WO2011118180A1 - アクリル系粘着テープ - Google Patents
アクリル系粘着テープ Download PDFInfo
- Publication number
- WO2011118180A1 WO2011118180A1 PCT/JP2011/001618 JP2011001618W WO2011118180A1 WO 2011118180 A1 WO2011118180 A1 WO 2011118180A1 JP 2011001618 W JP2011001618 W JP 2011001618W WO 2011118180 A1 WO2011118180 A1 WO 2011118180A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- meth
- acrylic
- weight
- acrylate
- acrylic polymer
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—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
- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- 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
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/41—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the carrier layer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/412—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of microspheres
-
- 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
- C09J2433/00—Presence of (meth)acrylic polymer
-
- 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
- C09J2433/00—Presence of (meth)acrylic polymer
- C09J2433/006—Presence of (meth)acrylic polymer in the substrate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
Definitions
- the present invention relates to an acrylic adhesive tape.
- an acrylic pressure-sensitive adhesive tape having an acrylic pressure-sensitive adhesive layer is excellent in light resistance, weather resistance, oil resistance, etc., and has adhesiveness such as adhesive strength, repulsion resistance, and retention properties (cohesive strength), and heat resistance. It is widely used because of its excellent aging resistance such as heat resistance and weather resistance.
- acrylic pressure-sensitive adhesive tapes having such characteristics are widely used as bonding materials in various industrial fields such as home appliances, building materials, and automobile interior / exterior materials. Therefore, various adhesive materials such as metal materials such as stainless steel and aluminum, various plastic materials such as polyethylene, polypropylene, polystyrene, ABS, (meth) acrylic resin, polycarbonate resin, and glass materials are applied to the acrylic adhesive tape. It is required to adhere to the body (joining object) with high reliability.
- Patent Documents 1 and 2 disclose an acrylic pressure-sensitive adhesive composition in which rosin or hydrogenated petroleum resin is added as a tackifier resin to an acrylic polymer.
- Acrylic adhesive tapes are always required to have improved adhesion to adherends, especially for polyolefin resins such as polyethylene and polypropylene, which are often used in home appliances, building materials, automotive interior and exterior materials, etc. There is a strong demand for improvement in adhesion to representative low-polar adherends.
- acrylic pressure-sensitive adhesive composition to which a tackifying resin such as rosin is added does not sufficiently meet the demand for improving the adhesion of the acrylic pressure-sensitive adhesive tape to the low-polar adherend. was there.
- the present invention has been made in view of these problems, and an object thereof is to provide a technique capable of improving the adhesiveness of an acrylic pressure-sensitive adhesive tape.
- An embodiment of the present invention is an acrylic adhesive tape.
- the acrylic pressure-sensitive adhesive tape includes a core layer and a surface layer provided on one or both sides of the core layer.
- the core layer includes an acrylic polymer (A)
- the surface layer includes an acrylic polymer (D And a (meth) acrylic monomer (E) having a weight average molecular weight of 1000 or more and less than 30000, comprising a (meth) acrylic monomer having a tricyclic or higher alicyclic structure as a monomer unit.
- the adhesiveness of the acrylic pressure-sensitive adhesive tape can be improved.
- the (meth) acrylic monomer may be a (meth) acrylic acid ester represented by the following general formula (1).
- CH 2 C (R 1 ) COOR 2 (1)
- R 1 is a hydrogen atom or a methyl group
- R 2 is an alicyclic hydrocarbon group having a tricyclic or higher alicyclic structure
- the alicyclic hydrocarbon group may have a bridged ring structure.
- the content of the (meth) acrylic polymer (E) may be 2 to 70 parts by weight with respect to 100 parts by weight of the acrylic polymer (D).
- the core layer may include fine particles (B) and bubbles (C).
- the adhesiveness of the acrylic pressure-sensitive adhesive tape can be improved.
- FIG. 1 is a schematic cross-sectional view showing a configuration of an acrylic pressure-sensitive adhesive tape according to an embodiment.
- the acrylic pressure-sensitive adhesive tape 10 includes a core layer 20, a surface layer 30 a provided on one surface of the core layer 20, and a surface layer 30 b provided on the other surface of the core layer 20.
- the surface layer 30a and the surface layer 30b are collectively referred to as a surface layer 30 as appropriate.
- the core layer 20 includes an acrylic polymer (A), fine particles (B), and bubbles (C) as necessary.
- A acrylic polymer
- B fine particles
- C bubbles
- the acrylic polymer (A) which is a pressure-sensitive adhesive composition constituting the core layer 20, is, for example, a (meth) acrylic acid alkyl ester having a linear or branched alkyl group having 1 to 20 carbon atoms as a monomer unit. About 50% by weight or more.
- the acrylic polymer (A) can have a configuration in which (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms is used alone or in combination of two or more.
- the acrylic polymer (A) can be obtained by polymerizing (for example, solution polymerization, emulsion polymerization, UV polymerization) (meth) acrylic acid alkyl ester together with a polymerization initiator.
- the proportion of the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms is about 50 wt% or more and 99.9 wt% or less based on the total amount of monomer components for adjusting the acrylic polymer (A), Preferably it is about 60 to 95 weight%, More preferably, it is about 70 to 93 weight%.
- Examples of the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, Butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, (meth) acryl Hexyl acid, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate (2-ethylhexyl (meth) acrylate), isooctyl (meth) acrylate, nonyl (meth) acrylate, (Met
- (meth) acrylic acid ester other than (meth) acrylic acid alkyl ester for example, (Meth) acrylic acid ester having an alicyclic hydrocarbon group such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate; (Meth) acrylic acid ester having an aromatic hydrocarbon group such as phenyl (meth) acrylate; (Meth) acrylic acid ester obtained from terpene compound derivative alcohol; Etc.
- (Meth) acrylic acid ester having an alicyclic hydrocarbon group such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate
- (Meth) acrylic acid ester having an aromatic hydrocarbon group such as phenyl (meth) acrylate
- (Meth) acrylic acid ester obtained from terpene compound derivative alcohol Etc.
- the acrylic polymer (A) may contain other monomer components that can be copolymerized with the (meth) acrylic acid alkyl ester, if necessary, for the purpose of modifying cohesion, heat resistance, crosslinkability, and the like.
- a copolymerizable monomer A copolymerizable monomer). Therefore, the acrylic polymer (A) may contain a copolymerizable monomer together with the (meth) acrylic acid alkyl ester as the main component.
- the copolymerizable monomer a monomer having a polar group can be suitably used.
- Carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid; Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxydecyl (meth) acrylate, (meta Hydroxyl group-containing monomers such as hydroxyalkyl (meth) acrylates such as hydroxylauryl acrylate and (4-hydroxymethylcyclohexyl) methyl methacrylate; Acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; Sulphonic acid groups such as
- (N- substituted) amide monomers Succinimide monomers such as N- (meth) acryloyloxymethylenesuccinimide, N- (meth) acryloyl-6-oxyhexamethylenesuccinimide, N- (meth) acryloyl-8-oxyhexamethylenesuccinimide;
- Maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide;
- Itaconimides such as N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexitaconimide, N-cyclohexylitaconimide, N-laurylitaconimide System monomers;
- N-vinyl-2-pyrrolidone N-methylvinylpyrrolidon
- the acrylic polymer (A) contains a copolymerizable monomer together with the (meth) acrylic acid alkyl ester as a main component
- a carboxyl group-containing monomer can be suitably used.
- acrylic acid can be preferably used.
- the amount of the copolymerizable monomer used is not particularly limited. Usually, the copolymerizable monomer is used in an amount of about 0.1 to about 40% by weight based on the total amount of the monomer components for adjusting the acrylic polymer (A). , Preferably about 0.5 to about 30% by weight, more preferably about 1 to about 20% by weight.
- the copolymerizable monomer By containing about 0.1% by weight or more of the copolymerizable monomer, it is possible to prevent a decrease in cohesive force of the acrylic pressure-sensitive adhesive constituting the core layer 20 and to obtain a high shearing force. Further, by setting the content of the copolymerizable monomer to about 40% by weight or less, the cohesive force of the acrylic pressure-sensitive adhesive constituting the core layer 20 is prevented from becoming too high, and tackiness at room temperature (25 ° C.) is prevented. Can be improved.
- the acrylic polymer (A) may contain a polyfunctional monomer as necessary in order to adjust the cohesive strength of the acrylic pressure-sensitive adhesive tape.
- polyfunctional monomer examples include (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, and pentaerythritol.
- trimethylolpropane tri (meth) acrylate, hexanediol di (meth) acrylate, and dipentaerythritol hexa (meth) acrylate can be preferably used.
- Polyfunctional (meth) acrylate can be used individually or in combination of 2 or more types.
- the amount of the polyfunctional monomer used varies depending on the molecular weight, the number of functional groups, and the like, but is about 0.01 to about 3.0% by weight with respect to the total amount of monomer components for adjusting the acrylic polymer (A),
- the amount is preferably about 0.02 to about 2.0% by weight, and more preferably about 0.03 to about 1.0% by weight.
- the amount of the polyfunctional monomer used exceeds about 3.0% by weight with respect to the total amount of the monomer components for adjusting the acrylic polymer (A), for example, aggregation of the acrylic pressure-sensitive adhesive constituting the core layer 20 In some cases, the force becomes too high and the adhesive strength is reduced. On the other hand, if it is less than about 0.01% by weight, for example, the cohesive force of the acrylic pressure-sensitive adhesive constituting the core layer 20 may be reduced.
- the acrylic polymer (A) is obtained by utilizing a curing reaction by heat or ultraviolet rays using a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator (photoinitiator). It can be formed easily.
- a photopolymerization initiator can be preferably used because of the advantage that the polymerization time can be shortened.
- a polymerization initiator can be used individually or in combination of 2 or more types.
- thermal polymerization initiator examples include azo polymerization initiators (for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis ( 2-methylpropionic acid) dimethyl, 4,4'-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2 -(5-Methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-dimethylene) Isobutylamidine) dihydrochloride, etc.); peroxide polymerization initiators (eg, dibenzoyl peroxide, t-butylpermaleate, lauroy peroxide) Etc.); redox polymerization initiators, and the
- the amount of the thermal polymerization initiator used is not particularly limited as long as it can be conventionally used as a thermal polymerization initiator.
- the photopolymerization initiator is not particularly limited, but for example, benzoin ether photopolymerization initiator, acetophenone photopolymerization initiator, ⁇ -ketol photopolymerization initiator, aromatic sulfonyl chloride photopolymerization initiator, photoactive Oxime photopolymerization initiator, benzoin photopolymerization initiator, benzyl photopolymerization initiator, benzophenone photopolymerization initiator, ketal photopolymerization initiator, thioxanthone photopolymerization initiator, acylphosphine oxide photopolymerization initiator An agent or the like can be used.
- examples of the benzoin ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane- Examples include 1-one [trade name: Irgacure 651, manufactured by Ciba Specialty Chemicals], anisole methyl ether, and the like.
- acetophenone photopolymerization initiator for example, 1-hydroxycyclohexyl phenyl ketone [trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals], 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1- [4 -(2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one [trade name: Irgacure 2959, manufactured by Ciba Specialty Chemicals], 2-hydroxy-2-methyl-1- And phenyl-propan-1-one [trade name: Darocur 1173, manufactured by Ciba Specialty Chemicals], methoxyacetophenone, and the like.
- Irgacure 184 manufactured by Ciba Specialty Chemicals
- 4-phenoxydichloroacetophenone 4-t-butyl-dichloroacetophenone
- Examples of the ⁇ -ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) -phenyl] -2-hydroxy-2-methylpropane-1- ON etc. are mentioned.
- Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride.
- Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime.
- the benzoin photopolymerization initiator includes, for example, benzoin.
- examples of the benzyl photopolymerization initiator include benzyl and the like.
- examples of the benzophenone photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, ⁇ -hydroxycyclohexyl phenyl ketone, and the like.
- Examples of the ketal photopolymerization initiator include benzyl dimethyl ketal.
- thioxanthone photopolymerization initiator examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone and the like are included.
- acylphosphine photopolymerization initiator examples include bis (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) (2,4,4-trimethylpentyl) phosphine oxide, bis ( 2,6-dimethoxybenzoyl) -n-butylphosphine oxide, bis (2,6-dimethoxybenzoyl)-(2-methylpropan-1-yl) phosphine oxide, bis (2,6-dimethoxybenzoyl)-(1- Methylpropan-1-yl) phosphine oxide, bis (2,6-dimethoxybenzoyl) -t-butylphosphine oxide, bis (2,6-dimethoxybenzoyl) cyclohexylphosphine oxide, bis (2,6-dimethoxybenzoyl) octylphosphine Oxides, bis (2 Methoxy
- the amount of the photopolymerization initiator used is not particularly limited. For example, it is about 0.01 to about 5 parts by weight, preferably about 0.05 to about 100 parts by weight based on 100 parts by weight of the monomer component for adjusting the acrylic polymer (A). It is blended in an amount within the range of about 3 parts by weight.
