WO2023282008A1 - 両面粘着シート - Google Patents

両面粘着シート Download PDF

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Publication number
WO2023282008A1
WO2023282008A1 PCT/JP2022/024104 JP2022024104W WO2023282008A1 WO 2023282008 A1 WO2023282008 A1 WO 2023282008A1 JP 2022024104 W JP2022024104 W JP 2022024104W WO 2023282008 A1 WO2023282008 A1 WO 2023282008A1
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WO
WIPO (PCT)
Prior art keywords
sensitive adhesive
pressure
mass
double
adhesive sheet
Prior art date
Application number
PCT/JP2022/024104
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English (en)
French (fr)
Japanese (ja)
Inventor
啓迪 住田
卓也 藤田
直宏 加藤
一樹 箕浦
栄一 井本
Original Assignee
日東電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2022049428A external-priority patent/JP2023008802A/ja
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN202280044521.XA priority Critical patent/CN117580921A/zh
Priority to KR1020247003412A priority patent/KR20240032059A/ko
Publication of WO2023282008A1 publication Critical patent/WO2023282008A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present invention relates to a double-sided adhesive sheet.
  • a mobile phone which is a typical mobile device, tends to have thinned main components.
  • the display part of a portable device is mainly composed of an LCD module and a backlight unit, and various sheet-like parts are laminated in order to exhibit functions such as light emission, reflection, light blocking, and light guiding. Therefore, a double-sided adhesive sheet (double-sided adhesive tape) is used for assembling (bonding) these parts.
  • portable electronic devices are often exposed to the risk of falling due to their usage patterns.
  • double-sided pressure-sensitive adhesive sheets used in portable electronic devices are required to have impact resistance so that they are less likely to be damaged or peeled off from parts due to the impact of dropping the portable electronic device.
  • Patent Documents 1 to 3 disclose, for example, known double-sided pressure-sensitive adhesive sheets that are used in mobile electronic devices and have excellent impact resistance.
  • Patent Documents 1 to 3 do not mention that both impact resistance and reworkability are excellent.
  • the present invention was conceived under such circumstances, and its object is to provide a double-sided pressure-sensitive adhesive sheet that has excellent impact resistance and excellent reworkability.
  • the present inventors have found a double-sided pressure-sensitive adhesive sheet having no substrate, wherein the pressure-sensitive adhesive layer constituting the double-sided pressure-sensitive adhesive sheet contains a specific filler and has specific properties. It was found that the double-sided pressure-sensitive adhesive sheet having the above properties has excellent impact resistance and excellent reworkability.
  • the present invention has been completed based on these findings.
  • the present invention is a double-sided pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer,
  • the double-sided pressure-sensitive adhesive sheet has a thickness of 500 ⁇ m or less,
  • the pressure-sensitive adhesive layer contains a base polymer and a filler,
  • the average particle size of the filler is 80 ⁇ m or less,
  • a double-sided PSA sheet having a breaking stress of 0.5 MPa or more and a breaking strain of 600% or more.
  • the volume ratio of the filler to the total mass of the adhesive layer is preferably 0.01 ⁇ 10 ⁇ 2 to 20 ⁇ 10 ⁇ 2 cm 3 /g.
  • the content of the filler in the pressure-sensitive adhesive layer is preferably more than 0 parts by mass and 30 parts by mass or less with respect to 100 parts by mass as the total amount of the base polymer.
  • the filler is preferably one or more fillers selected from the group consisting of a filler whose surface is composed of an organic material other than an acrylic resin, a filler whose surface is composed of an inorganic material, and a filler having a hollow structure. .
  • the adhesive layer is preferably an acrylic adhesive layer containing an acrylic polymer as the base polymer.
  • the above acrylic polymer preferably has a structural part derived from an acrylic oligomer.
  • the adhesive layer preferably contains a tackifying resin.
  • the storage elastic modulus G' of the pressure-sensitive adhesive layer at 23°C is preferably 0.09 MPa or more.
  • the 180°C peel strength against a stainless steel plate is preferably 20 N/25 mm or more.
  • the double-sided pressure-sensitive adhesive sheet is preferably for fixing members to each other in electrical and electronic equipment.
  • the present invention comprises the double-sided pressure-sensitive adhesive sheet
  • the above-mentioned double-sided pressure-sensitive adhesive sheet provides an electric/electronic device in which members are fixed to each other by both pressure-sensitive adhesive surfaces.
  • the double-sided pressure-sensitive adhesive sheet of the present invention has excellent impact resistance and excellent reworkability. Therefore, when used in portable electronic devices, for example, it is difficult to peel off when subjected to a drop impact, and when the double-sided pressure-sensitive adhesive sheet is intentionally peeled off, the pressure-sensitive adhesive sheet is easily peeled off without being broken.
  • the double-sided pressure-sensitive adhesive sheet of the present invention is a double-sided pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer, and is a so-called "substrate-less" double-sided pressure-sensitive adhesive sheet that does not have a substrate.
  • the adhesive layer contains a base polymer and a filler as essential components.
  • the average particle size of the filler is 80 ⁇ m or less.
  • the pressure-sensitive adhesive layer may be referred to as "the pressure-sensitive adhesive layer of the present invention”.
  • the base polymer refers to the main component among the polymer components in the pressure-sensitive adhesive that constitutes the pressure-sensitive adhesive layer, for example, the polymer component contained in an amount exceeding 50% by mass.
  • the content of the base polymer in the pressure-sensitive adhesive layer is preferably 60% by mass or more, more preferably 70% by mass or more, relative to 100% by mass of the total amount of the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive layer constituting the double-sided pressure-sensitive adhesive sheet of the present invention may be a single layer or multiple layers.
  • the double-sided pressure-sensitive adhesive sheet of the present invention is composed of a plurality of pressure-sensitive adhesive layers, each of the plurality of pressure-sensitive adhesive layers is the pressure-sensitive adhesive layer of the present invention.
  • the plurality of pressure-sensitive adhesive layers may be the same pressure-sensitive adhesive layer, or may be pressure-sensitive adhesive layers having different compositions, thicknesses, physical properties, and the like.
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of the double-sided pressure-sensitive adhesive sheet of the present invention.
  • a double-sided pressure-sensitive adhesive sheet 1 is composed of a single pressure-sensitive adhesive layer 2 of the present invention. Release liners 3 and 4 are attached to the adhesive surfaces of the adhesive layer 2, respectively.
  • the pressure-sensitive adhesive that constitutes the pressure-sensitive adhesive layer of the present invention is not particularly limited. , polyester-based adhesives, urethane-based adhesives, polyether-based adhesives, polyamide-based adhesives, fluorine-based adhesives, and the like. Among them, acrylic pressure-sensitive adhesives are preferable as the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer from the viewpoints of adhesion, weather resistance, cost, and ease of designing the pressure-sensitive adhesive.
  • the pressure-sensitive adhesive layer is preferably an acrylic pressure-sensitive adhesive layer composed of an acrylic pressure-sensitive adhesive. Only one kind of the pressure-sensitive adhesive may be used, or two or more kinds thereof may be used.
  • the acrylic pressure-sensitive adhesive layer contains an acrylic polymer as a base polymer.
  • the acrylic polymer is a polymer containing an acrylic monomer (a monomer having a (meth)acryloyl group in the molecule) as a monomer component constituting the polymer. That is, the acrylic polymer contains structural units derived from acrylic monomers.
  • acrylic polymer may use only 1 type, and may use 2 or more types.
  • the said acrylic polymer may contain only 1 type of acrylic monomers as a monomer component, and may contain 2 or more types.
  • "(meth)acrylic” means "acrylic" and/or “methacrylic” (one or both of "acrylic” and “methacrylic"), and the same applies to others. .
  • the acrylic polymer is preferably a polymer composed (formed) of an acrylic monomer (A) having two or more non-aromatic rings as an essential monomer component. That is, the acrylic polymer preferably contains an acrylic monomer (A) as a structural unit.
  • the acrylic polymer may contain only one type of acrylic monomer (A) as a monomer component, or may contain two or more types thereof.
  • the bicyclic or more non-aromatic ring includes a bicyclic or more non-aromatic hydrocarbon ring and a bicyclic or more non-aromatic heterocyclic ring.
  • the non-aromatic ring may be either saturated or unsaturated.
  • Examples of the non-aromatic hydrocarbon ring having two or more rings include bridged hydrocarbon rings such as bicyclic aliphatic hydrocarbon rings and tricyclic or more aliphatic hydrocarbon rings.
  • Bicyclic hydrocarbon rings include pinane ring, pinene ring, bornane ring, norbornane ring, norbornene ring and the like.
  • Tricyclic or higher aliphatic hydrocarbon rings include, for example, dicyclopentane ring, dicyclopentene ring, adamantane ring, tricyclopentane ring, tricyclopentene ring and the like. .
