WO2022255210A1 - 粘着剤組成物、粘着剤および表面保護フィルム - Google Patents

粘着剤組成物、粘着剤および表面保護フィルム Download PDF

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WO2022255210A1
WO2022255210A1 PCT/JP2022/021507 JP2022021507W WO2022255210A1 WO 2022255210 A1 WO2022255210 A1 WO 2022255210A1 JP 2022021507 W JP2022021507 W JP 2022021507W WO 2022255210 A1 WO2022255210 A1 WO 2022255210A1
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meth
pressure
sensitive adhesive
acrylate
weight
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English (en)
French (fr)
Japanese (ja)
Inventor
裕充 森下
淳 ▲高▼嶋
匡哉 柴野
真人 山形
なるみ 塚本
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Nitto Denko Corp
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Nitto Denko Corp
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Priority to JP2023525766A priority Critical patent/JPWO2022255210A1/ja
Priority to KR1020237045062A priority patent/KR20240017003A/ko
Priority to CN202280039053.7A priority patent/CN117413037A/zh
Publication of WO2022255210A1 publication Critical patent/WO2022255210A1/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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • 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 an adhesive composition, an adhesive and a surface protection film.
  • This application claims priority based on Japanese Patent Application No. 2021-091007 filed on May 31, 2021, the entire contents of which are incorporated herein by reference.
  • pressure-sensitive adhesives also called pressure-sensitive adhesives; the same shall apply hereinafter
  • adhesives are widely used in the form of adhesive sheets for purposes such as bonding of parts and surface protection.
  • a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on one surface of a base material can be used as a surface protection sheet to prevent surface damage (scratches, stains, corrosion, etc.) during processing or transportation of various articles. preferably used.
  • the pressure-sensitive adhesive is formed from, for example, a pressure-sensitive adhesive composition containing an acrylic polymer copolymerized with a hydroxyl group-containing monomer and an isocyanate-based cross-linking agent.
  • a pressure-sensitive adhesive composition containing an acrylic polymer and an isocyanate-based cross-linking agent as described above undergoes rapid aging (cross-linking reaction) at room temperature after curing treatment such as heating from the viewpoint of production efficiency and performance stability. It is desirable to harden it. On the other hand, if the cross-linking reaction rate is excessively fast, a sufficient pot life (usable time) cannot be ensured, and conversely the productivity decreases. Therefore, in designing the pressure-sensitive adhesive composition, it is necessary to have a composition that satisfies both the progress of the crosslinking reaction and the pot life.
  • tin-based catalysts have been preferably used for the crosslinking reaction of isocyanate-based crosslinking because of their high catalytic activity, in order to promote the crosslinking reaction (for example, Patent Document 1).
  • Patent Document 1 tin-based catalysts have been preferably used for the crosslinking reaction of isocyanate-based crosslinking because of their high catalytic activity, in order to promote the crosslinking reaction.
  • Patent Document 1 tin-based catalysts
  • the adhesive is required to be peeled off smoothly without adhesive residue.
  • the pressure-sensitive adhesive is required to have a property that the peel strength does not change greatly depending on the difference in peel speed.
  • the peeling work will be performed at a high peeling speed, and if the peeling force increases due to the difference in peeling speed such as high-speed peeling, it will affect the peeling workability and make the peeling work less efficient. not.
  • the peeling force is peeled back from the object to be protected (adherend) after achieving the purpose of protecting the object, it is desirable that the peeling force has little dependence on the peeling speed.
  • the present invention was created in view of the above circumstances, and does not rely on a tin-based catalyst, in other words, regardless of whether a tin-based catalyst is used or not, it has a sufficient pot life and cures. It is an object of the present invention to provide a pressure-sensitive adhesive composition capable of rapidly aging after treatment and forming a pressure-sensitive adhesive whose peel strength is less dependent on the peel speed. Another related object is to provide a pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition and a surface protective film having the pressure-sensitive adhesive.
  • a pressure-sensitive adhesive composition containing an acrylic polymer and a cross-linking agent.
  • the acrylic polymer has an alkyl (meth)acrylate (m1) having a linear alkyl group having 5 to 18 carbon atoms at the ester end and a side chain having 3 or more carbon atoms and containing active hydrogen (meth) It is a polymer of a monomer component containing an acrylic monomer (m2).
  • the pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition having the composition described above has limited peel speed dependence of the peel strength, and thus can be excellent in peeling workability.
  • Patent Document 2 uses an acrylic polymer having a monomer composition in which n-butyl acrylate (BA) having an alkyl group having 4 carbon atoms and hydroxyethyl acrylate (HEA) are used in combination
  • Patent Document 3 uses , BA and methyl acrylate (MA), and HEA or 4-hydroxybutyl acrylate (4HBA) are used in monomer composition acrylic polymers.
  • Acrylate (IOA) and BA are used in combination, and acrylic polymers with monomer compositions in which 4HBA and HEA are used in combination are used. It is predicted that with the monomer composition under study, a sufficient pot life and aging progress will not be obtained, and the peel rate dependency will increase (Comparative Examples 2 to 4).
  • the adhesive composition disclosed herein achieves the above effects without containing a tin-based catalyst, but may contain a tin-based catalyst depending on the place of use, required properties, etc. .
  • the pressure-sensitive adhesive composition according to some preferred embodiments further contains a compound containing a Group 4 element as a catalyst.
  • a Group 4 element-containing compound as a catalyst, the effects of the technology disclosed herein can be achieved without using a tin-based catalyst.
  • Zirconium-containing compounds and titanium-containing compounds are preferably used as such compounds containing Group 4 elements.
  • a zirconium-containing compound or a titanium-containing compound as a catalyst, it is easy to form a colorless pressure-sensitive adhesive.
  • the cross-linking agent includes an isocyanate-based cross-linking agent.
  • an isocyanate-based cross-linking agent as a cross-linking agent, the effects of the technology disclosed herein are preferably exhibited.
  • the (meth)acrylic monomer (m2) contains a hydroxyalkyl (meth)acrylate having a hydroxyalkyl group with 4 to 10 carbon atoms.
  • the (meth)acrylic monomer (m2) more preferably contains 4-hydroxybutyl acrylate (4HBA).
  • the alkyl (meth)acrylate (m1) comprises n-heptyl acrylate (HpA). HpA is preferably used as the alkyl (meth)acrylate (m1).
  • a pressure-sensitive adhesive formed from any of the pressure-sensitive adhesive compositions disclosed herein is provided.
  • Such an adhesive has a sufficient pot life without containing a tin-based catalyst as an essential component before curing treatment such as heating, and rapidly ages (crosslinking reaction) after curing treatment. can harden.
  • the pressure-sensitive adhesive has a limited peel speed dependence of the peel strength, the peel speed Easy to peel off regardless.
  • the adhesive has a gel fraction of 70% or more.
  • a pressure-sensitive adhesive having a gel fraction of 70% or more is less likely to cause deformation or damage such as dents due to external force during production, and less likely to cause changes in appearance.
  • Such a pressure-sensitive adhesive tends to form a pressure-sensitive adhesive sheet having a smooth surface. For example, when a transparent pressure-sensitive adhesive sheet is formed and an adherend is inspected through the pressure-sensitive adhesive sheet, highly accurate inspection is possible, which is preferable.
  • a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer made of any pressure-sensitive adhesive disclosed herein is provided.
  • the pressure-sensitive adhesive sheet disclosed herein when used in the form of a pressure-sensitive adhesive sheet, is easy to peel off regardless of the peel speed because the peel strength depends on the peel speed. Therefore, it is suitable as a surface protection film. After the surface protective film is attached to the object to be protected, it is usually peeled off (re-peeled) from the object to be protected when the protective purpose is achieved.
  • the surface protective film has a low-speed adhesive strength of 2.0 N/25 mm or less measured at a tensile speed of 300 mm/min after storage at 23°C for 3 days.
  • a surface protective film that satisfies this characteristic has a suppressed increase in adhesive strength over time and a suppressed peeling force when peeled from a protected object, so that it is easily peeled off.
  • FIG. 1 is a cross-sectional view schematically showing the configuration of a pressure-sensitive adhesive sheet according to one embodiment
  • the term “adhesive” refers to a material that exhibits a soft solid (viscoelastic) state in a temperature range around room temperature and has the property of easily adhering to an adherend under pressure, as described above. .
  • the adhesive as used herein generally has a complex tensile elastic modulus E * (1 Hz) as defined in "C. A. Dahlquist, “Adhesion: Fundamental and Practice", McLaren & Sons (1966), p. 143". It may be a material having properties satisfying ⁇ 10 7 dyne/cm 2 (typically, a material having the above properties at 25°C).
  • biomass-derived carbon means carbon derived from biomass materials, that is, materials derived from renewable organic resources (renewable carbon).
  • the biomass material is typically a material derived from biological resources (typically photosynthetic plants) that can be sustainably reproduced in the presence of sunlight, water, and carbon dioxide.
  • materials derived from fossil resources that are depleted by use after mining are excluded from the concept of biomass materials here.
  • the biomass-carbon ratio of the pressure-sensitive adhesive composition and pressure-sensitive adhesive that is, the ratio of biomass-derived carbon to the total carbon contained in the pressure-sensitive adhesive composition and pressure-sensitive adhesive, is the carbon isotope with a mass number of 14 measured according to ASTM D6866. can be estimated from body content.
  • (Meth)acrylic monomer refers to a monomer having at least one (meth)acryloyl group in one molecule.
  • (meth)acryloyl is a generic term for acryloyl and methacryloyl. Therefore, the concept of a (meth)acrylic monomer as used herein can include both a monomer having an acryloyl group (acrylic monomer) and a monomer having a methacryloyl group (methacrylic monomer).
  • the adhesive composition disclosed here contains an acrylic polymer.
  • “acrylic polymer” refers to a polymer derived from a monomer component containing more than 50% by weight of (meth)acrylic monomer.
  • the content of the (meth)acrylic monomer in the monomer component is preferably 70% by weight or more, and may be 80% by weight or more. In some aspects, the content of the (meth)acrylic monomer in the monomer component may be 90% by weight or more, 95% by weight or more, or 100% by weight.
  • the proportion of the (meth)acrylic monomer in the total monomer components may be, for example, less than 99% by weight, may be less than 95% by weight, or may be less than 93% by weight. It may be less than weight percent.
  • the monomer component constituting the acrylic polymer is an alkyl (meth)acrylate (m1) having a linear alkyl group having 5 to 18 carbon atoms at the ester end (hereinafter also referred to as “C 5-18 linear alkyl (meth)acrylate” ) is included as one of the features.
  • alkyl (meth)acrylates with relatively long straight-chain alkyl groups of 5 to 18 carbon atoms increases curability based on the entanglement and orientation of the alkyl groups, and adhesion during high-speed peeling. It is thought that the increase in force is suppressed and the peel speed dependency is improved.
  • the reaction between the cross-linking point of the acrylic polymer for example, the active hydrogen located at the end of the side chain of the acrylic polymer
  • the cross-linking agent is moderately suppressed, and a sufficient pot life can be secured.
  • the above C 5-18 linear alkyl (meth)acrylate can also be represented by the following formula (1).