- the amount of the photopolymerization initiator used is less than about 0.01 part by weight, the polymerization reaction may be insufficient.
- a photoinitiator may absorb an ultraviolet-ray and an ultraviolet-ray may not reach the inside of an adhesive layer. In this case, the polymerization rate is lowered, or the molecular weight of the produced polymer is reduced.
- the cohesive force of the acrylic pressure-sensitive adhesive constituting the core layer 20 is reduced, and when the film is peeled off from the core layer 20, a part of the acrylic pressure-sensitive adhesive remains on the film, and the film can be reused. It may not be possible.
- a photopolymerization initiator can be used individually or in combination of 2 or more types.
- crosslinking agent in addition to the above-mentioned polyfunctional monomer.
- a crosslinking agent a commonly used crosslinking agent can be used.
- epoxy crosslinking agent, isocyanate crosslinking agent, silicone crosslinking agent, oxazoline crosslinking agent, aziridine crosslinking agent, silane crosslinking agent, alkyl etherification A melamine type crosslinking agent, a metal chelate type crosslinking agent, etc. can be mentioned.
- an isocyanate-based crosslinking agent and an epoxy-based crosslinking agent can be preferably used.
- examples of isocyanate-based crosslinking agents include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene.
- examples include diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, and adducts of these with polyols such as trimethylolpropane.
- Epoxy crosslinking agents include bisphenol A, epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane tri Examples include glycidyl ether, diglycidyl aniline, diamine glycidyl amine, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine and 1,3-bis (N, N′-diamine glycidylaminomethyl) cyclohexane. be able to.
- the acrylic polymer (A) is a partial polymer (acrylic polymer syrup) obtained by irradiating a mixture of the monomer component and the polymerization initiator with ultraviolet rays (UV) to partially polymerize the monomer component. ) Can also be adjusted.
- the weight average molecular weight (Mw) of the acrylic polymer (A) is, for example, 30,000 to 5000000.
- fine particles (B) can be added to the acrylic polymer (A) constituting the core layer.
- examples of the function and effect of the fine particles (B) include an improvement in shear adhesive strength and workability of the acrylic pressure-sensitive adhesive tape.
- metal particles such as copper, nickel, aluminum, chromium, iron, stainless steel, or metal oxide particles
- carbide particles such as silicon carbide, boron carbide, and nitrogen carbide
- aluminum nitride, silicon nitride, boron nitride Nitride particles such as: Ceramic particles typified by oxides such as glass, alumina and zirconium; Inorganic fine particles such as calcium carbide, aluminum hydroxide, glass and silica; Natural raw material particles such as volcanic shirasu and sand; Polystyrene and poly Polymer particles such as methyl methacrylate, phenol resin, benzoguanamine resin, urea resin, silicone resin, nylon, polyester, polyurethane, polyethylene, polypropylene, polyamide, polyimide; hollow organic bodies such as vinylidene chloride and acrylic; nylon beads, acrylic beads, Organic spheres such as recone beads.
- hollow fine particles can be preferably used.
- hollow inorganic fine particles are preferable from the viewpoint of the efficiency and weight of polymerization using an ultraviolet reaction.
- examples thereof include glass balloons such as hollow glass balloons; hollow balloons made of metal compounds such as hollow alumina balloons; porcelain hollow balloons such as hollow ceramic balloons, and the like.
- hollow glass balloon examples include a trade name: glass microballoon (manufactured by Fuji Silysia Chemical Co., Ltd.) and trade names: Cell Star Z-20, Cell Star Z-27, Cell Star CZ-31T, Cell Star Z-36, Cell Star Z-39. Cell Star Z-39, Cell Star T-36, Cell Star PZ-6000 (all manufactured by Tokai Kogyo Co., Ltd.), trade name: Cyrus Fine Balloon (manufactured by Fine Balloon Co., Ltd.), and the like.
- the particle diameter (average particle diameter) of the fine particles (B) is not particularly limited, but may be selected from the range of, for example, about 1 to about 500 ⁇ m, preferably about 5 to about 200 ⁇ m, more preferably about 10 to about 150 ⁇ m. it can.
- the specific gravity of the fine particles (B) is not particularly limited, but for example, about 0.1 to about 1.8 g / cm 3 , preferably about 0.2 to about 1.5 g / cm 3 , more preferably about 0.2. It can be selected from the range of about 0.5 / cm 3 .
- the specific gravity of the fine particles (B) is smaller than about 0.1 g / cm 3 , the fine particles (B) are lifted up and mixed uniformly when mixed and mixed in the acrylic adhesive. It may be difficult. Moreover, the glass strength is low and the glass is easily broken. On the other hand, if it is larger than about 1.8 g / cm 3 , there is a risk that the transmittance of ultraviolet rays is lowered and the efficiency of ultraviolet reaction is lowered. Moreover, the acrylic adhesive which comprises the core layer 20 becomes heavy, and workability
- the amount of the fine particles (B) used is not particularly limited. For example, when the amount used is less than about 10% by volume with respect to the total volume of the core layer 20, the effect of adding the fine particles (B) is low. On the other hand, if the usage amount exceeds about 50% by volume, the adhesive force of the acrylic pressure-sensitive adhesive constituting the core layer 20 may be reduced.
- bubbles (C) can be added to the acrylic polymer (A) constituting the core layer.
- the acrylic pressure-sensitive adhesive tape 10 can exhibit good adhesion to a curved surface or an uneven surface, and can also exhibit good repulsion resistance. it can.
- the bubbles (C) contained in the core layer 20 are basically closed-cell type bubbles, but closed-cell type bubbles and open-cell type bubbles may be mixed.
- the bubble (C) usually has a spherical shape (particularly a true spherical shape), but does not need to be a true spherical shape, such as having irregularities on the surface.
- the average bubble diameter (diameter) of the bubbles (C) is not particularly limited, but can be selected, for example, from the range of about 1 to about 1000 ⁇ m, preferably about 10 to about 500 ⁇ m, more preferably about 30 to about 300 ⁇ m. .
- the gas component contained in the bubble (C) (the gas component forming the bubble (C); hereinafter referred to as the bubble-forming gas as appropriate) is not particularly limited, and is inert such as nitrogen, carbon dioxide, or argon. In addition to gas, various gas components such as air can be used.
- a gas for forming bubbles (C) it is important to use a gas that does not inhibit the reaction when a polymerization reaction or the like is performed in a state in which the bubble-forming gas is contained.
- nitrogen can be preferably used from the viewpoint of not inhibiting the polymerization reaction and the like, and from the viewpoint of cost.
- the amount of the bubbles (C) contained in the core layer 20 is not particularly limited, and can be appropriately selected depending on the application.
- the amount of the bubbles (C) contained in the core layer 20 is, for example, about 5 to about 50% by volume, preferably about 8 to about 40 volumes with respect to the total volume of the core layer 20 containing the bubbles (C). %. If the amount of bubbles mixed is less than about 5% by volume, the effect of mixing bubbles (C) cannot be obtained, and if it exceeds about 50% by volume, the possibility of bubbles penetrating through the core layer 20 increases and adhesion performance and appearance are improved. May decrease.
- the method for forming the core layer 20 containing bubbles (C) is not particularly limited.
- the core layer 20 containing the bubbles (C) may be formed, for example, by using a core layer material mixed with bubble forming gas in advance, or (2) a core not mixed with bubble forming gas. You may form by mixing a foaming agent with a layer material.
- the foaming agent used is not particularly limited, and can be appropriately selected from known foaming agents, for example. As such a foaming agent, for example, thermally expandable microspheres can be used.
- a thickener In addition to the above-described components, a thickener, thixotropic agent, extender, etc. may be added to the core layer 20 as necessary.
- the thickener include acrylic rubber, epichlorohydrin rubber, butyl rubber and the like.
- thixotropic agents include colloidal silica and polyvinyl pyrrolidone.
- the bulking agent include calcium carbonate, titanium oxide, and clay.
- a plasticizer, an anti-aging agent, an antioxidant, and the like may be appropriately added to the core layer 20.
- the surface layer 30 includes an acrylic polymer (D) and a (meth) acrylic monomer having a tricyclic or higher alicyclic structure as a monomer unit, and a (meth) acrylic polymer having a weight average molecular weight of 1000 or more and less than 30000.
- (E) (hereinafter referred to as (meth) acrylic polymer (E) as appropriate).
- each component of the surface layer 30 will be described.
- the acrylic polymer (D) as the adhesive composition used for the surface layer 30 can be selected from the compounds (various monomer components) exemplified as the acrylic polymer (A) of the core layer 20.
- the acrylic polymer (D) used for the surface layer 30 may have the same component and composition ratio as the acrylic polymer (A) of the core layer 20, and the acrylic polymer (A) and components and composition of the core layer 20. The ratio may be different.
- the acrylic polymer (D) constituting the surface layer is a partially polymerized product in which the monomer component is partially polymerized by irradiating a mixture containing the monomer component and the polymerization initiator with ultraviolet rays (UV).
- (Acrylic polymer syrup) Acrylic polymer syrup is mixed with a (meth) acrylic polymer (E) to be described later to prepare an acrylic pressure-sensitive adhesive composition.
- This pressure-sensitive adhesive composition is applied to a predetermined substrate and irradiated with ultraviolet rays.
- the weight average molecular weight (Mw) of the acrylic polymer (D) is, for example, 30,000 to 5000000.
- the (meth) acrylic polymer (E) is a polymer having a weight average molecular weight smaller than that of the acrylic polymer (D), functions as a tackifying resin, and is less likely to cause polymerization inhibition during UV polymerization.
- the (meth) acrylic polymer (E) includes a (meth) acrylic monomer having a tricyclic or higher alicyclic structure as a monomer unit, and has a weight average molecular weight of 1000 or more and less than 30000. It is. Adhesion of acrylic pressure-sensitive adhesive tape to low-polar adherends made of polyethylene, polypropylene, etc. by giving (meth) acrylic polymer (E) a bulky structure such as a tricyclic or higher alicyclic structure Can be significantly improved.
- the (meth) acrylic monomer constituting the (meth) acrylic polymer (E) is, for example, a (meth) acrylic acid ester represented by the following general formula (1).
- CH 2 C (R 1 ) COOR 2 (1)
- R 1 is a hydrogen atom or a methyl group
- R 2 is an alicyclic hydrocarbon group having a tricyclic or higher alicyclic structure
- the alicyclic hydrocarbon group preferably has a three-dimensional structure such as a bridged ring structure.
- the adhesiveness of the acrylic pressure-sensitive adhesive tape can be further improved.
- the adhesive force with respect to a low polarity adherend such as polypropylene can be more remarkably improved.
- both repulsion resistance and retention characteristics can be achieved.
- the adhesive strength, repulsion resistance and retention characteristics are combined at a high level.
- Acrylic adhesive tape can be obtained.
- the reason why such characteristics can be obtained is that by including a bulky structure such as an alicyclic structure of three or more rings having a bridged ring structure, the cohesive force of uncrosslinked components in the acrylic adhesive tape is increased. It is estimated that.
- the alicyclic hydrocarbon group having a bridged ring structure include a dicyclopentanyl group represented by the following formula (2a), a dicyclopentenyl group represented by the following formula (2b), and the following formula (2c). ), A tricyclopentanyl group represented by the following formula (2d), a tricyclopentenyl group represented by the following formula (2e), and the like.
- Examples of (meth) acrylic monomers having a tricyclic or higher alicyclic structure having such a bridged ring structure include dicyclopentanyl methacrylate, dicyclopentanyl acrylate, and dicyclopentanyloxyethyl.
- the (meth) acrylic polymer (E) may contain other monomer components (copolymerizable monomers) copolymerizable with the (meth) acrylic monomer as necessary. That is, the (meth) acrylic polymer (E) may contain a copolymerizable monomer together with a (meth) acrylic monomer having a tricyclic or higher alicyclic structure as a main component.