  • the number of atoms constituting the non-aromatic ring is preferably 6-12, more preferably 7-10. Further, in the acrylic monomer (A), the non-aromatic ring is directly bonded to the (meth)acryloyl group, or bonded to the (meth)acryloyl group via an oxygen atom or an oxyalkylene group. preferably.
  • the bicyclic or higher non-aromatic ring is preferably a bicyclic or higher non-aromatic hydrocarbon ring, more preferably a bicyclic or tricyclic non-aromatic hydrocarbon ring, and more preferably bornane.
  • ring, norbornane ring, norbornene ring, dicyclopentane ring, and dicyclopentene ring are preferable as the group having two or more non-aromatic rings, which the acrylic monomer (A) has.
  • the Tg of the homopolymer of the acrylic monomer (A) is preferably 0°C or higher, more preferably 10°C or higher, and even more preferably 60°C or higher. When the Tg is 0°C or higher, the impact resistance is more excellent.
  • the above Tg is, for example, 200° C. or lower.
  • the "glass transition temperature (Tg) when forming a homopolymer” means "the glass transition temperature of the homopolymer of the monomer ( Tg)", specifically, numerical values are listed in "Polymer Handbook” (3rd edition, John Wiley & Sons, Inc., 1987).
  • the Tg of a homopolymer of a monomer not described in the above literature refers to, for example, a value obtained by the following measuring method (see JP-A-2007-51271).
  • a reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser was charged with 100 parts by mass of a monomer, 0.2 parts by mass of 2,2'-azobisisobutyronitrile and ethyl acetate as a polymerization solvent. 200 parts by mass are added and stirred for 1 hour while nitrogen gas is introduced. After oxygen is removed from the polymerization system in this manner, the temperature is raised to 63° C. and the reaction is allowed to proceed for 10 hours. Then, it is cooled to room temperature to obtain a homopolymer solution having a solid concentration of 33% by mass.
  • the homopolymer solution is then cast onto a release liner and dried to form a test sample (sheet homopolymer) having a thickness of about 2 mm. Then, this test sample was punched out into a disk shape with a diameter of 7.9 mm, sandwiched between parallel plates, and subjected to shear strain at a frequency of 1 Hz using a viscoelasticity tester (trade name “ARES”, manufactured by Rheometrics Co., Ltd.). The viscoelasticity is measured in the shear mode at a heating rate of 5°C/min in the region of -70 to 150°C, and the peak top temperature of tan ⁇ is defined as the Tg of the homopolymer.
  • ARES viscoelasticity tester
  • acrylic monomer (A) examples include (meth)acrylic acid esters having a bicyclic aliphatic hydrocarbon ring such as isobornyl (meth)acrylate; dicyclopentanyl (meth)acrylate; , dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-methyl -2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and the like (meth)acrylic acid esters having a tricyclic or higher aliphatic hydrocarbon ring.
  • (meth)acrylic acid esters having a bicyclic aliphatic hydrocarbon ring such as isobornyl (meth)acrylate; dicyclopentanyl (meth)acrylate; ,
  • the proportion of the acrylic monomer (A) in the total amount of 100% by mass of all monomer components constituting the acrylic polymer is preferably 1 to 30% by mass, more preferably 2 to 13% by mass.
  • the proportion of the acrylic monomer (A) in the total amount of 100% by mass of all monomer components constituting the acrylic polymer is preferably 1 to 30% by mass, more preferably 2 to 13% by mass.
  • the above ratio is 1% by mass or more, reworkability is improved.
  • the above proportion is 30% by mass or less, the tan ⁇ peak top value of the pressure-sensitive adhesive layer is high, and the impact resistance and reworkability are excellent.
  • the acrylic polymer is composed (formed) of an acrylic monomer (A) and a (meth)acrylic acid alkyl ester (sometimes referred to as "(meth)acrylic acid alkyl ester (B)") as a monomer component. Polymers are preferred.
  • the (meth)acrylic acid alkyl ester (B) is preferably a (meth)acrylic acid alkyl ester having a linear or branched alkyl group.
  • only 1 type may be used for (meth)acrylic-acid alkylester (B), and 2 or more types may be used for it.
  • the (meth)acrylic acid alkyl ester having a linear or branched alkyl group is not particularly limited, but examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, ( meth)isopropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, (meth)acrylate isopentyl acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, (meth)acrylate ) isononyl acrylate, decyl (me
  • the (meth)acrylic acid alkyl ester having a linear or branched alkyl group has a linear or branched alkyl group having 2 to 7 carbon atoms from the viewpoint of further improving impact resistance.
  • a (meth)acrylic acid alkyl ester having such a compound is preferable, and butyl (meth)acrylate is more preferable. It may also contain methyl (meth)acrylate.
  • the ratio of the (meth)acrylic acid alkyl ester (B) in the total amount of 100% by mass of all the monomer components constituting the acrylic polymer is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 80% by mass or more.
  • the ratio is preferably 99% by mass or less, more preferably 95% by mass or less.
  • the ratio of butyl (meth)acrylate is within the above range.
  • the above acrylic polymer may contain a copolymerizable monomer together with the acrylic monomer (A) and the (meth)acrylic acid alkyl ester (B) as monomer components constituting the polymer. That is, the acrylic polymer may contain a copolymerizable monomer as a structural unit.
  • the above copolymerizable monomers may be used alone or in combination of two or more.
  • a carboxy group-containing monomer and/or an acid anhydride monomer are preferable from the viewpoint of being able to form a pressure-sensitive adhesive layer having good adhesiveness even if it is thin.
  • the carboxy group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid.
  • the acid anhydride monomer include maleic anhydride and itaconic anhydride.
  • the ratio of the carboxy group-containing monomer and/or the acid anhydride monomer in the total amount of 100% by mass of all the monomer components constituting the acrylic polymer is not particularly limited, but is preferably 0.2% by mass or more, More preferably, it is 1% by mass or more.
  • the above ratio is preferably 15% by mass or less, more preferably 10% by mass or less.
  • the acrylic monomer (A) and the (meth)acrylic acid alkyl ester (B) have a good quantitative balance and form a pressure-sensitive adhesive layer having good adhesion even if it is thin. It becomes possible.
  • the copolymerizable monomer may further contain a functional group-containing monomer for the purpose of introducing a cross-linking point into the acrylic polymer or increasing the cohesion of the acrylic polymer.
  • a functional group-containing monomer examples include hydroxyl group-containing monomers, nitrogen atom-containing monomers (excluding acrylic monomers (A)), keto group-containing monomers, alkoxysilyl group-containing monomers, and sulfonic acid group-containing monomers. , phosphate group-containing monomers, and the like. Only one kind of the functional group-containing monomer may be used, or two or more kinds thereof may be used.
  • hydroxy group-containing monomer examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) ) hydroxyalkyl (meth)acrylates such as acrylates; unsaturated alcohols such as vinyl alcohol and allyl alcohol; polypropylene glycol mono(meth)acrylates;
  • Examples of the nitrogen atom-containing monomers include amide group-containing monomers, amino group-containing monomers, and cyano group-containing monomers.
  • Examples of the amide group-containing monomer include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methylolpropane(meth)acrylamide, N -Methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide and the like.
  • amino group-containing monomer examples include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, t-butylaminoethyl (meth)acrylate and the like.
  • cyano group-containing monomer examples include acrylonitrile and methacrylonitrile.
  • keto group-containing monomer examples include diacetone (meth)acrylamide, diacetone (meth)acrylate, vinyl methyl ketone, vinyl ethyl ketone, allyl acetoacetate, and vinyl acetoacetate.
  • alkoxysilyl group-containing monomer examples include 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-( meth)acryloxypropylmethyldiethoxysilane and the like.
  • sulfonic acid group-containing monomer examples include styrenesulfonic acid, allylsulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid, sulfopropyl (meth)acrylate, (meth) ) acryloyloxynaphthalenesulfonic acid and the like.
  • Examples of the phosphoric acid group-containing monomer include 2-hydroxyethyl acryloyl phosphate.
  • the ratio of the functional group-containing monomer in the total amount of 100% by mass of all the monomer components constituting the acrylic polymer is, for example, 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 5% by mass. % or more, or 10% by mass or more.
  • the above ratio may be, for example, 40% by mass or less, 20% by mass or less, or may be substantially absent.
  • substantially not included refers to unintentional inclusion, such as unavoidable mixing, rather than active blending. It is 0.01% by mass or less.
  • the copolymerizable monomer may further contain other monomers.
  • the other monomers include vinyl ester monomers such as vinyl acetate, vinyl propionate, and vinyl laurate; aromatic vinyl compounds such as styrene, substituted styrene ( ⁇ -methylstyrene, etc.), and vinyl toluene; ethylene, propylene.