  • CH2 C( R1 ) COOR2 (1)
  • R 1 in the above formula (1) is a hydrogen atom or a methyl group.
  • R 2 is a linear alkyl group having 5 to 18 carbon atoms.
  • the number of carbon atoms in the straight-chain alkyl group of the C 5-18 straight-chain alkyl (meth)acrylate is preferably 14 or less, more preferably 12 or less, still more preferably 11 or less, and particularly preferably from the viewpoint of adhesive properties and aging speed. is 10 or less (eg 9 or 8 or less).
  • the number of carbon atoms is preferably 6 or more, more preferably 7 or more, from the viewpoint of effectively exhibiting the effect and properties of making the alkyl group longer.
  • C 5-18 linear alkyl (meth)acrylates include n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, n -nonyl (meth)acrylate, n-decyl (meth)acrylate, n-undecyl (meth)acrylate, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, n-pentadecyl (Meth)acrylate, n-hexadecyl (meth)acrylate, n-heptadecyl (meth)acrylate, n-octadecyl (meth)acrylate and the like.
  • the C 5-18 linear alkyl (meth)acrylates can be used sing
  • the proportion of the C5-18 straight-chain alkyl (meth)acrylate in the total monomer components is set according to the purpose of use, required properties, etc., and may be, for example, 1% by weight or more, preferably 10% by weight or more. , preferably 30% by weight or more, more preferably 50% by weight or more (for example, more than 50% by weight), may be 70% by weight or more, may be 80% by weight or more, may be 85% by weight or more, or may be 90% by weight % or more, 92% by weight or more, or 95% by weight or more.
  • the properties based on the C 5-18 linear alkyl (meth)acrylate can be effectively exhibited.
  • C 5-18 linear alkyl (The proportion of meth)acrylates may be, for example, less than 99% by weight, less than 98% by weight, less than 97% by weight.
  • the upper limit of the proportion of C 5-18 linear alkyl (meth)acrylate in the total monomer component may be 95% by weight or less from the viewpoint of obtaining the effect of using other monomers. , 75% by weight or less, 60% by weight or less, 50% by weight or less (for example, less than 50% by weight), or 30% by weight or less.
  • Alkyl (meth)acrylate having a chain alkyl group at the ester end contained as a monomer component of the acrylic polymer above C 5-18 straight chain accounts for the whole
  • the proportion of alkyl (meth)acrylate may be, for example, 1% by weight or more, suitably 10% by weight or more, preferably 30% by weight or more, more preferably 50% by weight or more (for example, more than 50% by weight). and may be 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, or 99% by weight or more.
  • the above-mentioned chain alkyl group is a concept that includes linear and branched alkyl groups, and does not include cyclic alkyl groups called alicyclic.
  • the technology disclosed herein can be preferably practiced in a mode using an acrylic polymer having a monomer composition containing only C 5-18 linear alkyl (meth)acrylate as the chain alkyl (meth)acrylate. Therefore, the upper limit of the ratio of C 5-18 straight-chain alkyl (meth)acrylate to the whole chain alkyl (meth)acrylate is 100% by weight.
  • the ratio of C 5-18 straight chain alkyl (meth ) acrylates to the total chain alkyl (meth)acrylate is From the viewpoint of obtaining the effect of using (meth) acrylate, it may be 95% by weight or less, 75% by weight or less, 60% by weight or less, or 50% by weight or less (for example, less than 50% by weight). It may be 30% by weight or less.
  • the C 5-18 linear alkyl (meth)acrylates include one or more C 5-11 linear alkyl (meth)acrylates and one or more C 12-18 You may use together with a linear alkyl (meth)acrylate.
  • the ratio of the two to be used can be set according to the adhesive property, the action and properties based on the alkyl group of each monomer, and the like.
  • the proportion of C 5-11 linear alkyl (meth)acrylate in C 5-18 linear alkyl (meth)acrylate may be, for example, 1% by weight or more, 10% by weight or more, or 30% by weight.
  • C 5-11 linear alkyl (meth)acrylate in C 5-18 linear alkyl (meth)acrylate may be 99% by weight or less, may be 90% by weight or less, or may be 80% by weight. It can be below.
  • an alkyl (meth)acrylate having a straight-chain alkyl group having 9 or less carbon atoms (eg, 8 or less, preferably 7) at the ester end is preferably used.
  • the straight-chain alkyl group preferably has 6 or more carbon atoms.
  • n-heptyl (meth)acrylate is used as the C 5-18 linear alkyl (meth)acrylate.
  • n-heptyl (meth)acrylate the effects of the technology disclosed herein can be exhibited particularly favorably.
  • n-heptyl acrylate is particularly preferable from the viewpoint of adhesive properties.
  • the ratio of n-heptyl (meth)acrylate in the total monomer components is set according to the purpose of use, required properties, etc., and may be, for example, 1% by weight or more, preferably 10% by weight or more. is 30% by weight or more, more preferably 50% by weight or more (for example, more than 50% by weight), may be 70% by weight or more, may be 80% by weight or more, may be 85% by weight or more, or may be 90% by weight or more. , 92% by weight or more, or 95% by weight or more.
  • n-heptyl (meth)acrylate among the total monomer components The proportion may be, for example, less than 99% by weight, less than 98% by weight, less than 97% by weight.
  • the proportion of n-heptyl(meth)acrylate in the total monomer components is 95% by weight or less from the viewpoint of obtaining the effect of using various monomers other than n-heptyl(meth)acrylate. 75% by weight or less, 60% by weight or less, 50% by weight or less (for example, less than 50% by weight), or 30% by weight or less.
  • the ratio of n-heptyl (meth)acrylate to the total linear alkyl (meth)acrylate contained as a monomer component of the acrylic polymer may be, for example, 1% by weight or more, and is suitably 10% by weight or more. , preferably 30% by weight or more, more preferably 50% by weight or more (for example, more than 50% by weight), may be 70% by weight or more, may be 80% by weight or more, may be 90% by weight or more, or may be 95% by weight or more , or 99% by weight or more.
  • the technology disclosed herein can be preferably implemented in a mode using an acrylic polymer having a monomer composition containing only n-heptyl (meth)acrylate as the chain alkyl (meth)acrylate. Therefore, the upper limit of the ratio of n-heptyl (meth)acrylate to the total chain alkyl (meth)acrylate is 100% by weight. In some other embodiments, the ratio of n-heptyl (meth)acrylate to the total chain alkyl (meth)acrylate is 95% by weight from the viewpoint of obtaining the effect of using other chain alkyl (meth)acrylate. 75% by weight or less, 60% by weight or less, 50% by weight or less (for example, less than 50% by weight), or 30% by weight or less.
  • the monomer component constituting the acrylic polymer is an alkyl (meth)acrylate (C 1-4 chain alkyl (meth)acrylate) having a chain alkyl group having 1 to 4 carbon atoms at the ester end. It may or may not be included.
  • C 1-4 chained alkyl (meth)acrylates that may be used include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate Acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate and the like.
  • n-butyl acrylate (BA) is preferably used because it tends to provide good adhesive properties.
  • the C 1-4 chain alkyl (meth)acrylates can be used singly or in combination of two or more.
  • the ratio of the C 1-4 chain alkyl (meth)acrylate to the total chain alkyl (meth)acrylate contained in the monomer component may be, for example, 90% by weight or less, 70% by weight or less, or 50% by weight. % (for example, less than 50% by weight), 30% by weight or less, 10% by weight or less, or 1% by weight or less.
  • the technology disclosed herein can be preferably practiced in a mode in which the monomer component does not substantially contain C 1-4 chain alkyl (meth)acrylate.
  • the ratio of the C 1-4 chain alkyl (meth)acrylate to the total chain alkyl (meth)acrylate contained in the monomer component is For example, it may be 1% by weight or more, suitably 10% by weight or more, preferably 30% by weight or more, may be 50% by weight or more, or may be 70% by weight or more.
  • the expression that the monomer component does not substantially contain the monomer A means that the monomer A is not used at least intentionally. , the unintentional inclusion of the monomer A in an amount of, for example, about 0.01% by weight or less is permissible.
  • the monomer component constituting the acrylic polymer may contain an alkyl (meth)acrylate having a branched alkyl group having 5 to 18 carbon atoms at the ester end (C 5-18 branched alkyl (meth)acrylate). Well, it doesn't have to be included.
  • C 5-18 branched alkyl (meth)acrylates that may be used include isopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 1-methylheptyl (meth)acrylate, isooctyl (meth)acrylate, isononyl ( meth)acrylate, isodecyl (meth)acrylate, isostearyl (meth)acrylate and the like.
  • the C 5-18 branched alkyl (meth)acrylates can be used singly or in combination of two or more.
  • C 5-18 branched alkyl (meth)acrylates 2-ethylhexyl acrylate (2EHA) and isooctyl acrylate (IOA) are preferably used. Also, from the viewpoint of improving the biomass carbon ratio of the acrylic polymer, 1-methylheptyl (meth)acrylate and isostearyl (meth)acrylate are preferably used as the C 5-18 branched alkyl (meth)acrylate. These C 5-18 branched alkyl (meth)acrylates can be produced using biomass-derived alcohols.
  • the proportion of the C5-18 branched alkyl (meth)acrylate in the total linear alkyl (meth)acrylate contained in the monomer component may be, for example, 90% by weight or less, 70% by weight or less, or 50% by weight. or less (for example, less than 50% by weight), 30% by weight or less, 10% by weight or less, or 1% by weight or less.
  • the technology disclosed herein can preferably be practiced in an aspect in which the monomer component is substantially free of C 5-18 branched alkyl (meth)acrylates.
  • the ratio of the C 5-18 branched alkyl (meth)acrylate to the total chain alkyl (meth)acrylate contained in the monomer component is, for example, It may be 1% by weight or more, suitably 10% by weight or more, preferably 30% by weight or more, may be 50% by weight or more, or may be 70% by weight or more.
  • the monomer component constituting the acrylic polymer may contain an alkyl (meth)acrylate having a chain alkyl group with 19 or more carbon atoms at the ester end (chain alkyl (meth)acrylate with 19 or more carbon atoms). , may not be included.
  • the C19 or higher chain alkyl (meth)acrylates may be used singly or in combination of two or more.
  • the ratio of the C19 or higher chain alkyl (meth)acrylate to the total chain alkyl (meth)acrylate contained in the monomer component may be, for example, 90% by weight or less, 70% by weight or less, or 50% by weight.
  • the technique disclosed herein can be preferably implemented in a mode in which the monomer component does not substantially contain C19 or higher chain alkyl (meth)acrylate.
  • the monomer component is an alkyl (meth)acrylate having a biomass-derived alkyl group at the ester end (hereinafter also referred to as "biomass chain alkyl (meth)acrylate”) as the chain alkyl (meth)acrylate. .).
  • biomass chain alkyl (meth)acrylate a biomass-derived alkyl group at the ester end
  • the biomass chain alkyl (meth)acrylate is not particularly limited, and is, for example, an ester of a biomass-derived alkanol and a biomass-derived or non-biomass-derived (meth)acrylic acid.
