WO2023074468A1 - Composition d'agent adhésif, agent adhésif, feuille adhésive et film de protection de surface - Google Patents

Composition d'agent adhésif, agent adhésif, feuille adhésive et film de protection de surface Download PDF

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Publication number
WO2023074468A1
WO2023074468A1 PCT/JP2022/038756 JP2022038756W WO2023074468A1 WO 2023074468 A1 WO2023074468 A1 WO 2023074468A1 JP 2022038756 W JP2022038756 W JP 2022038756W WO 2023074468 A1 WO2023074468 A1 WO 2023074468A1
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meth
pressure
sensitive adhesive
acrylate
weight
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PCT/JP2022/038756
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English (en)
Japanese (ja)
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裕充 森下
匡哉 柴野
真人 山形
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日東電工株式会社
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Priority to CN202280070236.5A priority Critical patent/CN118119682A/zh
Publication of WO2023074468A1 publication Critical patent/WO2023074468A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]

Definitions

  • the present invention relates to an adhesive composition, an adhesive, an adhesive sheet and a surface protection film.
  • 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.
  • the pressure-sensitive adhesive is formed from, for example, a pressure-sensitive adhesive composition containing an acrylic polymer and a cross-linking agent.
  • Patent Documents 1 to 3 Prior art documents disclosing this type of prior art include Patent Documents 1 to 3.
  • a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on one surface of a substrate is also preferable as a surface protective film that prevents surface damage (scratches, stains, corrosion, etc.) during processing or transportation of various articles. It's being used.
  • a surface protection film that is peeled off (re-peeled) from the object to be protected (adherend) after achieving the purpose of protecting the object to be protected the adhesive does not leave adhesive residue on the adherend. Light releasability is required so that it can be peeled off smoothly.
  • the peeling speed of re-peeling at the actual work site may be low or high. If the peeling force varies greatly due to the difference in peeling speed, the peeling workability is affected and the peeling work is not efficient. For this reason, it is required that the pressure-sensitive adhesive used in a mode of use in which it is re-peeled from the adherend does not change its peeling force significantly depending on the difference in peeling speed. Specifically, the pressure-sensitive adhesive is required to exhibit light releasability at least in low-speed detachment, and to keep the release force low even in high-speed detachment (suppression of release force increase in high-speed detachment). be done.
  • the present invention was created in view of the above circumstances, and is a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive that can achieve light release properties in low-speed release and suppression of increase in release force in high-speed release.
  • a pressure-sensitive adhesive sheet that can achieve light release properties in low-speed release and suppression of increase in release force in high-speed release.
  • Another related object is to provide a pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet having the pressure-sensitive adhesive, and a surface protection film comprising the pressure-sensitive adhesive sheet.
  • a pressure-sensitive adhesive composition containing an acrylic polymer and an epoxy-based cross-linking agent.
  • the acrylic polymer is a polymer of a monomer component containing an alkyl (meth)acrylate having a linear alkyl group having 5 to 18 carbon atoms at the ester end.
  • the monomer component further contains (meth)acrylic acid.
  • a cross-linking agent e.g., an epoxy-based cross-linking agent
  • the cross-linking reaction with a cross-linking agent proceeds favorably, increasing curability and improving light release properties in low-speed release. It is easy to form a pressure-sensitive adhesive that can suppress an increase in peel strength during high-speed peeling and an increase in adhesive strength over time.
  • the alkyl (meth)acrylate having a linear alkyl group having 5 to 18 carbon atoms at the ester end includes n-heptyl acrylate (HpA).
  • HpA is preferably used as the alkyl (meth)acrylate having a linear alkyl group having 5 to 18 carbon atoms at the ester end.
  • a pressure-sensitive adhesive formed from any of the pressure-sensitive adhesive compositions disclosed herein is provided.
  • Such an adhesive exhibits light release properties in low-speed peeling and suppresses the increase in peel force in high-speed peeling. Easy to peel off regardless of the peeling speed.
  • 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.
  • a PSA with a high gel fraction is preferable because it exhibits light release properties during low-speed release, suppresses an increase in release force during high-speed release, and suppresses an increase in adhesive strength over time.
  • 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 exhibits light release properties in low-speed peeling and suppresses the increase in peel force in high-speed peeling, so regardless of the peel speed Easy to peel off. 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.