  • the proportion of the other monomers in the total amount of 100% by mass of all monomer components constituting the acrylic polymer may be, for example, 0.05% by mass or more, or 0.5% by mass or more.
  • the above ratio may be, for example, 20% by mass or less, 10% by mass or less, 5% by mass or less, or may be substantially absent.
  • the acrylic polymer may contain, as a monomer component constituting the polymer, a polyfunctional monomer copolymerizable with the monomer component forming the acrylic polymer, in order to form a crosslinked structure in the polymer skeleton.
  • the polyfunctional monomer include hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, penta Polyfunctional (meth)acrylates such as erythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate; epoxy (meth)acrylates (e.g., poly glycidyl (meth)acrylate), polyester (meth)acrylate, urethane
  • the acrylic polymer may have a structure derived from an acrylic oligomer.
  • examples of such an acrylic polymer include a polymer containing an acrylic polymer (sometimes referred to as "acrylic polymer (C)") and a polymerization reaction product of a composition containing the acrylic oligomer. Having a structural part derived from an acrylic oligomer results in higher breaking strain and better reworkability.
  • the composition containing the acrylic oligomer may further contain a monomer component (sometimes referred to as "monomer component (D)").
  • a monomer component sometimes referred to as "monomer component (D)"
  • Each of the acrylic polymer (C), the acrylic oligomer, and the monomer component (D) may be used alone or in combination of two or more.
  • the acrylic polymer may be a polymerization reaction product obtained by polymerizing a composition containing one or more selected from the group consisting of an acrylic partial polymer, an acrylic oligomer, and a monomer component (D). good.
  • the monomer component (D) contains at least an acrylic monomer.
  • the above-mentioned "partioned "partially polymerized product” may also be referred to as "prepolymer", “syrup", and the like.
  • Each of the acrylic partial polymer, acrylic oligomer, and monomer component (D) may be used alone or in combination of two or more.
  • the acrylic polymer (C), the acrylic partial polymer, and the acrylic oligomer are all compounds composed of an acrylic monomer as an essential monomer component.
  • the acrylic monomer and the monomer component (D), which are monomer components constituting the acrylic polymer (C), the acrylic partial polymer, and the acrylic oligomer, are exemplified as the monomer components constituting the acrylic polymer. and those described.
  • the acrylic polymer (C) may be a polymer that forms the base polymer alone, or may be a polymer that forms the base polymer together with the polymerization reaction product of the composition containing the acrylic oligomer.
  • the acrylic polymer (C) contains an acrylic monomer as a structural unit.
  • the acrylic polymer (C) preferably contains a (meth)acrylic acid alkyl ester (B) as a structural unit.
  • the (meth)acrylic acid alkyl ester (B) is preferably a (meth)acrylic acid alkyl ester having a linear or branched alkyl group having 2 to 7 carbon atoms, more preferably butyl (meth)acrylate. is.
  • the acrylic monomer contained as the structural unit may be of one type or two or more types.
  • the proportion of the (meth)acrylic acid alkyl ester (B) in 100% by mass of the total amount of all monomer components constituting the acrylic polymer (C) is preferably 50% by mass or more, more preferably 60% by mass. above, more preferably at least 65% by mass.
  • the ratio is preferably 99% by mass or less, more preferably 95% by mass or less.
  • the acrylic polymer (C) may contain the above copolymerizable monomer as a structural unit.
  • a carboxy group-containing monomer and/or acid Anhydride monomers are preferred.
  • the acrylic polymer (C) may contain the acrylic monomer (A) as a structural unit.
  • the ratio of the carboxy group-containing monomer and/or the acid anhydride monomer in the total amount of 100% by mass of all monomer components constituting the acrylic polymer (C) is not particularly limited, but is preferably 0.2% by mass or more. It is preferably 1% by mass or more, more preferably 1% by mass or more. The proportion is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.
  • a pressure-sensitive adhesive layer is formed that has a good quantitative balance with the (meth)acrylic acid alkyl ester (B), has excellent impact resistance, and has good adhesion even if it is thin. It becomes possible.
  • the acrylic partial polymer is obtained by polymerizing the monomer components at a polymerization conversion rate of 95% by mass or less, for example.
  • the polymerization conversion rate is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, even more preferably 40% by mass or less, and particularly preferably 35% by mass or less.
  • the polymerization conversion rate is preferably 1% by mass or more, more preferably 5% by mass or more.
  • the above acrylic partial polymer contains an acrylic monomer as a structural unit.
  • the above acrylic partial polymer preferably contains a (meth)acrylic acid alkyl ester (B) as a structural unit.
  • the (meth)acrylic acid alkyl ester (B) is preferably a (meth)acrylic acid alkyl ester having a linear or branched alkyl group having 2 to 7 carbon atoms, more preferably butyl (meth)acrylate. is.
  • the acrylic monomer contained as the structural unit may be of one type or two or more types.
  • the proportion of the (meth)acrylic acid alkyl ester (B) in 100% by mass of the total amount of all monomer components constituting the acrylic partial polymer is preferably 50% by mass or more, more preferably 60% by mass. above, more preferably at least 65% by mass.
  • the ratio is preferably 99% by mass or less, more preferably 95% by mass or less.
  • the acrylic partial polymer may contain the copolymerizable monomer as a structural unit.
  • copolymerizable monomers a carboxy group-containing monomer and/or acid Anhydride monomers are preferred.
  • the ratio of the carboxy group-containing monomer and/or the acid anhydride monomer in the total amount of 100% by mass of all the monomer components constituting the acrylic partial polymer is not particularly limited, but is preferably 0.2% by mass or more. It is preferably 1% by mass or more, more preferably 1% by mass or more. The proportion is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.
  • the above ratio is within the above range, the quantitative balance between the acrylic monomer (A) and the (meth)acrylic acid alkyl ester (B) is good, the impact resistance is excellent, and the adhesion is good even if the film is thin. It becomes possible to form a pressure-sensitive adhesive layer having
  • the acrylic partial polymer may contain an acrylic monomer (A) as a structural unit.
  • the proportion of the acrylic monomer (A) in the total amount of 100% by mass of all the monomer components constituting the partially polymerized product is not particularly limited, but is preferably 3% by mass or more, more preferably 10% by mass. % by mass or more.
  • the ratio is preferably 40% by mass or less, more preferably 30% by mass or less.
  • the acrylic oligomer preferably has a weight average molecular weight of 2,500 to 10,000, more preferably 3,000 to 8,000.
  • the said weight average molecular weight can be calculated
  • the above acrylic oligomer contains an acrylic monomer as a structural unit.
  • the acrylic oligomer preferably contains an acrylic monomer (A) as a structural unit.
  • the acrylic monomer contained as the structural unit may be of one type or two or more types.
  • the acrylic monomer (A) accounts for preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 55% by mass in the total amount of 100% by mass of all monomer components constituting the acrylic oligomer. % by mass or more.
  • the ratio is preferably 90% by mass or less, more preferably 80% by mass or less.
  • the acrylic oligomer preferably contains a (meth)acrylic acid alkyl ester (B) as a structural unit.
  • a (meth)acrylic acid alkyl ester (B) methyl methacrylate (MMA) is preferable.
  • the proportion of the (meth)acrylic acid alkyl ester (B) in all monomer components constituting the acrylic oligomer is preferably 10% by mass or more, more preferably 20% by mass or more.
  • the proportion is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less.
  • the acrylic oligomer may contain the copolymerizable monomer as a structural unit.
  • the content of the acrylic oligomer is preferably 0.5 to 35 parts by mass, more preferably 2 parts by mass, with respect to the total amount of 100 parts by mass of the acrylic polymer (C) and/or the acrylic partial polymer. to 20 parts by mass, more preferably 4 to 10 parts by mass.
  • the storage elastic modulus G' tends to be high and the breaking stress tends to be high, resulting in better reworkability.
  • the acrylic polymer and the acrylic polymer (C) are obtained by polymerizing a composition containing one or more selected from the group consisting of the acrylic partial polymer, the acrylic oligomer, and the monomer component (D). be done.
  • These polymerization methods are not particularly limited, but include, for example, a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a thermal polymerization method, and a polymerization method by active energy ray irradiation (active energy ray polymerization method).
  • the bulk polymerization method, the thermal polymerization method, and the active energy ray polymerization method are preferable from the viewpoints of the transparency of the pressure-sensitive adhesive layer and the cost.
  • various general solvents may be used in the polymerization of the above-mentioned monomer components.
  • the solvent include esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; cyclohexane, methylcyclohexane and the like. alicyclic hydrocarbons; and organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone.
  • a solvent may use only 1 type, and may use 2 or more types.
  • a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator (photoinitiator) may be used depending on the type of polymerization reaction.
  • a polymerization initiator may use only 1 type, and may use 2 or more types.