  • biomass-derived alkanols include biomass ethanol, alkanols derived from plant sources such as palm oil, palm kernel oil, coconut oil, castor oil, and the like. When the number of carbon atoms in the biomass-derived alkanol is 3 or more, the alkanol may be linear or branched.
  • an ester of a biomass-derived alkanol and a non-biomass-derived (meth)acrylic acid is used as the biomass linear alkyl (meth)acrylate used to synthesize the acrylic polymer.
  • the greater the number of carbon atoms in the alkanol the more the number of biomass-derived carbons accounts for the total number of carbon atoms contained in the biomass chain alkyl (meth)acrylate, that is, the chain alkyl ( The biomass carbon ratio of meth)acrylate is increased.
  • the chain alkyl group derived from biomass has a large number of carbon atoms in order to reduce dependence on fossil resource-based materials.
  • the number of carbon atoms in the chain alkyl group that constitutes the chain alkyl (meth)acrylate is too large, it tends to be difficult to obtain adhesive properties such as adhesive strength. It can also be disadvantageous in terms of gender.
  • a biomass chain-like alkyl (meth)acrylate can be used for any of the alkyl (meth)acrylates.
  • a biomass chain alkyl (meth)acrylate is used as the C 5-18 straight chain alkyl (meth)acrylate
  • a biomass chain alkyl (meth)acrylate may be used as the above C 12-18 linear alkyl (meth)acrylate.
  • at least a portion thereof e.g., one or two types, or all, i.e., all types
  • Alkyl (meth)acrylates can be used.
  • the C 5-18 linear alkyl (meth)acrylate is an alkyl (meth)acrylate having a biomass-derived C 5-18 linear alkyl group at the ester end (hereinafter “biomass C 5-18 linear (also referred to as “chain alkyl (meth)acrylate”) is used.
  • biomass C 5-18 linear alkyl (meth)acrylate By using biomass C 5-18 linear alkyl (meth)acrylate, the effect of the technology disclosed herein (sufficient pot The effect of having a long life, rapidly progressing aging after the curing treatment, and less dependence of the peel force on the peel speed) is preferably realized.
  • the biomass C 5-18 linear alkyl (meth)acrylates are esters of biomass-derived alkanols with biomass-derived or non-biomass-derived (meth)acrylic acid, e.g. Esters with (meth)acrylic acid may be used. In such compounds, only the linear alkyl groups are derived from biomass.
  • the number of carbon atoms in the straight-chain alkyl group of the biomass C 5-18 straight-chain alkyl (meth)acrylate is preferably 14 or less, more preferably 12 or less, still more preferably 11 or less, particularly from the viewpoint of adhesive properties and aging speed. It is preferably 10 or less (eg, 9 or 8 or less). Also, the number of carbon atoms is preferably 6 or more, more preferably 7 or more. For example, in an embodiment using an ester of a biomass-derived alkanol and a non-biomass-derived (meth)acrylic acid as the biomass C 5-18 linear alkyl (meth)acrylate, by increasing the carbon number of the linear alkyl group , the biomass carbon ratio of the synthesized acrylic polymer can be increased.
  • the ratio of the biomass C5-18 straight-chain alkyl (meth)acrylate to the total C5-18 straight-chain alkyl (meth)acrylate used as the monomer component of the acrylic polymer may be, for example, 1% by weight or more. , 10% by weight or more is suitable, preferably 30% by weight or more, more preferably 50% by weight or more (for example, more than 50% by weight); % or more, 95% by weight or more, or 99% by weight or more.
  • the technology disclosed herein can be preferably implemented in a mode using an acrylic polymer having a monomer composition containing only biomass C 5-18 linear alkyl (meth)acrylate as the C 5-18 linear alkyl (meth)acrylate. . Therefore, the upper limit of the ratio of biomass C 5-18 linear alkyl (meth)acrylate to the total C 5-18 linear alkyl (meth)acrylate is 100% by weight. In some other embodiments, the proportion of biomass C 5-18 linear alkyl (meth)acrylates in total C 5-18 linear alkyl (meth)acrylates may be 95% by weight or less, and may be 70% by weight. % or less, 50 wt % or less (for example, less than 50 wt %), 30 wt % or less, 10 wt % or less, or 1 wt % or less.
  • the biomass C 5-18 linear alkyl (meth)acrylates include one or more C 5-11 linear alkyl (meth)acrylates (hereinafter “biomass C 5-11 linear alkyl (meth)acrylates meth)acrylate”) and one or more C 12-18 linear alkyl (meth)acrylates may be used in combination.
  • the C 12-18 linear alkyl (meth)acrylate may be one having a biomass-derived linear alkyl group (biomass C 12-18 linear alkyl (meth)acrylate), or a non-biomass-derived may have a straight-chain alkyl group.
  • both the C 5-11 linear alkyl (meth)acrylate and the C 12-18 linear alkyl (meth)acrylate are preferably biomass-derived materials.
  • the ratio of biomass C 5-11 linear alkyl (meth)acrylate to C 5-18 linear alkyl (meth)acrylate may be, for example, 1% by weight or more, 10% by weight or more, or 30% by weight or more. It may be at least 50% by weight, at least 70% by weight, at least 90% by weight, or at least 99% by weight.
  • the proportion of biomass C5-11 linear alkyl (meth)acrylate in C5-18 linear alkyl (meth)acrylate may be 99% by weight or less, may be 90% by weight or less, and may be 70% by weight. % or less, 50 wt% or less, 30 wt% or less, 10 wt% or less, or 1 wt% or less.
  • the C 5-18 linear alkyl (meth)acrylate is n-heptyl (meth)acrylate having a biomass-derived n-heptyl group (hereinafter also referred to as “biomass heptyl (meth)acrylate”).
  • biomass heptyl (meth)acrylate By using biomass heptyl (meth)acrylate, the effects of the technology disclosed herein can be exhibited particularly favorably while reducing dependence on fossil resource-based materials. Among them, biomass heptyl acrylate is particularly preferable from the viewpoint of adhesive properties.
  • the ratio of biomass heptyl (meth)acrylate to the total C 5-18 linear alkyl (meth)acrylate used as the monomer component of the acrylic polymer may be, for example, 1% by weight or more, and 10% by weight or more is suitable, preferably 30 wt% or more, more preferably 50 wt% or more (e.g., more than 50 wt%), may be 70 wt% or more, may be 80 wt% or more, may be 85 wt% or more, may be 90 wt% or more. It may be at least 92% by weight, or at least 95% by weight.
  • the effect of use can be effectively expressed while improving the biomass carbon ratio of the acrylic polymer.
  • the technology disclosed herein can be preferably practiced in a mode using an acrylic polymer with a monomer composition containing only biomass heptyl (meth)acrylate as the C 5-18 linear alkyl (meth)acrylate. Therefore, the upper limit of the proportion of biomass heptyl (meth)acrylate in the total C 5-18 linear alkyl (meth)acrylate is 100% by weight.
  • the proportion of biomass heptyl (meth)acrylate in total C 5-18 linear alkyl (meth)acrylates may be 95 wt% or less, may be 75 wt% or less, and may be 60 wt% or less. It may be less than or equal to 50 wt% (for example, less than 50 wt%), less than or equal to 30 wt%, less than or equal to 10 wt%, or less than or equal to 1 wt%.
  • the monomer component constituting the acrylic polymer contains a (meth)acrylic monomer (m2) having a side chain containing an active hydrogen.
  • the carbon number of the side chain containing the active hydrogen is 3 or more.
  • the side chain of the (meth)acrylic monomer (m2) refers to a chain structure bonded to a (meth)acryloyl group, and in the (meth)acrylic monomer (m2) represented by the following formula (2) , R4 .
  • R3 in the above formula is a hydrogen atom or a methyl group.
  • R 4 is a side chain containing an active hydrogen as described above, such as an organic group having a hydroxyl group and/or a carboxy group.
  • Such a side chain (R 4 ) becomes a side chain of the polymer after polymerization of the (meth)acrylic monomer (m2).
  • a (meth)acrylic monomer (m2) having an active hydrogen in a side chain having a relatively long carbon number of 3 or more the active hydrogen serving as a cross-linking point and the cross-linking agent are close to each other, and aging (cross-linking reaction) occurs. is thought to progress rapidly.
  • the length of the side chain of the (meth) acrylic monomer (m2) is changed from the range of 3 or more carbon atoms
  • the (meth)acrylic monomers (m2) can be used singly or in combination of two or more.
  • the (meth)acrylic monomer (m2) may be biomass-derived or non-biomass-derived.
  • the (meth)acrylic monomer (m2) includes a (meth)acrylic monomer having a hydroxyl group or a carboxy group as a side chain containing active hydrogen, in other words, a hydroxyl group-containing (meth)acrylic monomer, a carboxy group-containing ( meth)acrylic monomers can be used.
  • a cross-linking point is introduced into the acrylic polymer, and the pressure-sensitive adhesive can be cured by reaction with a cross-linking agent such as an isocyanate-based cross-linking agent.
  • the carbon number of the side chain is, for example, 3-10, preferably 4-10, may be 4-8, or may be 4-6.
  • a hydroxyl group-containing (meth)acrylic monomer is preferably used as the (meth)acrylic monomer (m2).
  • Preferred examples of hydroxyl group-containing (meth)acrylic monomers include (meth)acrylic monomers having a hydroxyalkyl group with 3 or more carbon atoms. Among them, hydroxyalkyl (meth)acrylates having a hydroxyalkyl group having 3 or more carbon atoms at the ester end are more preferable, and among them, compounds in which the alkyl group constituting the hydroxyalkyl group is linear are more preferable. .
  • the hydroxyalkyl group of the hydroxyalkyl (meth)acrylate has, for example, 3 to 10 carbon atoms, preferably 4 to 10 carbon atoms, may be 4 to 8 carbon atoms, or may be 4 to 6 carbon atoms.
  • hydroxyl group-containing (meth)acrylic monomers include 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.
  • hydroxyl group-containing (meth)acrylic monomers may be used singly or in combination of two or more.
  • the carboxy group-containing (meth)acrylic monomer used as the (meth)acrylic monomer (m2) is not particularly limited, and carboxypentyl (meth)acrylate, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxypropyl hexahydrophthalate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl-2- Hydroxyethyl-phthalic acid, 2-(meth)acryloyloxyethyl maleic acid, carboxypolycaprolactone mono(meth)acrylate, 2-(meth)acryloyloxyethyl tetrahydrophthalic acid and the like.
  • one or two or more (meth)acrylic monomers having a carboxyl group with 3 or more carbon atoms may be selected and used from among the light ester series and light acrylate series available from Kyoeisha Chemical Co., Ltd. can be done. Specific examples include the trade name "Light Ester HO-MS (N)" (2-methacryloyloxyethyl succinic acid) and "HOA-MPE (N)” (2-acryloyloxyethyl-2-hydroxyethyl - phthalic acid) and the like.
  • the content of the (meth)acrylic monomer (m2) is, for example, 0.01% by weight or more of the total monomer components, and 0.1% by weight or more. may be present, suitably greater than 0.5 wt. It can be more than that.