  • a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer with a gel fraction of 70% or more is provided.
  • the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing an acrylic polymer and a cross-linking agent, and the acrylic polymer is an alkyl ( It is a polymer of monomer components containing meth)acrylate.
  • a pressure-sensitive adhesive layer having a gel fraction of 70% or more is less likely to be deformed or damaged, such as dents due to external force, during production, and is less likely to change in appearance.
  • a pressure-sensitive adhesive sheet having such a pressure-sensitive adhesive layer tends to have a smooth surface, and is preferable because, for example, when an adherend is inspected through the pressure-sensitive adhesive sheet and configured as a transparent pressure-sensitive adhesive sheet, highly accurate inspection is possible.
  • the pressure-sensitive adhesive sheet tends to exhibit light release properties in low-speed peeling, suppress an increase in peel force in high-speed peeling, and be capable of suppressing an increase in adhesive strength over time.
  • the cross-linking agent includes an epoxy-based cross-linking agent.
  • the monomer component further contains (meth)acrylic acid.
  • the surface protective film has an initial high-speed adhesive strength of 3.0 N/25 mm or less measured at a tensile speed of 30 m/min after aging in a 50°C environment for 3 days.
  • a surface protective film that satisfies this property has a low peeling force even if it is peeled off from an object to be protected, which is an adherend, at a high speed.
  • 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).
  • (meth)acrylic acid is meant to comprehensively refer to acrylic acid and methacrylic acid.
  • 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 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”).
  • C 5-18 linear alkyl (meth)acrylate One of the features is to include Although not particularly limited, the use of alkyl (meth)acrylates with relatively long linear alkyl groups of 5 to 18 carbon atoms increases curability based on the entanglement and orientation of the alkyl groups, and adhesion during low-speed peeling. It is thought that the force is kept low and the increase in adhesive strength during high-speed peeling is suppressed.
  • 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 10 or less, from the viewpoint of adhesive properties. (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.
  • the proportion of C 5-18 linear alkyl (meth)acrylate in the total monomer components is, for example, less than 99% by weight. may be 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.
  • the above C 5-11 linear alkyl (meth)acrylate is an alkyl (meth) having a linear alkyl group having 10 or less carbon atoms (more preferably 9 or less, for example 8 or less, preferably 7) at the ester end.
  • Acrylates are 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.
  • the proportion of n-heptyl (meth) acrylate in the total monomer components may be, for example, less than 99% by weight. It may be less than 98 wt%, or less than 97 wt%. In some other embodiments, 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 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 while reducing dependence on fossil resource-based materials, the effects of the technology disclosed here (lower adhesive force in low-speed peeling, high-speed peeling The effect of suppressing the increase in peeling force in ( ) 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, and particularly preferably 10, from the viewpoint of adhesive properties. or less (eg 9 or 8 or less). Also, the number of carbon atoms is preferably 5 or more, more preferably 6 or more, and still more preferably 7 or more.
  • 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 forming the acrylic polymer may contain other monomers (copolymerizable monomers) copolymerizable with the chain alkyl (meth)acrylate in addition to the chain alkyl (meth)acrylate. good.
  • the copolymerizable monomers may be used singly or in combination of two or more.
  • the above-mentioned copolymerizable monomer can be useful for introducing cross-linking points into the acrylic polymer and increasing the cohesive strength of the acrylic polymer.
  • the copolymerizable monomer may be biomass-derived or non-biomass-derived.
  • a carboxy group-containing monomer is used as the copolymerizable monomer.
  • a carboxy group-containing monomer as a copolymerizable monomer component for introducing a cross-linking point into an acrylic polymer in combination with a cross-linking agent (for example, an epoxy-based cross-linking agent)
  • a cross-linking agent for example, an epoxy-based cross-linking agent
  • carboxy group-containing monomers examples include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; ethylenically unsaturated dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid, and their anhydrides (maleic anhydride, isotanoic anhydride, etc.). Among them, acrylic acid and methacrylic acid are preferred, and acrylic acid is more preferred.
  • the carboxy group-containing monomers may be used singly or in combination of two or more.
  • the content of the carboxy group-containing monomer (preferably (meth)acrylic acid) in the monomer component forming the acrylic polymer may be, for example, 0.01% by weight or more of the total monomer component, or 0.1 weight percent or more, suitably greater than 0.5 wt. , 3% by weight or more.