  • the thermal polymerization initiator is not particularly limited. , benzoyl peroxide, hydrogen peroxide, etc.), substituted ethane-based initiators such as phenyl-substituted ethane, aromatic carbonyl compounds, redox-based polymerization initiators, and the like.
  • the azo polymerization initiator disclosed in JP-A-2002-69411 is preferable.
  • the azo polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis(2-methylpropionate)dimethyl, 4,4'-azobis-4-cyanovaleric acid and the like.
  • the amount of the thermal polymerization initiator to be used may be a normal amount, for example, 0.005 to 1 part by mass, preferably 0.01 to 1 part by mass based on 100 parts by mass of the monomer component. can do.
  • the photopolymerization initiator is not particularly limited. Examples include active oxime-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzyl-based photopolymerization initiators, benzophenone-based photopolymerization initiators, ketal-based photopolymerization initiators, and thioxanthone-based photopolymerization initiators. Other examples include acylphosphine oxide photopolymerization initiators and titanocene photopolymerization initiators.
  • benzoin ether-based photopolymerization initiator examples include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one, anisole methyl ether and the like.
  • acetophenone-based photopolymerization initiator examples include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 4-phenoxydichloroacetophenone, 4-(t-butyl ) and dichloroacetophenone.
  • Examples of the ⁇ -ketol-based photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one, and the like. be done.
  • Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride.
  • Examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,1-propanedione-2-(O-ethoxycarbonyl)-oxime.
  • Examples of the benzoin-based photopolymerization initiator include benzoin.
  • Examples of the benzyl-based photopolymerization initiator include benzyl.
  • benzophenone-based photopolymerization initiator examples include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, ⁇ -hydroxycyclohexylphenyl ketone, and the like.
  • ketal-based photopolymerization initiator examples include benzyl dimethyl ketal.
  • Examples of the thioxanthone-based photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone.
  • Examples of the acylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.
  • titanocene photopolymerization initiator examples include bis( ⁇ 5 -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl ) and titanium.
  • the amount of the photopolymerization initiator used may be a normal amount, for example, 0.01 to 3 parts by mass, preferably 0.1 to 1.5 parts by mass with respect to 100 parts by mass of the monomer component. You can choose from
  • the above acrylic polymer may be crosslinked with a crosslinking agent.
  • a cross-linking agent By using a cross-linking agent, it is possible to form a cross-linked structure in the acrylic polymer in the acrylic pressure-sensitive adhesive layer and control the gel fraction.
  • the cross-linking agent is appropriately selected according to the functional groups in the side chains of the acrylic partial polymer, for example.
  • the above-mentioned cross-linking agent only one kind of the above-mentioned cross-linking agent may be used, or two or more kinds thereof may be used.
  • the cross-linking agent is not particularly limited. cross-linking agent, metal salt cross-linking agent, carbodiimide cross-linking agent, oxazoline cross-linking agent, aziridine cross-linking agent, amine cross-linking agent, hydrazine cross-linking agent, silicone cross-linking agent, silane cross-linking agent (silane coupling agent), etc. mentioned.
  • the content of the cross-linking agent is not particularly limited, but is preferably 0.001 to 20 parts by mass, more preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the total amount of the monomer components constituting the acrylic polymer. parts, particularly preferably 0.5 to 10 parts by mass.
  • the above isocyanate-based cross-linking agent is a compound (polyfunctional isocyanate compound) having an average of two or more isocyanate groups per molecule.
  • examples of the isocyanate-based cross-linking agent include aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates.
  • aliphatic polyisocyanates examples include 1,2-ethylene diisocyanate; tetramethylene diisocyanates such as 1,2-tetramethylene diisocyanate, 1,3-tetramethylene diisocyanate and 1,4-tetramethylene diisocyanate; - hexamethylene diisocyanates such as hexamethylene diisocyanate, 1,3-hexamethylene diisocyanate, 1,4-hexamethylene diisocyanate, 1,5-hexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,5-hexamethylene diisocyanate; 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, lysine diisocyanate and the like.
  • alicyclic polyisocyanates examples include isophorone diisocyanate; cyclohexyl diisocyanates such as 1,2-cyclohexyl diisocyanate, 1,3-cyclohexyl diisocyanate and 1,4-cyclohexyl diisocyanate; 1,2-cyclopentyl diisocyanate, 1,3 - cyclopentyl diisocyanate such as cyclopentyl diisocyanate; hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and the like.
  • aromatic polyisocyanates examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, and 2,2′-diphenylmethane diisocyanate.
  • isocyanate-based cross-linking agent examples include trimethylolpropane/tolylene diisocyanate adduct (trade name “Coronate L”, manufactured by Tosoh Corporation), trimethylolpropane/hexamethylene diisocyanate adduct (trade name “Coronate HL ”, manufactured by Tosoh Corporation), trimethylolpropane/xylylene diisocyanate adduct (trade name “Takenate D-110N”, manufactured by Mitsui Chemicals, Inc.).
  • the content of the isocyanate-based cross-linking agent when using the isocyanate-based cross-linking agent as the cross-linking agent is not particularly limited, but is 0.5 parts by mass with respect to 100 parts by mass of the total amount of the monomer components constituting the acrylic polymer.
  • the above is preferable, more preferably 1 part by mass or more, and still more preferably 1.5 parts by mass or more.
  • the content is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less.
  • epoxy-based cross-linking agent examples include N,N,N',N'-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis(N,N-diglycidyl aminomethyl)cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether , glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether,
  • the content of the epoxy-based cross-linking agent when using the epoxy-based cross-linking agent as the cross-linking agent is not particularly limited, it exceeds 0 parts by mass with respect to the total amount of 100 parts by mass of the monomer components constituting the acrylic polymer. is preferably 1 part by mass or less, more preferably 0.001 to 0.5 parts by mass, still more preferably 0.002 to 0.2 parts by mass, still more preferably 0.005 to 0.1 parts by mass, particularly preferably It is 0.008 to 0.05 parts by mass.
  • any one that generates radical active species by heat and promotes cross-linking of the base polymer can be used as appropriate. It is preferred to use a peroxide with a temperature of 80-160°C, more preferably a peroxide with a temperature of 90-140°C.
  • peroxide-based crosslinking agent examples include di(2-ethylhexyl) peroxydicarbonate (1-minute half-life temperature: 90.6° C.), di(4-t-butylcyclohexyl) peroxydicarbonate (1 minute half-life temperature: 92.1 ° C.), di-sec-butyl peroxydicarbonate (1 minute half-life temperature: 92.4 ° C.), t-butyl peroxyneodecanoate (1 minute half-life temperature: 103 .5 ° C.), t-hexyl peroxypivalate (1 minute half-life temperature: 109.1 ° C.), t-butyl peroxypivalate (1 minute half-life temperature: 110.3 ° C.), dilauroyl peroxide ( 1 minute half-life temperature: 116.4° C.), di-n-octanoyl peroxide (1 minute half-life temperature: 117.4° C.), 1,1,3,3-tetramethylbut
  • the half-life of the peroxide-based cross-linking agent is an index that represents the decomposition rate of the peroxide, and refers to the time it takes for the residual amount of the peroxide to halve.
  • the decomposition temperature for obtaining a half-life at an arbitrary time and the half-life time at an arbitrary temperature are described in the manufacturer's catalog etc. For example, NOF Corporation's "Organic Peroxide Catalog 9th Edition ( May 2003)”.
  • HPLC high performance liquid chromatography
  • the content of the cross-linking agent when a peroxide-based cross-linking agent is used as the cross-linking agent is not particularly limited. preferably 0.02 to 2 parts by mass, more preferably 0.05 to 1 part by mass.
  • an organic cross-linking agent or a polyfunctional metal chelate may be used in combination.
  • Polyfunctional metal chelates are those in which polyvalent metals are covalently or coordinately bonded to organic compounds.
  • Polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, and Ti. mentioned.
  • Atoms in the organic compounds that are covalently or coordinately bonded include oxygen atoms, and the organic compounds include alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds, ketone compounds, and the like.
  • the above-mentioned cross-linking agent includes an isocyanate-based cross-linking agent. Further, it is more preferable to contain another cross-linking agent together with the isocyanate-based cross-linking agent.
  • an epoxy-based cross-linking agent is preferable.
  • the pressure-sensitive adhesive layer of the present invention can have an appropriate hardness.
  • the apparent cohesive strength of the pressure-sensitive adhesive layer can be increased, the breaking stress and breaking strain can be set within appropriate ranges, and both impact resistance and reworkability can be excellent.
  • Only one type of the filler may be used, or two or more types may be used.
  • the shape of the filler is particulate.
  • the average particle diameter of the filler is 80 ⁇ m or less, preferably 60 ⁇ m or less, more preferably 40 ⁇ m or less.