- copolymerizable monomers examples include Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate , T-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, (meth ) Octyl acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acryl
- Examples of other copolymerizable monomers include Alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxypropyl (meth) acrylate monomer; (Meth) acrylic acid alkali metal salts and the like; Di (meth) acrylic acid ester of ethylene glycol, di (meth) acrylic acid ester of diethylene glycol, di (meth) acrylic acid ester of triethylene glycol, di (meth) acrylic acid ester of polyethylene glycol, di (meta) of propylene glycol ) Di (meth) acrylate monomers of (poly) alkylene glycols such as acrylate esters, di (meth) acrylate esters of dipropylene glycol, di (meth) acrylate esters of tripropylene
- the (meth) acrylic polymer (E) may be introduced with a functional group having reactivity with an epoxy group or an isocyanate group.
- a functional group having reactivity with an epoxy group or an isocyanate group examples include a hydroxyl group, a carboxyl group, an amino group, an amide group, and a mercapto group, and a monomer having such a functional group when the (meth) acrylic polymer (E) is produced. Is preferably used (copolymerized).
- the weight average molecular weight of the (meth) acrylic polymer (E) is 1000 or more and less than 30000, preferably 1500 or more and less than 20000, and more preferably 2000 or more and less than 10,000. If the weight average molecular weight of the (meth) acrylic polymer (E) is 30000 or more, the effect of improving the adhesive force in the adhesive tape may not be sufficiently obtained. Moreover, since it becomes low molecular weight as it is less than 1000, the adhesive force of an adhesive tape and the fall of a retention characteristic may be caused.
- the measurement of the weight average molecular weight can be obtained by polystyrene conversion by the GPC method. Specifically, it is measured on a HPLC 8020 manufactured by Tosoh Corporation using two TSKgelGMH-H (20) columns as a column and a tetrahydrofuran solvent at a flow rate of about 0.5 ml / min.
- the content of the (meth) acrylic polymer (E) is preferably 2 to 70 parts by weight and more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the acrylic polymer (D).
- the (meth) acrylic polymer (E) is added in excess of 70 parts by weight, the elastic modulus of the pressure-sensitive adhesive layer formed from the acrylic pressure-sensitive adhesive composition according to this embodiment is increased, and the adhesiveness at low temperature is poor. Or may not develop adhesive force even at room temperature.
- the addition amount is less than 2 parts, the effect may not be obtained.
- the (meth) acrylic polymer (E) has a glass transition temperature (Tg) of about 20 ° C. to 300 ° C., preferably about 30 ° C. to 300 ° C., more preferably about 40 ° C. to 300 ° C. Is desirable.
- Tg glass transition temperature
- Table 1 shows glass transition temperatures of typical materials that can be included as a monomer component of the (meth) acrylic polymer (E) in the present embodiment.
- the glass transition temperature shown in Table 1 is a nominal value described in literatures, catalogs, or the like, or a value calculated based on the following formula (3) (Fox formula).
- 1 / Tg W1 / Tg1 + W2 / Tg2 + ... + Wn / Tgn (3)
- Tg is the glass transition temperature (unit: K) of the (meth) acrylic polymer (E)
- the above formula (3) is a calculation formula in the case where the (meth) acrylic polymer (E) is composed of n types of monomer components of the monomer 1, the monomer 2,.
- DCPMA dicyclopentanyl methacrylate
- DCPA dicyclopentanyl acrylate
- IBXMA isobornyl methacrylate
- IBXA isobornyl acrylate
- CHMA cyclohexyl methacrylate
- MMA methyl methacrylate
- ADMA 1-adamantyl methacrylate
- ADA 1-adamantyl acrylate
- DCPMA / IBXMA40 Copolymer of DCPMA 60 parts by weight and IBXMA 40 parts by weight
- DCPMA / MMA40 Copolymer of DCPMA 60 parts by weight and MMA 40 parts by weight
- DCPMA / MMA60 Copolymer of 40 parts by weight of DCPMA and 60 parts by weight of MMA
- IBXMA / MMA60 40 parts by weight of IBXMA and MMA60 Part by weight of copolymer
- ADMA / MMA40 copolymer AD of 60 parts by weight of ADMA
- the (meth) acrylic polymer (E) is obtained by polymerizing the (meth) acrylic monomer having the above-described structure by a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, a suspension polymerization, a bulk polymerization, or the like. It is made with.
- a chain transfer agent can be used during the polymerization.
- the chain transfer agent used include compounds having a mercapto group such as octyl mercaptan, dodecyl mercaptan, t-dodecyl mercaptan, mercaptoethanol; thioglycolic acid, ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, T-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, decyl thioglycolate, dodecyl thioglycolate, thioglycolate of ethylene glycol, thioglycol
- the amount of the chain transfer agent used is not particularly limited, but is usually about 0.1 to about 20 parts by weight, preferably about 0.2 parts by weight, based on 100 parts by weight of the (meth) acrylic monomer. To about 15 parts by weight, more preferably about 0.3 to about 10 parts by weight.
- the (meth) acrylic-type polymer (E) of a suitable molecular weight can be obtained by adjusting the addition amount of a chain transfer agent.
- a chain transfer agent can be used individually or in combination of 2 or more types.
- the ratio of the thickness of the surface layer 30a (or the surface layer 30b) to the total thickness of the thickness of the core layer 20 and the surface layer 30a (or the surface layer 30b) is preferably about 3 to about 70%. If the ratio is less than about 3%, desired adhesion may not be obtained. Moreover, when the said ratio becomes higher than 70%, the effect expected when it has the core layer 20 containing a bubble (C), such as stress relaxation property as a pressure-sensitive adhesive tape and step absorbability, may not be acquired.
- the total thickness of the acrylic adhesive tape 10 (the sum of the thickness of the core layer 20 and the thickness of the surface layer 30) is about 0.4 mm to about 4.0 mm, preferably about 0 mm. .5 mm to about 2.5 mm.
- Multilayering method Although the method of laminating
- the core layer 20 After applying the core layer 20 to the previously cured surface layer 30a (or surface layer 30b), the core layer 20 is cured, and subsequently the surface layer 30b (or surface layer 30a) is applied to the core layer 20, A method of curing the surface layer 30b (or the surface layer 30a), or after coating the surface layer 30a (or the surface layer 30b on the other surface) on one surface of the core layer 20 previously cured, the surface layer 30a (or the surface layer 30b) Next, after the surface layer 30b (or the surface layer 30a on one surface) is applied to the other surface of the core layer 20, the surface layer 30b (or the surface layer 30a) is cured: In this method, the surface layer 30b is cured.
- each layer may be a coating roll such as a roll coater or comma coater, or a slot die.
- a coating roll such as a roll coater or comma coater
- a slot die for applying each layer may be used.
- composition for core layer The (meth) acrylic acid alkyl ester, copolymerizable monomer, and polymerization initiator described above are mixed to partially polymerize the (meth) acrylic acid alkyl ester and the copolymerizable monomer. Thereby, a partial polymer (acrylic polymer syrup) having a predetermined polymerization rate is produced. Next, a predetermined amount of hollow glass microspheres (trade name: Cellstar Z-27, manufactured by Tokai Kogyo Co., Ltd.) is added to the acrylic polymer syrup.
- hollow glass microspheres trade name: Cellstar Z-27, manufactured by Tokai Kogyo Co., Ltd.
- the volume of the hollow glass microspheres in the total volume of the core layer composition precursor is, for example, about 1.5% by volume.
- the core layer composition precursor is introduced between the teeth on the stator and the teeth on the rotor in the apparatus, and nitrogen gas is passed through the through hole while rotating the rotor at a high speed.
- nitrogen gas is passed through the through hole while rotating the rotor at a high speed.
- a bubble is mixed with the composition precursor for core layers, and the composition for core layers is obtained.
- the bubbles are mixed so as to be about 20% by volume with respect to the total volume of the core layer composition.
- the (meth) acrylic monomer (E) for the surface layer is prepared by blending the above-described (meth) acrylic monomer, chain transfer agent, polymerization initiator, and, if necessary, a copolymerizable monomer into a predetermined solvent. To do. Next, the above-mentioned acrylic polymer syrup (partially polymerized product) and the obtained (meth) acrylic polymer (E) are mixed to obtain a surface layer composition.
- the composition for a core layer is applied onto the release-treated surface of a polyester film (release liner) that has been subjected to a single-side release treatment using, for example, a roll coater.
- release liner a polyester film
- the same type of release liner is bonded to the other surface of the coated core layer composition.
- the both surfaces are bonded together so that the release-treated surface of the release liner faces the other surface of the core layer composition.
- ultraviolet irradiation is performed using, for example, a black light lamp.
- the core layer 20 is produced by the above procedure.
- the surface layer composition is applied onto the release-treated surface of a polyester film (release liner) that has been subjected to a single-side release treatment using, for example, a roll coater.
- release liner a polyester film
- the same type of release liner is bonded to the other surface of the applied surface layer composition.
- both surfaces are bonded together so that the release-treated surface of the release liner faces the other surface of the surface layer composition.
- ultraviolet irradiation is performed using, for example, a black light lamp.
- the surface layer 30 is produced by the above procedure.
- the surface layer composition and the core layer composition may contain various additives that are common in the field of pressure-sensitive adhesive compositions as optional components.
- optional components include plasticizers, softeners, fillers, colorants (pigments, dyes, etc.), antioxidants, leveling agents, stabilizers, preservatives, and the like.
- Conventionally known additives can be used as such additives.
- the pressure-sensitive adhesive layer disclosed herein is fixed to one side or both sides of a sheet-like base material (support), that is, without intention to separate the pressure-sensitive adhesive layer from the base material.
- a sheet-like base material support
- It may be a so-called adhesive tape with a base material provided.
- an adhesive tape for example, Composition of sheet-like substrate / core layer / surface layer, Configuration of sheet-like substrate / surface layer / core layer / surface layer, Composition of surface layer / core layer / sheet-like substrate / core layer / surface layer, The structure of surface layer / core layer / surface layer / sheet-like substrate / surface layer / core layer / surface layer can be mentioned.
- an adhesive sheet, an adhesive label, an adhesive film etc. may be included by the concept of an adhesive tape here.
- Plastic films such as polypropylene film, ethylene-propylene copolymer film, polyester film, polyvinyl chloride film; Foam substrates such as polyurethane foam and polyethylene foam; Kraft paper, crepe paper, Japanese paper, etc .; Cotton, soft cloth, etc .; Nonwoven fabrics such as polyester nonwoven fabrics and vinylon nonwoven fabrics; Metal foil such as aluminum foil and copper foil; Can be appropriately selected and used depending on the application of the adhesive tape.
- any of an unstretched film and a stretched (uniaxially stretched or biaxially stretched) film can be used.
- the surface of the substrate on which the pressure-sensitive adhesive layer is provided may be subjected to surface treatment such as application of a primer and corona discharge treatment.
- the thickness of the substrate can be appropriately selected according to the purpose, but is generally about 10 ⁇ m to 500 ⁇ m (typically 10 ⁇ m to 200 ⁇ m).
- the acrylic pressure-sensitive adhesive tape according to the present embodiment includes, for example, PP (polypropylene), ABS (acrylonitrile-butadiene-styrene copolymer), SBS (styrene-butadiene-styrene block copolymer), PC (polycarbonate), PVC (Various resins including acrylic resins such as vinyl chloride (PMMA) and PMMA (polymethyl methacrylate resin), and members made of metals such as SUS and aluminum, automobiles (its body coating film), housing materials, home appliances, etc. It can use suitably for the use joined (fixed) to the surface.
- PP polypropylene
- ABS acrylonitrile-butadiene-styrene copolymer
- SBS styrene-butadiene-styrene block copolymer
- PC polycarbonate
- PVC Various resins including acrylic resins such as vinyl chloride (PMMA) and PMMA (polymethyl methacrylate resin),
- the acrylic pressure-sensitive adhesive tape according to this embodiment is suitably used for applications in which various optical members are bonded to, for example, a liquid crystal cell, an optical polyester film, a touch panel member, or the like. Therefore, the technique shown here includes a laminate in which an adhesive layer containing an acrylic adhesive composition is provided on an optical member.
- This laminate typically has a form in which the pressure-sensitive adhesive layer on the optical member is protected by a release liner.
- the optical member provided with such an adhesive layer can be easily attached to, for example, the surface of a plastic cover lens panel, glass, liquid crystal cell, or the like.
- the optical member is not particularly limited, and may be a polarizing film, a retardation film, a transparent conductive film (ITO film), or the like.
- Such an optical member may have a single layer structure made of the same material or a multilayer structure made of a plurality of materials.
- a method of forming the pressure-sensitive adhesive layer on the optical member a method of directly applying or a method of transferring can be appropriately employed as in the case of forming the pressure-sensitive adhesive layer on the substrate.
- the pressure-sensitive adhesive layer formed on the release liner is transferred to the base surface of the optical member.
- the acrylic pressure-sensitive adhesive tape includes the core layer 20 and the surface layer 30 provided on one or both sides of the core layer 20.