  • the content of the carboxy group-containing monomer (preferably (meth)acrylic acid) in the entire monomer component is, for example, less than 15% by weight, and is suitably 10% by weight or less. In a preferred embodiment, it may be 8% by weight or less, 6% by weight or less, or 5% by weight or less.
  • the cohesive force is improved, and it is easy to adjust to a good adhesive force that can be removed, for example, it can be removed again. It is easy to form a pressure-sensitive adhesive suitable for surface protection applications.
  • the carboxy group-containing monomer preferably (meth)acrylic acid
  • the monomer component forming the acrylic polymer may contain other copolymerizable monomers.
  • Other copolymerizable monomers are defined as monomers different from the chain alkyl (meth)acrylate and the carboxy group-containing monomer.
  • Other copolymerizable monomers can be used singly or in combination of two or more.
  • Suitable copolymerizable monomers include the following. Hydroxyl group-containing monomers: for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate hydroxyalkyl (meth)acrylates such as; unsaturated alcohols such as vinyl alcohol and allyl alcohol; 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, less than 50% by weight (for example, less than 30% by weight), preferably less than 10% by weight, and less than 5% by weight. More preferably, it may be 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.
  • 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 60% or more, may be 65% or more, 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 employed.
  • 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, more than 100 ⁇ 10 4 , 110 ⁇ 10 4 or more, 120 ⁇ 10 4 or more, or 130 ⁇ 10 4 or more.
  • the Mw of the acrylic polymer By setting the Mw of the acrylic polymer to a predetermined value or more, the cohesive force of the pressure-sensitive adhesive is improved, and it is easy to prevent the occurrence of adhesive residue on the surface of the adherend. Moreover, from the viewpoint of adhesion to the adherend, 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 ). By setting the Mw to a predetermined value or less, 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 epoxy-based cross-linking agents, isocyanate-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, melamine-based cross-linking agents, peroxide-based cross-linking agents, urea-based cross-linking agents, and metal alkoxide-based cross-linking agents.
  • 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 15 parts by weight or less, preferably 10 parts by weight. 8 parts by weight or less, 7 parts by weight or less, 0.5 parts by weight or more is suitable, and 1 part by weight or more is also acceptable.
  • 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 epoxy-based cross-linking agent.
  • Epoxy-based cross-linking agents may be used singly or in combination of two or more.
  • the epoxy-based cross-linking agent may be biomass-derived or non-biomass-derived.
  • a biomass-derived epoxy-based cross-linking agent 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 epoxy-based cross-linking agent may be used in combination with another cross-linking agent such as an isocyanate-based cross-linking agent.
  • epoxy-based cross-linking agent a compound having two or more epoxy groups in one molecule can be used without particular limitation.
  • An epoxy-based cross-linking agent having 3 to 5 epoxy groups in one molecule is preferred.
  • Epoxy-based cross-linking agents may be used singly or in combination of two or more.
  • Specific examples of epoxy-based cross-linking agents include N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and 1,6-hexane.
  • epoxy-based cross-linking agents include Mitsubishi Gas Chemical Company's trade name “TETRAD-C” and trade name “TETRAD-X”, DIC's trade name “Epiclon CR-5L”, and Nagase ChemteX Corporation. and "TEPIC-G” manufactured by Nissan Chemical Industries, Ltd. under the trade name of "Denacol EX-512".
  • the amount of the epoxy-based cross-linking agent used may be, for example, approximately 0.1 parts by weight or more, 0.5 parts by weight or more, or 1.0 parts by weight or more, relative to 100 parts by weight of the acrylic polymer. It may be greater than 1.5 parts by weight. From the viewpoint of obtaining a higher use effect, the amount of the epoxy-based 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 epoxy-based cross-linking agent to be used relative to 100 parts by weight of the acrylic polymer is usually appropriately 20 parts by weight or less, and may be 10 parts by weight or less, 8 parts by weight or less, or 6 parts by weight or less. 5 parts by weight or less (for example, less than 5 parts by weight) may be used.
