sensitive adhesive sheet of Comparative Example 3 was prepared in the same manner as the pressure-sensitive adhesive sheet of Example 1 except for the following.
  • a photobase generator product name “WPBG-345”, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • WPBG-345 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • Comparative Example 4 A pressure-sensitive adhesive sheet of Comparative Example 4 was prepared in the same manner as the pressure-sensitive adhesive sheet of Example 1, except that no photoacid generator was used in the preparation of the pressure-sensitive adhesive composition.
  • a sample for measurement was produced. Specifically, after peeling off the second film from the adhesive sheet, the exposed surface of the adhesive sheet was attached to Eagle Glass (thickness: 0.55 mm, manufactured by Matsunami Glass Co., Ltd.). Thus, a sample including the eagle glass, the adhesive sheet, and the first film in this order was produced. Next, after peeling off the first film from the sample, the average transmittance of the adhesive sheet in the sample at a wavelength of 400 to 700 nm was measured by a transmittance measurement device (product name "U4150 spectrophotometer", manufactured by Hitachi High-Tech Science Co., Ltd. ).
  • the transmittance measurement was performed with the sample placed in the apparatus so that the eagle glass of the sample was positioned on the light source side and the adhesive sheet of the same sample was positioned on the detector side (the first transmission rate measurement).
  • the transmittance spectrum obtained by measuring only the eagle glass under the same conditions was used as a baseline.
  • Table 1 shows the average transmittance T 1 (%) of the adhesive sheet before light irradiation.
  • the sample was irradiated with ultraviolet (UV) light.
  • UV ultraviolet
  • the pressure-sensitive adhesive sheet in the sample was irradiated with UV from the first film side (first UV irradiation).
  • the acid generated from the photoacid generator reacted with the leuco dye, and the adhesive sheet darkened.
  • a UV-LED lamp with a wavelength of 365 nm in a Quark Technology UV-LED irradiation device (model number “QEL-350-RU6W-CW-MY”) is used as a light source, and the wavelength is in the range of 320 to 390 nm.
  • the integrated irradiation light amount was set to 8000 mJ/cm 2 .
  • the average transmittance of the colored adhesive sheet in the sample at a wavelength of 400 to 700 nm is measured by a transmittance measurement device (product name "U4150 spectrophotometer", Hitachi High-Tech Science (manufactured by Co., Ltd.) (second transmittance measurement).
  • the method and conditions for the second transmittance measurement are the same as those for the first transmittance measurement described above.
  • Table 1 shows the measured average transmittance T 2 (%).
  • the pressure-sensitive adhesive sheet of Comparative Example 1 contains a color-forming compound and a photoacid generator, and therefore has a coloring property by light irradiation. have no gender.
  • Each pressure-sensitive adhesive sheet of Comparative Examples 2 and 3 contains a color-developing compound, but does not contain a thermal acid generator or a photoacid generator, and thus has neither coloring property due to heating nor coloring property due to light irradiation.
  • the pressure-sensitive adhesive sheet of Comparative Example 4 is produced in a state of being colored to a certain degree by the action of the color-forming compound and the thermal acid generator, but since it does not contain a photo-acid generator, it does not have coloration due to light irradiation.
  • the pressure-sensitive adhesive sheet of Example 1 was produced in a state colored to a certain degree by the action of the color-forming compound and the thermal acid generator, and furthermore contained a photo-acid generator, so that it discolored (darkened) when irradiated with light. coloration).
  • the pressure-sensitive adhesive sheets of Examples 2 and 3 were produced in a state of being colored to a certain degree by the action of the color-forming compound and the thermal acid generator, and furthermore, contained a photobase generator, so discoloration (lightening) due to light irradiation was observed. have Each of the pressure-sensitive adhesive sheets of Examples 1 to 3 is suitable for forming a plurality of colored portions with different shading levels.
  • the color-changeable pressure-sensitive adhesive sheet of the present invention is used, for example, in the manufacturing process of display panels to bond elements included in the laminated structure of the same panels.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
PCT/JP2022/032983 2021-09-16 2022-09-01 可変色粘着シートおよびその着色方法 WO2023042676A1 (ja)

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WO2020189390A1 (ja) * 2019-03-15 2020-09-24 日東電工株式会社 粘着剤組成物、粘着剤層及び粘着シート
WO2020188984A1 (ja) * 2019-03-15 2020-09-24 日東電工株式会社 粘着剤、中間積層体の製造方法および中間積層体
WO2020262048A1 (ja) * 2019-06-27 2020-12-30 日東電工株式会社 粘着シート、および粘着シート貼付品の製造方法

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

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Publication number Priority date Publication date Assignee Title
WO2020189390A1 (ja) * 2019-03-15 2020-09-24 日東電工株式会社 粘着剤組成物、粘着剤層及び粘着シート
WO2020188984A1 (ja) * 2019-03-15 2020-09-24 日東電工株式会社 粘着剤、中間積層体の製造方法および中間積層体
WO2020262048A1 (ja) * 2019-06-27 2020-12-30 日東電工株式会社 粘着シート、および粘着シート貼付品の製造方法

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