- the core layer 20 includes an acrylic polymer (A)
- the surface layer 30 includes an acrylic polymer (D) and a (meth) acrylic monomer having a tricyclic or higher alicyclic structure as monomer units, A (meth) acrylic polymer (E) having a weight average molecular weight of 1000 or more and less than 30000. Therefore, the adhesiveness of an acrylic adhesive tape can be improved.
- the surface layers 30a and 30b are provided on both sides of the core layer 20, respectively, but only the surface layer 30a or the surface layer 30b may be provided on the core layer 20.
- the core layer 20 includes the acrylic polymer (A) as the pressure-sensitive adhesive composition, the fine particles (B), and the bubbles (C). However, if the core layer 20 includes at least the acrylic polymer (A). Good.
- Table 2 shows the components of the composition for the surface layer in the acrylic pressure-sensitive adhesive tapes according to Examples 1 to 7 and Comparative Examples 1 to 5.
- the reaction solution was put in a temperature atmosphere of 130 ° C., and toluene, the chain transfer agent, and the unreacted monomer were removed by drying to obtain a solid (meth) acrylic polymer 1.
- the obtained (meth) acrylic polymer 1 had a glass transition temperature of 175 ° C. and a weight average molecular weight of 4,600.
- DCPMA dicyclopentanyl methacrylate
- GSH 2-mercaptoethanol
- the reaction solution was put in a temperature atmosphere of 130 ° C., and toluene, the chain transfer agent, and the unreacted monomer were removed by drying to obtain a solid (meth) acrylic polymer 2.
- the obtained (meth) acrylic polymer 2 had a glass transition temperature of 175 ° C. and a weight average molecular weight of 3,600.
- the reaction solution was added to a temperature atmosphere of 130 ° C., and toluene, the chain transfer agent, and the unreacted monomer were removed by drying to obtain a solid (meth) acrylic polymer 3.
- the obtained (meth) acrylic polymer 3 had a glass transition temperature of 175 ° C. and a weight average molecular weight of 3,300.
- the reaction solution was added to a temperature atmosphere of 130 ° C., and toluene, the chain transfer agent, and the unreacted monomer were removed by drying to obtain a solid (meth) acrylic polymer 5.
- the obtained (meth) acrylic polymer 5 had a glass transition temperature of 175 ° C. and a weight average molecular weight of 3000.
- the reaction solution was charged into a temperature atmosphere of 130 ° C., and toluene, the chain transfer agent, and the unreacted monomer were removed by drying to obtain a solid (meth) acrylic polymer 6.
- the obtained (meth) acrylic polymer 6 had a glass transition temperature of 120 ° C. and a weight average molecular weight of 3,600.
- the reaction solution was put in a temperature atmosphere of 130 ° C., and toluene, the chain transfer agent, and the unreacted monomer were removed by drying, and a solid (meth) acrylic polymer 7 was obtained.
- the obtained (meth) acrylic polymer 7 had a glass transition temperature of 66 ° C. and a weight average molecular weight of 3,700.
- the reaction solution was put in a temperature atmosphere of 130 ° C., and toluene, chain transfer agent, and unreacted monomer were removed by drying, and a solid (meth) acrylic polymer 8 was obtained.
- the obtained (meth) acrylic polymer 8 had a glass transition temperature of 97 ° C. and a weight average molecular weight of 3,300.
- the reaction solution was added to a temperature atmosphere of 130 ° C., and toluene, chain transfer agent, and unreacted monomer were removed by drying, and a solid (meth) acrylic polymer 9 was obtained.
- the obtained (meth) acrylic polymer 9 had a glass transition temperature of 250 ° C. and a weight average molecular weight of 4,100.
- Example 1 Adjustment of composition for surface layer After adding 20 parts by weight of the above-mentioned (meth) acrylic polymer 1 and 0.085 parts by weight of trimethylolpropane triacrylate to 100 parts by weight of the above-mentioned acrylic polymer syrup 1, they are mixed uniformly. A surface layer composition was prepared.
- the surface layer composition described above was applied to the release surface of a 38 ⁇ m thick polyester film (trade name: MRF, manufactured by Mitsubishi Chemical Polyester Co., Ltd.) with one side peeled with silicone so that the final thickness was 50 ⁇ m. Thus, a coating layer was formed.
- a 38 ⁇ m thick polyester film (trade name: MRN, manufactured by Mitsubishi Chemical Polyester Co., Ltd.) having one surface peeled off with silicone on the surface of the applied surface layer composition is peeled off on the coating layer side. It coat
- the surface pressure-sensitive adhesive layer sheet thus obtained was irradiated with ultraviolet rays having an illuminance of 5 mW / cm 2 (measured with Topcon UVR-T1 having a maximum sensitivity of about 350 nm) using a black light lamp (manufactured by Toshiba Corporation). Irradiated for 360 seconds. In this way, a surface layer composed of an acrylic pressure-sensitive adhesive layer having a thickness of 50 ⁇ m was obtained. The gel fraction of the surface pressure-sensitive adhesive layer was 61.5% by weight. The polyester film coated on both sides of the pressure-sensitive adhesive layer functions as a release liner.
- the volume of the hollow glass microspheres in the total volume of the core layer composition precursor was about 26% by volume.
- Teeth on the stator in a device comprising a stator having a large number of fine teeth on a disk having a through hole in the center, and a rotor facing the stator and having fine teeth similar to the stator on the disk;
- the obtained core layer composition precursor was introduced between the teeth on the rotor.
- nitrogen gas was introduce
- the composition for core layers was obtained.
- the resulting core layer composition was applied to a thickness of 1.2 mm on the release-treated surface of a 38 ⁇ m-thick polyester film (polyester release liner) having one surface peel-treated by a roll coater.
- polyester release liner was bonded to the surface of the applied core layer composition so that the release treatment surface of the release liner was on the core layer composition side.
- ultraviolet rays with an illuminance of 5 mW / cm 2 were irradiated from both sides for 3 minutes using a black light lamp.
- the core layer which consists of a 1.2-mm-thick acrylic adhesive layer was obtained.
- Example 2 (Example 2) Implementation was performed except that 20 parts by weight of the above-mentioned (meth) acrylic polymer 2 and 0.085 parts by weight of trimethylolpropane triacrylate were added to 100 parts by weight of the above-mentioned acrylic polymer syrup 1.
- an acrylic pressure-sensitive adhesive tape was obtained.
- the gel fraction of the obtained adhesive layer for surface layers was 67.7 weight%.
- Example 3 (Example 3) Implemented except that the surface layer was prepared by adding 20 parts by weight of the above-mentioned (meth) acrylic polymer 3 and 0.12 parts by weight of trimethylolpropane triacrylate to 100 parts by weight of the above-mentioned acrylic polymer syrup 1.
- an acrylic pressure-sensitive adhesive tape was obtained.
- the gel fraction of the obtained pressure-sensitive adhesive layer for the surface layer was 59.7% by weight.
- Example 4 Implementation was performed except that 20 parts by weight of the above-mentioned (meth) acrylic polymer 4 and 0.14 parts by weight of trimethylolpropane triacrylate were added to 100 parts by weight of the above-mentioned acrylic polymer syrup 1.
- an acrylic pressure-sensitive adhesive tape was obtained.
- the gel fraction of the obtained adhesive layer for surface layers was 68.5 weight%.
- Example 5 (Example 5) Implemented except that 20 parts by weight of the above-mentioned (meth) acrylic polymer 5 and 0.18 parts by weight of trimethylolpropane triacrylate were added to 100 parts by weight of the above-mentioned acrylic polymer syrup 2 to prepare a surface layer.
- an acrylic pressure-sensitive adhesive tape was obtained.
- the gel fraction of the obtained adhesive layer for surface layers was 62.1 weight%.
- Example 6 A surface layer was prepared by adding 20 parts by weight of the aforementioned (meth) acrylic polymer 6 and 0.11 part by weight of 1,6-hexanediol diacrylate to 100 parts by weight of the acrylic polymer syrup 2 described above. Except that, an acrylic pressure-sensitive adhesive tape was obtained in the same manner as in Example 1. The gel fraction of the obtained adhesive layer for surface layers was 69.7 weight%.
- Example 7 Implemented except that the surface layer was prepared by adding 20 parts by weight of the above-mentioned (meth) acrylic polymer 9 and 0.12 parts by weight of trimethylolpropane triacrylate to 100 parts by weight of the above-mentioned acrylic polymer syrup 1.
- an acrylic pressure-sensitive adhesive tape was obtained.
- the gel fraction of the obtained pressure-sensitive adhesive layer for the surface layer was 74.7% by weight.
- Example 2 A surface layer was prepared by adding 20 parts by weight of the above-mentioned (meth) acrylic polymer 7 and 0.14 parts by weight of 1,6-hexanediol diacrylate to 100 parts by weight of the above-mentioned acrylic polymer syrup 1. Except that, an acrylic pressure-sensitive adhesive tape was obtained in the same manner as in Example 1. The gel fraction of the obtained pressure-sensitive adhesive layer for the surface layer was 74.9% by weight.
- a surface layer was prepared by adding 20 parts by weight of the above-mentioned (meth) acrylic polymer 7 and 0.11 part by weight of 1,6-hexanediol diacrylate to 100 parts by weight of the above-mentioned acrylic polymer syrup 2. Except that, an acrylic pressure-sensitive adhesive tape was obtained in the same manner as in Example 1. The gel fraction of the obtained adhesive layer for surface layers was 67.7 weight%.
- the release liner (polyester film) on the surface layer side was peeled off, and the adhesive layer on the surface layer side was attached to the polypropylene plate and the acrylic plate by one-way crimping with a 5 kg roller. After affixing the acrylic adhesive tape to the polypropylene plate and the acrylic plate, it was left in an environment at 23 ° C. for 30 minutes. Then, the other end of the acrylic adhesive tape was peeled off at a speed of 300 mm / min in a peeling direction of 180 degrees, and the adhesive force (resistance force) (unit: N / 25 mm) to the adherend at that time was measured.
- the acrylic adhesive tape according to each example and each comparative example was cut into a width of 10 mm and a length of 90 mm. Then, the release liner on the core layer side in the acrylic pressure-sensitive adhesive tape according to each example and each comparative example is peeled off and bonded to a clean aluminum plate having a thickness of 0.5 mm, a width of 10 mm, and a length of 90 mm, and this is tested. It was a piece. Next, the test piece was curved so that the curvature would be R50 mm by placing the aluminum plate side of the test piece along the cylinder. Then, the release liner (polyester film) on the surface layer side was peeled off and laminated on the polypropylene plate.
- the test piece is laminated on a polypropylene plate, and after 24 hours at room temperature (25 ° C.), the distance that the acrylic adhesive tape floats, that is, from the surface of the polypropylene plate to the adhesive layer for the surface layer of the acrylic adhesive tape.
- Distance (average of heights at both ends) (unit: mm).
- the case where the floated distance was 5 mm or less was judged as good ( ⁇ ), and the case where the floated distance exceeded 5 mm was judged as defective (x).
- Table 3 shows the measurement results.
- the numerical value shown in Table 3 is an average value about arbitrary plural points.
- Acrylic adhesive tape 20 core layer, 30, 30a, 30b surface layer.