  • the content of the (meth)acrylic monomer (m2) (preferably a hydroxyl group-containing (meth)acrylic monomer) in the entire monomer component is, for example, less than 15% by weight, and may be 10% by weight or less. Suitably, in some preferred embodiments, it may be 8 wt% or less, 6 wt% or less, or 5 wt% or less.
  • the cohesive force is improved, and it is easy to adjust to a good removable adhesive force, for example, it is suitable for removable surface protection applications. It is easy to form a sticky adhesive.
  • the monomer components that form the acrylic polymer include other monomers copolymerizable therewith (other copolymerizable monomers). may contain Other copolymerizable monomers are defined as monomers different from the chain alkyl (meth)acrylate and (meth)acrylic monomer (m2). Other copolymerizable monomers can be used singly or in combination of two or more.
  • Non-limiting examples of other copolymerizable monomers include the following.
  • Carboxy group-containing monomers for example acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and the like.
  • Acid anhydride group-containing monomers for example maleic anhydride, itaconic anhydride.
  • Hydroxyl-containing monomers eg 2-hydroxyethyl (meth)acrylate.
  • Monomers containing sulfonic or phosphoric acid groups for example, styrenesulfonic acid, allylsulfonic acid, sodium vinylsulfonate, 2-(meth)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid, sulfo propyl (meth)acrylate, (meth)acryloyloxynaphthalenesulfonic acid, 2-hydroxyethyl acryloyl phosphate and the like.
  • Epoxy group-containing monomers For example, epoxy group-containing acrylates such as glycidyl (meth)acrylate and 2-ethylglycidyl (meth)acrylate, allyl glycidyl ether, glycidyl ether (meth)acrylate, and the like. Cyano group-containing monomers: for example acrylonitrile, methacrylonitrile and the like. Isocyanate group-containing monomers: for example, 2-isocyanatoethyl (meth)acrylate and the like.
  • Amido group-containing monomers for example, (meth)acrylamide; N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-diisopropyl(meth) N,N-dialkyl(meth)acrylamides such as acrylamide, N,N-di(n-butyl)(meth)acrylamide, N,N-di(t-butyl)(meth)acrylamide; N-ethyl(meth) N-alkyl (meth)acrylamides such as acrylamide, N-isopropyl (meth)acrylamide, N-butyl (meth)acrylamide, Nn-butyl (meth)acrylamide; N-vinylcarboxylic acid amides such as N-vinylacetamide ; monomers having a hydroxyl group and an amide group, such as N-hydroxyalkyl (me
  • N-vinyl-2-pyrrolidone N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N- Vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-(meth)acryloyl-2-pyrrolidone, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-vinylmorpholine, N-vinyl-3 -morpholinone, N-vinyl-2-caprolactam, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, N-vinylpyrazole, N-vinylisoxazole, N-vinyl thiazole, N-
  • Maleimides For example, N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide and the like.
  • Itaconimides for example, N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, N-lauryl itaconimide and the like.
  • Aminoalkyl (meth)acrylates for example, aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, t (meth)acrylate - butylaminoethyl.
  • Alkoxy group-containing monomers for example, 2-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, (meth)acrylic acid
  • Alkoxyalkyl (meth)acrylates such as butoxyethyl and ethoxypropyl (meth)acrylate
  • Alkoxyalkylene glycol (meth)acrylates such as methoxyethylene glycol (meth)acrylate and methoxypolypropylene glycol (meth)acrylate.
  • Vinyl esters For example, vinyl acetate, vinyl propionate and the like.
  • Vinyl ethers For example, vinyl alkyl ethers such as methyl vinyl ether and ethyl vinyl ether.
  • Aromatic vinyl compounds for example, styrene, ⁇ -methylstyrene, vinyltoluene and the like.
  • Olefins For example, ethylene, butadiene, isoprene, isobutylene and the like.
  • (Meth)acrylates having an alicyclic hydrocarbon group for example, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate and the like.
  • (Meth)acrylates having an aromatic hydrocarbon group for example, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate and the like.
  • heterocycle-containing (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate, halogen atom-containing (meth)acrylates such as vinyl chloride and fluorine atom-containing (meth)acrylates, silicon atom-containing such as silicone (meth)acrylates (meth)acrylates, (meth)acrylates obtained from terpene compound derivative alcohols, and the like.
  • the monomer component that constitutes the acrylic polymer may or may not contain the other copolymerizable monomers.
  • the amount of the other copolymerizable monomer is not particularly limited, and may be appropriately selected according to the purpose and application.
  • the content of other copolymerizable monomers in the monomer component is, for example, suitably less than 30% by weight, preferably less than 10% by weight, more preferably less than 5% by weight, and less than 3% by weight. (for example, less than 1% by weight).
  • the technology disclosed herein can be preferably practiced in a mode in which the monomer component does not substantially contain other copolymerizable monomers.
  • the amount of the carboxy group-containing monomer used in the monomer component forming the acrylic polymer is, for example, less than 10% by weight, may be less than 3% by weight, may be less than 1% by weight, or may be less than 0% by weight. It may be less than 0.5% by weight, or less than 0.1% by weight.
  • the technology disclosed herein can be preferably implemented in a mode in which the monomer component does not substantially contain a carboxy group-containing monomer. By limiting the amount of the carboxy group-containing monomer used or not using it, the adhesive strength can be easily adjusted to an appropriate removable range, for example, forming a pressure sensitive adhesive suitable for removable surface protection applications. It's easy to do.
  • biomass carbon ratio of the monomer component constituting the acrylic polymer may be, for example, 1% or more, suitably 10% or more, preferably 30% or more, more preferably 30% or more. is 50% or more (eg, more than 50%), may be 70% or more, may be 80% or more, or may be 90% to 100%.
  • the method for obtaining the acrylic polymer is not particularly limited, and various polymerization methods known as synthesis methods for acrylic polymers, such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and photopolymerization. can be adopted as appropriate.
  • a solution polymerization method can be preferably employed.
  • An embodiment employing a solution polymerization method can be advantageous from the viewpoint of transparency, adhesion performance, and the like.
  • a method for supplying the monomers when carrying out solution polymerization a batch charging method for supplying all monomer raw materials at once, a continuous supply (dropping) method, a divided supply (dropping) method, or the like can be appropriately adopted.
  • the polymerization temperature at the time of solution polymerization can be appropriately selected according to the type of monomer and solvent used, the type of polymerization initiator, etc. ° C.).
  • the solvent (polymerization solvent) used for solution polymerization can be appropriately selected from conventionally known organic solvents (toluene, ethyl acetate, etc.).
  • the initiator used for polymerization may be a conventionally known polymerization initiator (for example, an azo polymerization initiator such as 2,2'-azobisisobutyronitrile (AIBN) or a peroxide polymerization initiator). initiator, etc.).
  • the amount of the polymerization initiator used may be a normal amount, for example, about 0.005 to 1 part by weight (typically about 0.01 to 1 part by weight) per 100 parts by weight of the monomer component. ).
  • the weight-average molecular weight (Mw) of the acrylic polymer is usually about 10 ⁇ 10 4 or more.
  • An acrylic polymer having such an Mw tends to yield a pressure-sensitive adhesive exhibiting good cohesiveness.
  • the Mw of the acrylic polymer is, for example, 30 ⁇ 10 4 or more, preferably 50 ⁇ 10 4 or more, from the viewpoint of removable adhesive strength, cohesive strength, and the like. , 70 ⁇ 10 4 or more.
  • the Mw of the acrylic polymer is usually approximately 500 ⁇ 10 4 or less, may be 300 ⁇ 10 4 or less, or may be 100 ⁇ 10 4 . or less (for example, less than 100 ⁇ 10 4 ).
  • the pressure-sensitive adhesive tends to have appropriate fluidity and wettability (adhesion) to the adherend is likely to be obtained.
  • the surface protection film does not peel off from the adherend during use, and can preferably fulfill its protective function. It is particularly significant that the Mw of the acrylic polymer obtained by the solution polymerization method is within the preferred range described above.
  • the Mw of the acrylic polymer can be measured by gel permeation chromatography (GPC) and calculated as a value converted to standard polystyrene. Specifically, it can be obtained by measuring under the following conditions using a GPC measurement device with the trade name "HLC-8220GPC" (manufactured by Tosoh Corporation). The same applies to the examples described later.
  • GPC gel permeation chromatography
  • crosslinking agent The adhesive compositions disclosed herein contain a cross-linking agent.
  • a cross-linking agent can serve to increase the cohesive strength of the adhesive.
  • the cross-linking agent can be selected from various cross-linking agents known in the field of adhesives. Examples of such cross-linking agents include isocyanate cross-linking agents, epoxy cross-linking agents, oxazoline cross-linking agents, aziridine cross-linking agents, melamine cross-linking agents, peroxide cross-linking agents, urea cross-linking agents, and metal alkoxide cross-linking agents. , metal chelate cross-linking agents, metal salt cross-linking agents, carbodiimide cross-linking agents, amine cross-linking agents and the like.
  • a crosslinking agent can be used individually by 1 type or in combination of 2 or more types.
  • the cross-linking agent may be biomass-derived or non-biomass-derived.
  • a cross-linking agent derived from biomass is preferably used from the viewpoint of production of an acrylic pressure-sensitive adhesive that takes into consideration the suppression of dependence on fossil resource-based materials.
  • the technology disclosed herein can be preferably implemented in a mode in which both the acrylic polymer and the cross-linking agent contained in the pressure-sensitive adhesive composition are derived from biomass.
  • the amount of cross-linking agent used is not particularly limited.
  • the amount of the cross-linking agent used can be selected, for example, from the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the acrylic polymer. From the viewpoint of achieving both improved cohesive strength and adhesion to the adherend in a well-balanced manner, the amount of the cross-linking agent used relative to 100 parts by weight of the acrylic polymer is usually preferably 10 parts by weight or less, and 8 parts by weight. It may be less than or equal to 6 parts by weight or less, more preferably 0.5 parts by weight or more, and may be 1 part by weight or more.
  • By adjusting the amount of the cross-linking agent to be used in an appropriate range it is possible to increase the cohesive force of the pressure-sensitive adhesive, prevent the occurrence of adhesive residue on the adherend, and obtain adhesion to the adherend. .
  • the cross-linking agent preferably contains at least an isocyanate-based cross-linking agent.
  • the isocyanate-based cross-linking agents may be used singly or in combination of two or more.
  • the isocyanate-based cross-linking agent may be biomass-derived or non-biomass-derived.
  • a biomass-derived isocyanate-based cross-linking agent is preferably used from the standpoint of producing an acrylic pressure-sensitive adhesive that takes into account the suppression of dependence on fossil resource-based materials.
  • the isocyanate-based cross-linking agent may be used in combination with another cross-linking agent such as an epoxy-based cross-linking agent.
  • the isocyanate-based cross-linking agent a polyisocyanate-based cross-linking agent having two or more isocyanate groups per molecule is preferably used.
  • the number of isocyanate groups per molecule of the polyisocyanate-based cross-linking agent is preferably 2-10, for example 2-4, typically 2 or 3.
