WO2022071252A1 - Résine pour mélange maître de dispersion de pigment pour adhésif sensible à la pression, mélange maître de dispersion de pigment pour adhésif sensible à la pression, composition adhésive sensible à la pression colorée, et feuille adhésive sensible à la pression - Google Patents

Résine pour mélange maître de dispersion de pigment pour adhésif sensible à la pression, mélange maître de dispersion de pigment pour adhésif sensible à la pression, composition adhésive sensible à la pression colorée, et feuille adhésive sensible à la pression Download PDF

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WO2022071252A1
WO2022071252A1 PCT/JP2021/035468 JP2021035468W WO2022071252A1 WO 2022071252 A1 WO2022071252 A1 WO 2022071252A1 JP 2021035468 W JP2021035468 W JP 2021035468W WO 2022071252 A1 WO2022071252 A1 WO 2022071252A1
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Prior art keywords
sensitive adhesive
pressure
pigment
mass
resin
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PCT/JP2021/035468
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English (en)
Japanese (ja)
Inventor
真由 尾▲崎▼
武史 仲野
駿 飛永
修一 篠原
浩二 太田
Original Assignee
日東電工株式会社
三洋化成工業株式会社
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Application filed by 日東電工株式会社, 三洋化成工業株式会社 filed Critical 日東電工株式会社
Priority to JP2022553971A priority Critical patent/JPWO2022071252A1/ja
Priority to CN202180066952.1A priority patent/CN116323765A/zh
Priority to KR1020237010378A priority patent/KR20230079062A/ko
Publication of WO2022071252A1 publication Critical patent/WO2022071252A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of 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
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers

Definitions

  • the present invention relates to a resin for a pigment dispersion masterbatch for a pressure-sensitive adhesive, a pigment dispersion masterbatch for a pressure-sensitive adhesive, a colored pressure-sensitive adhesive composition, and a pressure-sensitive adhesive sheet.
  • a member using an adhesive can be peeled off by a simple operation, a design member having a colored adhesive layer on a base material and a decorative adhesive member are used in various fields. Then, a pressure-sensitive adhesive layer using a pigment as a coloring material that can realize various colors at a desired concentration and brightness, is less likely to fade even when used outdoors or exposed to ultraviolet rays, and has excellent weather resistance is studied. Has been done.
  • Patent Document 1 has a pressure-sensitive adhesive layer composed of a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive component and a pigment dispersion containing a pigment and a dispersion resin, and has a specific range of mass ratio between the pigment and the dispersion resin. A colored adhesive sheet is described.
  • Patent Document 2 describes a thin layer of a colored pressure-sensitive adhesive obtained by densely kneading and dispersing a pressure-sensitive adhesive based on a polyacrylic acid ester and pigment particles coated with an acrylic resin having no active group.
  • Patent Document 3 has a color tone correction function for adjusting the color tone of an optical member such as a display, and can be thinned, and has high adhesive strength and pigment dispersion even when exposed to a high temperature and high humidity environment for a long period of time.
  • a masterbatch containing a pigment is used as a means for coloring the resin.
  • the adhesive resin, the pigment, and the dispersant are simply mixed, and the dispersibility of the pigment in the adhesive resin is not sufficient, and the appearance of the colored adhesive layer may be uneven. there were.
  • the adhesion stability of the adhesive such as the adhesive strength decreasing with time.
  • master batches containing pigments are used, but since heat-melting and kneading cannot be performed with adhesives that do not undergo a thermoforming process, let's apply the master batch to adhesives. No effort was made.
  • the present invention has been made to solve the above-mentioned problems in the prior art, and is a resin for a pigment dispersion masterbatch for a pressure-sensitive adhesive, which can form a pressure-sensitive adhesive layer having both dispersibility and adhesion reliability of the pigment. And a pigment dispersion masterbatch for a pressure-sensitive adhesive, a colored pressure-sensitive adhesive composition, and a pressure-sensitive adhesive sheet.
  • the present inventors focused on the surface of the pigment by using the resin (A) having a specific glass transition temperature (Tg) and a specific acid value.
  • Tg glass transition temperature
  • the pigment for a pressure-sensitive adhesive having excellent dispersibility
  • the present invention is as follows.
  • the glass transition temperature of the resin (A) is ⁇ 80 to 40 ° C.
  • the resin for the pigment dispersion masterbatch for a pressure-sensitive adhesive according to [1] and the pigment are included.
  • a pigment dispersion masterbatch for a pressure-sensitive adhesive in which the content of the resin (A) is 45 to 90% by mass with respect to the total mass of the pigment and the resin (A).
  • a colored pressure-sensitive adhesive composition containing the pigment dispersion masterbatch for a pressure-sensitive adhesive according to [2] and a base polymer.
  • a pressure-sensitive adhesive layer comprising the colored pressure-sensitive adhesive composition according to [3] or [4]. Adhesive sheet.
  • a pressure-sensitive adhesive layer and a pressure-sensitive adhesive sheet exhibiting an excellent appearance and high adhesion reliability, a colored pressure-sensitive adhesive composition capable of forming the pressure-sensitive adhesive layer and the pressure-sensitive adhesive sheet, and a pigment dispersion for a pressure-sensitive adhesive having excellent dispersibility.
  • a resin for a master batch and a pigment dispersion master batch for an adhesive can be provided.
  • FIG. 1 is an example of a schematic cross-sectional view of the pressure-sensitive adhesive sheet according to the embodiment of the present invention.
  • FIG. 2 is an example of a schematic cross-sectional view of the pressure-sensitive adhesive sheet according to the embodiment of the present invention.
  • FIG. 3 is an example of a schematic cross-sectional view of the pressure-sensitive adhesive sheet according to the embodiment of the present invention.
  • adheresive refers to a material that exhibits a soft solid state (viscoelastic body) in a temperature range near room temperature and has the property of easily adhering to an adherend by pressure.
  • the pressure-sensitive adhesive referred to here is generally defined as "CA Dahlquiist,” Additional: Fundamental and Practice “, McLaren & Sons, (1966) P.143”, and generally has a complex tensile modulus E *. It can be a material having a property of satisfying (1 Hz) ⁇ 107 dyne / cm 2 (typically, a material having the above property at 25 ° C.).
  • the “main component” refers to a component contained in an amount of more than 50% by mass, unless otherwise specified. Further, in the present specification, the percentage based on mass and the like are synonymous with the percentage and the like based on weight.
  • the resin for a pigment dispersion masterbatch for a pressure-sensitive adhesive (hereinafter, may be simply referred to as a resin for a masterbatch) according to an embodiment of the present invention is a resin for a pigment dispersion masterbatch for a pressure-sensitive adhesive containing the resin (A).
  • the Tg of the resin (A) is ⁇ 80 to 40 ° C.
  • the acid value of the resin (A) is 1 to 50 (KOHmg / g).
  • the masterbatch is a high-concentration colorant used to uniformly and easily disperse a colorant such as a pigment or a dispersion other than the colorant depending on the purpose in the target dispersion medium.
  • a resin composition containing The pigment dispersion masterbatch is a resin composition for dispersing the pigment.
  • the resin for the pigment dispersion masterbatch for a pressure-sensitive adhesive according to the embodiment of the present invention is a resin used for the pigment dispersion masterbatch for a pressure-sensitive adhesive.
  • the present inventors made a masterbatch pigment into a pressure-sensitive adhesive composition by using a resin (A) having a specific Tg and a specific acid value. It was newly discovered that it can be dispersed in an object with good dispersibility. Then, the surface of the pigment was coated with the resin (A) to form a micromasterbatch, and a resin for a pigment dispersion masterbatch for an adhesive that was easily dispersed in the adhesive composition was successfully obtained.
  • the pressure-sensitive adhesive composition which will be described in detail later, contains a base polymer. Masterbatches containing conventional pigments are sometimes used for coloring resin for injection molding via heating process and kneading process by machine, and are designed to dissolve in resin for injection molding during heat treatment. Generally, a resin having a high Tg was used. In the embodiment of the present invention, Tg is higher than that of a commonly used resin dispersant from the viewpoints of ease of mixing with a resin (base polymer) used for a pressure-sensitive adhesive, dispersibility, compatibility, solubility in a solvent, and the like.
  • the low resin (A) it was possible to obtain a resin for a pigment dispersion master batch for a pressure-sensitive adhesive that can be highly dispersed in the pressure-sensitive adhesive composition.
  • the surface of the pigment of the present invention is prepared in advance before the pressure-sensitive adhesive composition and the pigment are mixed.
  • the resin for the pigment dispersion master batch for the pressure-sensitive adhesive according to the embodiment forming a micromaster batch, and then mixing with the pressure-sensitive adhesive composition, not only the dispersibility is improved and the appearance unevenness of the pressure-sensitive adhesive layer is suppressed. It is possible to form an adhesive layer having excellent adhesion reliability.
  • the resin (A) is preferably contained as a main component in the resin for a pigment dispersion masterbatch for a pressure-sensitive adhesive according to the embodiment of the present invention.
  • the resin (A) needs to be designed so that the glass transition temperature (Tg) is ⁇ 80 to 40 ° C.
  • Tg glass transition temperature
  • the Tg of the resin (A) needs to be 40 ° C. or lower, preferably 20 ° C. or lower, more preferably 20 ° C. or lower. It is 0 ° C. or lower.
  • the Tg of the resin (A) needs to be ⁇ 80 ° C. or higher, preferably ⁇ 70 ° C. or higher, and more preferably ⁇ 60 ° C. or higher.
  • the resin (A) melts when the resin (A) and the pigment are mixed by kneading or the like, and the resin (A) is melted at the moment when the agglomeration of the pigment is loosened. A) is likely to be adsorbed on the pigment at multiple points. As a result, the fine particles of the pigment are coated on the resin (A), and micromaster batching with excellent dispersion stability becomes possible.
  • the Tg of the resin (A) means a Tg obtained by the Fox formula based on the composition of the monomer component used for the synthesis of the resin (A).
  • Tg is the glass transition temperature (unit: K) of the copolymer
  • Wi is the mass fraction of the monomer i in the copolymer (copolymerization ratio based on the mass)
  • Tgi is the monomer i. Represents the glass transition temperature (unit: K) of the homopolymer.
  • the glass transition temperature of the homopolymer used for calculating Tg the value described in the publicly known material shall be used.
  • the monomers listed below the following values are used as the glass transition temperature of the homopolymer of the monomer.
  • 2-Ethylhexyl acrylate -70 ° C Isononyl acrylate -60 ° C n-Butyl acrylate -55 ° C Ethyl acrylate-22 ° C Methyl acrylate 8 °C Methyl methacrylate 105 ° C 2-Hydroxyethyl acrylate -15 ° C 4-Hydroxybutyl acrylate -40 ° C Vinyl acetate 32 ° C Acrylic acid 106 °C Methacrylic acid 228 ° C N-vinyl-2-pyrrolidone 54 ° C
  • the Tg of the resin (A) can be adjusted by appropriately changing the monomer composition (that is, the type and amount ratio of the monomers used for synthesizing the polymer).
  • the type of the resin (A) is not particularly limited as long as the Tg is in the above range, and those known in the masterbatch field can be used.
  • various rubber-like polymers such as acrylic polymers, rubber polymers, polyester polymers, urethane polymers, polyether polymers, silicone polymers, polyamide polymers, and fluoropolymers.
  • An acrylic polymer or a rubber polymer is preferable, and an acrylic polymer is more preferable, from the viewpoint of dispersibility in a pressure-sensitive adhesive, cost, and the like.
  • the resin (A) is an acrylic polymer will be mainly described, but the present embodiment is not intended to limit the resin (A) to one composed of an acrylic polymer.
  • the "acrylic polymer” refers to a polymer containing a monomer unit derived from a monomer having at least one (meth) acryloyl group in one molecule as a monomer unit constituting the polymer.
  • a monomer having at least one (meth) acryloyl group in one molecule is also referred to as an “acrylic monomer”. Therefore, the acrylic polymer in this specification is defined as a polymer containing a monomer unit derived from an acrylic monomer.