  • the average particle size is preferably 0.5 ⁇ m or more, more preferably 1.5 ⁇ m or more, and still more preferably 10 ⁇ m or more.
  • the said average particle diameter is a median diameter (D50) measured by a dynamic light-scattering method.
  • D50 median diameter
  • the filler may be either organic or inorganic.
  • materials constituting the above inorganic substances include metals such as copper, silver, gold, platinum, nickel, aluminum, chromium, iron, and stainless steel; aluminum oxide, silicon oxide (silicon dioxide), titanium oxide, zirconium oxide, and zinc oxide.
  • tin oxide copper oxide, nickel oxide and other metal oxides
  • aluminum hydroxide, boehmite magnesium hydroxide, calcium hydroxide, zinc hydroxide, silicic acid, iron hydroxide, copper hydroxide, barium hydroxide, zirconium oxide water hydrates, tin oxide hydrates, basic magnesium carbonate, hydrotalcite, dawsonite, borax, zinc borate and other metal hydroxides and hydrated metal compounds
  • nitrides such as aluminum nitride, silicon nitride, boron nitride, gallium nitride
  • carbonates such as calcium carbonate
  • titanates such as barium titanate and potassium titanate
  • carbon black, carbon tube (carbon nanotube), carbon fiber carbonaceous materials such as diamond
  • inorganic materials such as glass
  • natural raw material particles such as volcanic shirasu, clay, sand, and the like.
  • materials constituting the above organic matter include polystyrene, acrylic resin (e.g., polymethyl methacrylate), phenol resin, benzoguanamine resin, urea resin, silicone resin, polyester, polyurethane, polyethylene, polypropylene, polyamide (e.g., nylon), and polyimide. , and polymers such as polyvinylidene chloride.
  • the filler may have a hollow body structure.
  • the hollow portion (internal space of the hollow particles) of the filler having the hollow body structure may be in a vacuum state or may be filled with a medium.
  • the medium include inert gases such as nitrogen and argon, air, and volatile solvents.
  • a filler whose surface is composed of an organic or inorganic substance other than an acrylic resin and a filler having a hollow body structure are preferable. These fillers have little interaction with the acrylic component in the acrylic pressure-sensitive adhesive layer or have a hollow body structure, so that the pressure-sensitive adhesive layer is less likely to break when stretched, and is more excellent in reworkability.
  • the volume ratio of the filler to the total mass of the adhesive layer of the present invention is preferably 0.01 ⁇ 10 ⁇ 2 to 20 ⁇ 10 ⁇ 2 cm 3 /g, more preferably 0.5 ⁇ 10 ⁇ 2 to 10 ⁇ 10 ⁇ 2 cm 3 /g, more preferably 1 ⁇ 10 ⁇ 2 to 7 ⁇ 10 ⁇ 2 cm 3 /g.
  • the volume ratio is within the above range, the breaking stress and breaking strain are within appropriate ranges, and both impact resistance and reworkability are excellent. Further, when the volume ratio is 20 ⁇ 10 ⁇ 2 cm 3 /g or less, the initial adhesive strength to the adherend is more excellent.
  • the volume ratio of the filler is calculated by [volume of filler in adhesive layer (cm 3 )/total mass of adhesive layer (g)].
  • the content of the filler in the pressure-sensitive adhesive layer of the present invention is preferably more than 0 parts by mass and 30 parts by mass or less, more preferably 0.008 to 10 parts by mass, with respect to 100 parts by mass as the total amount of the base polymer. More preferably, it is 0.4 to 6 parts by mass.
  • the breaking stress and breaking strain are within appropriate ranges, and both impact resistance and reworkability are excellent.
  • the proportion of the filler in the adhesive layer of the present invention is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass, relative to 100% by mass of the total amount of the adhesive layer.
  • the hardness of the pressure-sensitive adhesive layer can be made appropriate. Moreover, it is excellent in reworkability.
  • the adhesive layer of the present invention preferably further contains a tackifying resin.
  • a tackifying resin With a tackifying resin, the adhesive layer tends to have better adhesion even though it is thinner.
  • the pressure-sensitive adhesive layer contains an acrylic polymer as a base polymer and a tackifying resin, it has excellent adhesion to the adherend and is more difficult to peel off.
  • the tackifying resin examples include phenol-based tackifying resins, terpene-based tackifying resins, rosin-based tackifying resins, hydrocarbon-based tackifying resins, epoxy-based tackifying resins, polyamide-based tackifying resins, and elastomer-based tackifying resins. resins, ketone-based tackifying resins, and the like.
  • Other examples of the tackifier resin include low polymers of (meth)acrylic acid alkyl esters such as low polymers of dicyclopentanyl methacrylate (DCPMA) and methyl methacrylate (MMA). Only one type of the tackifying resin may be used, or two or more types may be used.
  • phenol-based tackifier resin examples include terpene phenol resins, hydrogenated terpene phenol resins, alkylphenol resins, and rosin phenol resins.
  • the terpene phenol resin is a polymer containing a terpene residue and a phenol residue, and is a copolymer of a terpene and a phenol compound (terpene-phenol copolymer resin), a homopolymer or a copolymer of a terpene.
  • Phenol-modified ones phenol-modified terpene resins
  • terpenes constituting the terpene phenol resin include monoterpenes such as ⁇ -pinene, ⁇ -pinene, and limonene (d-form, l-form, d/l-form (dipentene), etc.).
  • the above hydrogenated terpene phenol resin is a resin having a structure obtained by hydrogenating the above terpene phenol resin.
  • the above alkylphenol resin is a resin (oily phenolic resin) obtained from alkylphenol and formaldehyde. Examples of the alkylphenol resin include novolac type and resol type.
  • the rosin phenol resin is a phenol-modified rosin or various rosin derivatives described later.
  • the rosin phenol resin can be obtained, for example, by adding phenol to rosins or various rosin derivatives described later with an acid catalyst and thermally polymerizing them.
  • the terpene-based tackifying resin examples include polymers of terpenes (typically monoterpenes) such as ⁇ -pinene, ⁇ -pinene, d-limonene, l-limonene and dipentene.
  • the terpene polymer may be a single terpene homopolymer or a copolymer of two or more terpenes. Examples of homopolymers of terpenes include ⁇ -pinene polymer, ⁇ -pinene polymer, and dipentene polymer.
  • the modified terpene-based tackifying resin is a modified terpene resin (modified terpene resin). Examples of the modified terpene resins include styrene-modified terpene resins and hydrogenated terpene resins.
  • the rosin-based tackifying resins include rosins and rosin derivative resins.
  • the rosins include unmodified rosins (fresh rosins) such as gum rosin, wood rosin and tall oil rosin; disproportionated rosin, polymerized rosin, other chemically modified rosins, etc.).
  • the rosin derivative resin include derivatives of the above rosins.
  • rosin derivative resin examples include rosin esters such as an unmodified rosin ester that is an ester of an unmodified rosin and an alcohol, and a modified rosin ester that is an ester of a modified rosin and an alcohol; Unsaturated fatty acid-modified rosins modified with fatty acids; Unsaturated fatty acid-modified rosin esters obtained by modifying rosin esters with unsaturated fatty acids; Rosins or rosin alcohols obtained by reducing the carboxy groups of the above rosin derivatives; Rosins Alternatively, metal salts of the various rosin derivatives described above may be used. Specific examples of the rosin esters include unmodified rosin or modified rosin methyl ester, triethylene glycol ester, glycerin ester, pentaerythritol ester, and the like.
  • hydrocarbon-based tackifying resin examples include aliphatic hydrocarbon resins, aromatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, and aliphatic/aromatic petroleum resins (styrene-olefin copolymers, etc.). , aliphatic/alicyclic petroleum resins, hydrogenated hydrocarbon resins, coumarone-based resins, and coumarone-indene-based resins.
  • the content of the tackifying resin in the pressure-sensitive adhesive layer of the present invention is not particularly limited, but for example, 1 part by mass or more (for example, 1 to 100 parts by mass), preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more.
  • the content is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, from the viewpoint of excellent heat-resistant cohesive strength.
  • the adhesive layer of the present invention may contain a coloring agent.
  • the pressure-sensitive adhesive layer is colored by containing a coloring agent, and the double-sided pressure-sensitive adhesive sheet of the present invention is excellent in visibility and design.
  • the coloring agent may be a pigment or a dye. Examples of coloring agents include black coloring agents, cyan coloring agents, magenta coloring agents, and yellow coloring agents. A black colorant is preferable from the viewpoint of better visibility and light-shielding properties.
  • the coloring agent may contain only one kind, or may contain two or more kinds.
  • the proportion of the coloring agent in the pressure-sensitive adhesive layer of the present invention is preferably 0.5 to 10% by weight, more preferably 1 to 6% by weight, based on 100% by weight of the total amount of the pressure-sensitive adhesive layer.