  • the polyisocyanate-based crosslinking agent include aromatic polyisocyanates such as tolylene diisocyanate and xylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate; and aliphatic polyisocyanates such as hexamethylene diisocyanate.
  • lower aliphatic polyisocyanates such as butylene diisocyanate, pentamethylene diisocyanate and hexamethylene diisocyanate
  • alicyclic polyisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate
  • Aromatic diisocyanates such as 4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and polymethylene polyphenyl diisocyanate
  • L trimethylolpropane/hexamethylene diisocyanate trimer adduct
  • isocyanurate form of hexamethylene diisocyanate manufactured by Tosoh, trade name "Coronate HX”
  • aliphatic diisocyanates such as pentamethylene diisocyanate and hexamethylene diisocyanate, isocyanurates of such aliphatic diisocyanates, and the like.
  • the proportion of aliphatic polyisocyanates (aliphatic diisocyanates, isocyanurates of aliphatic diisocyanates, etc.) in the total amount of the isocyanate-based cross-linking agent is, for example, more than 50% by weight. It may be 70% by weight or more, or 90% by weight or more (for example, 95 to 100% by weight).
  • the amount of the isocyanate-based cross-linking agent used may be, for example, about 0.1 parts by weight or more, 0.5 parts by weight or more, or 1.0 parts by weight or more with respect to 100 parts by weight of the acrylic polymer. or more than 1.5 parts by weight. From the viewpoint of obtaining a higher use effect, the amount of the isocyanate cross-linking agent used relative to 100 parts by weight of the acrylic polymer may be, for example, more than 2.0 parts by weight, may be 2.5 parts by weight or more, or may be 3.0 parts by weight. parts or more, or 3.5 parts by weight or more.
  • the amount of the isocyanate-based cross-linking agent used relative to 100 parts by weight of the acrylic polymer is usually suitably 20 parts by weight or less, and may be 10 parts by weight or less, may be 8 parts by weight or less, or may be 6 parts by weight or less. 5 parts by weight or less (for example, less than 5 parts by weight) or 4.5 parts by weight or less (for example, less than 4.0 parts by weight).
  • the adhesive composition disclosed herein preferably contains a catalyst.
  • a catalyst By using a catalyst, the curing reaction of the pressure-sensitive adhesive composition (typically, the cross-linking reaction of the above-mentioned cross-linking agent) can proceed efficiently, and stable adhesion can be achieved from an early stage after the pressure-sensitive adhesive sheet is produced. It's easy to do.
  • the catalyst is also called a cross-linking catalyst. Examples of catalysts include tin (Sn)-containing compounds (tin-based catalysts), zirconium (Zr)-containing compounds (zirconium-based catalysts), titanium (Ti)-containing compounds (titanium-based catalysts), iron (Fe)-containing compounds (iron-based catalysts).
  • a catalyst can be used individually by 1 type or in combination of 2 or more types.
  • the technology disclosed herein does not exclude the use of tin-based catalysts, it realizes rapid aging and sufficient pot life without using tin-based catalysts, which have been widely used for their high catalytic activity. can do. Accordingly, in some embodiments, the catalyst used in the adhesive composition is free of tin-containing compounds. This makes it possible to obtain a pressure-sensitive adhesive that is environmentally friendly and safe.
  • a compound containing a Group 4 element is used as the catalyst.
  • a Group 4 element-containing compound as a catalyst, the effects of the technology disclosed herein can be achieved without using a tin-based catalyst.
  • the Group 4 element-containing compound tends to undergo less hue change such as coloring than other catalysts such as iron-based catalysts. Therefore, for example, in a mode of use in which the adhesive is required to have transparency and optical properties, it is preferable to use a Group 4 element-containing compound as a catalyst.
  • the Group 4 element-containing compound can be used singly or in combination of two or more.
  • a zirconium-containing compound (zirconium-based catalyst) and a titanium-containing compound (titanium-based catalyst) are preferable.
  • the zirconium-containing compound which is a suitable example of the catalyst, is not particularly limited, and examples thereof include zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium ethylacetoacetate, and zirconium octylate compounds. .
  • Titanium-containing compounds which are other suitable examples of the catalyst, are not particularly limited, and examples thereof include tetraisopropyl titanate, tetra-n-butyl titanate, butyl titanate dimer, tetraoctyl titanate, and titanium acetylacetonate. , titanium tetraacetylacetonate, titanium ethylacetoacetate and the like.
  • catalysts include tin-containing compounds (organotin-containing compounds) such as dioctyltin dilaurate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diacetylacetonate, tetra-n-butyltin, trimethyltin hydroxide, butyltin oxide.
  • tin-containing compounds organotin-containing compounds
  • aluminum-containing compounds such as aluminum secondary butoxide, aluminum trisacetylacetonate, aluminum bisethylacetoacetate, and aluminum trisethylacetoacetate
  • iron-containing compounds organic iron-containing compounds
  • the amount of catalyst used is not particularly limited.
  • the amount of the catalyst used can be, for example, about 0.0001 parts by weight or more, preferably about 0.001 parts by weight or more, and about 0.005 parts by weight or more (for example, 0.01 parts by weight or more).
  • the amount of the catalyst used is about 0.02 parts by weight or more, and may be about 0.03 parts by weight or more, based on 100 parts by weight of the acrylic polymer.
  • the amount of the catalyst used can be, for example, about 1 part by weight or less, preferably about 0.1 part by weight or less, and about 0.05 part by weight or less, relative to 100 parts by weight of the acrylic polymer. may By using the appropriate amount of catalyst, the cross-linking reaction rate can be adjusted.
  • the pressure-sensitive adhesive composition can optionally contain a compound that causes keto-enol tautomerism as a cross-linking retarder.
  • a compound that produces keto-enol tautomerism can be preferably used in a pressure-sensitive adhesive composition containing an isocyanate-based cross-linking agent. Thereby, the effect of extending the pot life of the pressure-sensitive adhesive composition can be exhibited.
  • Various ⁇ -dicarbonyl compounds can be used as compounds that cause keto-enol tautomerism.
  • ⁇ -diketones such as acetylacetone and 2,4-hexanedione
  • acetoacetates such as methyl acetoacetate and ethyl acetoacetate
  • propionyl acetates such as ethyl propionylacetate
  • isobutyryl such as ethyl isobutyrylacetate.
  • acetic acid esters malonic acid esters such as methyl malonate and ethyl malonate; and the like.
  • acetylacetone and acetoacetates The compounds that cause keto-enol tautomerism can be used singly or in combination of two or more.
  • the amount of the compound that causes keto-enol tautomerism may be, for example, 0.1 parts by weight or more, and 0.5 parts by weight or more with respect to 100 parts by weight of the acrylic polymer contained in the pressure-sensitive adhesive composition. For example, it can be 1 part by weight or more. In some preferred embodiments, from the viewpoint of obtaining a sufficient pot life, the amount of the compound that causes keto-enol tautomerism is, for example, 3 parts per 100 parts by weight of the acrylic polymer contained in the pressure-sensitive adhesive composition. It is at least 5 parts by weight, more preferably at least 6 parts by weight, and may be at least 8 parts by weight, or at least 10 parts by weight. The amount used may be, for example, 30 parts by weight or less, suitably 25 parts by weight or less, and may be, for example, 20 parts by weight or less, or may be 15 parts by weight or less.
  • additives can be blended into the adhesive composition as necessary.
  • additives include surface lubricants, leveling agents, tackifying resins, plasticizers, softeners, fillers, colorants (pigments, dyes, etc.), antistatic agents, antioxidants, preservatives, light stabilizers. agents, ultraviolet absorbers, polymerization inhibitors, silane coupling agents, and the like.
  • the content of these optional additives can be appropriately set according to the purpose of use.
  • the amount of the optional additive used is, for example, less than 10 parts by weight, and is suitably about 3 parts by weight or less (for example, about 1 part by weight or less) with respect to 100 parts by weight of the acrylic polymer.
  • the proportion of the acrylic polymer in the solid content (nonvolatile content) of the pressure-sensitive adhesive composition is suitably 80% by weight or more, preferably 85% by weight or more, and 90% by weight or more (for example, 90% by weight or more and 99.9% by weight or less).
  • the form of the pressure-sensitive adhesive composition disclosed herein is not particularly limited, and water-based pressure-sensitive adhesive compositions, solvent-based pressure-sensitive adhesive compositions, and the like are preferred.
  • the water-based pressure-sensitive adhesive composition refers to a pressure-sensitive adhesive composition in the form of containing a pressure-sensitive adhesive (pressure-sensitive adhesive layer-forming component) in a water-based solvent (water-based solvent). It is a concept that includes a water-dispersed pressure-sensitive adhesive composition in which the pressure-sensitive adhesive is dispersed in water and a water-soluble pressure-sensitive adhesive composition in which the pressure-sensitive adhesive is dissolved in water.
  • the solvent-type adhesive composition refers to an adhesive composition in the form of containing an adhesive in an organic solvent.
  • the organic solvent contained in the solvent-based pressure-sensitive adhesive composition one or more organic solvents (toluene, ethyl acetate, etc.) that can be used in the above solution polymerization can be used without particular limitation.
  • the technology disclosed herein can be preferably practiced in a mode comprising a pressure-sensitive adhesive layer formed from a solvent-based pressure-sensitive adhesive composition.
  • the effects of the technique disclosed herein are preferably achieved.
  • the adhesive composition disclosed herein preferably has a gel fraction of 70% or more after drying.
  • a pressure-sensitive adhesive having a gel fraction of 70% or more is less likely to cause deformation or damage such as dents due to external force during production, and less likely to cause changes in appearance.
  • Such a pressure-sensitive adhesive tends to form a pressure-sensitive adhesive sheet having a smooth surface. For example, when a transparent pressure-sensitive adhesive sheet is formed and an adherend is inspected through the pressure-sensitive adhesive sheet, highly accurate inspection is possible, which is preferable.
  • by setting the gel fraction high it is easy to form a pressure-sensitive adhesive with excellent removability.
  • the gel fraction is more preferably over 80%, may be over 85% (e.g., 90% or more), may be 92% or more, or may be 94% or more (e.g., 95% or more). ) can be used.
  • the gel fraction may be 100%, but may be, for example, less than 99% or less than 95% (for example, 94% or less) from the viewpoint of adhesion to the adherend.
  • the drying conditions for the pressure-sensitive adhesive composition for measuring the gel fraction are 130° C. for 20 seconds. Specifically, the gel fraction is measured by the method described in Examples below. Since the gel fraction after drying of the adhesive composition can be the gel fraction of the adhesive (layer), the gel fraction of the adhesive (layer) constituting the adhesive sheet described later is also set from the above range. can be
  • the pressure-sensitive adhesive composition contains a biomass-derived material, and the biomass-carbon ratio of the non-volatile matter (also the biomass-carbon ratio of the pressure-sensitive adhesive) can be a predetermined value or higher.
  • the non-volatile biomass carbon ratio of the pressure-sensitive adhesive composition is, for example, 1% or more, may be 10% or more, preferably 30% or more, and more preferably 50% or more.
  • a high biomass carbon ratio of the pressure-sensitive adhesive means that the amount of fossil resource-based materials such as petroleum used is small. From this point of view, the higher the biomass carbon ratio of the adhesive, the better.