  • a typical example of the acrylic polymer is an acrylic polymer in which the proportion of the acrylic monomer in the total monomer components used in the synthesis of the acrylic polymer is more than 50% by mass.
  • (meth) acryloyl means acryloyl and methacryloyl comprehensively.
  • (meth) acrylate means acrylate and methacrylate, and
  • (meth) acrylic means acrylic and methacrylic, respectively.
  • the acrylic polymer for example, a polymer of a monomer raw material containing an alkyl (meth) acrylate as a main monomer and further containing a submonomer having copolymerizability with the main monomer is preferable.
  • the main monomer means a component that occupies more than 50% by mass of the monomer composition in the above-mentioned monomer raw material.
  • alkyl (meth) acrylate for example, a compound represented by the following formula (1) can be preferably used.
  • CH 2 C (R 1 ) COOR 2 (1)
  • R 1 in the above formula (1) is a hydrogen atom or a methyl group.
  • R 2 is a chain alkyl group having 1 to 20 carbon atoms.
  • such a range of the number of carbon atoms may be expressed as "C 1-20 ".
  • the main monomer is an alkyl (meth) acrylate in which R 2 is a chain alkyl group of C 1-14 (for example, C 2-10 , typically C 4-8 ). It is appropriate to do.
  • the main monomer is an alkyl acrylate in which R 1 is a hydrogen atom and R 2 is a chain alkyl group of C 4-8 (hereinafter, also simply referred to as C 4-8 alkyl acrylate). Is preferable.
  • alkyl (meth) acrylate in which R 2 is a C 1-20 chain alkyl group examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl.
  • alkyl (meth) acrylates can be used alone or in combination of two or more.
  • Preferred alkyl (meth) acrylates include n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA).
  • the proportion of alkyl (meth) acrylate in the monomer component constituting the acrylic polymer is typically more than 50% by mass, for example, 70% by mass or more, 85% by mass or more, and 90% by mass. It may be mass% or more. Further, the ratio of the alkyl (meth) acrylate to the monomer component is typically less than 100% by mass, and it is usually appropriate to be 99.5% by mass or less from the viewpoint of cohesive force and the like, 98. It may be mass% or less (for example, less than 97 mass%).
  • the above-mentioned monomer component contains 50% by mass or more of C 4-8 alkyl (meth) acrylate.
  • the ratio of C 4-8 alkyl (meth) acrylate in the monomer component may be 70% by mass or more, or 85% by mass or more (for example, 90% by mass or more).
  • the ratio of C 4-8 alkyl (meth) acrylate to the monomer component is usually preferably 99.5% by mass or less, and 98% by mass or less (for example, 97% by mass). %) May be used.
  • the monomer component constituting the resin (A) may contain a carboxy group-containing monomer.
  • the monomer component contains a carboxy group-containing monomer, the dispersed state of the pigment is easily improved. It can also be advantageous in improving dispersion stability.
  • the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, crotonic acid and isocrotonic acid; maleic acid, itaconic acid and citracon.
  • ethylenically unsaturated dicarboxylic acids such as acids and their anhydrides (maleic anhydride, itaconic anhydride, etc.); and the like. These can be used alone or in combination of two. Among them, acrylic acid (AA) and methacrylic acid (MAA) are mentioned as preferable carboxy group-containing monomers. AA is particularly preferred.
  • the content of the carboxy group-containing monomer in the monomer component constituting the resin (A) is not particularly limited, and for example, 0. It can be 2% by mass or more (typically 0.5% by mass or more), usually 1% by mass or more, and may be 2% by mass or more, or 3% by mass or more. good.
  • the content of the carboxy group-containing monomer is not particularly limited, and for example, 0. It can be 2% by mass or more (typically 0.5% by mass or more), usually 1% by mass or more, and may be 2% by mass or more, or 3% by mass or more. good.
  • the content of the carboxy group-containing monomer can be 3.2% by mass or more of the monomer component, more preferably 3.5% by mass or more, still more preferably 4% by mass or more. It may be 4.5% by mass or more.
  • the upper limit of the content of the carboxy group-containing monomer is not particularly limited, and may be, for example, 15% by mass or less, 12% by mass or less, or 10% by mass or less.
  • the content of the carboxy group-containing monomer is 7% by mass or less (typically less than 7% by mass, for example, 6.8% by mass or less, or 6.0% by mass or less) of the monomer component. However, it can be preferably carried out.
  • Copolymers having copolymerizability with the main monomer, alkyl (meth) acrylate can be useful for introducing cross-linking points in the acrylic polymer and enhancing the cohesive force of the acrylic polymer.
  • the submonomer for example, the following functional group-containing monomers (however, the above-mentioned carboxy group-containing monomer is not included) can be used alone or in combination of two or more.
  • Hydroxyl-containing monomers Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; Unsaturated alcohols such as vinyl alcohol and allyl alcohol; polypropylene glycol mono (meth) acrylate.
  • Amide group-containing monomers For example, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-methoxymethyl.
  • Amino group-containing monomer For example, aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate.
  • Monomers having an epoxy group for example, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, allyl glycidyl ether.
  • Cyano group-containing monomers for example, acrylonitrile, methacrylonitrile.
  • Keto group-containing monomer For example, diacetone (meth) acrylamide, diacetone (meth) acrylate, vinylmethyl ketone, vinyl ethyl ketone, allyl acetoacetate, vinyl acetoacetate.
  • Monomers having a nitrogen atom-containing ring for example, N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinyl.
  • Alkoxysilyl group-containing monomers for example 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxy Propylmethyldiethoxysilane.
  • the content of the functional group-containing monomer in the monomer component is not particularly limited.
  • the content of the functional group-containing monomer in the monomer component can be, for example, 0.1% by mass or more, and usually 0.5% by mass or more. It is appropriate to do so, and it may be 1% by mass or more.
  • the content of the functional group-containing monomer in the monomer component is determined.
  • the monomer component substantially does not contain a functional group-containing monomer (for example, an embodiment in which the monomer component is substantially composed of only an alkyl (meth) acrylate and a carboxy group-containing monomer).
  • the fact that the monomer component does not substantially contain the functional group-containing monomer means that the functional group-containing monomer is not used at least intentionally, for example, 0.05% by mass or less (typically 0.01). It is acceptable that the functional group-containing monomer (% by mass or less) is unintentionally contained.
  • the acrylic polymer having such a monomer composition may be one in which the pigment dispersion masterbatch for a pressure-sensitive adhesive, which will be described later, can be easily dispersed.
  • the monomer component constituting the acrylic polymer may contain a copolymerization component other than the above-mentioned submonomer for the purpose of improving the cohesive force and the like.
  • copolymerization components include vinyl ester-based monomers such as vinyl acetate, vinyl propionate, vinyl laurate; aromatic vinyl compounds such as styrene, substituted styrene ( ⁇ -methylstyrene, etc.), vinyl toluene; cyclohexyl (cyclohexyl).
  • Cycloalkyl (meth) acrylates such as meta) acrylates, cyclopentyl (meth) acrylates, isobornyl (meth) acrylates; aryl (meth) acrylates (eg phenyl (meth) acrylates), aryloxyalkyl (meth) acrylates (eg phenoxyethyl (eg phenoxyethyl) Aromatic ring-containing (meth) acrylates such as meth) acrylates) and arylalkyl (meth) acrylates (eg, benzyl (meth) acrylates); olefinic monomers such as ethylene, propylene, isoprene, butadiene, and isobutylene; vinyl chloride, chloride.
  • Chlorine-containing monomers such as vinylidene; isocyanate group-containing monomers such as 2- (meth) acryloyloxyethyl isocyanate; alkoxy group-containing monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; Vinyl ether-based monomer; 2 or more (for example, 3 or more) polymerizable functional groups (for example, (meth) acryloyl group) in one molecule such as 1,6-hexanediol di (meth) acrylate and trimethyl propantri (meth) acrylate. ), And the like.
  • the amount of the other copolymerization component may be appropriately selected depending on the purpose and application, and is not particularly limited, and is usually preferably 0.05% by mass or more from the viewpoint of appropriately exerting the effect of use. It may be 0.5% by mass or more. Further, from the viewpoint of facilitating the balance of adhesive performance, it is usually appropriate that the content of the other copolymerization component in the monomer component is 20% by mass or less, and 10% by mass or less (for example, 5% by mass or less). ) May be used. In the present embodiment, it may be preferably carried out even in an embodiment in which the monomer component does not substantially contain other copolymerization components.
  • the fact that the monomer component does not substantially contain other copolymerization components means that the other copolymerization components are not used at least intentionally, and the other copolymerization components are, for example, 0.01% by mass or less. , It can be tolerated to be included unintentionally.
  • the acrylic polymer having such a monomer composition may be one in which the pigment dispersion masterbatch for a pressure-sensitive adhesive, which will be described later, can be easily dispersed.
  • the method for obtaining the acrylic polymer is not particularly limited, and various polymerization methods known as synthetic methods for the acrylic polymer, such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, and a photopolymerization method. Can be adopted as appropriate.
  • a solution polymerization method can be preferably adopted.
  • the polymerization temperature at the time of solution polymerization can be appropriately selected depending on the type of monomer and solvent used, the type of polymerization initiator and the like, and is, for example, 20 ° C to 170 ° C (typically 40 ° C to 140 ° C). ).
  • the solvent (polymerization solvent) used for solution polymerization can be appropriately selected from conventionally known organic solvents.
  • aromatic compounds such as toluene (typically aromatic hydrocarbons); acetates such as ethyl acetate; aliphatic or alicyclic hydrocarbons such as hexane and cyclohexane; 1,2-dichloroethane and the like.
  • Alkanes halides lower alcohols such as isopropyl alcohol (eg, monohydric alcohols having 1 to 4 carbon atoms); ethers such as tert-butylmethyl ether; ketones such as methyl ethyl ketone; etc. Any one kind of solvent or two or more kinds of mixed solvents can be used.
  • the initiator used for the polymerization can be appropriately selected from the conventionally known polymerization initiators according to the type of the polymerization method.
  • one or more azo-based polymerization initiators such as 2,2'-azobisisobutyronitrile (AIBN) may be preferably used.
  • Other examples of polymerization initiators include persulfates such as potassium persulfate; peroxide-based initiators such as benzoyl peroxide and hydrogen peroxide; substituted ethane-based initiators such as phenyl-substituted ethane; aromatic carbonyl compounds. ; Etc. can be mentioned.
  • polymerization initiator is a redox-based initiator in which a peroxide and a reducing agent are combined.
  • a polymerization initiator can be used alone or in combination of two or more.
  • the amount of the polymerization initiator used may be a normal amount, for example, from 0.005 to 1 part by mass (typically 0.01 to 1 part by mass) with respect to 100 parts by mass of the monomer component. You can choose.
  • a polymerization reaction solution in which the resin (A) is dissolved in an organic solvent can be obtained.
  • the pressure-sensitive adhesive layer in the present embodiment may contain the above-mentioned polymerization reaction solution or the resin (A) solution obtained by subjecting the reaction solution to an appropriate post-treatment.
  • the resin (A) a resin obtained by removing the solvent from the above-mentioned polymerization reaction solution can be used.
  • the resin (A) synthesized by a polymerization method other than solution polymerization for example, emulsion polymerization, photopolymerization, bulk polymerization, etc.
  • the weight average molecular weight (Mw) of the resin (A) (preferably an acrylic polymer) in the technique disclosed herein is not particularly limited and may be, for example, in the range of 10 ⁇ 10 4 to 500 ⁇ 10 4 .
  • the Mw of the resin (A) is 30 ⁇ 10 4 to 200 ⁇ 10 4 (more preferably 45 ⁇ 10 4 to 150 ⁇ 10 4 , typically 65 ⁇ 10 4 to 130 ⁇ 10 4 ). ) Is preferable.
  • Mw means a value in terms of standard polystyrene obtained by GPC (gel permeation chromatography).
  • GPC gel permeation chromatography
  • a model name “HLC-8320GPC” columnumn: TSKgelGMH-H (S), manufactured by Tosoh Corporation) can be used.