- the present invention can be used for an acrylic adhesive tape.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
Description
CH2=C(R1)COOR2 (1)
[式(1)中、R1は、水素原子またはメチル基であり、R2は、三環以上の脂環式構造を有する脂環式炭化水素基である]
芯層20は、アクリル系ポリマー(A)と、必要に応じて微粒子(B)と、気泡(C)とを含む。以下、芯層20の各構成要素について詳述する。
芯層20を構成する、粘着性組成物であるアクリル系ポリマー(A)は、例えば、炭素数1~20の直鎖または分岐鎖状のアルキル基を有する(メタ)アクリル酸アルキルエステルをモノマー単位として約50重量%以上含有する。また、アクリル系ポリマー(A)は、炭素数1~20のアルキル基を有する(メタ)アクリル酸アルキルエステルが単独で、または2種以上が組み合わされた構成とすることができる。アクリル系ポリマー(A)は、重合開始剤とともに、(メタ)アクリル酸アルキルエステルを重合(たとえば、溶液重合、エマルション重合、UV重合)させることにより得ることができる。
シクロペンチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート等の脂環式炭化水素基を有する(メタ)アクリル酸エステル;
フェニル(メタ)アクリレート等の芳香族炭化水素基を有する(メタ)アクリル酸エステル;
テルペン化合物誘導体アルコールから得られる(メタ)アクリル酸エステル;
等が挙げられる。
アクリル酸、メタクリル酸、カルボキシエチルアクリレート、カルボキシペンチルアクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸、イソクロトン酸等のカルボキシル基含有モノマー;
(メタ)アクリル酸ヒドロキシエチル、(メタ)アクリル酸ヒドロキシプロピル、(メタ)アクリル酸ヒドロキシブチル、(メタ)アクリル酸ヒドロキシヘキシル、(メタ)アクリル酸ヒドロキシオクチル、(メタ)アクリル酸ヒドロキシデシル、(メタ)アクリル酸ヒドロキシラウリル、(4-ヒドロキシメチルシクロへキシル)メチルメタクリレート等の(メタ)アクリル酸ヒドロキシアルキル等の水酸基含有モノマー;
無水マレイン酸、無水イタコン酸等の酸無水物基含有モノマー;
スチレンスルホン酸、アリルスルホン酸、2-(メタ)アクリルアミド-2-メチルプロパンスルホン酸、(メタ)アクリルアミドプロパンスルホン酸、スルホプロピル(メタ)アクリレート、(メタ)アクリロイルオキシナフタレンスルホン酸等のスルホン酸基含有モノマー;
2-ヒドロキシエチルアクリロイルホスフェート等のリン酸基含有モノマー;
(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、N,N-ジエチル(メタ)アクリルアミド、N,N-ジプロピル(メタ)アクリルアミド、N,N-ジイソプロピル(メタ)アクリルアミド、N,N-ジ(n-ブチル)(メタ)アクリルアミド、N,N-ジ(t-ブチル)(メタ)アクリルアミド等のN,N-ジアルキル(メタ)アクリルアミド、N-エチル(メタ)アクリルアミド、N-イソプロピル(メタ)アクリルアミド、N-ブチル(メタ)アクリルアミド、N-n-ブチル(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、N-エチロール(メタ)アクリルアミド、N-メチロールプロパン(メタ)アクリルアミド、N-メトキシメチル(メタ)アクリルアミド、N-メトキシエチル(メタ)アクリルアミド、N-ブトキシメチル(メタ)アクリルアミド、N-アクリロイルモルホリン等の(N-置換)アミド系モノマー;
N-(メタ)アクリロイルオキシメチレンスクシンイミド、N-(メタ)アクリロイル-6-オキシヘキサメチレンスクシンイミド、N-(メタ)アクリロイル-8-オキシヘキサメチレンスクシンイミド等のスクシンイミド系モノマー;
N-シクロヘキシルマレイミド、N-イソプロピルマレイミド、N-ラウリルマレイミド、N-フェニルマレイミド等のマレイミド系モノマー;
N-メチルイタコンイミド、N-エチルイタコンイミド、N-ブチルイタコンイミド、N-オクチルイタコンイミド、N-2-エチルへキシルイタコンイミド、N-シクロへキシルイタコンイミド、N-ラウリルイタコンイミド等のイタコンイミド系モノマー;
N-ビニル-2-ピロリドン、N-メチルビニルピロリドン、N-ビニルピリジン、N-ビニルピペリドン、N-ビニルピリミジン、N-ビニルピペラジン、N-ビニルピラジン、N-ビニルピロール、N-ビニルイミダゾール、N-ビニルオキサゾール、N-(メタ)アクリロイル-2-ピロリドン、N-(メタ)アクリロイルピペリジン、N-(メタ)アクリロイルピロリジン、N-ビニルモルホリン、N-ビニル-2-ピペリドン、N-ビニル-3-モルホリノン、N-ビニル-2-カプロラクタム、N-ビニル-1,3-オキサジン-2-オン、N-ビニル-3,5-モルホリンジオン、N-ビニルピラゾール、N-ビニルイソオキサゾール、N-ビニルチアゾール、N-ビニルイソチアゾール、N-ビニルピリダジン等の窒素含有複素環系モノマー;
N-ビニルカルボン酸アミド類;
N-ビニルカプロラクタム等のラクタム系モノマー;
アクリロニトリル、メタクリロニトリル等のシアノアクリレートモノマー;
(メタ)アクリル酸アミノエチル、(メタ)アクリル酸N,N-ジメチルアミノエチル、(メタ)アクリル酸N,N-ジメチルアミノエチル、(メタ)アクリル酸t-ブチルアミノエチル等の(メタ)アクリル酸アミノアルキル系モノマー;
(メタ)アクリル酸メトキシエチル、(メタ)アクリル酸エトキシエチル等の(メタ)アクリル酸アルコキシアルキル系モノマー;
スチレン、α-メチルスチレン等のスチレン系モノマー;
(メタ)アクリル酸グリシジル等のエポキシ基含有アクリル系モノマー;
(メタ)アクリル酸ポリエチレングリコール、(メタ)アクリル酸ポリプロピレングリコール、(メタ)アクリル酸メトキシエチレングリコール、(メタ)アクリル酸メトキシポリプロピレングリコール等のグリコール系アクリルエステルモノマー;
(メタ)アクリル酸テトラヒドロフルフリル、フッ素原子含有(メタ)アクリレート、シリコーン(メタ)アクリレート等の複素環、ハロゲン原子、ケイ素原子等を有するアクリル酸エステル系モノマー;
イソプレン、ブタジエン、イソブチレン等のオレフィン系モノマー;
メチルビニルエーテル、エチルビニルエーテル等のビニルエーテル系モノマー;
酢酸ビニル、プロピオン酸ビニル等のビニルエステル類;
ビニルトルエン、スチレン等の芳香族ビニル化合物;
エチレン、ブタジエン、イソプレン、イソブチレン等のオレフィンまたはジエン類;
ビニルアルキルエーテル等のビニルエーテル類;
塩化ビニル;
(メタ)アクリル酸メトキシエチル、(メタ)アクリル酸エトキシエチル等(メタ)アクリル酸アルコキシアルキル系モノマー;
ビニルスルホン酸ナトリウム等のスルホン酸基含有モノマー;
シクロヘキシルマレイミド、イソプロピルマレイミド等のイミド基含有モノマー;
2-イソシアナートエチル(メタ)アクリレート等のイソシアネート基含有モノマー;
N-アクリロイルモルホリン等のアミド基含有ビニルモノマー;
等が挙げられる。なお、これらの共重合性モノマーは単独でまたは2種以上を組み合わせて使用できる。
アクリル系ポリマー(A)の調製に際して、熱重合開始剤や光重合開始剤(光開始剤)等の重合開始剤を用いた熱や紫外線による硬化反応を利用して、アクリル系ポリマー(A)を容易に形成することができる。特に、重合時間を短くすることができる利点等から、光重合開始剤を好適に用いることができる。重合開始剤は単独でまたは2種以上を組み合わせて使用することができる。
本実施形態において、芯層を構成するアクリル系ポリマー(A)には、微粒子(B)を添加することができる。微粒子(B)の作用効果としては、アクリル系粘着テープのせん断接着力や加工性の向上が挙げられる。
本実施形態において、芯層を構成するアクリル系ポリマー(A)には、気泡(C)を添加することができる。芯層20が気泡(C)を含有することにより、アクリル系粘着テープ10は曲面や凹凸面に対して良好な接着性を発揮することができ、また、良好な耐反撥性を発揮することができる。
上述した成分以外に、必要に応じて増粘剤、チキソトロープ剤、増量剤等が芯層20に添加されてもよい。増粘剤の例としては、アクリルゴム、エピクロルヒドリンゴム、ブチルゴム等が挙げられる。チキソトロープ剤の例としては、コロイドシリカ、ポリビニルピロリドン等が挙げられる。増量剤としては、炭酸カルシウム、酸化チタン、クレー等が挙げられる。その他、可塑剤、老化防止剤、酸化防止剤等が芯層20に適宜添加されてもよい。
表層30は、アクリル系ポリマー(D)と、三環以上の脂環式構造を有する(メタ)アクリル系モノマーをモノマー単位として含み、重量平均分子量が1000以上30000未満の(メタ)アクリル系重合体(E)(以下、適宜、(メタ)アクリル系重合体(E)と称する)とを含む。以下、表層30の各構成要素について説明する。
[アクリル系ポリマー(D)]
表層30に用いられる粘着性組成物としてのアクリル系ポリマー(D)は、芯層20のアクリル系ポリマー(A)として例示した化合物(各種モノマー成分)から選ぶことができる。表層30に用いられるアクリル系ポリマー(D)は、芯層20のアクリル系ポリマー(A)と成分および組成比が同等であってもよく、芯層20のアクリル系ポリマー(A)と成分および組成比が異なっていてもよい。
(メタ)アクリル系重合体(E)は、アクリル系ポリマー(D)よりも重量平均分子量が小さい重合体であり、粘着付与樹脂として機能し、かつUV重合の際に重合阻害を起こしにくいという利点を有する。(メタ)アクリル系重合体(E)は、三環以上の脂環式構造を有する(メタ)アクリル系モノマーをモノマー単位として含み、重量平均分子量が1000以上30000未満の(メタ)アクリル系重合体である。三環以上の脂環式構造のような嵩高い構造を(メタ)アクリル系重合体(E)に持たせることで、ポリエチレンやポリプロピレン等からなる低極性被着体に対するアクリル系粘着テープの接着性を顕著に向上させることができる。
CH2=C(R1)COOR2 (1)
[式(1)中、R1は、水素原子またはメチル基であり、R2は、三環以上の脂環式構造を有する脂環式炭化水素基である]
(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸s-ブチル、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸イソペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸-2-エチルヘキシル、(メタ)アクリル酸ヘプチル、(メタ)アクリル酸オクチル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸ノニル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸イソデシル、(メタ)アクリル酸ウンデシル、(メタ)アクリル酸ドデシルのような(メタ)アクリル酸アルキルエステル;
(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸イソボルニルのような(メタ)アクリル酸の脂環族アルコールとのエステル;
(メタ)アクリル酸フェニル、(メタ)アクリル酸ベンジルのような(メタ)アクリル酸アリールエステル;
テルペン化合物誘導体アルコールから得られる(メタ)アクリル酸エステル;
等の(メタ)アクリル酸エステルを挙げることができる。このような(メタ)アクリル酸エステルは単独であるいは2種以上を組み合わせて使用することができる。
(メタ)アクリル酸メトキシエチル、(メタ)アクリル酸エトキシエチル、(メタ)アクリル酸プロポキシエチル、(メタ)アクリル酸ブトキシエチル、(メタ)アクリル酸エトキシプロピルのような(メタ)アクリル酸アルコキシアルキル系モノマー;
(メタ)アクリル酸アルカリ金属塩等の塩;
エチレングリコールのジ(メタ)アクリル酸エステル、ジエチレングリコールのジ(メタ)アクリル酸エステル、トリエチレングリコールのジ(メタ)アクリル酸エステル、ポリエチレングリコールのジ(メタ)アクリル酸エステル、プロピレングリコールのジ(メタ)アクリル酸エステル、ジプロピレングリコールのジ(メタ)アクリル酸エステル、トリプロピレングリコールのジ(メタ)アクリル酸エステルのような(ポリ)アルキレングリコールのジ(メタ)アクリル酸エステルモノマー;
トリメチロールプロパントリ(メタ)アクリル酸エステルのような多価(メタ)アクリル酸エステルモノマー;
酢酸ビニル、プロピオン酸ビニル等のビニルエステル類;
塩化ビニリデン、(メタ)アクリル酸-2-クロロエチルのようなハロゲン化ビニル化合物;
2-ビニル-2-オキサゾリン、2-ビニル-5-メチル-2-オキサゾリン、2-イソプロペニル-2-オキサゾリンのようなオキサゾリン基含有重合性化合物;
(メタ)アクリロイルアジリジン、(メタ)アクリル酸-2-アジリジニルエチルのようなアジリジン基含有重合性化合物;
アリルグリシジルエーテル、(メタ)アクリル酸グリシジルエーテル、(メタ)アクリル酸-2-エチルグリシジルエーテルのようなエポキシ基含有ビニルモノマー;