  • black colorants include carbon black, carbon nanotubes, graphite (graphite), copper oxide, manganese dioxide, azo pigments such as azomethine azo black, aniline black, perylene black, titanium black, cyanine black, activated carbon, and ferrite. , magnetite, chromium oxide, iron oxide, molybdenum disulfide, complex oxide-based black dyes, anthraquinone-based organic black dyes, and azo-based organic black dyes.
  • carbon black include furnace black, channel black, acetylene black, thermal black and lamp black.
  • a black colorant C.I. I. Solvent Black 3, 7, 22, 27, 29, 34, 43, 70; C.I. I.
  • cyan colorant for example, C.I. I. Solvent Blue 25, 36, 60, 70, 93, 95; C.I. I. Acid Blue 6, 45; C.I. I. Pigment Blue 1, 2, 3, 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16, 17, 17:1, 18, 22, 25, 56, 60, 63, 65, 66; C.I. I. Bat Blue 4; 60, C.I. I. Pigment Green 7 and the like.
  • magenta colorant for example, C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 52, 58, 63, 81, 82, 83, 84, 100, 109, 111, 121, 122; C.I. I. disperse thread 9; C.I. I. Solvent Violet 8, 13, 14, 21, 27; C.I. I. Disperse Violet 1; C.I. I. Basic red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; C.I. I. Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28 and the like.
  • magenta colorants include C.I. I.
  • yellow colorants examples include C.I. I. Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162; I. Pigment Orange 31, 43; C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 24, 34, 35, 37, 42, 53, 55, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 108, 109, 110, 113, 114, 116, 117, 120, 128, 129, 133, 138, 139 , 147, 150, 151, 153, 154, 155, 156, 167, 172, 173, 180, 185, 195; I. Bat Yellow 1, 3, 20 and the like.
  • the pressure-sensitive adhesive layer of the present invention may optionally further contain a cross-linking accelerator, an anti-aging agent, an antioxidant, a plasticizer, a softening agent, a surfactant, an antistatic agent, a surface lubricant, a leveling agent, and a light stabilizer.
  • Additives such as agents, ultraviolet absorbers, polymerization inhibitors, foil-like materials, and rust preventives may be contained within a range that does not impair the effects of the present invention. Only one kind of the above additives may be used, or two or more kinds thereof may be used.
  • the pressure-sensitive adhesive layer of the present invention preferably has a tan ⁇ peak top between -20 and 0°C.
  • the peak top value is preferably 0.8 or more, more preferably 1.2 or more, and still more preferably 1.5 or more. Having a peak top of tan ⁇ between ⁇ 20 and 0° C. provides excellent impact resistance when, for example, a member to which a double-sided pressure-sensitive adhesive sheet is applied is dropped at high speed. When the peak top value is 0.8 or more, the impact resistance and reworkability are further improved.
  • the adhesive layer of the present invention preferably has a storage modulus G' at 23°C of 0.09 MPa or more, more preferably 0.10 MPa or more, and still more preferably 0.15 MPa or more.
  • a storage modulus G' at 23°C of 0.09 MPa or more, more preferably 0.10 MPa or more, and still more preferably 0.15 MPa or more.
  • the storage elastic modulus G' is 0.09 MPa or more, it has an appropriate hardness at room temperature and is more excellent in reworkability.
  • the storage elastic modulus G' is preferably 0.25 MPa or less.
  • the storage modulus G' can be calculated using a dynamic viscoelasticity measurement (DMA) device.
  • DMA dynamic viscoelasticity measurement
  • the pressure-sensitive adhesive layer of the present invention may be in any form, such as an emulsion type, a solvent type (solution type), an active energy ray-curable type, or a heat-melting type (hot-melt type).
  • solvent-type and active-energy-ray-curable adhesive compositions are preferred because they facilitate the formation of an adhesive layer with excellent productivity.
  • the active energy rays include ionizing radiation such as ⁇ -rays, ⁇ -rays, ⁇ -rays, neutron beams and electron beams, and ultraviolet rays, with ultraviolet rays being particularly preferred. That is, the active energy ray-curable pressure-sensitive adhesive layer is preferably an ultraviolet-curable pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive layer of the present invention can be formed, for example, by coating (coating) a pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer on a release liner and drying and curing the resulting pressure-sensitive adhesive composition layer, or It can be produced by applying (coating) the pressure-sensitive adhesive composition onto a release liner and irradiating the resulting pressure-sensitive adhesive composition layer with active energy rays to cure it. Moreover, you may heat-dry further as needed.
  • the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer of the present invention includes, for example, an acrylic pressure-sensitive adhesive composition containing an acrylic polymer as an essential component, or the acrylic partial polymer, the acrylic oligomer, or the acrylic and an acrylic pressure-sensitive adhesive composition containing a monomer mixture containing a system monomer as an essential component.
  • the former includes, for example, a so-called solvent-type acrylic pressure-sensitive adhesive composition. Also. Examples of the latter include so-called active energy ray-curable acrylic pressure-sensitive adhesive compositions.
  • the pressure-sensitive adhesive composition preferably contains an acrylic polymer (C) and/or an acrylic partial polymer and a filler, and may further contain the acrylic oligomer.
  • the pressure-sensitive adhesive composition further contains a cross-linking agent.
  • it may contain a tackifying resin, a coloring agent, and the like.
  • the double-sided pressure-sensitive adhesive sheet of the invention is composed of the pressure-sensitive adhesive layer of the invention.
  • the thickness of the double-sided pressure-sensitive adhesive sheet is 500 ⁇ m or less, preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less. When the thickness is 500 ⁇ m or less, the thickness of the double-sided pressure-sensitive adhesive sheet can be reduced.
  • the thickness of the double-sided pressure-sensitive adhesive sheet is preferably over 10 ⁇ m, more preferably 30 ⁇ m or more, and even more preferably 50 ⁇ m or more. When the thickness is more than 10 ⁇ m, the impact resistance and reworkability are more excellent.
  • the thickness of the double-sided pressure-sensitive adhesive sheet refers to the thickness from one pressure-sensitive adhesive surface to the other pressure-sensitive adhesive surface, that is, the thickness of the pressure-sensitive adhesive body, and does not include the release liner.
  • the breaking stress of the double-sided pressure-sensitive adhesive sheet of the present invention is 0.5 MPa or higher, preferably 0.7 MPa or higher, more preferably 0.9 MPa or higher, and even more preferably 1.0 MPa or higher.
  • the breaking stress is preferably 3.0 MPa or less, more preferably 2.0 MPa or less.
  • the breaking stress is 3.0 MPa or less, the impact resistance and reworkability are excellent.
  • the above breaking stress is a value measured under the conditions of a sample size of 40 mm ⁇ 40 mm, a thickness of about 0.2 mm, a distance between chucks of 10 mm, and a tensile speed of 50 mm/min under an environment of 23° C. and 50% RH.
  • the breaking strain of the double-sided pressure-sensitive adhesive sheet of the present invention is 600% or more, preferably 1000% or more, more preferably 1300% or more, and still more preferably 1500% or more.
  • the above breaking strain is a value measured under the conditions of a sample size of 40 mm ⁇ 40 mm, a thickness of about 0.2 mm, a distance between chucks of 40 mm, and a tensile speed of 50 mm/min under an environment of 23° C. and 50% RH.
  • the double-sided pressure-sensitive adhesive sheet of the present invention preferably has an energy (load x height) before one of the stainless steel plates is peeled off, as measured by the following DuPont impact test, and is preferably 0.1 or more. It is preferably 0.2 or more, more preferably 0.3 or more.
  • ⁇ Shock resistance test> A frame-shaped double-sided adhesive sheet with an outer diameter of 24.5 mm square and a width of 2 mm was placed on a stainless steel plate with a hole in the center of a square with an outer diameter of 2 mm and an outer diameter of 50 mm, and a stainless steel plate with a square with an outer diameter of 3 mm and an outer diameter of 25 mm.
  • the weight and height of the drop weight on the above evaluation sample were changed by 50 mm from 50 to 500 mm at 100 g, changed by 50 mm from 350 to 500 mm at 150 g, and 400 to 500 mm at 200 g.
  • the energy is changed by 50 mm from 350 to 500 mm, and the energy is increased until peeling occurs.
  • the energy that has already been evaluated is not tested, and the load and height are set so that the amount of energy does not overlap. After that, the energy until at least one of the stainless steel plates peels off is calculated by multiplying the load by the height.
  • the double-sided pressure-sensitive adhesive sheet of the present invention preferably has a 180° peel strength (adhesive strength to SUS plate) to a stainless steel plate (SUS plate) of 20 N/25 mm or more, more preferably, measured according to JISZ0237 (2000). is 25 N/25 mm or more, more preferably 30 N/25 mm or more. When the adhesion to SUS is 20 N/25 mm or more, good initial adhesion to adherends is exhibited.