  • the acid value of the resin (A) in the embodiment of the present invention needs to be designed to be 1 KOH mg / g to 50 KOH mg / g. From the viewpoint of improving the dispersion stability of the pigment, it is preferably 5 KOH mg / g or more, and more preferably 10 KOH mg / g or more. Further, the pressure is 50 KOHmg / g or less from the viewpoint of preventing corrosion of the adherend when the pressure-sensitive adhesive layer containing the resin for the pigment dispersion masterbatch for the pressure-sensitive adhesive according to the embodiment of the present invention is attached to the adherend. Is more preferable, and it is more preferably 30 KOH mg / g or less, and further preferably 20 KOH mg / g or less.
  • the acid value of the resin (A) can be a value measured by the potentiometric titration method specified in JIS K0070: 1992.
  • the acid value is the number of mg of potassium hydroxide required to neutralize the carboxylic acid in 1 g of the acrylic polymer.
  • the pigment dispersion masterbatch for a pressure-sensitive adhesive according to the embodiment of the present invention is used for a pressure-sensitive adhesive, and is a masterbatch for dispersing the pigment in the pressure-sensitive adhesive.
  • excellent pigment dispersibility can be obtained, and a pressure-sensitive adhesive layer having high adhesion reliability can be obtained.
  • the pigment dispersion masterbatch for a pressure-sensitive adhesive contains a resin for a pigment dispersion masterbatch for a pressure-sensitive adhesive and a pigment.
  • the content of the resin (A) is 45 to 90% by mass with respect to the total mass of the pigment and the resin (A).
  • the content of the resin (A) with respect to the total mass of the pigment and the resin (A) shall be 45% by mass or more from the viewpoint of facilitating shearing during kneading of the pigment and the resin (A) and crushing of the pigment. Is more preferable, 50% by mass or more is more preferable, and 60% by mass or more is further preferable.
  • the content is preferably 90% by mass or less, more preferably 85% by mass or less, and more preferably 80% by mass or less. Is even more preferable.
  • the surface of the pigment is coated with the resin (A) in the process of dispersing the pigment in the resin (A), and the shape thereof is not particularly limited.
  • room temperature 25 ° C.
  • it may be in the form of a solid such as powder or granules or in the form of a slurry.
  • the conventional masterbatch is solid at room temperature, but the pigment dispersion masterbatch for an adhesive according to the embodiment of the present invention has a lower Tg of the resin (A) than the resin used in the conventional masterbatch. It can be slurry at room temperature. A slurry is preferable because it improves the dispersibility in the pressure-sensitive adhesive composition.
  • the type of pigment used in this embodiment is not particularly limited, and either an organic pigment or an inorganic pigment can be used.
  • organic pigments examples include azo lake pigments, insoluble monoazo pigments, insoluble disazo pigments, condensed azo pigments, chelate azo pigments and other azo pigments; phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments and iso Polycyclic pigments such as indolinone pigments and quinophthalone pigments; chelates such as basic dye type chelate and acidic dye type chelate; nitro pigments; nitroso pigments and the like can be mentioned. These can be used alone or in admixture of two or more.
  • the inorganic pigment examples include titanium oxide, iron oxide, red pepper, chromium oxide, prussian blue, ultramarine, molybdenum red, iron black, and chrome yellow. These can be used alone or in admixture of two or more. Among them, an isoindolenone pigment, a quinacridone pigment, a condensed azo pigment, a phthalocyanine pigment, a quinophthalone pigment, and an anthraquinone pigment are preferably used in consideration of light resistance.
  • organic pigment examples include Pigment Yellow 1 (color index (hereinafter referred to as CI) 11680), Pigment Yellow 3 (CI 11710), and Pigment Yellow 14 (CI). 21095), Pigment Yellow 17 (CI21105), Pigment Yellow 42 (CI77492), Pigment Yellow 74 (CI11741), Pigment Yellow 83 (CI21108). , Pigment Yellow 93 (CI 20710), Pigment Yellow 98 (CI 11727), Pigment Yellow 109 (CI 56284), Pigment Yellow 110 (CI 56280), Pigment -Yellow 128 (CI20037), Pigment Yellow 129 (CI48042), Pigment Yellow 138 (CI56300), Pigment Yellow 139 (CI56298), Pigment Yellow.
  • CI color index
  • CI 11680 Pigment Yellow 3
  • Pigment Yellow 14 21095
  • Pigment Yellow 17 CI21105
  • Pigment Yellow 42 CI77492
  • Pigment Yellow 74 CI11741
  • Pigment Yellow 83 CI21108
  • Pigment Red 22 (CI 12315), Pigment Red 48: 2 (CI 15865: 2), Pigment Red 112 (CI 12370), Pigment Red 122 (CI 12370). 73915), Pigment Red 170 (CI12475), Pigment Red 176 (CI12515), Pigment Red 177 (CI65300), Pigment Red 178 (CI71). 155), Pigment Red 179 (C.I. I. 71130), Pigment Red 185 (CI 12516), Pigment Red 202 (CI 73907), Pigment Red 208 (CI 12514), Pigment Red 254 (CI 56110).
  • Pigment Red 255 (CI 561050), Pigment Red 264, Pigment Red 272 (CI 561150), Pigment Violet 19 (CI 73900), Pigment Violet 23 (CI) .51319)
  • Pigment Blue 15: 1 (CI 74160), Pigment Blue 15: 3 (CI 74160), Pigment Blue 15: 4 (CI 74160), Pigment Blue 60 (CI 69800), Pigment Green 7 (CI 74260), Pigment Green 36 (CI 74265) and the like, with one or more mixtures being preferred.
  • the inorganic pigments include Pigment Yellow 42 (CI 77492), Pigment White 6 (CI 77891), Pigment Blue 27 (CI 77510), and Pigment Blue 29 (CI) CI77007), Pigment Black 7 (CI77266) and the like, and one kind or a mixture of two or more kinds are preferable.
  • Pigment Yellow 74 (CI 11741), Pigment Yellow 109 (CI 56284), Pigment Yellow 110 (CI 56280), Pigment Yellow 128. (CI 200737), Pigment Yellow 138 (CI 56300), Pigment Yellow 150 (CI 12764), Pigment Yellow 155 (CI 200310), Pigment Yellow 180 (C) I. 21290), Pigment Green 7 (CI 74260), Pigment Green 36 (CI 74265), Pigment Red 122 (CI 73915), Pigment Red 177 (CI) .65300), Pigment Red 202 (CI 73907), Pigment Red 254 (CI 56110), Pigment Violet 19 (CI 73900), Pigment Violet 23 (CI 51319).
  • Pigment Blue 15: 1 (CI 74160), Pigment Blue 15: 3 (CI 74160), Pigment Blue 15: 4 (CI 74160), Pigment Blue 15: 6.
  • Pigment Blue 60 (CI 69800), Pigment Black 7 (CI 77266) and the like are preferred.
  • the green pigments include Pigment Green 7 (CI 74260), Pigment Green 36 (CI 74265), Pigment Yellow 138 (CI 56300), and Pigment Yellow 150 (C.I. 56300).
  • One or more pigments selected from the group consisting of I.12764) can be preferably used.
  • As the blue pigment pigments of Pigment Blue 15: 6 (CI 74160) and / or Pigment Violet 23 (CI 51319) can be preferably used.
  • the pigment may be powdery, granular, wet cake or slurry.
  • the average particle size of the pigment is not particularly limited. From the viewpoint of ease of handling, the lower limit of the average particle size of the pigment may be, for example, 10 nm or more, 50 nm or more, 100 nm or more, or 150 nm or more. ..
  • the upper limit of the average particle size of the pigment is, for example, 500 nm or less, may be 300 nm or less, may be 250 nm or less, or may be 200 nm or less from the viewpoint of optical characteristics such as haze of the coloring pressure-sensitive adhesive. good.
  • the average particle size of the above pigment refers to the volume average particle size, and specifically, the particle size at an integrated value of 50% in the particle size distribution measured based on the particle size distribution measuring device based on the laser scattering / diffraction method. 50% volume average particle size; hereinafter, it may be abbreviated as D50 ).
  • the measuring device for example, the product name “Microtrack MT3000II” manufactured by Microtrack Bell Co., Ltd. or an equivalent product thereof can be used.
  • additives such as plasticizers, lubricants, antioxidants, and antistatic agents may be added to the pigment dispersion masterbatch for adhesives according to the embodiment of the present invention, if necessary.
  • the method for producing the pigment dispersion masterbatch for a pressure-sensitive adhesive according to the embodiment of the present invention is not particularly limited, but the resin (A) and the pigment can be obtained by using, for example, a three-roll mill, a Banbury mixer, a two-screw extruder, a kneader, or the like. Is kneaded and the pigment is coated while being dispersed in the resin (A).
  • the temperature at the time of dispersion is usually 100 to 180 ° C., and the dispersion time is usually 1 minute to 1 hour.
  • the pigment dispersion masterbatch for a pressure-sensitive adhesive according to the embodiment of the present invention is used for a pressure-sensitive adhesive, and a colored pressure-sensitive adhesive composition can be obtained by dispersing the pigment dispersion masterbatch for a pressure-sensitive adhesive in the pressure-sensitive adhesive composition. Can be done.
  • a colored pressure-sensitive adhesive composition containing a pigment dispersion masterbatch for a pressure-sensitive adhesive according to an embodiment of the present invention will be described.
  • the colored pressure-sensitive adhesive composition includes a pigment dispersion masterbatch for a pressure-sensitive adhesive and a base polymer.
  • the colored pressure-sensitive adhesive composition is a colored pressure-sensitive adhesive composition, and may be a pressure-sensitive adhesive composition containing a base polymer to which a pigment dispersion masterbatch for a pressure-sensitive adhesive is added.
  • the form of adding the pigment dispersion masterbatch for a pressure-sensitive adhesive to the pressure-sensitive adhesive composition is not particularly limited.
  • the pigment dispersion master batch for a pressure-sensitive adhesive may be added directly to the pressure-sensitive adhesive composition, or may be added to the pressure-sensitive adhesive composition in the form of a dispersion liquid in which the pigment dispersion master batch for a pressure-sensitive adhesive is dispersed in a dispersion medium. You may. By dispersing the pigment dispersion masterbatch for a pressure-sensitive adhesive in a wet manner using a dispersion medium, it becomes in a solvated state with the dispersion medium, and the dispersibility when added to the pressure-sensitive adhesive composition is improved.
  • the median diameter of the pigment particles in the dispersion is preferably 10 nm or more, preferably 30 nm or more, from the viewpoint of the viscosity of the dispersion. It is more preferably 50 nm or more, and further preferably 50 nm or more. Further, from the viewpoint of productivity such as avoiding filter clogging in the coloring pressure-sensitive adhesive manufacturing process, it is preferably 10 ⁇ m or less, more preferably 3 ⁇ m or less, and further preferably 1 ⁇ m or less.
  • a median diameter measuring method it is possible to measure using ethyl acetate as a dispersion medium using a laser diffraction / scattering type particle size distribution measuring device LA-950 (manufactured by HORIBA, Ltd.). By calculating and measuring the relative refractive index from the respective refractive indexes of ethyl acetate and the pigment used, it is possible to measure the dispersed particles of the pigment in the dispersion liquid. From the measurement result, the median diameter of the dispersed particles of the pigment in the dispersion liquid can be obtained.
  • the dispersion medium constituting the dispersion is not particularly limited, and water (ion exchange water, back-penetration water, distilled water, etc.) and various organic solvents (alcohols such as ethanol; ketones such as acetone; butyl cellosolve, propylene glycol monomethyl) are not particularly limited.
  • organic solvents alcohols such as ethanol; ketones such as acetone; butyl cellosolve, propylene glycol monomethyl
  • examples include ethers such as ether acetate; esters such as ethyl acetate; aromatic hydrocarbons such as toluene; mixed solvents thereof), and aqueous mixed solvents of water and the above organic solvent.
  • the dispersion liquid may contain a dispersant described later.
  • the colored pressure-sensitive adhesive composition contains a pigment dispersion masterbatch for a pressure-sensitive adhesive and a base polymer, and further contains additives such as a dispersant described later as optional components. obtain.