(メタ)アクリル酸-2-ヒドロキシエチル、(メタ)アクリル酸-2-ヒドロキシプロピル、(メタ)アクリル酸とポリプロピレングリコールまたはポリエチレングリコールとのモノエステル、ラクトン類と(メタ)アクリル酸-2-ヒドロキシエチルとの付加物のようなヒドロキシル基含有ビニルモノマー;
フッ素置換(メタ)アクリル酸アルキルエステルのような含フッ素ビニルモノマー;
アクリル酸、メタクリル酸、カルボキシエチルアクリレート、カルボキシペンチルアクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸、イソクロトン酸等のカルボキシル基含有モノマー;
スチレンスルホン酸、アリルスルホン酸、2-(メタ)アクリルアミド-2-メチルプロパンスルホン酸、(メタ)アクリルアミドプロパンスルホン酸、スルホプロピル(メタ)アクリレート、(メタ)アクリロイルオキシナフタレンスルホン酸等のスルホン酸基含有モノマー;
2-ヒドロキシエチルアクリロイルホスフェート等のリン酸基含有モノマー;
無水マレイン酸、無水イタコン酸等の酸無水物基含有モノマー;
2-クロルエチルビニルエーテル、モノクロロ酢酸ビニルのような反応性ハロゲン含有ビニルモノマー;
スチレン、α-メチルスチレン、ビニルトルエン等の芳香族ビニル化合物系モノマー;
(メタ)アクリルアミド、N-イソプロピル(メタ)アクリルアミド、N-ブチル(メタ)アクリルアミド、N,N-ジエチル(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、N-エチロール(メタ)アクリルアミド、N-メチロールプロパン(メタ)アクリルアミド、N-メトキシエチル(メタ)アクリルアミド、N-ブトキシメチル(メタ)アクリルアミド、N-アクリロイルモルホリンのようなアミド基含有ビニルモノマー;
N-(メタ)アクリロイルオキシメチレンスクシンイミド、N-(メタ)アクリロイル-6-オキシヘキサメチレンスクシンイミド、N-(メタ)アクリロイル-8-オキシヘキサメチレンスクシンイミド等のスクシンイミド系モノマー;
N-シクロヘキシルマレイミド、N-イソプロピルマレイミド、N-ラウリルマレイミド、N-フェニルマレイミド等のマレイミド系モノマー;
N-メチルイタコンイミド、N-エチルイタコンイミド、N-ブチルイタコンイミド、N-オクチルイタコンイミド、N-2-エチルへキシルイタコンイミド、N-シクロへキシルイタコンイミド、N-ラウリルイタコンイミド等のイタコンイミド系モノマー;
N-ビニル-2-ピロリドン、N-メチルビニルピロリドン、N-ビニルピリジン、N-ビニルピペリドン、N-ビニルピリミジン、N-ビニルピペラジン、N-ビニルピラジン、N-ビニルピロール、N-ビニルイミダゾール、N-ビニルオキサゾール、N-(メタ)アクリロイル-2-ピロリドン、N-(メタ)アクリロイルピペリジン、N-(メタ)アクリロイルピロリジン、N-ビニルモルホリン、N-ビニルピラゾール、N-ビニルイソオキサゾール、N-ビニルチアゾール、N-ビニルイソチアゾール、N-ビニルピリダジン等の窒素含有複素環系モノマー;
N-ビニルカルボン酸アミド類;
N-ビニルカプロラクタム等のラクタム系モノマー;
(メタ)アクリロニトリル等のシアノアクリレートモノマー;
(メタ)アクリル酸アミノエチル、(メタ)アクリル酸N,N-ジメチルアミノエチル、(メタ)アクリル酸N,N-ジメチルアミノエチル、(メタ)アクリル酸t-ブチルアミノエチル等の(メタ)アクリル酸アミノアルキル系モノマー;
シクロヘキシルマレイミド、イソプロピルマレイミド等のイミド基含有モノマー;
2-イソシアナートエチル(メタ)アクリレート等のイソシアネート基含有モノマー;
(メタ)アクリル酸ヒドロキシエチル、(メタ)アクリル酸ヒドロキシプロピル、(メタ)アクリル酸ヒドロキシブチル、(メタ)アクリル酸ヒドロキシヘキシル、(メタ)アクリル酸ヒドロキシオクチル、(メタ)アクリル酸ヒドロキシデシル、(メタ)アクリル酸ヒドロキシラウリル、(4-ヒドロキシメチルシクロへキシル)メチルメタクリレート等の(メタ)アクリル酸ヒドロキシアルキル等の水酸基含有モノマー;
(メタ)アクリル酸テトラヒドロフルフリル、フッ素原子含有(メタ)アクリレート、シリコーン(メタ)アクリレート等の複素環、ハロゲン原子、ケイ素原子等を有するアクリル酸エステル系モノマー;
イソプレン、ブタジエン、イソブチレン等のオレフィン系モノマー;
メチルビニルエーテル、エチルビニルエーテル等のビニルエーテル系モノマー;
エチレン、ブタジエン、イソプレン、イソブチレン等のオレフィンまたはジエン類;
ビニルアルキルエーテル等のビニルエーテル類;
塩化ビニル;
ビニルトリメトキシシラン、γ-メタクリロキシプロピルトリメトキシシラン、アリルトリメトキシシラン、トリメトキシシリルプロピルアリルアミン、2-メトキシエトキシトリメトキシシランのような有機ケイ素含有ビニルモノマー;
その他、ビニル基を重合したモノマー末端にラジカル重合性ビニル基を有するマクロモノマー類
等を挙げることができる。これらのモノマーは、単独であるいは組み合わせて前記(メタ)アクリル系モノマーと共重合させることができる。
1/Tg=W1/Tg1+W2/Tg2+・・・+Wn/Tgn (3)
[式(3)中、Tgは(メタ)アクリル系重合体(E)のガラス転移温度(単位:K)、Tgi(i=1、2、・・・n)はモノマーiがホモポリマーを形成した際のガラス転移温度(単位:K)、Wi(i=1、2、・・・n)はモノマーiの全モノマー成分中の重量分率を表す。]
上記式(3)は、(メタ)アクリル系重合体(E)が、モノマー1、モノマー2、・・・、モノマーnのn種類のモノマー成分から構成される場合の計算式である。
DCPMA:ジシクロペンタニルメタクリレート
DCPA:ジシクロペンタニルアクリレート
IBXMA:イソボルニルメタクリレート
IBXA:イソボルニルアクリレート
CHMA:シクロヘキシルメタクリレート
MMA:メチルメタクリレート
ADMA:1―アダマンチルメタクリレート
ADA:1―アダマンチルアクリレート
DCPMA/IBXMA40:DCPMA60重量部とIBXMA40重量部の共重合体
DCPMA/MMA40:DCPMA60重量部とMMA40重量部の共重合体
DCPMA/MMA60:DCPMA40重量部とMMA60重量部の共重合体
IBXMA/MMA60:IBXMA40重量部とMMA60重量部の共重合体
ADMA/MMA40:ADMA60重量部とMMA40重量部の共重合体
ADA/MMA40:ADA60重量部とMMA40重量部の共重合体
(メタ)アクリル系重合体(E)は、たとえば、上述した構造を有する(メタ)アクリル系モノマーを、溶液重合法やバルク重合法、乳化重合法、懸濁重合、塊状重合等により重合することで作製される。
(メタ)アクリル系重合体(E)の分子量を調整するためにその重合中に連鎖移動剤を用いることができる。使用する連鎖移動剤の例としては、オクチルメルカプタン、ドデシルメルカプタン、t-ドデシルメルカプタン、メルカプトエタノール等のメルカプト基を有する化合物;チオグリコール酸、チオグリコール酸エチル、チオグリコール酸プロピル、チオグリコール酸ブチル、チオグリコール酸t-ブチル、チオグリコール酸2-エチルヘキシル、チオグリコール酸オクチル、チオグリコール酸デシル、チオグリコール酸ドデシル、エチレングリコールのチオグリコール酸エステル、ネオペンチルグリコールのチオグリコール酸エステル、ペンタエリスリトールのチオグリコール酸エステルが挙げられる。
芯層20の厚さと表層30a(または表層30b)の厚さとを合わせた総厚に対する表層30a(または表層30b)の厚さの比率は、好ましくは約3~約70%である。当該比率が約3%未満であると、所望の接着性が得られない場合がある。また、当該比率が70%より高くなると、粘着テープとしての応力緩和性や段差吸収性といった、気泡(C)を含有する芯層20を有する場合に期待される効果が得られない場合がある。なお、特に限定するものではないが、アクリル系粘着テープ10の総厚(芯層20の厚さと表層30の厚さの合計)は、約0.4mm~約4.0mm、好ましくは、約0.5mm~約2.5mmである。
芯層20と表層30とを積層する方法は特に限定されないが、たとえば、以下に示す方法を適用することができる。
(1)芯層20および表層30を別々に硬化させた後、芯層20の一方の面に表層30aをラミネートし、芯層20の他方の面に表層30bをラミネートすることにより多層化する方法:当該方法は、各層の厚み精度を高くすることができるという利点を有する。
(2)予め硬化させた表層30a(または表層30b)に芯層20を塗工した後、芯層20を硬化させ、続いて芯層20に表層30b(または表層30a)を塗工した後、表層30b(または表層30a)を硬化させる方法、あるいは、予め硬化させた芯層20の一方の面に表層30a(または他方の面に表層30b)を塗工した後、表層30a(または表層30b)を硬化させ、続いて芯層20の他方の面に表層30b(または一方の面に表層30a)を塗工した後、表層30b(または表層30a)を硬化させる方法:当該方法では、硬化させた層に別の層を塗布するため、各層の厚み精度を高くすることができる。また、硬化させた層に別の層を一括塗工することができるため、製造工程の簡素化や製造時間の短縮を図ることができる。
(3)塗布された表層30(または芯層20)に芯層20(または表層30)を逐次あるいは同時に塗布して硬化させる方法:当該方法では、表層30、芯層20ともに一括塗工が可能である。
[芯層用組成物の調整]
上述した(メタ)アクリル酸アルキルエステル、共重合性モノマー、および重合開始剤を混合して、(メタ)アクリル酸アルキルエステルと共重合性モノマーとを部分的に重合させる。これにより、所定の重合率を有する部分重合物(アクリル系ポリマーシロップ)を作製する。次いで、このアクリル系ポリマーシロップに所定量の中空ガラス微小球(商品名:セルスターZ-27、東海工業株式会社製)を添加する。中空ガラス微小球を添加したシロップに、フッ素系界面活性剤(商品名:サーフロンS-393、セイケミカル株式会社製;側鎖にポリオキシエチレン基およびフッ素化炭化水素基を有するアクリル系共重合体;Mw=8300、0.5重量部)を添加して、芯層用組成物前駆体を調製する。なお、芯層用組成物前駆体において、芯層用組成物前駆体の全体積に占める中空ガラス微小球の容積は、たとえば、約1.5容積%である。
所定の溶媒に、上述した(メタ)アクリル系モノマー、連鎖移動剤、重合開始剤、および必要に応じて共重合性モノマーを配合し、表層用の(メタ)アクリル系重合体(E)を調整する。次いで、上述したアクリル系ポリマーシロップ(部分重合物)、および得られた(メタ)アクリル系重合体(E)を混合して、表層用組成物を得る。
芯層用組成物を、たとえばロールコーターにて、片面剥離処理されたポリエステルフィルム(剥離ライナー)の剥離処理された面上に塗布する。次いで、塗布された芯層用組成物のもう片方の面に、同種の剥離ライナーを貼り合わせる。このとき、剥離ライナーの剥離処理された面が芯層用組成物のもう片方の面と対向するようにして両者が貼り合わせられる。次いで、たとえばブラックライトランプにて、紫外線照射が実施される。以上の手順により芯層20が作製される。
表層用組成物を、たとえばロールコーターにて、片面剥離処理されたポリエステルフィルム(剥離ライナー)の剥離処理された面上に塗布する。次いで、塗布された表層用組成物のもう片方の面に、同種の剥離ライナーを貼り合わせる。このとき、剥離ライナーの剥離処理された面が表層用組成物のもう片方の面と対向するようにして両者が貼り合わせられる。次いで、たとえばブラックライトランプにて、紫外線照射が実施される。以上の手順により表層30が作製される。
上述した手順で得られた芯層20と表層30について、それぞれ片方の面に貼り合わされた剥離ライナーを剥がし、それぞれの粘着面同士を貼り合わせる。これにより、アクリル系粘着テープ10が作製される。
シート状基材/芯層/表層の構成、
シート状基材/表層/芯層/表層の構成、
表層/芯層/シート状基材/芯層/表層の構成、
表層/芯層/表層/シート状基材/表層/芯層/表層の構成
等を挙げることがえきる。なお、ここでいう粘着テープの概念には、粘着シート、粘着ラベル、粘着フィルム等と称されるものが包含され得る。
ポリプロピレンフィルム、エチレン-プロピレン共重合体フィルム、ポリエステルフィルム、ポリ塩化ビニルフィルム等のプラスチックフィルム;
ポリウレタンフォーム、ポリエチレンフォーム等のフォーム基材;
クラフト紙、クレープ紙、和紙等の紙;
綿布、スフ布等の布;
ポリエステル不織布、ビニロン不織布等の不織布;
アルミニウム箔、銅箔等の金属箔;
等を、粘着テープの用途に応じて適宜選択して用いることができる。上記プラスチックフィルムとしては、無延伸フィルムおよび延伸(一軸延伸または二軸延伸)フィルムのいずれも使用可能である。また、基材のうち粘着剤層が設けられる面には、下塗剤の塗付、コロナ放電処理等の表面処理が施されていてもよい。基材の厚みは目的に応じて適宜選択できるが、一般的には概ね10μm~500μm(典型的には10μm~200μm)程度である。
2EHA:2-エチルヘキシルアクリレート
NVP:N-ビニル-2-ピロリドン
AA:アクリル酸
DCPMA:ジシクロペンタニルメタクリレート
DCPMA低:DCPMA(実施例1~3)よりも低重合度のジシクロペンタニルメタクリレート
DCPA:ジシクロペンタニルアクリレート
IBXMA:イソボルニルメタクリレート
CHMA:シクロヘキシルメタクリレート