  • the adhesive strength to SUS is preferably 50 N/25 mm or less, more preferably 45 N/25 mm or less, in order to achieve excellent reworkability.
  • the double-sided pressure-sensitive adhesive sheet may have a release liner attached to the surface (adhesive surface) of the pressure-sensitive adhesive layer until use.
  • the adhesive surfaces on both sides of the double-sided pressure-sensitive adhesive sheet may be protected by two release liners, respectively, or one release liner having release surfaces on both sides is wound into a roll. It may be protected in a form (wound body).
  • a release liner is used as a protective material for the pressure-sensitive adhesive layer, and is peeled off when applied to an adherend. Note that the release liner may not necessarily be provided.
  • a conventional release paper or the like can be used, and is not particularly limited. etc.
  • the base material having the release treatment layer include plastic films and paper surface-treated with release agents such as silicone, long-chain alkyl, fluorine, and molybdenum sulfide.
  • the fluorine-based polymer in the low-adhesive substrate made of the fluorine polymer include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chloro fluoroethylene-vinylidene fluoride copolymer and the like.
  • the non-polar polymer include olefin resins (eg, polyethylene, polypropylene, etc.).
  • the release liner can be formed by a known or commonly used method. Also, the thickness of the release liner is not particularly limited.
  • the double-sided pressure-sensitive adhesive sheet is preferably for attaching to electrical and electronic members, which is used by being attached to members provided in electrical and electronic equipment.
  • the above-mentioned double-sided pressure-sensitive adhesive sheet is particularly preferably used for bonding parts provided in electrical and electronic equipment to both adhesive surfaces of the double-sided pressure-sensitive adhesive sheet, i.e., for fixing members to each other in electrical and electronic equipment.
  • the double-sided pressure-sensitive adhesive sheet may be used for fixing the members together or temporarily fixing them. For example, when a double-sided adhesive sheet is used for fixing or temporarily fixing parts provided in electrical and electronic equipment, there are cases in which it is necessary to peel off the double-sided adhesive sheet and rework due to a problem in attaching the double-sided adhesive sheet.
  • the double-sided pressure-sensitive adhesive sheet must be peeled off in order to repair, replace, inspect, recycle, or the like a member having an adherend to which the double-sided pressure-sensitive adhesive sheet is attached.
  • the double-sided pressure-sensitive adhesive sheet is used, for example, for fixing or temporarily fixing parts (members) provided in electrical and electronic equipment, the frequency of removing the double-sided pressure-sensitive adhesive sheet is particularly high.
  • the above-mentioned double-sided pressure-sensitive adhesive sheet is preferably used by pasting the outer frames of optical members (especially electrical and electronic devices) together. Therefore, the double-sided pressure-sensitive adhesive sheet can be preferably used even if it has a width of 5 mm or less, preferably 3 mm or less.
  • Electric and electronic equipment refers to equipment that corresponds to at least either electrical equipment or electronic equipment.
  • Examples of the electric/electronic devices include image display devices such as liquid crystal displays, electroluminescence displays, and plasma displays, and mobile electronic devices.
  • Examples of the portable electronic devices include mobile phones, smartphones, tablet computers, notebook computers, and various wearable devices (for example, wrist wear types that are worn on the wrist like wristwatches, clips, straps, etc. that are attached to a part of the body) Modular type to be worn, eyewear type including glasses type (monocular type and binocular type, including head-mounted type), clothing type that can be attached to shirts, socks, hats, etc.
  • the term “portable” means not only being able to be carried but also having a level of portability that allows an individual (a typical adult) to carry it relatively easily. shall mean.
  • the double-sided pressure-sensitive adhesive sheet is used, for example, so that the pressure-sensitive adhesive layer adheres to the member of the portable electronic device.
  • Example 1 A reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser was charged with 68 parts by weight of toluene, 95 parts by weight of butyl acrylate (BA), and 5 parts by weight of acrylic acid (AA). Nitrogen substitution was performed for more than one hour. Add azobisisobutyronitrile as an initiator, then raise the temperature of the inner bath to 62°C, maintain the same temperature, and continue until the reaction is almost complete, then cool to complete the polymerization reaction.
  • azobisisobutyronitrile as an initiator
  • the pressure-sensitive adhesive composition is coated on a release-treated layer of a 38 ⁇ m-thick polyethylene terephthalate film (product name “MRF #38”, manufactured by Mitsubishi Chemical Corporation) whose one side has been release-treated with silicone, and dried.
  • a double-sided pressure-sensitive adhesive sheet of Example 1 was produced by forming a pressure-sensitive adhesive layer of 200 ⁇ m.
  • Examples 2-4 A double-sided pressure-sensitive adhesive sheet of each example was produced in the same manner as in Example 1, except that the blending amount of the filler was changed as shown in Table 1.
  • Example 5 As a filler, instead of polyethylene powder (trade name “Frick UF-80”, manufactured by Sumitomo Seika Co., Ltd.) 0.1 part by mass, silicone rubber particles (trade name “Torayfil E-606”, manufactured by Toray Industries, Inc.) 1 A double-sided pressure-sensitive adhesive sheet of Example 5 was produced in the same manner as in Example 1, except that parts by mass were used.
  • polyethylene powder trade name “Frick UF-80”, manufactured by Sumitomo Seika Co., Ltd.
  • silicone rubber particles trade name “Torayfil E-606”, manufactured by Toray Industries, Inc.
  • Examples 6-8 A double-sided pressure-sensitive adhesive sheet of each example was produced in the same manner as in Example 5, except that the blending amount of the filler was changed as shown in Table 1.
  • Example 9 As a filler, instead of 0.1 parts by mass of polyethylene powder (trade name “Frick UF-80”, manufactured by Sumitomo Seika Co., Ltd.), hollow microspheres (trade name “MFL-81GCA”, manufactured by Matsumoto Yushi Seiyaku Co., Ltd., Shell composition: acrylonitrile-based copolymer, surface treatment with calcium carbonate) A double-sided pressure-sensitive adhesive sheet of Example 9 was produced in the same manner as in Example 1, except that 0.01 part by mass was used.
  • polyethylene powder trade name “Frick UF-80”, manufactured by Sumitomo Seika Co., Ltd.
  • hollow microspheres trade name “MFL-81GCA”, manufactured by Matsumoto Yushi Seiyaku Co., Ltd., Shell composition: acrylonitrile-based copolymer, surface treatment with calcium carbonate
  • Examples 10-11 A double-sided pressure-sensitive adhesive sheet of each example was produced in the same manner as in Example 9, except that the blending amount of the filler was changed as shown in Table 1.
  • Example 12 Polymer prepared in Example 1: 100 parts by mass, acrylic oligomer obtained in Production Example 1: 5 parts by mass, isocyanate-based cross-linking agent (trade name “Coronate L”, manufactured by Tosoh Corporation): 5 parts by mass part, and an epoxy cross-linking agent (trade name “Tetrad C”, manufactured by Mitsubishi Gas Chemical Co., Ltd.): 0.03 parts by mass, and a terpene phenol-based tackifier resin (trade name “YS Polystar T115”, Yasuhara Chemical Co., Ltd.
  • a double-sided pressure-sensitive adhesive sheet of Example 12 was produced in the same manner as in Example 1, except that the pressure-sensitive adhesive composition obtained above was used.
  • Examples 13-14 A double-faced pressure-sensitive adhesive sheet of each example was produced in the same manner as in Example 12, except that the blending amount of the epoxy-based cross-linking agent and the blending amount of the filler were changed as shown in Tables 1 and 2.
  • Example 15 As a filler, instead of hollow microspheres (trade name “MFL-010CA”, manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.) 0.01 part by mass, hollow microspheres (trade name “MFLUPR60”, manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd., shell composition : Acrylonitrile-based copolymer, surface treatment with calcium carbonate)
  • MFL-010CA hollow microspheres
  • MFLUPR60 manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd., shell composition : Acrylonitrile-based copolymer, surface treatment with calcium carbonate
  • Examples 16-17 A double-faced pressure-sensitive adhesive sheet of each example was produced in the same manner as in Example 15, except that the blending amount of the epoxy-based cross-linking agent and the blending amount of the filler were changed as shown in Table 2.
  • Example 18 Polymer prepared in Example 1: 100 parts by mass, isocyanate cross-linking agent (trade name “Coronate L”, manufactured by Tosoh Corporation): 5 parts by mass, and epoxy cross-linking agent (trade name “Tetrad C", Mitsubishi Gas Chemical Co., Ltd.): 0.02 parts by mass, and terpene phenol-based tackifying resin (trade name “YS Polyster T115”, Yasuhara Chemical Co., Ltd.): 20 parts by mass, spherical silicone rubber powder (trade name “DOWSIL EP-2600”, manufactured by Dow Toray Industries, Inc.): 5 parts by mass, and a black pigment containing carbon black (trade name "Multilac A903", manufactured by Toyocolor Co., Ltd.): 6 parts by mass are added for adhesion. An agent composition was obtained.