  • the amount of the epoxy-based cross-linking agent By adjusting the amount of the epoxy-based cross-linking agent to an appropriate range, it is possible to increase the cohesive strength of the pressure-sensitive adhesive, easily adjust the re-peelable adhesive strength, and suppress the increase in adhesive strength over time. In addition, it is possible to prevent the occurrence of adhesive residue on the adherend and to obtain good adhesion to the adherend. Also, by limiting the amount of the epoxy-based cross-linking agent used, it is easy to form a transparent pressure-sensitive adhesive.
  • the amount of the epoxy-based cross-linking agent used may be more than 4 parts by weight with respect to 100 parts by weight of the acrylic polymer, and may be 4.5 parts by weight. It may be greater than or equal to 5 parts by weight, or greater than 5.5 parts by weight.
  • the amount of the carboxy group-containing monomer used (the total amount when two or more carboxy group-containing monomers are used) epoxy system relative to WA
  • the ratio (WB/WA) (weight basis) of the amount WB of the cross-linking agent used is not particularly limited, but from the viewpoint of increasing the cohesive strength of the adhesive, it is preferably 0.7 or more, more preferably 0.8. or more, more preferably 0.9 or more (for example, 1.0 or more), and particularly preferably 1.1 or more.
  • the ratio (WB/WA) is usually 3.0 or less, 2.0 or less, 1.8 or less, 1.6 or less, 1.4 or less, or 1.3. It can be below.
  • 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 adhesive composition disclosed here may contain 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 can be suitably practiced even in a mode that does not contain a catalyst.
  • additives can be blended into the adhesive composition as needed.
  • 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 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 preferable.
  • 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 realized.
  • 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.
  • the gel fraction is more preferably over 80%, and may be over 85% (for example, 90% or more).
  • 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 3 minutes. 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, 65% or more, 70% or more, 75% or more, It may be 80% or more, or may be more 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 easy release properties in low-speed release and suppresses an increase in release force in high-speed release, so that it can be easily peeled regardless of the peel speed. In addition, there is a tendency that an increase in adhesive strength over time is suppressed. 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).
  • an optical component such as a polarizing plate.
  • 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 protection 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) that has been sufficiently aged has an initial low-speed adhesive strength (F0 Low ) measured at a tensile speed of 300 mm/min of 3.0 N/25 mm or less.
  • F0 Low initial low-speed adhesive strength measured at a tensile speed of 300 mm/min of 3.0 N/25 mm or less.
  • the aging of the pressure-sensitive adhesive sheet can be performed, for example, by storing the pressure-sensitive adhesive sheet in an environment of 50° C. for 3 days.
  • 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 initial low-speed adhesive strength (F0 Low ) is more preferably 1.0 N/25 mm or less (e.g., 0.2 N/25 mm or less), still more preferably 0.14 N/25 mm or less (e.g., less than 0.14 N/25 mm), particularly preferably 0.12 N/25 mm or less (for example, 0.1 N/25 mm or less).
  • the initial low-speed adhesive strength (F0 Low ) is suitably 0.01 N/25 mm or more, and may be 0.03 N/25 mm or more. , 0.05 N/25 mm or more.
  • the initial low-speed adhesive strength (F0 Low ) is measured by the method described in Examples below.
  • the fully aged pressure-sensitive adhesive sheet (preferably surface protective film) has an initial high-speed adhesive strength (F0 High ) measured at a tensile speed of 30 m/min of 5.0 N/25 mm or less.
  • F0 High initial high-speed adhesive strength
  • the aging of the pressure-sensitive adhesive sheet can be performed, for example, by storing the pressure-sensitive adhesive sheet in an environment of 50° C. for 3 days.
  • 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 initial high-speed adhesive strength (F0 High ) is more preferably 3.0 N/25 mm or less (for example, 2.0 N/25 mm or less), still more preferably 1.5 N/25 mm or less, especially It is preferably 1.2 N/25 mm or less (for example, 1.0 N/25 mm or less).
  • the initial high-speed adhesive strength (F0 High ) is suitably 0.1 N/25 mm or more, and may be 0.3 N/25 mm or more. , 0.5 N/25 mm or more.
  • the initial high-speed adhesive strength (F0 High ) is specifically measured by the method described in Examples below.
  • the fully aged pressure-sensitive adhesive sheet (preferably surface protective film) is attached to the adherend, stored at 50 ° C. for 7 days, and then measured at a tensile speed of 300 mm / min.