  • the non-volatile biomass carbon ratio of the adhesive composition may be 55% or more, 60% or more, 70% or more, 75% or more, or 80% or more. It may be greater than 80%.
  • the upper limit of the biomass carbon ratio is 100% by definition, and may be 99% or less. From the viewpoint of availability of materials, it may be 95% or less or 90% or less. From the viewpoint of facilitating good adhesion performance, in some embodiments, the non-volatile biomass carbon ratio of the pressure-sensitive adhesive composition may be, for example, 90% or less, 85% or less, or 80% or less. good.
  • the pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed from any of the pressure-sensitive adhesive compositions disclosed herein.
  • the pressure-sensitive adhesive sheet may be a pressure-sensitive adhesive sheet with a substrate having the pressure-sensitive adhesive layer on one or both sides of a non-releasable substrate (supporting substrate), and the pressure-sensitive adhesive layer is held by a release liner. It may be a substrate-less pressure-sensitive adhesive sheet (that is, a pressure-sensitive adhesive sheet having no non-releasable substrate).
  • the pressure-sensitive adhesive sheet disclosed herein has a limited peel speed dependence of the peel force, so it is easy to peel off regardless of the peel speed. Therefore, it is suitable as a surface protection film that can be peeled again after use.
  • the structure of an adhesive sheet according to one embodiment is schematically shown in FIG.
  • the pressure-sensitive adhesive sheet 1 includes a sheet-like support base material (for example, a resin film) 10 having a first surface 10A and a second surface 10B, and a base material provided with an adhesive layer 21 provided on the first surface 10A side. It is configured as a single-sided adhesive sheet with The pressure-sensitive adhesive layer 21 is fixedly provided on the first surface 10A side of the supporting substrate 10 , that is, without the intention of separating the pressure-sensitive adhesive layer 21 from the supporting substrate 10 .
  • a sheet-like support base material for example, a resin film
  • the pressure-sensitive adhesive layer 21 is fixedly provided on the first surface 10A side of the supporting substrate 10 , that is, without the intention of separating the pressure-sensitive adhesive layer 21 from the supporting substrate 10 .
  • Such a single-sided adhesive pressure-sensitive adhesive sheet 1 is suitable as a surface protection film that is used by attaching the pressure-sensitive adhesive surface to the surface of an adherend (object to be protected, for example, an optical component such as a polarizing plate) 50 .
  • the surface (adhesive surface) 21A of the pressure-sensitive adhesive layer 21 is protected by a release liner 31 having a release surface on at least the side facing the pressure-sensitive adhesive layer 21. It can be a component of the pressure-sensitive adhesive sheet 100 with a release liner.
  • the adhesive sheet 1 is wound so that the adhesive surface 21A becomes the second surface (back surface) of the supporting substrate 10.
  • 10B may be in a protected form (roll form).
  • Examples of the release liner include a release liner having a release layer on the surface of a liner substrate such as a resin film or paper, and a low-grade resin such as a polyolefin resin (e.g., polyethylene, polypropylene) or a fluororesin.
  • a release liner or the like made of an adhesive material can be used.
  • the release layer may be formed by surface-treating the liner base material with a release treatment agent such as a silicone-based, long-chain alkyl-based, fluorine-based, or molybdenum sulfide-based release agent.
  • a material formed using a biomass-derived material or a recycled material (recycled film, etc.) can be preferably used, similarly to the base material of the pressure-sensitive adhesive sheet described later.
  • the concept of the adhesive sheet referred to here may include items called adhesive tapes, adhesive labels, adhesive films, and the like.
  • the pressure-sensitive adhesive sheet may be in the form of a roll or sheet. Also, the pressure-sensitive adhesive sheet may be processed into various shapes.
  • the formation of the adhesive (layer) from the adhesive composition can be performed by a conventionally known method.
  • a PSA layer A pressure-sensitive adhesive sheet can be formed by forming a layer consisting of a pressure-sensitive adhesive.
  • a method (direct method) of forming a pressure-sensitive adhesive layer by directly applying (typically applying) a pressure-sensitive adhesive composition to the substrate and curing the composition is preferably adopted. can do.
  • a method of applying a pressure-sensitive adhesive composition to a surface having releasability (release surface) and curing the composition to form a pressure-sensitive adhesive layer on the surface and transferring the pressure-sensitive adhesive layer to a substrate may be adopted.
  • the release surface the surface of a release liner, the back surface of a base material subjected to a release treatment, or the like can be used.
  • curing of the pressure-sensitive adhesive composition can be performed by subjecting the pressure-sensitive adhesive composition to a curing treatment such as drying, crosslinking, polymerization, or cooling. Two or more curing treatments may be performed simultaneously or stepwise.
  • the pressure-sensitive adhesive composition is carried out using known or commonly used coaters such as gravure roll coaters, reverse roll coaters, kiss roll coaters, dip roll coaters, die coaters, bar coaters, knife coaters, and spray coaters. can be done.
  • the adhesive composition may be applied by impregnation, curtain coating, or the like.
  • the drying temperature can be, for example, about 40 to 150°C, preferably about 60 to 130°C.
  • aging may be performed for the purpose of adjusting component migration in the pressure-sensitive adhesive layer, progressing the cross-linking reaction, relaxing distortion that may exist in the substrate or the pressure-sensitive adhesive layer, and the like. good.
  • the thickness of the adhesive layer is, for example, approximately 1 ⁇ m or more, preferably approximately 3 ⁇ m or more (for example, approximately 5 ⁇ m or more). From the viewpoint of adhesion to adherends, etc., the thickness is preferably about 10 ⁇ m or more, more preferably about 14 ⁇ m or more, and even more preferably about 17 ⁇ m or more.
  • the thickness can be, for example, approximately 100 ⁇ m or less, suitably approximately 50 ⁇ m or less (for example, approximately 30 ⁇ m or less), and preferably approximately 25 ⁇ m or less.
  • a pressure-sensitive adhesive layer having the thickness described above is suitable as a pressure-sensitive adhesive layer for use as a surface protective film.
  • the material of the supporting substrate used as the support of the pressure-sensitive adhesive sheet disclosed herein is not particularly limited, and for example, a resin film can be preferably employed.
  • the resin film may be formed by molding various resin materials into a film shape.
  • the resin material those capable of forming a resin film excellent in one or more of properties such as transparency, mechanical strength, thermal stability, moisture shielding property, and isotropy are preferred.
  • polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate; celluloses such as diacetyl cellulose and triacetyl cellulose; polycarbonates; acrylic polymers such as polymethyl methacrylate;
  • a resin film composed of a resin material as a component can be preferably used as the substrate.
  • resin material constituting the resin film examples include styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymers; polyolefins such as polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, and ethylene-propylene.
  • styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymers
  • polyolefins such as polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, and ethylene-propylene.
  • Polyvinyl chlorides Polyamides such as nylon 6, nylon 6,6 and aromatic polyamides; Alternatively, polyimides, polysulfones, polyethersulfones, polyetheretherketones, polyphenylene sulfides, fluorine-based resins, polyvinyl alcohols, polyvinyl acetates, polyvinylidene chlorides, polyvinyl butyrals, polyarylates, poly
  • a resin film composed of a resin material containing oxymethylenes, epoxy resins, or the like as a main component may be used as the substrate.
  • the resin material constituting the resin film may be a blend of two or more of these.
  • the term "resin film” means a non-porous structure and typically substantially voidless resin film. Therefore, the resin film is a concept distinguished from foam films, nonwoven fabrics, and woven fabrics.
  • base materials include foam sheets made of polyurethane foam, polyethylene foam, polychloroprene foam, etc., and various fibrous substances (natural fibers such as hemp and cotton, synthetic fibers such as polyester and vinylon). , Semi-synthetic fibers such as acetate, etc.) Woven and non-woven fabrics made by spinning alone or blended; etc.
  • a base material having a structure in which these are combined may be used.
  • Examples of such a substrate having a composite structure include a substrate having a structure in which a metal foil and the plastic film are laminated, and a plastic sheet reinforced with inorganic fibers such as glass cloth.
  • the base material may be formed from a biomass-derived material or may be formed from a non-biomass-derived material.
  • a biomass-derived base material (typically a resin film) is preferably used from the viewpoint of pressure-sensitive adhesive sheet production that takes into account the suppression of dependence on fossil resource-based materials.
  • the base material may be formed using recyclable materials or recycled materials (also referred to as recycled materials).
  • a resin film is preferably used as such a recycled material. Since resin films (e.g., polyester films such as PET films) can be recycled, sustainable reproduction can be achieved by reusing used resin films regardless of whether plant-derived materials are used or not. is possible, and the environmental load can be reduced. Such recyclable resin films and recycled resin films are also called recycled films.
  • the recycled material (for example, recycled film) may be formed from a biomass-derived material, or may be formed from a non-biomass-derived material.
  • a resin film in which a resin (polyester resin) containing polyester as a main component (a component containing more than 50% by weight) is molded into a film shape is used as the base material.
  • a resin film (PET film) in which the polyester is mainly PET, a resin film (PEN film) in which the polyester is mainly PEN, or the like can be preferably employed.
  • the base material may have a single-layer structure or a multilayer structure. Therefore, a resin film that can be used as a substrate may also have a single-layer structure or a multi-layer structure of two or more layers (for example, a three-layer structure). A resin film having a single-layer structure can be preferably used as the substrate.
  • additives such as antioxidants, ultraviolet absorbers, antistatic components, plasticizers, colorants (pigments, dyes, etc.) are blended with the base material (typically a resin film) as necessary.
  • the base material typically a resin film
  • the adhesive layer side surface of the base material may be subjected to surface treatment such as chromic acid treatment, ozone exposure, flame exposure, high voltage shock exposure, and ionizing radiation treatment.
  • a surface treatment may be, for example, a treatment for enhancing adhesion between the substrate and the pressure-sensitive adhesive layer.
  • the surface of the substrate on the pressure-sensitive adhesive layer side may be subjected to a primer treatment. Silicone primer treatment is preferred from the viewpoint of adhesion to the silicone-based pressure-sensitive adhesive.
  • the backside of the substrate can be hardcoated. As a result, the scratch resistance of the back surface of the base material is improved, and when the adhesive sheet is used as a protective sheet, more excellent protective performance can be exhibited.
  • the base material may be subjected to antistatic treatment from the viewpoint of suppressing the generation of static electricity.
  • the substrate may also be subjected to various treatments such as antifouling, anti-fingerprint, anti-glare, and anti-reflection treatments.
  • the thickness of the base material can be appropriately selected in consideration of the application, purpose, usage pattern, etc. of the adhesive sheet.
  • a base material having a thickness of about 10 ⁇ m or more is suitable from the standpoint of workability such as strength and handleability, and the thickness is preferably about 20 ⁇ m or more, more preferably about 30 ⁇ m or more (for example, 35 ⁇ m or more).
  • the thickness of the substrate is suitably about 200 ⁇ m or less, preferably about 150 ⁇ m or less, more preferably about 100 ⁇ m or less, even more preferably about 75 ⁇ m or less (for example, 50 ⁇ m or less) from the viewpoint of cost.