  • a double-sided pressure-sensitive adhesive sheet of Example 18 was produced in the same manner as in Example 1, except that the pressure-sensitive adhesive composition obtained above was used.
  • Examples 19-20 A double-sided pressure-sensitive adhesive sheet of each example was produced in the same manner as in Example 18, except that the blending amount of the filler was changed as shown in Table 2.
  • Example 21 As a filler, in addition to 5 parts by mass of spherical silicone rubber powder (trade name “DOWSIL EP-2600”, manufactured by Dow Toray Industries, Inc.), polyethylene particles (trade name “Flowbeads HE-3040”, Sumitomo Seika Co., Ltd. A double-sided pressure-sensitive adhesive sheet of the example was prepared in the same manner as in Example 18, except that 5 parts by mass of the product (manufactured by the manufacturer) was used.
  • spherical silicone rubber powder trade name “DOWSIL EP-2600”, manufactured by Dow Toray Industries, Inc.
  • polyethylene particles trade name “Flowbeads HE-3040”, Sumitomo Seika Co., Ltd.
  • a double-sided pressure-sensitive adhesive sheet of the example was prepared in the same manner as in Example 18, except that 5 parts by mass of the product (manufactured by the manufacturer) was used.
  • Example 22 As a filler, instead of spherical silicone rubber powder (trade name “DOWSIL EP-2600”, Dow Toray Industries, Inc.) 5 parts by mass, polyethylene particles (trade name “Flowbeads HE-3040”, manufactured by Sumitomo Seika Co., Ltd. ) A double-sided pressure-sensitive adhesive sheet of Example 22 was prepared in the same manner as in Example 18, except that 10 parts by mass of the composition was used.
  • spherical silicone rubber powder trade name “DOWSIL EP-2600”, Dow Toray Industries, Inc.
  • polyethylene particles trade name “Flowbeads HE-3040”, manufactured by Sumitomo Seika Co., Ltd.
  • Comparative example 1 A double-sided pressure-sensitive adhesive sheet of Comparative Example 1 was produced in the same manner as in Example 1, except that no filler was blended.
  • Comparative example 2 A double-sided pressure-sensitive adhesive sheet of Comparative Example 2 was produced in the same manner as in Example 1, except that the amount of the filler compounded was 40 parts by mass.
  • Comparative example 3 Polymer prepared in Example 1: 100 parts by mass, acrylic oligomer obtained in Production Example 1: 5 parts by mass, isocyanate compound (trade name “Coronate L", manufactured by Tosoh Corporation): 5 parts by mass and Epoxy compound (trade name “Tetrad C”, manufactured by Mitsubishi Gas Chemical Co., Ltd.): 0.02 parts by mass is added, and a terpene phenol-based tackifying resin (trade name “YS Polystar T115”, manufactured by Yasuhara Chemical Co., Ltd.): 20 Part by mass, polyethylene powder as a filler (trade name "Frick UF-80", manufactured by Sumitomo Seika Co., Ltd.): 5 parts by mass, and black pigment containing carbon black (trade name "Multilac A903", Toyocolor Co., Ltd. (manufacturer): 6 parts by mass were added to prepare a pressure-sensitive adhesive composition.
  • isocyanate compound trade name "Coronate L", manufactured by Tosoh Corporation
  • the pressure-sensitive adhesive composition obtained above is coated on a release-treated layer of a 38 ⁇ m-thick polyethylene terephthalate film (product name “MRF #38”, manufactured by Mitsubishi Chemical Corporation) whose one side is release-treated with silicone, and dried. to form a pressure-sensitive adhesive layer with a thickness of 178 ⁇ m. Then, the release liner (trade name “MRE #25”, manufactured by Mitsubishi Chemical Corporation) provided on the surface of the prepared adhesive layer is peeled off to expose the adhesive layer, and the PET film (thickness 12 ⁇ m) was laminated on the exposed surface of the pressure-sensitive adhesive layer. Thus, a single-sided pressure-sensitive adhesive sheet (thickness: 190 ⁇ m) of Comparative Example 3, in which the pressure-sensitive adhesive layer was formed on the substrate layer, was produced.
  • Comparative example 4 As a filler, instead of 0.1 part by mass of polyethylene powder (trade name “Frick UF-80”, manufactured by Sumitomo Seika Co., Ltd.), polyethylene particles (trade name “Flow Beads CL-2507”, manufactured by Sumitomo Seika Co., Ltd. ) A double-sided pressure-sensitive adhesive sheet of Comparative Example 4 was prepared in the same manner as in Example 1, except that 2 parts by mass of the adhesive was used.
  • a pressure-sensitive adhesive layer having a thickness of about 2 mm was prepared by stacking a plurality of pressure-sensitive adhesive layers prepared in Examples and Comparative Examples. A disk-shaped sample with a diameter of 7.9 mm was punched out of this adhesive layer and fixed by sandwiching it between parallel plates. (manufactured by A Instruments Co., Ltd.), dynamic viscoelasticity was measured under the following conditions, and the peak top value of storage elastic modulus G′ (23° C.) and tan ⁇ was calculated. It was confirmed that all pressure-sensitive adhesive layers had a tan ⁇ peak top within the range of -20 to 0°C. Measurement mode: Shear mode Temperature range: -70°C to 150°C Heating rate: 5°C/min Measurement frequency: 1Hz
  • a cylindrical measurement table with a length of 50 mm, an outer diameter of 49 mm, and an inner diameter of 43 mm is installed on the pedestal of a DuPont impact tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and a test piece is placed on it, a square stainless steel plate. (stainless steel plate without holes) was placed on the bottom side.
  • a stainless steel striking core with a tip radius of 3.1 mm is placed on the test piece, and the weight and height of the falling weight are changed by 50 mm from 50 to 500 mm at 100 g, by 50 mm from 350 to 500 mm at 150 g, and then to 200 g.
  • the energy was changed by 50 mm from 400 to 500 mm, and at 300 g by 50 mm from 350 to 500 mm, the energy was increased until peeling occurred. At this time, no test was performed on the energy that had already been evaluated, and the load and height were set so that the amount of energy would not overlap. After that, the energy until at least one of the stainless steel plates (for Comparative Example 3, the stainless steel plate attached to the adhesive layer) peeled off was calculated by multiplying the load by the height, and the result was obtained.
  • the reworkability required for practical use is 2 or more, preferably 3 or more in the following criteria.
  • Rank 1 The tape is torn and cannot be peeled.
  • Rank 2 The tape is not torn and can be peeled off by pulling at a speed of less than 0.2 m/min.
  • Rank 3 The tape is torn by pulling at a speed of 0.2 m/min or more. peelable without

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Citations (6)

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JP2012067279A (ja) * 2010-08-27 2012-04-05 Nitto Denko Corp アクリル系粘着剤組成物、アクリル系粘着剤層およびアクリル系粘着テープ
JP2014148570A (ja) * 2013-01-31 2014-08-21 Dainippon Printing Co Ltd 粘着剤組成物
US20150315425A1 (en) * 2014-04-30 2015-11-05 Samsung Sdi Co., Ltd. Adhesive film and optical display including the same
WO2020121605A1 (ja) * 2018-12-13 2020-06-18 Dic株式会社 粘着シート
JP2021024907A (ja) * 2019-08-01 2021-02-22 日東電工株式会社 両面粘着テープ
WO2021039878A1 (ja) * 2019-08-30 2021-03-04 Dic株式会社 粘着テープ

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JP7027357B2 (ja) 2019-02-07 2022-03-01 日東電工株式会社 両面粘着テープ
JP6975189B2 (ja) 2019-02-07 2021-12-01 日東電工株式会社 両面粘着テープ

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Publication number Priority date Publication date Assignee Title
JP2012067279A (ja) * 2010-08-27 2012-04-05 Nitto Denko Corp アクリル系粘着剤組成物、アクリル系粘着剤層およびアクリル系粘着テープ
JP2014148570A (ja) * 2013-01-31 2014-08-21 Dainippon Printing Co Ltd 粘着剤組成物
US20150315425A1 (en) * 2014-04-30 2015-11-05 Samsung Sdi Co., Ltd. Adhesive film and optical display including the same
WO2020121605A1 (ja) * 2018-12-13 2020-06-18 Dic株式会社 粘着シート
JP2021024907A (ja) * 2019-08-01 2021-02-22 日東電工株式会社 両面粘着テープ
WO2021039878A1 (ja) * 2019-08-30 2021-03-04 Dic株式会社 粘着テープ

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