IBXA:イソボルニルアクリレート
ADMA:1-アダマンチルメタクリレート
GSH酸:チオグリコール酸
GSH:2-メルカプトエタノール
LSH:ラウリルメルカプタン
トルエン100重量部、ジシクロペンタニルメタクリレート(DCPMA)(商品名:FA-513M、日立化成工業株式会社製)100重量部、および連鎖移動剤としてチオグリコール酸(GSH酸)3重量部を4つ口フラスコに投入した。そして、70℃にて窒素雰囲気下で1時間攪拌した後、熱重合開始剤としてアゾビスイソブチロニトリル0.2重量部を投入し、70℃で2時間反応させ、続いて80℃で2時間反応させた。その後、反応液を130℃の温度雰囲気下に投入し、トルエン、連鎖移動剤、および未反応モノマーを乾燥除去させ、固形状の(メタ)アクリル系重合体1を得た。得られた(メタ)アクリル系重合体1のガラス転移温度は175℃、重量平均分子量は4600であった。
トルエン100重量部、ジシクロペンタニルメタクリレート(DCPMA)(商品名:FA-513M、日立化成工業株式会社製)100重量部、および連鎖移動剤として2-メルカプトエタノール(チオグリコール、GSH)3重量部を4つ口フラスコに投入した。そして、70℃にて窒素雰囲気下で1時間攪拌した後、熱重合開始剤としてアゾビスイソブチロニトリル0.2重量部を投入し、70℃で2時間反応させ、続いて80℃で2時間反応させた。その後、反応液を130℃の温度雰囲気下に投入し、トルエン、連鎖移動剤、および未反応モノマーを乾燥除去させ、固形状の(メタ)アクリル系重合体2を得た。得られた(メタ)アクリル系重合体2のガラス転移温度は175℃、重量平均分子量は3600であった。
トルエン100重量部、ジシクロペンタニルメタクリレート(DCPMA)(商品名:FA-513M、日立化成工業株式会社製)100重量部、および連鎖移動剤としてラウリルメルカプタン(LSH)8重量部を4つ口フラスコに投入した。そして、70℃にて窒素雰囲気下で1時間攪拌した後、熱重合開始剤としてアゾビスイソブチロニトリル0.2重量部を投入し、70℃で2時間反応させ、続いて80℃で2時間反応させた。その後、反応液を130℃の温度雰囲気下に投入し、トルエン、連鎖移動剤、および未反応モノマーを乾燥除去させ、固形状の(メタ)アクリル系重合体3を得た。得られた(メタ)アクリル系重合体3のガラス転移温度は175℃、重量平均分子量は3300であった。
トルエン100重量部、ジシクロペンタニルメタクリレート(DCPMA)(商品名:FA-513M、日立化成工業株式会社製)60重量部、イソボルニルメタクリレート(IBXMA)40重量部、および連鎖移動剤としてチオグリコール酸(GSH酸)3重量部を4つ口フラスコに投入した。そして、70℃にて窒素雰囲気下で1時間攪拌した後、熱重合開始剤としてアゾビスイソブチロニトリル0.2重量部を投入し、70℃で2時間反応させ、続いて80℃で2時間反応させた。その後、反応液を130℃の温度雰囲気下に投入し、トルエン、連鎖移動剤、および未反応モノマーを乾燥除去させ、固形状の(メタ)アクリル系重合体4を得た。得られた(メタ)アクリル系重合体4のガラス転移温度は174℃、重量平均分子量は4800であった。
トルエン100重量部、ジシクロペンタニルメタクリレート(DCPMA)(商品名:FA-513M、日立化成工業株式会社製)100重量部、および連鎖移動剤としてチオグリコール酸(GSH酸)5重量部を4つ口フラスコに投入した。そして、75℃にて窒素雰囲気下で1時間攪拌した後、熱重合開始剤としてアゾビスイソブチロニトリル0.2重量部を投入し、75℃で2時間反応させ、続いて80℃で2時間反応させた。その後、反応液を130℃の温度雰囲気下に投入し、トルエン、連鎖移動剤、および未反応モノマーを乾燥除去させ、固形状の(メタ)アクリル系重合体5を得た。得られた(メタ)アクリル系重合体5のガラス転移温度は175℃、重量平均分子量は3000であった。
トルエン100重量部、ジシクロペンタニルアクリレート(DCPA)(商品名:FA-513AS、日立化成工業株式会社製)100重量部、および連鎖移動剤としてラウリルメルカプタン(LSH)8重量部を4つ口フラスコに投入した。そして、70℃にて窒素雰囲気下で1時間攪拌した後、熱重合開始剤としてアゾビスイソブチロニトリル0.2重量部を投入し、70℃で2時間反応させ、続いて80℃で2時間反応させた。その後、反応液を130℃の温度雰囲気下に投入し、トルエン、連鎖移動剤、および未反応モノマーを乾燥除去させ、固形状の(メタ)アクリル系重合体6を得た。得られた(メタ)アクリル系重合体6のガラス転移温度は120℃、重量平均分子量は3600であった。
トルエン100重量部、シクロヘキシルメタクリレート(CHMA)100重量部、および連鎖移動剤として2-メルカプトエタノール(チオグリコール、GSH)3重量部を4つ口フラスコに投入した。そして、70℃にて窒素雰囲気下で1時間攪拌した後、熱重合開始剤としてアゾビスイソブチロニトリル0.2重量部を投入し、70℃で2時間反応させ、続いて80℃で2時間反応させた。その後、反応液を130℃の温度雰囲気下に投入し、トルエン、連鎖移動剤、および未反応モノマーを乾燥除去させ、固形状の(メタ)アクリル系重合体7を得た。得られた(メタ)アクリル系重合体7のガラス転移温度は66℃、重量平均分子量は3700であった。
トルエン100重量部、イソボルニルアクリレート(IBXA)100重量部、および連鎖移動剤として2-メルカプトエタノール(チオグリコール、GSH)3重量部を4つ口フラスコに投入した。そして、70℃にて窒素雰囲気下で1時間攪拌した後、熱重合開始剤としてアゾビスイソブチロニトリル0.2部を投入し、70℃で2時間反応させ、続いて80℃で2時間反応させた。その後、反応液を130℃の温度雰囲気下に投入し、トルエン、連鎖移動剤、および未反応モノマーを乾燥除去させ、固形状の(メタ)アクリル系重合体8を得た。得られた(メタ)アクリル系重合体8のガラス転移温度は97℃、重量平均分子量は3300であった。
トルエン100重量部、1―アダマンチルメタクリレート(ADMA)100重量部、および連鎖移動剤としてチオグリコール酸(GSH酸)3重量部を4つ口フラスコに投入した。そして、70℃にて窒素雰囲気下で1時間攪拌した後、熱重合開始剤としてアゾビスイソブチロニトリル0.2部を投入し、70℃で2時間反応させ、続いて80℃で2時間反応させた。その後、反応液を130℃の温度雰囲気下に投入し、トルエン、連鎖移動剤、および未反応モノマーを乾燥除去させ、固形状の(メタ)アクリル系重合体9を得た。得られた(メタ)アクリル系重合体9のガラス転移温度は250℃、重量平均分子量は4100であった。
2-エチルヘキシルアクリレート(2EHA)86重量部、N-ビニル-2-ピロリドン(NVP)14重量部、光重合開始剤(商品名:イルガキュア184、チバスペシャルティケミカルズ社製)0.05重量部、および光重合開始剤(商品名:イルガキュア651、チバスペシャルティケミカルズ社製)0.05重量部を4つ口フラスコに投入した。そして、混合物を窒素雰囲気下で紫外線に曝露して部分的に光重合させることによって、重合率約11重量%の部分重合物(アクリル系ポリマーシロップ1)を得た。
2-エチルヘキシルアクリレート(2EHA)94重量部、アクリル酸(AA)6重量部、光重合開始剤(商品名:イルガキュア184、チバスペシャルティケミカルズ社製)0.05重量部、および光重合開始剤(商品名:イルガキュア651、チバスペシャルティケミカルズ社製)0.05重量部を4つ口フラスコに投入した。そして、混合物を窒素雰囲気下で紫外線に曝露して部分的に光重合させることによって、重合率約8重量%の部分重合物(アクリル系ポリマーシロップ2)を得た。
2-エチルヘキシルアクリレート(2EHA)90重量部、およびアクリル酸(AA)10重量部から構成されるモノマー混合物に、光重合開始剤(商品名:イルガキュア651、チバスペシャルティケミカルズ社製)0.05重量部と、光重合開始剤(商品名:イルガキュア184、チバスペシャルティケミカルズ社製)0.05重量部とを配合した。そして、混合物の粘度(BH粘度計、No.5ローター、10rpm、測定温度:30℃)が15Pa・sになるまで紫外線を照射して部分重合物(アクリル系ポリマーシロップ3)を得た。
(表層用組成物の調整)
上述したアクリル系ポリマーシロップ1の100重量部に、上述した(メタ)アクリル系重合体1を20重量部、およびトリメチロールプロパントリアクリレート0.085重量部を添加した後、これらを均一に混合し表層用組成物を調製した。
片面をシリコーンで剥離処理した厚み38μmのポリエステルフィルム(商品名:MRF、三菱化学ポリエステル株式会社製)の剥離処理面に、上述した表層用組成物を最終的な厚みが50μmになるように塗布して塗布層を形成した。次いで、塗布された表層用組成物の表面に、片面をシリコーンで剥離処理した厚み38μmのポリエステルフィルム(商品名:MRN、三菱化学ポリエステル株式会社製)を、当該フィルムの剥離処理面が塗布層側になるようにして被覆した。これにより、表層用組成物の塗布層(表層用粘着剤層)を酸素から遮断した。このようにして得られた表層用粘着剤層シートに、ブラックライトランプ(株式会社東芝製)を用いて照度5mW/cm2(約350nmに最大感度をもつトプコンUVR-T1で測定)の紫外線を360秒間照射した。このようにして、厚さ50μmのアクリル系粘着剤層からなる表層を得た。表層用粘着剤層のゲル分率は、61.5重量%であった。粘着剤層の両面に被覆されたポリエステルフィルムは、剥離ライナーとして機能する。
上述したアクリル系ポリマーシロップ3の100重量部に、1,6-ヘキサンジオールジアクリレート0.08重量部を添加した後、さらに、当該シロップに対して9.5部となるように中空ガラス微小球(商品名:セルスターZ-27、東海工業株式会社製)を添加した。
ロールコーターにより、片面を剥離処理した厚さ38μmのポリエステルフィルム(ポリエステル製剥離ライナー)の剥離処理面に、得られた芯層用組成物を厚さ1.2mmとなるように塗布した。次いで、塗布された芯層用組成物の表面に、同種のポリエステル製剥離ライナーを、当該剥離ライナーの剥離処理面が芯層用組成物側になるようにして貼り合わせた。次いで、ブラックライトランプを用いて照度5mW/cm2の紫外線を両面から3分間照射した。このようにして、厚さ1.2mmのアクリル系粘着剤層からなる芯層を得た。
上述した手順で得られた芯層と表層について、それぞれ片方の面に貼り合わされた剥離ライナーを剥がし、それぞれの粘着面同士を貼り合わせて、実施例1に係るアクリル系粘着テープを得た。
上述したアクリル系ポリマーシロップ1の100重量部に、上述した(メタ)アクリル系重合体2を20重量部、トリメチロールプロパントリアクリレート0.085重量部を添加して表層を作製したこと以外は実施例1と同様にして、アクリル系粘着テープを得た。得られた表層用粘着剤層のゲル分率は、67.7重量%であった。
上述したアクリル系ポリマーシロップ1の100重量部に、上述した(メタ)アクリル系重合体3を20重量部、トリメチロールプロパントリアクリレート0.12重量部を添加して表層を作製したこと以外は実施例1と同様にして、アクリル系粘着テープを得た。得られた表層用粘着剤層のゲル分率は、59.7重量%であった。
上述したアクリル系ポリマーシロップ1の100重量部に、上述した(メタ)アクリル系重合体4を20重量部、トリメチロールプロパントリアクリレート0.14重量部を添加して表層を作製したこと以外は実施例1と同様にして、アクリル系粘着テープを得た。得られた表層用粘着剤層のゲル分率は、68.5重量%であった。
上述したアクリル系ポリマーシロップ2の100重量部に、上述した(メタ)アクリル系重合体5を20重量部、トリメチロールプロパントリアクリレート0.18重量部を添加して表層を作製したこと以外は実施例1と同様にして、アクリル系粘着テープを得た。得られた表層用粘着剤層のゲル分率は、62.1重量%であった。
上述したアクリル系ポリマーシロップ2の100重量部に、上述した(メタ)アクリル系重合体6を20重量部、1,6-ヘキサンジオールジアクリレート0.11重量部を添加して表層を作製したこと以外は実施例1と同様にして、アクリル系粘着テープを得た。得られた表層用粘着剤層のゲル分率は、69.7重量%であった。
上述したアクリル系ポリマーシロップ1の100重量部に、上述した(メタ)アクリル系重合体9を20重量部、トリメチロールプロパントリアクリレート0.12重量部を添加して表層を作成したこと以外は実施例1と同様にして、アクリル系粘着テープを得た。得られた表層用粘着剤層のゲル分率は、74.7重量%であった。
上述したアクリル系ポリマーシロップ1の100重量部に、1,6-ヘキサンジオールジアクリレート0.045重量部を添加して表層を作製したこと以外は実施例1と同様にして、アクリル系粘着テープを得た。得られた表層用粘着剤層のゲル分率は、77.4重量%であった。
上述したアクリル系ポリマーシロップ1の100重量部に、上述した(メタ)アクリル系重合体7を20重量部、1,6-ヘキサンジオールジアクリレート0.14重量部を添加して表層を作製したこと以外は実施例1と同様にして、アクリル系粘着テープを得た。得られた表層用粘着剤層のゲル分率は、74.9重量%であった。
上述したアクリル系ポリマーシロップ1の100重量部に、上述した(メタ)アクリル系重合体8を20重量部、トリメチロールプロパントリアクリレート0.1重量部を添加して表層を作製したこと以外は実施例1と同様にして、アクリル系粘着テープを得た。得られた表層用粘着剤層のゲル分率は、71.9重量%であった。