  • a substrate having the thickness described above is suitable, for example, as a substrate for a surface protective film.
  • the pressure-sensitive adhesive sheet (preferably surface protective film) has a low-speed adhesive strength (F1(D3)) of 2.0 N measured at a tensile speed of 300 mm/min after being stored at 23°C for 3 days. /25 mm or less.
  • F1(D3) low-speed adhesive strength
  • a pressure-sensitive adhesive sheet (preferably a surface protection film) that satisfies this property has a suppressed increase in adhesive strength over time, and a low peel strength when peeled from an adherend (for example, an object to be protected). Therefore, it is easy to peel off.
  • the low-speed adhesion after storage for 3 days is more preferably 1.0 N/25 mm or less, still more preferably 0.5 N/25 mm or less, and particularly preferably 0.5 N/25 mm or less. It is 1 N/25 mm or less (for example, less than 0.1 N/25 mm).
  • the low-speed adhesion after storage for 3 days is suitably 0.01 N/25 mm or more, and 0.03 N/25 mm or more. , or 0.05 N/25 mm or more.
  • the low-speed adhesion after storage for 3 days (F1(D3)) is measured by the method described in Examples below.
  • the pressure-sensitive adhesive sheet (preferably surface protective film) has a low speed adhesive strength (F1 (D3)) measured at a tensile speed of 300 mm / min after storage at 23 ° C. for 3 days, After storage for 7 days, the adhesive strength difference (
  • a pressure-sensitive adhesive sheet in which the difference in low-speed adhesive strength after 3 days and 7 days is suppressed in this way enables stable adhesion from an early stage after the production of the pressure-sensitive adhesive sheet due to rapid aging (crosslinking reaction).
  • the adhesive force difference (
  • the low-speed adhesion after 3-day storage (F1(D3)) and the low-speed adhesion after 7-day storage (F1(D7)) are specifically measured by the method described in Examples below.
  • the pressure-sensitive adhesive sheet (preferably surface protective film) has a high-speed adhesive strength (F2(D3)) of 5.0 N measured at a tensile speed of 30 m/min after being stored at 23°C for 3 days. /25 mm or less.
  • F2(D3) high-speed adhesive strength
  • a pressure-sensitive adhesive sheet that satisfies these properties has a suppressed peel force when peeled from an adherend at a relatively high speed, and therefore tends to exhibit excellent peelability regardless of the peel speed.
  • the high-speed adhesive strength after storage for 3 days (F2 (D3)) is more preferably 3.0 N/25 mm or less, still more preferably 2.0 N/25 mm or less, and particularly preferably 1.0 N/25 mm or less.
  • the high-speed adhesive strength after storage for 7 days is suitably 0.1 N/25 mm or more, and 0.3 N/25 mm or more. , or 0.5 N/25 mm or more.
  • the high-speed adhesive strength after storage for 3 days is measured by the method described in Examples below.
  • the pressure-sensitive adhesive sheet after storage at 23 ° C. for 3 days, has a high speed adhesive strength (F2 (D3)) measured at a tensile speed of 30 m / min and After storage for 3 days, the adhesive strength difference (
  • the pressure-sensitive adhesive sheet in which the difference between the high-speed adhesive strength and the low-speed adhesive strength is suppressed in this way has little dependence of the peeling force on the peeling speed, and the peeling operation is easy.
  • ) is more preferably within 1.8 N/25 mm, more preferably within 1.5 N/25 mm, and within 1.2 N/25 mm. may be less than 1.0 N/25 mm, or less than 0.8 N/25 mm.
  • the adhesive sheet preferably has transparency with a total light transmittance of about 50% or more. More preferably, the transparent pressure-sensitive adhesive sheet has a total light transmittance of 80% or more (for example, 85% or more). The upper limit of the total light transmittance may be about 99% or less (for example, 95% or less) in applications where transparency is required.
  • a transparent pressure-sensitive adhesive sheet is preferable because it enables highly accurate inspection, for example, when an adherend is inspected through the pressure-sensitive adhesive sheet.
  • Such an adhesive sheet is suitable as a surface protective film.
  • As the value of the total light transmittance a value measured according to JIS K 7361-1 can be adopted.
  • a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition disclosed herein can be used for various purposes. Since the pressure-sensitive adhesive disclosed herein has little dependence on the peel speed of the peel strength and is excellent in peeling workability at the time of re-peeling, for example, after it is attached to an object to be protected, when the purpose of protection is achieved, it is usually , is suitable as a surface protection film to be peeled off (re-peeled) from an object to be protected.
  • the object to be protected by the surface protective film is not particularly limited, and it can be used as a protective film for various products, parts, and the like.
  • the surface protective film is particularly suitable as a surface protective film for protecting the surface of optical parts (for example, optical parts used as liquid crystal display panel components such as polarizing plates and wavelength plates) during processing and transportation. is. More specifically, the surface protective film protects the optical member during the production, transportation, etc. of the optical member used as a component of liquid crystal display panels, plasma display panels (PDP), organic electroluminescence (EL) displays, and the like. Suitable for protective applications. In particular, surfaces applied to optical components such as polarizing plates (polarizing films, e.g., reflective polarizing films) for liquid crystal display panels, wavelength plates, retardation plates, optical compensation films, brightness enhancement films, light diffusion sheets, reflection sheets, etc. Useful as a protective film.
  • polarizing plates polarizing films, e.g., reflective polarizing films
  • the pressure-sensitive adhesive composition disclosed herein in some embodiments, can contain an acrylic polymer with a high biomass carbon ratio, so that a conventional general acrylic pressure-sensitive adhesive (i.e., a low biomass carbon ratio
  • a conventional general acrylic pressure-sensitive adhesive i.e., a low biomass carbon ratio
  • the pressure-sensitive adhesive sheet disclosed herein can typically be preferably used as a pressure-sensitive adhesive sheet (for example, a surface protective film) with reduced dependence on fossil resource-based materials.
  • Preparation Example A4 96 parts of n-butyl acrylate (BA) and 4 parts of 4HBA as monomer components and ethyl acetate (polymerization solvent) were added to a flask equipped with a reflux device, a stirrer, a nitrogen gas inlet tube and a thermometer so that the solid content concentration was 30%. Further, 0.2 parts of AIBN as a polymerization initiator is added, nitrogen gas is introduced while gently stirring, the liquid temperature in the flask is maintained at around 60 ° C., and the polymerization reaction is performed for 6 hours, and then 70 ° C. for 2 hours to obtain a solution of acrylic polymer (A4). Mw of the obtained acrylic polymer (A4) was 1,060,000.
  • Acrylic polymers (A5) and (A6) were prepared in the same manner as the acrylic polymer (A1) solution except that the monomer components were changed as shown in Table 2.
  • the Mws of the obtained acrylic polymers (A5) and (A6) were 760,000 and 880,000, respectively.
  • Acrylic polymers (A8) and (A9) were prepared in the same manner as the acrylic polymer (A1) solution except that the monomer components were changed as shown in Table 3.
  • the Mws of the obtained acrylic polymers (A8) and (A9) were 810,000 and 670,000, respectively.
  • HxA indicates n-hexyl acrylate
  • OcA indicates n-octyl acrylate.
  • Preparation Example A10 The polymerization conditions were the same as in Preparation Example A1, except that the polymerization reaction was performed for 2 hours while maintaining the liquid temperature in the flask at about 60 ° C., and the conditions were aged at 70 ° C. for 6 hours. of the acrylic polymer (A10) was obtained.
  • Acrylic polymers (A11) and (A12) were prepared in the same manner as the acrylic polymer (A1) solution except that the monomer components were changed as shown in Table 3. Mw of the obtained acrylic polymers (A11) and (A12) were 640,000 and 620,000, respectively.
  • Acrylic polymer (A15) was prepared in the same manner as the acrylic polymer (A1) solution except that the monomer components were changed as shown in Table 4 and the solid content concentration of the monomer components was changed to 31%. Mw of the obtained acrylic polymer (A15) was 770,000.
  • PnA refers to n-pentyl acrylate.
  • Example 2 The same method as in Example 1 except that the amount of the isocyanate cross-linking agent (B1) used was changed to 3.5 parts (solid content) with respect to 100 parts of the solid content of the acrylic polymer (A1) solution after dilution.
  • a pressure-sensitive adhesive composition was prepared in , and a pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 using this pressure-sensitive adhesive composition.
  • Example 3 In Example 1, instead of 4 parts (solid content) of the isocyanate cross-linking agent (B1), an isocyanate cross-linking agent (B2) (trade name “STABIO D-370N”, Mitsui Chemicals, Inc., isocyanurate of pentamethylene diisocyanate) was used. Body) 3 parts (solid content) were used.
  • a pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except for this, and a pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 using this pressure-sensitive adhesive composition.
  • the isocyanate-based cross-linking agent (B2) is a compound having a biomass carbon ratio of 70%, which is produced from a biomass-derived material.
  • Example 4 The same method as in Example 3 except that the amount of the isocyanate cross-linking agent (B2) used was changed to 2.6 parts (solid content) with respect to 100 parts of the solid content of the diluted acrylic polymer (A1) solution.
  • a pressure-sensitive adhesive composition was prepared in , and a pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 using this pressure-sensitive adhesive composition.
  • Example 1 ⁇ Comparative example 1 (reference example)>
  • the solution of the acrylic polymer (A2) obtained in Preparation Example A2 was used instead of the solution of the acrylic polymer (A1), and the tin catalyst obtained in Preparation Example C2 was used instead of the zirconium catalyst solution. liquid was used.
  • a pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except for this, and a pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 using this pressure-sensitive adhesive composition.
  • Example 2 the solution of the acrylic polymer (A2) obtained in Preparation Example A2 was used in place of the solution of the acrylic polymer (A1).
  • a pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except for this, and a pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 using this pressure-sensitive adhesive composition.
  • Example 3 In Example 1, the solution of the acrylic polymer (A3) obtained in Preparation Example A3 was used in place of the solution of the acrylic polymer (A1). A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except for this, and a pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 using this pressure-sensitive adhesive composition.
  • Example 4 In Example 1, the solution of acrylic polymer (A4) obtained in Preparation Example A4 was used in place of the solution of acrylic polymer (A1). A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except for this, and a pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 using this pressure-sensitive adhesive composition.
  • Example 5 A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that the amount of acetylacetone added was changed to 6% of the diluted polymer solution, and this pressure-sensitive adhesive composition was used in the same manner as in Example 1.
  • a pressure-sensitive adhesive sheet according to this example was obtained by the method.
  • Example 6 A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that the amount of the zirconium catalyst used was changed from 0.015 parts to 0.01 parts (solid content). A pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1.
  • Example 7 A pressure-sensitive adhesive composition was prepared in the same manner as in Example 5 except that the amount of the zirconium catalyst used was changed from 0.015 parts to 0.03 parts (solid content). A pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1.
  • Example 8 In Example 2, the solution of the acrylic polymer (A5) obtained in Preparation Example A5 was used instead of the solution of the acrylic polymer (A1). A pressure-sensitive adhesive composition was prepared in the same manner as in Example 2 except for this, and a pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 using this pressure-sensitive adhesive composition.