  • the blending amount of the pigment dispersion masterbatch for a pressure-sensitive adhesive in the colored pressure-sensitive adhesive composition is not particularly limited. Usually, it is appropriate to make 0.5 parts by mass or more with respect to 100 parts by mass of the base polymer, and from the viewpoint of light-shielding property, preferably 1.0 part by mass or more, more preferably 2.0 parts by mass or more. More preferably, it is 3.0 parts by mass or more (for example, 4.0 parts by mass or more).
  • the upper limit of the blending amount of the pigment dispersion master batch for adhesives is 20 parts by mass or less with respect to 100 parts by mass of the base polymer. It is more preferably 10 parts by mass or less, further preferably 8 parts by mass or less, and further preferably 6 parts by mass or less.
  • the “base polymer” in the present embodiment means the main component of the rubber-like polymer contained in the pressure-sensitive adhesive.
  • the rubber-like polymer means a polymer that exhibits rubber elasticity in a temperature range near room temperature.
  • the type of the base polymer is not particularly limited, and those known in the field of adhesives can be used.
  • various rubber-like polymers such as acrylic polymers, rubber polymers, polyester polymers, urethane polymers, polyether polymers, silicone polymers, polyamide polymers, and fluoropolymers. It can be contained as a polymer.
  • an acrylic polymer or a rubber polymer as a base polymer.
  • the base polymer is an acrylic polymer from the viewpoint of dispersibility of the pigment dispersion masterbatch for a pressure-sensitive adhesive.
  • the pressure-sensitive adhesive composition containing an acrylic polymer as a base polymer will be mainly described, but it is not intended to limit the pressure-sensitive adhesive composition in the present embodiment to one composed of an acrylic polymer.
  • the acrylic polymer for example, a polymer of a monomer raw material containing an alkyl (meth) acrylate as a main monomer and further containing a submonomer having copolymerizability with the main monomer is preferable.
  • the main monomer means a component that occupies more than 50% by mass of the monomer composition in the above-mentioned monomer raw material.
  • alkyl (meth) acrylate for example, a compound represented by the following formula (1) can be preferably used.
  • CH 2 C (R 1 ) COOR 2 (1)
  • R 1 in the above formula (1) is a hydrogen atom or a methyl group.
  • R 2 is a chain alkyl group having 1 to 20 carbon atoms.
  • such a range of the number of carbon atoms may be expressed as "C 1-20 ".
  • the main monomer is an alkyl (meth) acrylate in which R 2 is a chain alkyl group of C 1-14 (for example, C 2-10 , typically C 4-8 ). It is appropriate to do.
  • the main monomer is an alkyl acrylate in which R 1 is a hydrogen atom and R 2 is a chain alkyl group of C 4-8 (hereinafter, also simply referred to as C 4-8 alkyl acrylate). Is preferable.
  • alkyl (meth) acrylate in which R 2 is a C 1-20 chain alkyl group examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl.
  • alkyl (meth) acrylates can be used alone or in combination of two or more.
  • Preferred alkyl (meth) acrylates include n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA).
  • the proportion of alkyl (meth) acrylate in the monomer component constituting the acrylic polymer is typically more than 50% by mass, for example, 70% by mass or more, 85% by mass or more, and 90% by mass. It may be mass% or more. Further, the ratio of the alkyl (meth) acrylate to the monomer component is typically less than 100% by mass, and it is usually appropriate to be 99.5% by mass or less from the viewpoint of cohesive force and the like, 98. It may be mass% or less (for example, less than 97 mass%).
  • the above-mentioned monomer component contains 50% by mass or more of C 1-4 alkyl (meth) acrylate.
  • the ratio of C 1-4 alkyl (meth) acrylate in the monomer component may be 70% by mass or more, or 85% by mass or more (for example, 90% by mass or more).
  • the ratio of C 1-4 alkyl (meth) acrylate to the monomer component is 99.5% by mass or less, and 98% by mass or less (for example, 97% by mass). %) May be used.
  • the above-mentioned monomer component may be preferably carried out in an embodiment containing 50% by mass or more (for example, 70% by mass or more, 85% by mass or more, or 90% by mass or more) of C 2-4 alkyl acrylate.
  • C 2-4 alkyl acrylate include ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate (BA), isobutyl acrylate, s-butyl acrylate and t-butyl acrylate.
  • the C 2-4 alkyl acrylate may be used alone or in combination of two or more. According to such an aspect, it is easy to realize an adhesive sheet having good adhesion to an adherend.
  • the ratio of C 1-4 alkyl (meth) acrylate in the monomer component is 99.5% by mass or less, and 98% by mass or less ( For example, it may be less than 97% by mass).
  • the monomer component may contain 50% by mass or more of C 5-20 alkyl (meth) acrylate (for example, 70% by mass or more, 85% by mass or more, or 90% by mass or more).
  • C 5-20 alkyl (meth) acrylate C 6-14 alkyl (meth) acrylate is preferable.
  • C 6-10 alkyl acrylates eg C 8-10 alkyl acrylates
  • the ratio of C 5-20 alkyl (meth) acrylate to the monomer component is usually preferably 99.5% by mass or less, and 98% by mass or less (for example, 97). It may be less than% by mass).
  • the monomer component constituting the base polymer may contain a carboxy group-containing monomer.
  • the monomer component contains a carboxy group-containing monomer, it becomes easy to obtain a pressure-sensitive adhesive layer showing excellent adhesion reliability.
  • the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, crotonic acid and isocrotonic acid; maleic acid, itaconic acid and citracon.
  • ethylenically unsaturated dicarboxylic acids such as acids and their anhydrides (maleic anhydride, itaconic anhydride, etc.); and the like. These can be used alone or in combination of two. Among them, acrylic acid (AA) and methacrylic acid (MAA) are mentioned as preferable carboxy group-containing monomers. AA is particularly preferred.
  • the content of the carboxy group-containing monomer in the monomer component constituting the base polymer is not particularly limited, and is, for example, 0.2% by mass or more of the monomer component. It can be (typically 0.5% by mass or more), usually 1% by mass or more, and may be 2% by mass or more, or 3% by mass or more.
  • the content of the carboxy group-containing monomer can be 3.2% by mass or more of the monomer component, more preferably 3.5% by mass or more, still more preferably 4% by mass or more. It may be 4.5% by mass or more.
  • the upper limit of the content of the carboxy group-containing monomer is not particularly limited, and may be, for example, 15% by mass or less, 12% by mass or less, or 10% by mass or less.
  • the content of the carboxy group-containing monomer is 7% by mass or less (typically less than 7% by mass, for example, 6.8% by mass or less, or 6.0% by mass or less) of the monomer component. However, it can be preferably carried out.
  • Copolymers having copolymerizability with the main monomer, alkyl (meth) acrylate can be useful for introducing cross-linking points in the acrylic polymer and enhancing the cohesive force of the acrylic polymer.
  • the submonomer for example, the following functional group-containing monomers (however, the above-mentioned carboxy group-containing monomer is not included) can be used alone or in combination of two or more.
  • Hydroxyl-containing monomers Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; Unsaturated alcohols such as vinyl alcohol and allyl alcohol; polypropylene glycol mono (meth) acrylate.
  • Amide group-containing monomers For example, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-methoxymethyl.
  • Amino group-containing monomer For example, aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate.
  • Monomers having an epoxy group for example, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, allyl glycidyl ether.
  • Cyano group-containing monomers for example, acrylonitrile, methacrylonitrile.
  • Keto group-containing monomer For example, diacetone (meth) acrylamide, diacetone (meth) acrylate, vinylmethyl ketone, vinyl ethyl ketone, allyl acetoacetate, vinyl acetoacetate.
  • Monomers having a nitrogen atom-containing ring for example, N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinyl.
  • Alkoxysilyl group-containing monomers for example 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxy Propylmethyldiethoxysilane.
  • the content of the functional group-containing monomer in the monomer component is not particularly limited.
  • the content of the functional group-containing monomer in the monomer component can be, for example, 0.1% by mass or more, and usually 0.5% by mass or more. It is appropriate to do so, and it may be 1% by mass or more. Further, from the viewpoint of facilitating the balance of adhesive performance in relation to the main monomer and the carboxy group-containing monomer, it is usually appropriate that the content of the functional group-containing monomer in the monomer component is 40% by mass or less.
  • the monomer component substantially does not contain a functional group-containing monomer (for example, an embodiment in which the monomer component is substantially composed of only an alkyl (meth) acrylate and a carboxy group-containing monomer).
  • the fact that the monomer component does not substantially contain the functional group-containing monomer means that the functional group-containing monomer is not used at least intentionally, for example, 0.05% by mass or less (typically 0.01). It is acceptable that the functional group-containing monomer (% by mass or less) is unintentionally contained.
  • the acrylic polymer having such a monomer composition may be one in which the pigment dispersion masterbatch for a pressure-sensitive adhesive can be easily dispersed.
  • the monomer component constituting the acrylic polymer may contain a copolymerization component other than the above-mentioned submonomer for the purpose of improving the cohesive force and the like.
  • copolymerization components include vinyl ester-based monomers such as vinyl acetate, vinyl propionate, vinyl laurate; aromatic vinyl compounds such as styrene, substituted styrene ( ⁇ -methylstyrene, etc.), vinyl toluene; cyclohexyl (cyclohexyl).
  • Cycloalkyl (meth) acrylates such as meta) acrylates, cyclopentyl (meth) acrylates, isobornyl (meth) acrylates; aryl (meth) acrylates (eg phenyl (meth) acrylates), aryloxyalkyl (meth) acrylates (eg phenoxyethyl (eg phenoxyethyl) Aromatic ring-containing (meth) acrylates such as (meth) acrylates) and arylalkyl (meth) acrylates (eg, benzyl (meth) acrylates); olefinic monomers such as ethylene, propylene, isoprene, butadiene, and isobutylene; vinyl chloride, chloride.
  • Chlorine-containing monomers such as vinylidene; isocyanate group-containing monomers such as 2- (meth) acryloyloxyethyl isocyanate; alkoxy group-containing monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; Vinyl ether-based monomer; 2 or more (for example, 3 or more) polymerizable functional groups (for example, (meth) acryloyl group) in one molecule such as 1,6-hexanediol di (meth) acrylate and trimethyl propantri (meth) acrylate. ), And the like.
  • the amount of the other copolymerization component may be appropriately selected depending on the purpose and application, and is not particularly limited, and is usually 0.05% by mass or more from the viewpoint of appropriately exerting the effect of use. It is suitable, and may be 0.5% by mass or more. Further, from the viewpoint of facilitating the balance of adhesive performance, it is usually appropriate that the content of the other copolymerization component in the monomer component is 20% by mass or less, and 10% by mass or less (for example, 5% by mass or less). ) May be used. In the present embodiment, it may be preferably carried out even in an embodiment in which the monomer component does not substantially contain other copolymerization components.
  • the fact that the monomer component does not substantially contain other copolymerization components means that the other copolymerization components are not used at least intentionally, and the other copolymerization components are, for example, 0.01% by mass or less. , It can be tolerated to be included unintentionally.
  • the acrylic polymer having such a monomer composition may be one in which the pigment dispersion masterbatch for a pressure-sensitive adhesive can be easily dispersed.
  • the method for obtaining the acrylic polymer is not particularly limited, and various polymerization methods known as synthetic methods for the acrylic polymer, such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, and a photopolymerization method. Can be appropriately adopted, and a photopolymerization method or a solution polymerization method can be preferably adopted.
  • the initiator used for the polymerization can be appropriately selected from conventionally known thermal polymerization initiators, photopolymerization initiators and the like, depending on the polymerization method.
  • the polymerization initiator may be used alone or in combination of two or more.
  • any suitable photopolymerization initiator can be adopted as the photopolymerization initiator as long as the effects of the present invention are not impaired.
  • the photopolymerization initiator may be only one kind or two or more kinds.
  • the photopolymerization initiator is not particularly limited, and is, for example, a benzoin ether-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, an ⁇ -ketol-based photopolymerization initiator, an aromatic sulfonyl chloride-based photopolymerization initiator, and photoactivity.