  • the low-speed adhesive strength (F1 Low ) over time is preferably 3.0 N/25 mm or less.
  • the aging of the pressure-sensitive adhesive sheet can be performed, for example, by storing the pressure-sensitive adhesive sheet in an environment of 50° C. for 3 days.
  • 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 adhesive strength over time (F1 Low ) is more preferably 1.0 N/25 mm or less (e.g., 0.2 N/25 mm or less), and still more preferably 0.14 N/25 mm or less (e.g., less than 0.14 N/25 mm), particularly preferably 0.12 N/25 mm or less (for example, 0.1 N/25 mm or less).
  • the low-speed adhesion over time (F1 Low ) is suitably 0.01 N/25 mm or more, and may be 0.03 N/25 mm or more. , 0.05 N/25 mm or more.
  • the low-speed adhesion over time (F1 Low ) is specifically measured by the method described in Examples below.
  • the fully aged pressure-sensitive adhesive sheet (preferably surface protective film) is attached to the adherend, stored at 50° C. for 7 days, and then measured at a tensile speed of 30 m / min.
  • the high-speed adhesive strength (F1 High ) over time is preferably 5.0 N/25 mm or less.
  • the aging of the pressure-sensitive adhesive sheet can be performed, for example, by storing the pressure-sensitive adhesive sheet in an environment of 50° C. for 3 days. 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 force F1 High over time is more preferably 3.0 N/25 mm or less (for example, 2.0 N/25 mm or less), still more preferably 1.5 N/25 mm or less, and particularly preferably It is 1.2 N/25 mm or less (for example, 1.0 N/25 mm or less).
  • the high-speed adhesion over time (F1 High ) is suitably 0.1 N/25 mm or more, and may be 0.3 N/25 mm or more. , 0.5 N/25 mm or more.
  • the time-dependent high-speed adhesive strength (F1 High ) is measured by the method described in Examples below.
  • 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.
  • the pressure-sensitive adhesive disclosed herein is easy to peel regardless of the peeling speed, and is excellent in peeling workability at the time of re-peeling.
  • It is usually suitable as a surface protective film that is peeled off (removed) 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.
  • 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.
  • 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.
  • 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.
  • the weight average molecular weight (Mw) of the obtained acrylic polymer (A1) was 770,000.
  • the above HpA is a compound having a biomass-derived heptyl group at the ester end, synthesized using biomass-derived heptyl alcohol.
  • Example 2 A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that the acrylic polymer used was changed to the acrylic polymer (A2) obtained in Preparation Example A2.
  • a pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1.
  • Example 1 A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that the acrylic polymer used was changed to the acrylic polymer (A3) obtained in Preparation Example A3, and this pressure-sensitive adhesive composition was used. A pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1.
  • Example 2 A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that the acrylic polymer used was changed to the acrylic polymer (A4) obtained in Preparation Example A4, and this pressure-sensitive adhesive composition was used. A pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1.
  • Adhesive force to glass over time F1 Prepare multiple adhesive sheets, cut them into 25 mm width and 80 mm length sizes, rub them 10 times with a clean cloth impregnated with ethanol, and wash them with a clean soda glass plate. to obtain a sample for adhesive strength evaluation.
  • the evaluation sample was left in an environment of 50° C. for 7 days. After 7 days, the sample was taken out and allowed to stand at room temperature (23° C.) for 1 hour.
  • Adhesion [N/25 mm] was measured under each condition of 30 m/min.
  • 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.
  • Table 1 shows an overview and evaluation results of each example.
  • the above HpA is a compound having a biomass-derived heptyl group at the ester end, synthesized using biomass-derived heptyl alcohol.
  • Example 6 The solution of the acrylic polymer (A5) obtained in Preparation Example A5 was diluted with ethyl acetate to a solid content concentration of 22%, and the solution was added with an epoxy cross-linking agent (B1) per 100 parts of the solid content of the solution. (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "Tetrad C”) 6 parts (solid content) was added and stirred to obtain an acrylic pressure-sensitive adhesive composition according to this example.
  • an epoxy cross-linking agent (B1) per 100 parts of the solid content of the solution.