  • Example 9 In Example 1, the solution of acrylic polymer (A6) obtained in Preparation Example A6 was used instead of the solution of acrylic polymer (A1). A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except for this, and a pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 using this pressure-sensitive adhesive composition.
  • Example 10 the solution of acrylic polymer (A7) obtained in Preparation Example A7 was used in place of the solution of acrylic polymer (A1). Except that, prepare a pressure-sensitive adhesive composition in the same manner as in Example 1, apply the above pressure-sensitive adhesive composition adjusted to a solid content concentration of 20% on a PET film, and dry at 130 ° C. for 20 seconds. The solvent was further removed to form an adhesive layer (thickness: 21 ⁇ m). Thereafter, the adhesive layer surface was covered with a release film to obtain an adhesive sheet according to this example.
  • Example 11 In Example 1, 0.04 part (solid content) of the titanium catalyst solution obtained in Preparation Example C3 was used in place of 0.015 part (solid content) of the zirconium catalyst solution. A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except for this, and a pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 using this pressure-sensitive adhesive composition.
  • Example 12 In Example 1, the tin catalyst solution obtained in Preparation Example C2 was used in place of the zirconium catalyst solution. A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except for this, and a pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 using this pressure-sensitive adhesive composition.
  • Example 13 In Example 1, the iron-based catalyst solution obtained in Preparation Example C4 was used instead of the zirconium catalyst solution. A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except for this, and a pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 using this pressure-sensitive adhesive composition.
  • Example 14 In Example 1, 0.2 parts (solid content) of the aluminum catalyst solution obtained in Preparation Example C5 was used instead of 0.0015 parts (solid content) of the zirconium catalyst solution. A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except for this, and a pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 using this pressure-sensitive adhesive composition.
  • Example 15-16> the solution of acrylic polymer (A8) obtained in Preparation Example A8 or the solution of acrylic polymer (A9) obtained in Preparation Example A9 was used instead of the solution of acrylic polymer (A1). did. Except for this, a PSA composition was prepared in the same manner as in Example 1, and a PSA sheet according to each example was obtained in the same manner as in Example 1 using the PSA composition.
  • Example 2 a solution of acrylic polymer (A10) was used in place of the solution of acrylic polymer (A1). Also, the amount of acetylacetone added was changed to 6% of the polymer solution after dilution.
  • a pressure-sensitive adhesive composition was prepared in the same manner as in Example 2 except for the above. Using this adhesive composition, a pressure-sensitive adhesive sheet according to each example was obtained in the same manner as in Example 1 except that the thickness of the pressure-sensitive adhesive layer was changed to 10 ⁇ m (Example 17) or 5 ⁇ m (Example 18). rice field.
  • Example 2 a solution of acrylic polymer (A11) or (A12) was used in place of the solution of acrylic polymer (A1). Also, the amount of acetylacetone added was changed to 6% of the polymer solution after dilution.
  • a pressure-sensitive adhesive composition according to each example was prepared in the same manner as in Example 2 except for the above, and a pressure-sensitive adhesive sheet according to each example was obtained in the same manner as in Example 1 using the above-described pressure-sensitive adhesive composition. .
  • Example 2 a solution of acrylic polymer (A13) was used in place of the solution of acrylic polymer (A1). Also, the amount of acetylacetone added was changed to 9% (Example 21) or 12% (Example 22) of the diluted polymer solution.
  • a pressure-sensitive adhesive composition according to each example was prepared in the same manner as in Example 2 except for the above, and a pressure-sensitive adhesive sheet according to each example was obtained in the same manner as in Example 1 using the above-described pressure-sensitive adhesive composition. .
  • Example 2 a solution of acrylic polymer (A13) was used in place of the solution of acrylic polymer (A1). Also, the amount of acetylacetone added was changed to 6% of the polymer solution after dilution. Furthermore, the amount of the zirconium catalyst used was changed from 0.015 parts to 0.03 parts (solid content) (Example 23) or 0.05 parts (solid content) (Example 24).
  • a pressure-sensitive adhesive composition according to each example was prepared in the same manner as in Example 2 except for the above, and a pressure-sensitive adhesive sheet according to each example was obtained in the same manner as in Example 1 using the above-described pressure-sensitive adhesive composition. .
  • Example 25 ⁇ Example 25>
  • a solution of acrylic polymer (A14) was used in place of the solution of acrylic polymer (A1).
  • the amount of acetylacetone added was changed to 6% of the polymer solution after dilution.
  • a pressure-sensitive adhesive composition according to this example was prepared in the same manner as in Example 2 except for the above, and the same method as in Example 1 was performed using the pressure-sensitive adhesive composition adjusted to have a solid content concentration of 20%. to obtain a pressure-sensitive adhesive sheet according to this example.
  • Example 2 a solution of acrylic polymer (A15) was used in place of the solution of acrylic polymer (A1). Also, the amount of acetylacetone added was changed to 6% (Example 26) or 9% (Example 27) of the diluted polymer solution. Furthermore, the amount of the zirconium catalyst used was changed from 0.015 parts to 0.03 parts (solid content) (Example 26) or 0.05 parts (solid content) (Example 27).
  • a pressure-sensitive adhesive composition according to each example was prepared in the same manner as in Example 2 except for the above, and a pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 using the above-described pressure-sensitive adhesive composition. .
  • Example 28 In Example 20, instead of 3.5 parts (solid content) of the isocyanate cross-linking agent (B1), an isocyanate cross-linking agent (B3) (trade name "Coronate L", trimethylolpropane/tolylene diisocyanate trimer addition 75% ethyl acetate solution of the product, manufactured by Tosoh Corporation) 4 parts (solid content) was used. Also, the amount of the zirconium catalyst used was changed from 0.015 parts to 0.03 parts (solid content). A pressure-sensitive adhesive composition according to this example was prepared in the same manner as in Example 20 except for the above, and a pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 using the above-described pressure-sensitive adhesive composition.
  • B3 trade name "Coronate L"
  • the pressure-sensitive adhesive composition solution was sealed in a glass sample bottle having a volume of 225 mL and left at room temperature (23° C.) for 8 hours.
  • the viscosity of the adhesive composition solution immediately after preparation and after standing at room temperature for 8 hours was measured with a rheometer (manufactured by Thermo Fisher Scientific, trade name "RheoStress 600").
  • the pot life was evaluated according to the following criteria from the viscosity measurement value of the pressure-sensitive adhesive composition solution.
  • the viscosity difference at 1 / s immediately after preparation and after standing at room temperature for 8 hours is 10.0 Pa s or less
  • ⁇ The viscosity difference at 1 / s immediately after preparation and after standing at room temperature for 8 hours is more than 10.0 Pa s
  • a plurality of pressure-sensitive adhesive sheets were prepared and left (stored) in a room temperature (23° C.) environment immediately after the pressure-sensitive adhesive sheets were produced. After 1 day, 3 days, and 7 days from standing at room temperature, each adhesive sheet was cut into a size of 25 mm in width and 80 mm in length, and rubbed 10 times with a clean cloth impregnated with ethanol onto a clean soda glass plate. , and a 2-kg roller was rolled to make one reciprocation.
  • a high-speed peel tester was used to bond under the conditions of a peel angle of 180° and a tensile speed of 300 m/min, and under the conditions of a peel angle of 180° and a tensile speed of 30 m/min.
  • the force [N/25mm] was measured.
  • a soda glass plate (product number “S200423”) manufactured by Matsunami Glass Co., Ltd. or an equivalent thereof is used.
  • As the high-speed peeling tester a trade name "VPA-H200” manufactured by Kyowa Interface Science Co., Ltd. or its equivalent is used.
  • the low-speed adhesive strength at a tensile speed of 300 m / min is F1
  • the high-speed adhesive strength at a tensile speed of 30 m / min is F2
  • D1 and D3 are respectively 1 day, 3 days, and 7 days after storage at room temperature. , D7.
  • the low-speed adhesive strength after 3 days of storage at room temperature is expressed as F1 (D3).
  • peel strength (adhesive strength) peel speed Dependence was determined according to the following criteria. ⁇ :
  • Tables 1 to 4 show an overview and evaluation results of each example.
  • an alkyl (meth)acrylate (m1) having a linear alkyl group having 5 to 18 carbon atoms at the ester end and a side chain having 3 or more carbon atoms and containing active hydrogen are in Examples 1 to 28 using a pressure-sensitive adhesive composition containing an acrylic polymer containing a (meth)acrylic monomer (m2) as a monomer component and a cross-linking agent, Comparative Example 1 using a tin catalyst It had a pot life equal to or longer than that of (Reference Example), and exhibited aging (crosslinking reaction) progressability equal to that of Comparative Example 1 and limited peel rate dependence.
  • Comparative Examples 2 to 4 in which the alkyl (meth)acrylate (m1) was not used as the monomer component of the acrylic polymer, there was a tendency for the release rate dependency to increase.
  • Comparative Example 2 in which the (meth)acrylic monomer (m2) was not used as the monomer component of the acrylic polymer, the difference in adhesive strength over time was large, and aging tended to proceed slowly.
  • Comparative Example 4 in which BA having a linear alkyl group of 4 carbon atoms at the ester end was used as the monomer component of the acrylic polymer, a sufficient pot life could not be obtained.
  • Example 1 from a comparison between Example 1 and Comparative Example 3, the use of an alkyl (meth)acrylate having a relatively long linear alkyl group improves the curability based on the entanglement and orientation of the alkyl groups. It is thought that the increase in adhesive strength during high-speed peeling was suppressed, and the peel speed dependency was improved.
  • Comparative Examples 2 and 3 by using a (meth)acrylic monomer (m2) having active hydrogen in a relatively long side chain having 3 or more carbon atoms, the cross-linking point and It is thought that the active hydrogen and the cross-linking agent were close to each other, and the aging (cross-linking reaction) progressed quickly.
  • m2 (meth)acrylic monomer having active hydrogen in a relatively long side chain having 3 or more carbon atoms
  • Example 1 Furthermore, from a comparison between Example 1 and Comparative Example 4, it was found that having a side chain alkyl group that was moderately longer than the side chain serving as a cross-linking point moderately inhibited the cross-linking reaction and provided a sufficient pot life. Conceivable.
  • the adhesive composition containing an acrylic polymer containing a monomer (m2) as a monomer component and a cross-linking agent it has a sufficient pot life without relying on a tin-based catalyst, and after curing treatment It can be seen that it is possible to form a pressure-sensitive adhesive that undergoes rapid aging and whose peel strength is less dependent on the peel speed.
  • Reference Signs List 1 adhesive sheet 10 support substrate 10A first surface 10B second surface (back surface) 21 adhesive layer 21A adhesive surface 31 release liner 100 adhesive sheet with release liner

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Adhesive Tapes (AREA)
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WO2024190830A1 (ja) * 2023-03-16 2024-09-19 リンテック株式会社 粘着シート
WO2024203752A1 (ja) * 2023-03-27 2024-10-03 日東電工株式会社 補強用フィルム、光学部材および電子部材

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