  • Oxym-based photopolymerization initiator benzoin-based photopolymerization initiator, benzyl-based photopolymerization initiator, benzophenone-based photopolymerization initiator, Ketal-based photopolymerization initiator, thioxanthone-based photopolymerization initiator, acylphosphine oxide-based photopolymerization initiator Agents and the like can be used.
  • benzoin ether-based photopolymerization initiator examples include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and 2,2-dimethoxy-1,2-diphenylethane-.
  • 1-on commercially available products include trade name "Irgacure 651", manufactured by BASF), anisole methyl ether and the like can be mentioned.
  • acetophenone-based photopolymerization initiator examples include 1-hydroxycyclohexylphenylketone (commercially available product, for example, trade name "Irgacure 184", manufactured by BASF), 4-phenoxydichloroacetophenone, 4-.
  • t-butyl-dichloroacetophenone 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one (as a commercial product, for example, the trade name "Irgacure 2959” , BASF), 2-hydroxy-2-methyl-1-phenyl-propane-1-one (commercially available products include, for example, trade name "Darocure 1173", BASF), methoxyacetophenone and the like. ..
  • the amount of the photopolymerization initiator used is not particularly limited, but is, for example, 0.01 parts by mass to 5 parts by mass, preferably 0.05 parts by mass or more with respect to 100 parts by mass of the monomer component used for preparing the acrylic polymer.
  • the amount can be within the range of 3 parts by mass.
  • the acrylic polymer is a partial polymer (acrylic polymer syrup) obtained by irradiating a mixture of the above-mentioned monomer components with a polymerization initiator with ultraviolet rays to polymerize a part of the monomer components.
  • it may be included in a colored pressure-sensitive adhesive composition for forming a colored pressure-sensitive adhesive layer.
  • a colored pressure-sensitive adhesive composition containing such an acrylic polymer syrup can be applied to a predetermined object to be coated and irradiated with ultraviolet rays to complete the polymerization. That is, the acrylic polymer syrup can be grasped as a precursor of the acrylic polymer.
  • the pressure-sensitive adhesive layer disclosed herein is formed, for example, by using a colored pressure-sensitive adhesive composition containing an acrylic polymer as a base polymer in the form of the acrylic polymer syrup and, if necessary, an appropriate amount of a polyfunctional monomer. Can be done.
  • the polymerization solvent, and the initiator used for the polymerization As the preferred polymerization temperature when the solution polymerization method is used, the polymerization solvent, and the initiator used for the polymerization, the contents described in the section of the resin (A) can be adopted.
  • a polymerization reaction solution in which the acrylic polymer is dissolved in an organic solvent can be obtained.
  • the colored pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer in the present embodiment may contain the above-mentioned polymerization reaction solution or an acrylic polymer solution obtained by subjecting the reaction solution to an appropriate post-treatment.
  • the acrylic polymer solution a solution prepared by preparing the polymerization reaction solution to an appropriate viscosity (concentration) can be used.
  • an acrylic polymer solution prepared by synthesizing an acrylic polymer by a polymerization method other than solution polymerization for example, emulsion polymerization, photopolymerization, bulk polymerization, etc.
  • a polymerization method other than solution polymerization for example, emulsion polymerization, photopolymerization, bulk polymerization, etc.
  • dissolving the acrylic polymer in an organic solvent may be used. good.
  • the colored pressure-sensitive adhesive composition of the present embodiment may further contain a component that contributes to improving the dispersibility of the pigment dispersion masterbatch for a pressure-sensitive adhesive.
  • the dispersibility-enhancing component may be, for example, a polymer, an oligomer, a liquid resin, a surfactant, or the like.
  • the dispersibility improving component is preferably dissolved in the base polymer composition.
  • the oligomer is, for example, a low molecular weight polymer of a monomer component containing one or more of the acrylic monomers as exemplified above (for example, Mw of less than 10 ⁇ 10 4 , preferably less than 5 ⁇ 10 4 ). It can be an acrylic oligomer).
  • the liquid resin is, for example, a tackifier resin having a softening point of 50 ° C. or lower, more preferably 40 ° C. or lower (typically, a tackifier resin such as a rosin-based, terpene-based, or hydrocarbon-based resin, for example, a hydrogenated rosin methyl ester. Etc.).
  • a dispersibility improving component it is possible to suppress uneven dispersion of the pigment and, by extension, suppress color unevenness of the pressure-sensitive adhesive layer formed by the colored pressure-sensitive adhesive composition. Therefore, it is possible to form a pressure-sensitive adhesive layer having better appearance quality.
  • the content of the dispersibility improving component is not particularly limited, and is usually 20% by mass or less (preferably) of the entire colored pressure-sensitive adhesive composition (pressure-sensitive adhesive layer) from the viewpoint of suppressing the influence on the pressure-sensitive adhesive properties (for example, deterioration of cohesiveness). Is 10% by mass or less, more preferably 7% by mass or less, for example, 5% by mass or less). In one embodiment, the content of the dispersibility improving component can be 10 times or less (preferably 5 times or less, for example, 3 times or less) the mass of the pigment dispersion masterbatch for a pressure-sensitive adhesive.
  • the content thereof is usually 0.2% by mass or more (typically 0.5% by mass or more, preferably 0.5% by mass or more) of the entire colored pressure-sensitive adhesive composition. 1% by mass or more) is appropriate.
  • the content of the dispersibility improving component can be 0.2 times or more (preferably 0.5 times or more, for example, 1 time or more) the mass of the pigment dispersion masterbatch for a pressure-sensitive adhesive.
  • the colored pressure-sensitive adhesive composition of the present embodiment may contain a pressure-sensitive adhesive resin.
  • a pressure-sensitive adhesive resin examples include phenol-based pressure-sensitive adhesive resin, terpene-based pressure-sensitive adhesive resin, modified terpen-based pressure-sensitive adhesive resin, rosin-based pressure-sensitive adhesive resin, hydrocarbon-based pressure-sensitive adhesive resin, epoxy-based pressure-sensitive adhesive resin, and polyamide-based pressure-sensitive adhesive resin.
  • One or more selected from various known pressure-sensitive adhesives such as an elastomer-based pressure-sensitive adhesive resin and a ketone-based pressure-sensitive adhesive resin can be used.
  • phenol-based tackifier resins examples include terpene phenolic resins, hydrogenated terpene phenolic resins, alkylphenolic resins and rosinphenolic resins.
  • the terpene phenolic resin refers to a polymer containing a terpene residue and a phenol residue, and is a copolymer of terpene and a phenol compound (terpene-phenol copolymer resin) and a homopolymer or copolymer of terpene. Is a concept that includes both phenol-modified products (phenol-modified terpene resin).
  • Preferable examples of terpenes constituting such a terpene phenolic resin are monoterpenes such as ⁇ -pinene, ⁇ -pinene, and limonene (including d-form, l-form, and d / l-form (dipentene)).
  • the hydrogenated terpene phenol resin refers to a hydrogenated terpene phenol resin having a structure obtained by hydrogenating such a terpene phenol resin. It is also called hydrogenated terpene phenolic resin.
  • the alkylphenol resin is a resin (oil-based phenol resin) obtained from alkylphenol and formaldehyde.
  • examples of the alkylphenol resin include novolak type and resol type.
  • the rosin phenolic resin is typically a phenolic product of rosins or the various rosin derivatives described above (including rosin esters, unsaturated fatty acid modified rosins and unsaturated fatty acid modified rosin esters).
  • the rosin phenol resin include a rosin phenol resin obtained by adding phenol to rosins or the above-mentioned various rosin derivatives with an acid catalyst and thermally polymerizing the resin.
  • terpene-based tackifier resins include polymers of terpenes (typically monoterpenes) such as ⁇ -pinene, ⁇ -pinene, d-limonene, l-limonene, and dipentene. It may be a homopolymer of one kind of terpenes or a copolymer of two or more kinds of terpenes. Examples of the homopolymer of one kind of terpenes include ⁇ -pinene polymer, ⁇ -pinene polymer, dipentene polymer and the like.
  • the modified terpene resin include modified terpene resins. Specific examples thereof include styrene-modified terpene resin and hydrogenated terpene resin.
  • rosin-based tackifier resin here includes both rosins and rosin derivative resins.
  • rosins include unmodified rosins (raw rosins) such as gum rosins, wood rosins, and tall oil rosins; modified rosins obtained by modifying these unmodified rosins by hydrogenation, disproportionation, polymerization, etc. (hydrogen-added rosins, non-modified rosins). Normalized rosins, polymerized rosins, other chemically modified rosins, etc.); are included.
  • the rosin derivative resin is typically a derivative of rosins as described above.
  • the concept of a rosin-based resin as used herein includes derivatives of unmodified rosins and derivatives of modified rosins (including hydrogenated rosins, disproportionated rosins and polymerized rosins).
  • rosin esters such as unmodified rosin esters, which are esters of unmodified rosins and alcohols, and modified rosin esters, which are esters of modified rosins and alcohols; for example, unmodified rosins modified with unsaturated fatty acids.
  • Saturated fatty acid-modified rosins for example, unsaturated fatty acid-modified rosin esters obtained by modifying rosin esters with unsaturated fatty acids; for example, rosins or various rosin derivatives described above (rosin esters, unsaturated fatty acid-modified rosins and unsaturated fatty acids).
  • rosin esters include fatty acid-modified rosin esters) carboxy group-reduced rosin alcohols; for example, rosins or metal salts of the various rosin derivatives described above; and the like.
  • rosin esters include methyl esters of unmodified rosins or modified rosins (hydrogenated rosin, disproportionated rosin, polymerized rosin, etc.), triethylene glycol esters, glycerin esters, pentaerythritol esters and the like.
  • hydrocarbon-based tackifier resins examples include aliphatic hydrocarbon resins, aromatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, aliphatic / aromatic petroleum resins (styrene-olefin copolymers, etc.). ), Various hydrocarbon-based resins such as aliphatic / alicyclic petroleum resins, hydrogenated hydrocarbon resins, kumaron-based resins, and kumaron-inden-based resins.
  • the softening point of the tackifying resin is not particularly limited. From the viewpoint of improving the cohesive force, in one embodiment, a tackifier resin having a softening point (softening temperature) of 80 ° C. or higher (preferably 100 ° C. or higher) can be preferably adopted. In the technique disclosed herein, the total amount of the tackifier resin contained in the pressure-sensitive adhesive layer is 100% by mass, and more than 50% by mass (more preferably more than 70% by mass, for example, more than 90% by mass) has the softening point. It can be preferably carried out in the embodiment of the tackifier resin having.
  • a phenol-based tackifier resin (terpene phenol resin or the like) having such a softening point can be preferably used.
  • the tackifier resin may contain, for example, a terpene phenol resin having a softening point of 135 ° C. or higher (further 140 ° C. or higher).
  • the upper limit of the softening point of the tackifying resin is not particularly limited. From the viewpoint of improving the adhesion to the adherend, in one embodiment, a tackifier resin having a softening point of 200 ° C. or lower (more preferably 180 ° C. or lower) can be preferably used.
  • the tackifier resin (typically a terpene phenolic resin) has a softening point of less than 130 ° C, for example 120 ° C or less.
  • the softening point of the tackifier resin can be measured based on the softening point test method (ring ball method) specified in JIS K2207.
  • the tackifier resin contains one or more types of phenol-based tackifier resin (typically, a terpene phenol resin).
  • the technique disclosed herein can be preferably carried out, for example, in an embodiment in which the total amount of the tackifier resin is 100% by mass, of which 25% by mass or more (more preferably 30% by mass or more) is a terpene phenol resin.
  • 50% by mass or more of the total amount of the tackifier resin may be a terpene phenol resin, and 80% by mass or more (for example, 90% by mass or more) may be a terpene phenol resin.
  • Substantially all of the tackifier resin (for example, 95 to 100% by mass, further 99 to 100% by mass) may be a terpene phenol resin.
  • the amount of the pressure-sensitive adhesive resin used is not particularly limited, and is, for example, in the range of 1 to 100 parts by mass with respect to 100 parts by mass of the base polymer. It can be set as appropriate. From the viewpoint of preferably exerting the effect of improving the peel strength, it is usually appropriate that the amount of the colored pressure-sensitive adhesive resin used with respect to 100 parts by mass of the base polymer (for example, acrylic polymer) is 5 parts by mass or more, and 10 parts by mass. It is preferably 5 parts by mass or more, and may be 15 parts by mass or more.