  • Examples 3 to 6 using a pressure-sensitive adhesive composition containing an acrylic polymer containing C 5-18 linear alkyl (meth)acrylate as a monomer component and a cross-linking agent also, compared to Comparative Example 1 using n-butyl acrylate and Comparative Example 2 using 2-ethylhexyl acrylate, the initial adhesive strength was low when peeled at low speed, and even when peeled at high speed A tendency to suppress the increase in adhesive strength was observed. From the comparison of the results of Examples 1 to 3, it was found that the difference in the molecular weight (Mw) of the acrylic polymer caused a difference in the tendency of the adhesive strength to change over time for high-speed peeling.
  • Mw molecular weight
  • 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)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne une composition d'agent adhésif capable de former un agent adhésif légèrement détachable à une faible vitesse de décollement et pouvant supprimer une augmentation de la force de décollement à une vitesse de décollement élevée. La présente invention concerne également une feuille adhésive légèrement détachable à une faible vitesse de décollement et capable de supprimer une augmentation de la force de décollement à une vitesse de décollement élevée. La présente invention consiste en une composition d'agent adhésif contenant un polymère acrylique et un agent de réticulation à base d'époxy. Le polymère acrylique est un polymère d'un composant monomère contenant un (méth)acrylate d'alkyle possédant un groupe alkyle linéaire avec 5 à 18 atomes de carbone à une terminaison ester. En outre, une feuille adhésive possédant une couche d'agent adhésif ayant une fraction de gel de 70 % ou plus est présente dans un autre mode de réalisation. La couche d'agent adhésif est composée d'une composition d'agent adhésif contenant un polymère acrylique et un agent de réticulation. Le polymère acrylique consiste en un polymère d'un composant monomère contenant un (méth)acrylate d'alkyle possédant un groupe alkyle linéaire avec 5 à 18 atomes de carbone au niveau d'une terminaison ester.
PCT/JP2022/038756 2021-10-25 2022-10-18 Composition d'agent adhésif, agent adhésif, feuille adhésive et film de protection de surface WO2023074468A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63225677A (ja) * 1987-03-13 1988-09-20 Nitto Electric Ind Co Ltd 感圧性接着剤
JPH11256111A (ja) * 1998-03-11 1999-09-21 Nitto Denko Corp 表面保護フイルム用粘着剤と表面保護フイルム
JP2001123139A (ja) * 1999-10-28 2001-05-08 Furukawa Electric Co Ltd:The 半導体加工用粘着テープ
JP2005146151A (ja) * 2003-11-17 2005-06-09 Soken Chem & Eng Co Ltd 保護シート用感圧接着剤
JP2011511853A (ja) * 2008-01-14 2011-04-14 エルジー・ケム・リミテッド 粘着剤組成物、これを含む保護フィルム及び偏光板並びに液晶表示装置
JP2020164844A (ja) * 2019-03-28 2020-10-08 積水化学工業株式会社 感圧粘着剤組成物及び粘着テープ
WO2021125278A1 (fr) * 2019-12-18 2021-06-24 積水化学工業株式会社 Composition d'adhésif, ruban adhésif, procédé de fixation de composant d'appareil électronique ou de composant monté sur véhicule, et procédé de fabrication de composant d'appareil électronique ou de composant monté sur véhicule

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63225677A (ja) * 1987-03-13 1988-09-20 Nitto Electric Ind Co Ltd 感圧性接着剤
JPH11256111A (ja) * 1998-03-11 1999-09-21 Nitto Denko Corp 表面保護フイルム用粘着剤と表面保護フイルム
JP2001123139A (ja) * 1999-10-28 2001-05-08 Furukawa Electric Co Ltd:The 半導体加工用粘着テープ
JP2005146151A (ja) * 2003-11-17 2005-06-09 Soken Chem & Eng Co Ltd 保護シート用感圧接着剤
JP2011511853A (ja) * 2008-01-14 2011-04-14 エルジー・ケム・リミテッド 粘着剤組成物、これを含む保護フィルム及び偏光板並びに液晶表示装置
JP2020164844A (ja) * 2019-03-28 2020-10-08 積水化学工業株式会社 感圧粘着剤組成物及び粘着テープ
WO2021125278A1 (fr) * 2019-12-18 2021-06-24 積水化学工業株式会社 Composition d'adhésif, ruban adhésif, procédé de fixation de composant d'appareil électronique ou de composant monté sur véhicule, et procédé de fabrication de composant d'appareil électronique ou de composant monté sur véhicule

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