  • the dispersibility of the pigment tends to be improved by containing a predetermined amount of a tackifier resin (for example, a terpene phenol resin having a softening point of 120 ° C. or lower).
  • a tackifier resin for example, a terpene phenol resin having a softening point of 120 ° C. or lower.
  • the amount of the colored pressure-sensitive adhesive resin used with respect to 100 parts by mass of the base polymer for example, acrylic polymer
  • the amount of the colored pressure-sensitive adhesive resin used with respect to 100 parts by mass of the base polymer for example, acrylic polymer
  • the base polymer for example, acrylic polymer
  • the colored pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer of the present embodiment may contain a cross-linking agent, if necessary.
  • the type of the cross-linking agent is not particularly limited, and a conventionally known cross-linking agent can be appropriately selected and used.
  • Examples of such a cross-linking agent include an isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, an oxazoline-based cross-linking agent, an aziridine-based cross-linking agent, a melamine-based cross-linking agent, a peroxide-based cross-linking agent, a urea-based cross-linking agent, and a metal alkoxide-based cross-linking agent.
  • Examples thereof include a cross-linking agent, a metal chelate-based cross-linking agent, a metal salt-based cross-linking agent, a carbodiimide-based cross-linking agent, a hydrazine-based cross-linking agent, an amine-based cross-linking agent, and a silane coupling agent.
  • the cross-linking agent may be used alone or in combination of two or more.
  • the total amount of cross-linking agent used is not particularly limited. For example, it can be 10 parts by mass or less with respect to 100 parts by mass of the base polymer (preferably an acrylic polymer), preferably in the range of 0.005 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass. You can choose from.
  • the colored pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer may be a leveling agent, a cross-linking aid, a plasticizer, a softening agent, an antistatic agent, an antioxidant, an ultraviolet absorber, an antioxidant, as necessary. It may contain various additives that are common in the field of pressure-sensitive adhesives, such as light stabilizers. As for such various additives, conventionally known additives can be used by a conventional method and do not particularly characterize the present invention, and therefore detailed description thereof will be omitted.
  • the pressure-sensitive adhesive layer of the present embodiment is not particularly limited as long as it is formed by the colored pressure-sensitive adhesive composition of the present embodiment, and is a water-based pressure-sensitive adhesive composition, a solvent-type pressure-sensitive adhesive composition, and a hot-melt type pressure-sensitive adhesive composition.
  • the material may be a pressure-sensitive adhesive layer formed from an active energy ray-curable pressure-sensitive adhesive composition.
  • the water-based pressure-sensitive adhesive composition refers to a pressure-sensitive adhesive composition in which a pressure-sensitive adhesive (sticking agent layer-forming component) is contained in a solvent containing water as a main component (water-based solvent), and is typically water-dispersed.
  • a type pressure-sensitive adhesive composition (a composition in which at least a part of the pressure-sensitive adhesive is dispersed in water) or the like is included.
  • the solvent-type pressure-sensitive adhesive composition refers to a pressure-sensitive adhesive composition in which the pressure-sensitive adhesive is contained in an organic solvent. This embodiment can be preferably carried out in an embodiment including a pressure-sensitive adhesive layer formed from a solvent-type pressure-sensitive adhesive composition from the viewpoint of pressure-sensitive adhesive properties and the like.
  • the pressure-sensitive adhesive layer When the pressure-sensitive adhesive layer has a multi-layer structure of two or more layers, it can be produced by laminating a pressure-sensitive adhesive layer formed in advance. Alternatively, the pressure-sensitive adhesive composition may be applied onto the pre-formed first pressure-sensitive adhesive layer and the pressure-sensitive adhesive composition may be cured to form the second pressure-sensitive adhesive layer, or at least one of the pressure-sensitive adhesive compositions. Is the colored pressure-sensitive adhesive composition according to the embodiment of the present invention.
  • the photo-curing pressure-sensitive adhesive layer is a part of the multi-layer structure. It may be a layer (for example, one layer) or all layers.
  • a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, or a spray coater is used.
  • a direct method of directly applying the colored pressure-sensitive adhesive composition to the base material to form the pressure-sensitive adhesive layer may be used.
  • a transfer method may be used in which the pressure-sensitive adhesive layer formed on the peeled surface is transferred to the substrate.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited and may be, for example, 3 ⁇ m to 2000 ⁇ m. From the viewpoint of adhesion to the adherend such as step followability, in some embodiments, the thickness of the pressure-sensitive adhesive layer may be, for example, 5 ⁇ m or more, 10 ⁇ m or more is appropriate, and 20 ⁇ m or more is preferable. It is preferably 30 ⁇ m or more. The thickness of the pressure-sensitive adhesive layer may be 50 ⁇ m or more, 50 ⁇ m or more, 70 ⁇ m or more, 100 ⁇ m or more, or 120 ⁇ m or more.
  • the thickness of the pressure-sensitive adhesive layer may be, for example, 1000 ⁇ m or less, 700 ⁇ m or less, or 500 ⁇ m or less in some embodiments. , 300 ⁇ m or less, 200 ⁇ m or less, or 170 ⁇ m or less.
  • the technique according to this aspect can also be preferably carried out in the form of a pressure-sensitive adhesive sheet described later in which the thickness of the pressure-sensitive adhesive layer is 130 ⁇ m or less, 90 ⁇ m or less, and 60 ⁇ m or less (for example, 40 ⁇ m or less).
  • the thickness of the adhesive layer is from the adhesive surface attached to the adherend to the surface opposite to the adhesive surface. The thickness of.
  • the pressure-sensitive adhesive sheet according to the embodiment of the present invention includes a pressure-sensitive adhesive layer (colored pressure-sensitive adhesive) formed by the above-mentioned colored pressure-sensitive adhesive composition. That is, the pressure-sensitive adhesive sheet according to the embodiment of the present invention includes a pressure-sensitive adhesive layer made of the above-mentioned colored pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive sheet of the present embodiment may be a pressure-sensitive adhesive sheet with a base material having the pressure-sensitive adhesive layer on one side (FIG. 2) or both sides (FIG. 3) of the sheet-like base material (support). It may be a base material-less adhesive sheet such as a form held by a peeling liner.
  • the concept of the pressure-sensitive adhesive sheet as used herein may include what is called an pressure-sensitive adhesive tape, a pressure-sensitive adhesive label, a pressure-sensitive adhesive film, or the like.
  • the pressure-sensitive adhesive layer is typically formed continuously, the pressure-sensitive adhesive layer is not limited to such a form, and the pressure-sensitive adhesive layer is formed in a regular or random pattern such as a dot shape or a striped shape. May be. Further, the pressure-sensitive adhesive sheet of the present embodiment may be in the form of a roll or in the form of a single leaf. Alternatively, the pressure-sensitive adhesive sheet may be further processed into various shapes.
  • the pressure-sensitive adhesive sheet of the present embodiment may have a base material-less mode (adhesive layer) without a base material as shown in FIG. 1 from the viewpoint of having a step-following property.
  • the adhesive sheet has a step followability, so that the adhesive sheet can be attached along the step. As a result, the adhesive sheet can be attached to the object without any gaps.
  • the pressure-sensitive adhesive sheet of the present embodiment may contain a supporting base material as shown in FIG.
  • the adhesive sheet can be accurately processed by punching or the like.
  • Such an adhesive sheet is preferable for applications where it is processed into a specific shape or narrowed and used.
  • the thickness of the supporting base material in the present embodiment is, for example, less than 75 ⁇ m.
  • the support base material having a limited thickness is preferably used in applications requiring thinning and weight reduction. Further, for example, by limiting the thickness of the supporting base material and relatively increasing the thickness of the pressure-sensitive adhesive layer, it is possible to improve the pressure-sensitive adhesive properties such as adhesion reliability.
  • the thickness of the supporting substrate is preferably 60 ⁇ m or less, more preferably 50 ⁇ m or less (for example, less than 50 ⁇ m), still more preferably 40 ⁇ m or less, particularly preferably 30 ⁇ m or less (for example, less than 30 ⁇ m, typically less than 30 ⁇ m). 25 ⁇ m or less).
  • the thickness of the supporting substrate may be 20 ⁇ m or less, 12 ⁇ m or less, or 7 ⁇ m or less (for example, 3 ⁇ m or less).
  • the lower limit of the thickness of the supporting base material is not particularly limited.
  • the thickness of the supporting base material is usually 0.5 ⁇ m or more (for example, 1 ⁇ m or more). In one embodiment, the thickness of the supporting substrate may be 3 ⁇ m or more. In another aspect, the thickness of the supporting substrate can be 8 ⁇ m or more, 13 ⁇ m or more, or 16 ⁇ m or more.
  • the structure and material of the supporting base material are not particularly limited, and are typically a film-like base material (also referred to as "base material film").
  • base film a film containing a resin film as the base film can be preferably used.
  • the base film is typically an independently shape-maintainable (independent) member.
  • the base film in the present embodiment may be substantially composed of such a base film.
  • the base film may include an auxiliary layer in addition to the base film. Examples of the auxiliary layer include a colored layer, a reflective layer, an undercoat layer, an antistatic layer, and the like provided on the surface of the base film.
  • the resin film is a film containing a resin material as a main component (for example, a component contained in the resin film in an amount of more than 50% by mass).
  • resin films include polyethylene (PE), polypropylene (PP), ethylene / propylene copolymer and other polyolefin resin films; polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) and the like.
  • PE polyethylene
  • PP polypropylene
  • PET polybutylene terephthalate
  • PEN polyethylene naphthalate
  • Polyethylene resin film polyurethane resin film; vinyl chloride resin film; vinyl acetate resin film; polyimide resin film; polyamide resin film; fluororesin film; cellophane; and the like.
  • the resin film may be a rubber-based film such as a natural rubber film or a butyl rubber film.
  • a polyester film is preferable from the viewpoint of handleability and processability, and a PET film is particularly preferable.
  • the "resin film” is typically a non-porous sheet, and is a concept that is distinguished from so-called non-woven fabrics and woven fabrics (in other words, a concept excluding non-woven fabrics and woven fabrics). be.
  • the base film may contain, if necessary, fillers (inorganic fillers, organic fillers, etc.), dispersants (surfactants, etc.), antioxidants, antioxidants, ultraviolet absorbers, antistatic agents, etc.
  • Various additives such as lubricants and plasticizers may be blended.
  • the blending ratio of the various additives is usually less than 30% by mass (for example, less than 20% by mass, typically less than 10% by mass).
  • the surface of the base film may be subjected to conventionally known surface treatments such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, and application of an undercoat agent.
  • a surface treatment may be a treatment for improving the adhesion between the base film and the pressure-sensitive adhesive layer, in other words, the anchoring property of the pressure-sensitive adhesive layer on the base film.
  • the back surface of the base material film may be subjected to a peeling treatment, if necessary.
  • a general silicone-based, long-chain alkyl-based, fluorine-based or other peeling treatment agent is applied in the form of a thin film typically of 0.01 ⁇ m to 1 ⁇ m (for example, 0.01 ⁇ m to 0.1 ⁇ m). It can be a process to do. By performing such a peeling treatment, it is possible to obtain an effect such as facilitating the rewinding of the wound body in which the adhesive sheet is wound in a roll shape.
  • a peeling liner can be used when forming the pressure-sensitive adhesive layer, producing the pressure-sensitive adhesive sheet, storing the pressure-sensitive adhesive sheet before use, distributing it, processing the shape, and the like.
  • the peeling liner is not particularly limited, and is, for example, a peeling liner having a peeling treatment layer on the surface of a liner base material such as a resin film or paper, a fluoropolymer (polytetrafluoroethylene or the like), or a polyolefin resin (polyethylene, etc.).
  • a peeling liner or the like made of a low adhesive material polypropylene or the like
  • the peeling treatment layer may be formed by surface-treating the liner base material with a peeling treatment agent such as a silicone-based, long-chain alkyl-based, fluorine-based, or molybdenum sulfide.
  • the total thickness of the pressure-sensitive adhesive sheet of the present embodiment (including the pressure-sensitive adhesive layer and further including the support base material in the configuration having the support base material, but not including the peeling liner) is not particularly limited.
  • the total thickness of the pressure-sensitive adhesive sheet is usually 200 ⁇ m or less from the viewpoint of thinning.
  • the lower limit of the thickness of the pressure-sensitive adhesive sheet is not particularly limited, and is usually 1 ⁇ m or more, for example, 3 ⁇ m or more is appropriate, preferably 6 ⁇ m or more, more preferably 10 ⁇ m or more (for example, 15 ⁇ m or more). be.
  • the total thickness of the pressure-sensitive adhesive sheet is 150 ⁇ m or less, more preferably 120 ⁇ m or less, still more preferably 70 ⁇ m or less, particularly preferably 50 ⁇ m or less (for example, 40 ⁇ m or less), and may be, for example, 35 ⁇ m or less. , 25 ⁇ m or less, and further may be 15 ⁇ m or less or 10 ⁇ m or less (for example, 7 ⁇ m or less). Even in a configuration using such a thin pressure-sensitive adhesive sheet, the light-shielding effect of the present embodiment can be preferably exhibited.
  • the ratio of the total thickness of the pressure-sensitive adhesive layer contained in the pressure-sensitive adhesive sheet to the total thickness of the pressure-sensitive adhesive sheet is not particularly limited.
  • the total thickness of the pressure-sensitive adhesive layer contained in the pressure-sensitive adhesive sheet is the total thickness of the pressure-sensitive adhesive layer provided on one surface of the base film and the pressure-sensitive adhesive layer provided on the other surface. say.
  • the thickness of the pressure-sensitive adhesive layer provided on the other surface is zero, and the thickness of the pressure-sensitive adhesive layer is zero on one of the above surfaces.
  • the thickness of the provided pressure-sensitive adhesive layer and the total thickness of the pressure-sensitive adhesive layer are the same.
  • the ratio of the total thickness of the pressure-sensitive adhesive layer to the total thickness of the pressure-sensitive adhesive sheet is 40% or more (preferably 50% or more, typically more than 50%, more preferably 60). % Or more, more preferably 70% or more). In one embodiment, the ratio of the total thickness of the pressure-sensitive adhesive layer to the total thickness of the pressure-sensitive adhesive sheet may be 75% or more, and further may be 80% or more.
  • the upper limit of the ratio of the total thickness of the pressure-sensitive adhesive layer to the total thickness of the pressure-sensitive adhesive sheet is not particularly limited, but it is usually appropriate to be 95% or less, and preferably 90% or less.
  • Applications of the pressure-sensitive adhesive layer and the pressure-sensitive adhesive sheet of the present embodiment include, for example, housings of electronic devices, structural parts for vehicles, vehicle-mounted products, housings of home electric appliances, structural parts, mechanical parts, and various automobile parts. , Parts for electronic devices, furniture, applications for household goods such as kitchen utensils, medical equipment, parts for building materials, other structural parts, exterior parts, and the like. More specifically as electronic devices and home appliances, home appliances such as refrigerators, washing machines, vacuum cleaners, microwave ovens, air conditioners, lighting equipment, electric water heaters, TVs, watches, ventilation fans, projectors, speakers, personal computers, mobile phones , Smartphones, digital cameras, tablet PCs, portable music players, portable game machines, chargers, electronic information devices such as batteries, and the like.
  • the standard deviation ⁇ was calculated for the transmittance at 10 points at 560 nm, and the in-plane color unevenness of the pressure-sensitive adhesive layer was evaluated.
  • the standard deviation ⁇ was less than 1.2, it was evaluated as ⁇ , and when it was 1.2 or more, it was evaluated as ⁇ .
  • the adhesive strength of the adhesive sheets of Examples and Comparative Examples was evaluated by performing a peeling adhesive strength test according to JIS Z 0237: 2009. That is, in an environment of a temperature of 23 ° C. and a relative humidity of 50% RH, a PET film having a thickness of 25 ⁇ m was attached to one of the adhesive surfaces of the double-sided adhesive sheet, lined with the adhesive, and cut to a width of 20 mm to prepare a measurement sample.
  • the other adhesive surface of the measurement sample was attached to a glass plate as an adherend by reciprocating a 2 kg roller once with an adhesive area of 20 mm in width and 100 mm in length. The measurement sample attached to the adherend in this way was left for 30 minutes.
  • DCPMA dicyclopentanyl methacrylate
  • MMA methyl methacrylate
  • TGR 3.5 parts by mass was put into a four-necked flask. Then, after stirring at 70 ° C. under a nitrogen atmosphere for 1 hour, 0.2 parts by mass of azobisisobutyronitrile was added as a thermal polymerization initiator, and the reaction was carried out at 70 ° C.
  • the obtained (meth) acrylic polymer had a glass transition temperature of 144 ° C. and a weight average molecular weight of 4300.
  • ⁇ Preparation of photopolymerizable composition (adhesive composition)> 2-Ethylhexyl acrylate (78 parts by mass), N-vinyl-2-pyrrolidone (18 parts by mass), and hydroxyethyl acrylate (4 parts by mass) as monomer components, and 2,2-dimethoxy-1, as a photopolymerization initiator, 2-Diphenyl-1-one (trade name "Irgacure 651", manufactured by Ciba Japan) (0.035 parts by mass), and 1-hydroxy-cyclohexyl-phenyl-ketone (trade name "Irgacure 184", Ciba Japan) (Manufactured by 0.035 parts by mass) was placed in a four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, a reflux cooler and a dropping funnel, and exposed to ultraviolet rays in a nitrogen atmosphere.
  • a partial polymer (monomer syrup) was obtained by partial photopolymerization.
  • this partial polymer 100 parts by mass
  • 1,6-hexanediol diacrylate 0.088 parts by mass
  • the above (meth) acrylic polymer 11.8 parts by mass
  • ⁇ -glycidoxypropyltri ⁇ -glycidoxypropyltri.
  • methoxysilane KBM-403, manufactured by Shinetsu Silicone Co., Ltd., 0.35 parts by mass
  • Adhesive Composition 1 In a reaction vessel equipped with a stirrer, a thermometer, a reflux cooler, and a nitrogen gas introduction tube, 60 parts by mass of n-butyl acrylate, 18 parts by mass of 4-hydroxybutyl acrylate, and 22 parts by mass of n-vinylpyrrolidone. A mixture containing 0.2 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator and 122 parts by mass of ethyl acetate as a solvent is stirred at 60 ° C. for 7 hours under a nitrogen atmosphere. (Polymerization reaction). As a result, a polymer solution containing an acrylic polymer was obtained. The weight average molecular weight (Mw) of the acrylic polymer in this polymer solution was 400,000.
  • AIBN 2,2'-azobisisobutyronitrile
  • Adhesive Composition 2 In a reaction vessel equipped with a stirrer, a thermometer, a reflux cooler, and a nitrogen gas introduction tube, 96 parts by mass of 2-ethylhexyl acrylate, 4 parts by mass of 2-hydroxyethyl acrylate, and 2,2'as a polymerization initiator. -A mixture containing 0.2 parts by mass of azobisisobutyronitrile (AIBN) and 122 parts by mass of ethyl acetate as a solvent was stirred at 60 ° C. for 7 hours in a nitrogen atmosphere (polymerization reaction). As a result, a polymer solution containing an acrylic polymer was obtained. The weight average molecular weight (Mw) of the acrylic polymer in this polymer solution was 600,000.
  • a masterbatch resin 2 was obtained in the same manner as the masterbatch resin 1 except that the composition of the monomers was changed as shown in Table 1.
  • a masterbatch resin 3 was obtained in the same manner as the masterbatch resin 1 except that the composition of the monomers was changed as shown in Table 1.
  • the monomer composition, Tg and acid value of the masterbatch resins 1 to 5 are as shown in Table 1.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) of the masterbatch resins 1 to 5 are also shown in Table 1.
  • Pigment Dispersion Liquid 1 Pigment for Adhesive Dispersion A pigment obtained by kneading 175 parts by mass of the masterbatch resin prepared above and 25 parts by mass of magenta pigment (Pigment Red 122) as a resin for a masterbatch with a plastomill (manufactured by Toyo Seiki Seisakusho Co., Ltd.). 72 parts by mass of the dispersed resin was mixed and dissolved in advance with 28 parts by mass of 2-ethylhexyl acrylate, charged into a vessel for a sand grinder, and 120 g of 0.4 mm ⁇ glass beads were added for dispersion.
  • magenta pigment Pigment Red 122
  • 72 parts by mass of the dispersed resin was mixed and dissolved in advance with 28 parts by mass of 2-ethylhexyl acrylate, charged into a vessel for a sand grinder, and 120 g of 0.4 mm ⁇ glass beads were added for dispersion.
  • the dispersed particle size of the pigment was measured by a laser diffraction / scattering type particle size distribution measuring device LA-950, and when the particle size did not change, the dispersion was terminated and the glass beads were removed to obtain a pigment dispersion liquid 1.
  • the median diameter of the dispersed particles of the pigment in the pigment dispersion liquid 1 was 100 nm.
  • Pigment Dispersion Liquid 2 28 parts by mass of 2-ethylhexyl acrylate, 54 parts by mass of the masterbatch resin 1 prepared above as a resin for a pigment dispersion masterbatch for an adhesive, and 18 parts by mass of a magenta pigment (Pigment Red 122) are mixed and dissolved in advance, and a sand grinder is used. 120 g of 0.4 mm ⁇ glass beads were added to the vessel for dispersion. The dispersed particle size of the pigment was measured by a laser diffraction / scattering type particle size distribution measuring device LA-950, and when the particle size did not change, the dispersion was terminated, and the glass beads were removed to obtain a pigment dispersion liquid 2. The median diameter of the dispersed particles of the pigment in the pigment dispersion liquid 2 was 800 nm.
  • Pigment Dispersion Liquid 3 When 54 parts by mass of pigment dispersant 1 (trade name "Floren DOPA 15BHFS” manufactured by Kyoeisha) was mixed in advance with 18 parts by mass of magenta pigment (Pigment Red 122) to form a uniform paste, 28 parts by mass of 2-ethylhexyl acrylate was added. In addition, it was charged in a vessel for a sand grinder, and 120 g of 0.4 mm ⁇ glass beads were added and dispersed.
  • pigment dispersant 1 trade name "Floren DOPA 15BHFS” manufactured by Kyoeisha
  • magenta pigment Pigment Red 122
  • the dispersed particle size of the pigment was measured by a laser diffraction / scattering type particle size distribution measuring device LA-950, and when the particle size did not change, the dispersion was terminated and the glass beads were removed to obtain a pigment dispersion liquid 3.
  • the median diameter of the dispersed particles of the pigment in the pigment dispersion liquid 3 was 100 nm.
  • the pigment dispersion liquid 4 was obtained in the same manner as in Production Example 3 except that the pigment dispersant 1 was replaced with the dispersant 2 (trade name “DISPER BYK-145” manufactured by Big Chemie Japan BYK).
  • the median diameter of the dispersed particles of the pigment in the pigment dispersion liquid 4 was 100 nm.
  • a pigment dispersion 5 was obtained in the same manner as in Production Example 3 except that the magenta pigment (Pigment Red 122) was replaced with a black pigment (Pigment Black 7) and the 2-ethylhexyl acrylate was replaced with ethyl acetate.
  • the median diameter of the dispersed particles of the pigment in the pigment dispersion liquid 5 was 100 nm.
  • Examples and comparative examples> (Preparation of Micro Masterbatch 1 (MMB1)) Using a lab plast mill (roller mixer R60) manufactured by Toyo Seiki, masterbatch resin 1 (75 parts by mass) and magenta pigment (Pigment Red 122) (25 parts by mass) are introduced into the mixer part and kneaded at 100 ° C. and 150 rpm. Was done. The sampled pigment dispersion was dissolved and dispersed in ethyl acetate, and the dispersed particle size of the pigment was measured by the laser diffraction / scattering type particle size distribution measuring device LA-950. An agent pigment dispersion micromaster batch (MMB1) was obtained.
  • MMB1 Micro Masterbatch 1
  • MMB2 Micro Masterbatch 2
  • MMB3 Micro Masterbatch 3 for an adhesive as a comparative example was obtained in the same manner as in the preparation of the micromasterbatch 1 (MMB1) except that the masterbatch resin 1 was replaced with the masterbatch resin 3.
  • micromasterbatch 4 (MMB4) for adhesive was prepared in the same manner as the preparation of the micromasterbatch 1 (MMB1) except that the magenta pigment (pigment red 122) was replaced with the blue pigment (pigment blue 15: 3). Obtained.
  • MMB5 Micro Masterbatch 5 for an adhesive was obtained in the same manner as in the preparation of the micromasterbatch 1 (MMB1) except that the magenta pigment (pigment red 122) was replaced with a yellow pigment (pigment yellow 185). ..
  • Micromasterbatch 6 Adhesives similar to the preparation of Micromasterbatch 1 (MMB1) except that the magenta pigment (Pigment Red 122) was replaced with a black pigment (Pigment Black 7) and the masterbatch resin 1 was replaced with a masterbatch resin 4. Micromaster batch 6 (MMB6) for use was obtained.
  • Micromasterbatch 1 (MMB7) except that the masterbatch resin 1 was replaced with the masterbatch resin 4 (60 parts by mass) and the magenta pigment (pigment red 122) was replaced with the black pigment (pigment black 7) (40 parts by mass). ) was prepared, and a micromasterbatch 7 (MMB7) for a pressure-sensitive adhesive was obtained.
  • Micromasterbatch 1 (MMB8) except that the masterbatch resin 1 was replaced with the masterbatch resin 5 (60 parts by mass) and the magenta pigment (pigment red 122) was replaced with the black pigment (pigment black 7) (40 parts by mass). ) was prepared, and a micromasterbatch 8 (MMB8) for a pressure-sensitive adhesive was obtained.
  • Example 1 (Preparation of Colored Adhesive Composition)
  • the MMB1 was added to the photopolymerizable composition so that the pigment concentration was 0.1% by mass, and mixed to obtain a colored pressure-sensitive adhesive composition.
  • the colored pressure-sensitive adhesive composition is applied to the peeled surface of a polyester film A (trade name "Diawheel MRF", manufactured by Mitsubishi Chemical Co., Ltd.) having a thickness of 38 ⁇ m, which is peeled from one side with silicone, so as to have a thickness of 50 ⁇ m.
  • a layer is formed, and a polyester film B (trade name "Diawheel MRF”, manufactured by Mitsubishi Chemical Co., Ltd.) having a thickness of 38 ⁇ m, which has been subjected to silicone peeling treatment on one side, is bonded to the coating layer.
  • Ultraviolet rays were irradiated by a UV-LED lamp whose lamp height was adjusted so that the intensity of the irradiation surface directly below the lamp from the surface on the B side was 200 mW / cm 2 . Polymerization was carried out until irradiation with a light intensity of 6000 mJ / cm 2 to form a pressure-sensitive adhesive layer (colored pressure-sensitive adhesive), and a pressure-sensitive adhesive sheet having a thickness of 50 ⁇ m was prepared.
  • Example 2 MMB1 was added to the photopolymerizable composition so that the pigment concentration was 0.5% by mass, and the colored pressure-sensitive adhesive composition and the pressure-sensitive adhesive sheet of Example 2 were prepared in the same manner as in Example 1 except that they were mixed. ..
  • Example 3 MMB1 was added to the photopolymerizable composition so that the pigment concentration was 1% by mass, and the colored pressure-sensitive adhesive composition and the pressure-sensitive adhesive sheet of Example 3 were prepared in the same manner as in Example 1 except that they were mixed.
  • Example 4 The pigment dispersion liquid 1 prepared above was added to the photopolymerizable composition so that the pigment concentration was 0.5% by mass, and mixed to obtain the colored pressure-sensitive adhesive composition of Example 4.
  • the pressure-sensitive adhesive sheet of Example 4 was produced in the same manner as in Example 1.
  • Example 5 In a polymer solution containing the acrylic polymer of the pressure-sensitive adhesive composition 1, 0.3 parts by mass (solid) of an isocyanate cross-linking agent (trade name "Takenate D160N", manufactured by Mitsui Chemicals, Inc.) as a cross-linking agent per 100 parts by mass of the acrylic polymer. (Division equivalent), dibutyltin dilaurate (trade name "OL-1") as a cross-linking catalyst, 1 mass% ethyl acetate solution (manufactured by Tokyo Fine Chemicals Co., Ltd.), 0.01 part by mass (solid content equivalent), and a cross-linking inhibitor.
  • an isocyanate cross-linking agent trade name "Takenate D160N", manufactured by Mitsui Chemicals, Inc.
  • OL-1 dibutyltin dilaurate
  • Example 6 An MMB4 solution diluted with ethyl acetate so that the pigment concentration becomes 13.4% by mass is added to the polymer solution containing the acrylic polymer of the pressure-sensitive adhesive composition 1 so that the pigment concentration becomes 0.5% by mass.
  • the colored pressure-sensitive adhesive composition and the pressure-sensitive adhesive sheet of Example 6 were prepared in the same manner as in Example 5 except that they were mixed.
  • Example 7 An MMB5 solution diluted with ethyl acetate so that the pigment concentration becomes 12.1% by mass is added to the polymer solution containing the acrylic polymer of the pressure-sensitive adhesive composition 1 so that the pigment concentration becomes 0.5% by mass.
  • the colored pressure-sensitive adhesive composition and the pressure-sensitive adhesive sheet of Example 7 were prepared in the same manner as in Example 5 except that they were mixed.
  • Example 8 An MMB6 solution diluted with ethyl acetate so that the pigment concentration was 2.5% by mass was added to the polymer solution containing the acrylic polymer of the pressure-sensitive adhesive composition 2 so that the pigment concentration was 1% by mass, and mixed.
  • the colored pressure-sensitive adhesive composition and the pressure-sensitive adhesive sheet of Example 8 were prepared in the same manner as in Example 5 except for the above.
  • Example 9 An MMB7 solution diluted with ethyl acetate so that the pigment concentration was 2.5% by mass was added to the polymer solution containing the acrylic polymer of the pressure-sensitive adhesive composition 2 so that the pigment concentration was 1% by mass, and mixed.
  • the colored pressure-sensitive adhesive composition and the pressure-sensitive adhesive sheet of Example 9 were prepared in the same manner as in Example 5 except for the above.
  • Example 10 An MMB8 solution diluted with ethyl acetate so that the pigment concentration was 2.5% by mass was added to the polymer solution containing the acrylic polymer of the pressure-sensitive adhesive composition 2 so that the pigment concentration was 1% by mass, and mixed.
  • the colored pressure-sensitive adhesive composition and the pressure-sensitive adhesive sheet of Example 10 were prepared in the same manner as in Example 5 except for the above.
  • Comparative Example 6 Coloring of Comparative Example 6 in the same manner as in Example 5 except that the pigment dispersion 5 was added to the polymer solution containing the acrylic polymer of the pressure-sensitive adhesive composition 2 so that the pigment concentration was 1% by mass and mixed. A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet were prepared.
  • the adhesive sheets of Examples 1 to 10 had no in-plane color unevenness and showed a good appearance, but Comparative Examples 1 to 3 and 5 had in-plane color unevenness and showed an appearance. It was inferior to.
  • the standard deviation of the transmittance at the wavelength where the transmittance was the lowest at 400 to 800 nm was as narrow as 0.37 to 1.10, and the color unevenness in the plane was small.
  • Comparative Examples 1 to 5 had a standard deviation of 1.20 to 2.41, which was wider than that of Examples, and showed a large amount of in-plane color unevenness.
  • the adhesive sheets of Examples 1 to 10 showed high adhesion reliability without any decrease in adhesive strength with time even in a high temperature and high humidity environment.
  • the adhesive sheets of Examples 4 and 6 showed a decrease in adhesive strength with time in a high temperature and high humidity environment.
  • a pressure-sensitive adhesive layer and a pressure-sensitive adhesive sheet exhibiting an excellent appearance and high adhesion reliability, a colored pressure-sensitive adhesive composition capable of forming the pressure-sensitive adhesive layer and the pressure-sensitive adhesive sheet, and a pigment dispersion for a pressure-sensitive adhesive having excellent dispersibility.
  • a resin for a master batch and a pigment dispersion master batch for an adhesive can be provided.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Adhesive Tapes (AREA)

Abstract

La présente invention concerne une résine pour un mélange maître de dispersion de pigment pour des adhésifs sensibles à la pression, la résine comprenant une résine (A), la résine (A) ayant une température de transition vitreuse de -80 à 40 °C et une valeur acide de 1-50 (KOHmg/g).
PCT/JP2021/035468 2020-09-30 2021-09-27 Résine pour mélange maître de dispersion de pigment pour adhésif sensible à la pression, mélange maître de dispersion de pigment pour adhésif sensible à la pression, composition adhésive sensible à la pression colorée, et feuille adhésive sensible à la pression WO2022071252A1 (fr)

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JP2022553971A JPWO2022071252A1 (fr) 2020-09-30 2021-09-27
CN202180066952.1A CN116323765A (zh) 2020-09-30 2021-09-27 粘合剂用颜料分散母料用树脂、粘合剂用颜料分散母料、着色粘合剂组合物和粘合片
KR1020237010378A KR20230079062A (ko) 2020-09-30 2021-09-27 점착제용 안료 분산 마스터배치용 수지, 점착제용 안료 분산 마스터배치, 착색 점착제 조성물 및 점착 시트

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06346040A (ja) * 1993-06-08 1994-12-20 Dainippon Ink & Chem Inc 着色された感圧接着剤層およびそれを使用した感圧接着テープまたはシート
JPH08281888A (ja) * 1995-04-17 1996-10-29 Nippon Petrochem Co Ltd 一軸配向体、積層体、不織布および織布ならびにそれらを用いた強化積層体
JP2000265133A (ja) * 1999-03-11 2000-09-26 Tomoegawa Paper Co Ltd 電子ディスプレイ用貼着フィルム
JP2003286461A (ja) * 2002-03-28 2003-10-10 Sekisui Chem Co Ltd 装飾用粘着シートの製造方法及び白色トナー
JP2013067782A (ja) * 2011-09-09 2013-04-18 Toyo Ink Sc Holdings Co Ltd 光学用粘着剤、光学用粘着シート及び積層体
WO2016146349A1 (fr) * 2015-03-13 2016-09-22 Tesa Se Composition adhésive sensible à la pression et bande noire transparente aux rayons infrarouges, procédé de préparation et utilisation correspondants

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6044355B2 (ja) 1980-07-11 1985-10-03 モダン・プラスチツク工業株式会社 耐候性の優れた着色粘着シ−ト
JP6675825B2 (ja) 2014-11-20 2020-04-08 リンテック株式会社 着色粘着シート

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06346040A (ja) * 1993-06-08 1994-12-20 Dainippon Ink & Chem Inc 着色された感圧接着剤層およびそれを使用した感圧接着テープまたはシート
JPH08281888A (ja) * 1995-04-17 1996-10-29 Nippon Petrochem Co Ltd 一軸配向体、積層体、不織布および織布ならびにそれらを用いた強化積層体
JP2000265133A (ja) * 1999-03-11 2000-09-26 Tomoegawa Paper Co Ltd 電子ディスプレイ用貼着フィルム
JP2003286461A (ja) * 2002-03-28 2003-10-10 Sekisui Chem Co Ltd 装飾用粘着シートの製造方法及び白色トナー
JP2013067782A (ja) * 2011-09-09 2013-04-18 Toyo Ink Sc Holdings Co Ltd 光学用粘着剤、光学用粘着シート及び積層体
WO2016146349A1 (fr) * 2015-03-13 2016-09-22 Tesa Se Composition adhésive sensible à la pression et bande noire transparente aux rayons infrarouges, procédé de préparation et utilisation correspondants

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JPWO2022071252A1 (fr) 2022-04-07
KR20230079062A (ko) 2023-06-05
CN116323765A (zh) 2023-06-23

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