上述したアクリル系ポリマーシロップ2の100重量部に、1,6-ヘキサンジオールジアクリレート0.07重量部を添加して表層を作製したこと以外は実施例1と同様にして、アクリル系粘着テープを得た。得られた表層用粘着剤層のゲル分率は、75.2重量%であった。
上述したアクリル系ポリマーシロップ2の100重量部に、上述した(メタ)アクリル系重合体7を20重量部、1,6-ヘキサンジオールジアクリレート0.11重量部を添加して表層を作製したこと以外は実施例1と同様にして、アクリル系粘着テープを得た。得られた表層用粘着剤層のゲル分率は、67.7重量%であった。
[180°引き剥がし粘着力試験]
各実施例、および各比較例に係るアクリル系粘着テープにおける芯層側の剥離ライナーを剥がし、プライマー処理が施された厚さ50μmのポリエチレンテレフタレートフィルムを貼り合せ、それを25mm幅に切断したものを試験片とした。また、イソプロピルアルコールにて清浄化した厚さ2mmのポリプロピレン板(品番1600、タキロン株式会社製)およびアクリル板(アクリライト、三菱レイヨン株式会社製)を用意した。そして、表層側の剥離ライナー(ポリエステルフィルム)を剥がし、5kgローラーの片道圧着によりポリプロピレン板およびアクリル板に表層側の粘着面を貼り付けた。ポリプロピレン板およびアクリル板にアクリル系粘着テープを貼り付けた後、23℃の環境下で30分間放置した。そして、アクリル系粘着テープの他端を300mm/分の速度で180度の剥離方向へ剥離し、その時の被着体に対する粘着力(抵抗力)(単位:N/25mm)を測定した。ポリプロピレン板およびアクリル板のそれぞれにおいて、粘着力が40N/25mm以上である場合を良好(○)とし、40N/25mm未満である場合を不良(×)とした。測定結果を表3に示す。
各実施例、および各比較例に係るアクリル系粘着テープを幅10mm、長さ90mmに切断した。そして、各実施例、および各比較例に係るアクリル系粘着テープにおける芯層側の剥離ライナーを剥がし、厚さ0.5mm、幅10mm、長さ90mmの清浄なアルミ板に貼り合せ、これを試験片とした。次いで、試験片のアルミ板側を円柱に沿わせることで、曲率がR50mmとなるように試験片を湾曲させた。そして、表層側の剥離ライナー(ポリエステルフィルム)を剥がして上述のポリプロピレン板にラミネートした。ポリプロピレン板に試験片をラミネートした状態で、常温(25℃)で24時間経過させた後に、アクリル系粘着テープが浮いた距離、すなわちポリプロピレン板の表面からアクリル系粘着テープの表層用粘着剤層までの距離(両端の高さの平均)(単位:mm)を測定した。浮いた距離が5mm以下である場合を良好(○)とし、浮いた距離が5mmを超えた場合を不良(×)とした。測定結果を表3に示す。なお、表3に示す数値は、任意の複数点についての平均値である。
各実施例、および各比較例に係るアクリル系粘着テープにおける芯層側の剥離ライナーを剥がし、プライマー処理が施された厚さ50μmのポリエチレンテレフタレートフィルムを貼り合せ、それを10mm幅に切断したものを試験片とした。トルエンにて清浄化したベークライト板に、幅10mm、長さ20mmの面積で試験片の粘着面を貼り合せ、60℃の環境下で30分間放置した。その後、500gの荷重がせん断方向にかかるよう試験片の一端におもりを吊るし、おもりを宙吊り状態として60℃の環境下で2時間放置して、保持特性を評価した。試験片が落下しなかった場合を良好(○)とし、落下した場合を不良(×)とした。測定結果を表3に示す。
Claims (5)
- 芯層と、
前記芯層の一方または両方の側に設けられた表層と、
を備え、
前記芯層は、アクリル系ポリマー(A)を含み、
前記表層は、アクリル系ポリマー(D)と、三環以上の脂環式構造を有する(メタ)アクリル系モノマーをモノマー単位として含み、重量平均分子量が1000以上30000未満の(メタ)アクリル系重合体(E)とを含むことを特徴とするアクリル系粘着テープ。 - 前記(メタ)アクリル系モノマーは、下記一般式(1)で表される(メタ)アクリル酸エステルである請求項1に記載のアクリル系粘着テープ。
CH2=C(R1)COOR2 (1)
[式(1)中、R1は、水素原子またはメチル基であり、R2は、三環以上の脂環式構造を有する脂環式炭化水素基である] - 前記脂環式炭化水素基は、橋かけ環構造を有する請求項2に記載のアクリル系粘着テープ。
- 前記(メタ)アクリル系重合体(E)の含有量がアクリル系ポリマー(D)100重量部に対して2~70重量部である請求項1乃至3のいずれか1項に記載のアクリル系粘着テープ。
- 前記芯層は、微粒子(B)と気泡(C)とを含む請求項1乃至4のいずれか1項に記載のアクリル系粘着テープ。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020127027680A KR101353747B1 (ko) | 2010-03-25 | 2011-03-18 | 아크릴계 점착 테이프 |
CN201180015846.7A CN102822292B (zh) | 2010-03-25 | 2011-03-18 | 丙烯酸类粘合带 |
EP11758991.1A EP2551315B1 (en) | 2010-03-25 | 2011-03-18 | Acrylic adhesive tape |
US13/611,501 US20130011672A1 (en) | 2010-03-25 | 2012-09-12 | Acrylic pressure-sensitive adhesive tape |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010-070369 | 2010-03-25 | ||
JP2010070369A JP5502543B2 (ja) | 2010-03-25 | 2010-03-25 | アクリル系粘着テープ |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/611,501 Continuation US20130011672A1 (en) | 2010-03-25 | 2012-09-12 | Acrylic pressure-sensitive adhesive tape |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011118180A1 true WO2011118180A1 (ja) | 2011-09-29 |
Family
ID=44672759
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/001618 WO2011118180A1 (ja) | 2010-03-25 | 2011-03-18 | アクリル系粘着テープ |
Country Status (6)
Country | Link |
---|---|
US (1) | US20130011672A1 (ja) |
EP (1) | EP2551315B1 (ja) |
JP (1) | JP5502543B2 (ja) |
KR (1) | KR101353747B1 (ja) |
CN (1) | CN102822292B (ja) |
WO (1) | WO2011118180A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015146312A1 (ja) * | 2014-03-26 | 2015-10-01 | ニッタ株式会社 | 仮固定用両面粘着テープおよびそれを用いた被加工物の仮固定方法 |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011202012A (ja) * | 2010-03-25 | 2011-10-13 | Nitto Denko Corp | アクリル系粘着剤組成物およびアクリル系粘着テープ |
CN103097483B (zh) | 2010-08-27 | 2016-03-09 | 日东电工株式会社 | 丙烯酸类粘合剂组合物、丙烯酸类粘合剂层以及丙烯酸类粘合带 |
US20140127503A1 (en) * | 2011-07-01 | 2014-05-08 | Nitto Denko Corporation | Multi-layered pressure-sensitive adhesive article and pressure-sensitive adhesive sheet |
KR101878505B1 (ko) | 2013-05-07 | 2018-07-13 | 주식회사 엘지화학 | 아크릴 폼 점착 테이프 및 이를 적용한 평판 디스플레이 |
JP6202958B2 (ja) | 2013-09-13 | 2017-09-27 | 日東電工株式会社 | 粘着シート |
US9977262B2 (en) * | 2014-03-12 | 2018-05-22 | Honeywell International, Inc. | Electrochromic lenses and methods of fabricating the same |
HUE052630T2 (hu) * | 2014-07-17 | 2021-05-28 | Henkel Ag & Co Kgaa | Fénnyel térhálósítható folyékony, optikailag tiszta ragasztó készítmény és alkalmazása |
JP6662793B2 (ja) | 2015-01-29 | 2020-03-11 | 三洋電機株式会社 | 非水電解質二次電池 |
WO2018009683A1 (en) | 2016-07-06 | 2018-01-11 | Eastman Chemical Company | (meth)acrylic oligomers |
US10478195B2 (en) * | 2016-08-04 | 2019-11-19 | Covidien Lp | Devices, systems, and methods for the treatment of vascular defects |
US10675036B2 (en) * | 2017-08-22 | 2020-06-09 | Covidien Lp | Devices, systems, and methods for the treatment of vascular defects |
KR20240060706A (ko) * | 2018-12-28 | 2024-05-08 | 생-고뱅 퍼포먼스 플라스틱스 코포레이션 | 접착제 조성물 및 이의 형성 방법 |
US20200208024A1 (en) * | 2018-12-28 | 2020-07-02 | Saint-Gobain Performance Plastics Corporation | Adhesive composition and methods of forming the same |
KR102462480B1 (ko) | 2022-09-07 | 2022-11-04 | 주식회사 유건코리아 | 피착제 종류와 상관없이 점착할 수 있는 아크릴계 점착 테이프 및 이의 제조방법 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5686979A (en) * | 1979-12-17 | 1981-07-15 | Hitachi Chem Co Ltd | Photosensitive self-adhesive or adhesive composition |
JPS58118872A (ja) * | 1982-01-11 | 1983-07-15 | Hitachi Chem Co Ltd | 放射線硬化型感圧性接着剤組成物 |
JPH06207151A (ja) | 1993-01-08 | 1994-07-26 | Sekisui Chem Co Ltd | アクリル系感圧接着剤組成物及び両面テープ |
JPH11504054A (ja) | 1995-04-20 | 1999-04-06 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | 粘着付与アクリル接着剤 |
JP2008174648A (ja) * | 2007-01-19 | 2008-07-31 | Toray Fine Chemicals Co Ltd | 接着剤組成物 |
JP2010184979A (ja) * | 2009-02-10 | 2010-08-26 | Nitta Ind Corp | 感温性粘着テープ |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4977286B2 (ja) * | 2000-03-07 | 2012-07-18 | 日東電工株式会社 | 重合体の製造方法 |
KR101370245B1 (ko) * | 2006-05-23 | 2014-03-05 | 린텍 가부시키가이샤 | 점접착제 조성물, 점접착 시트 및 반도체장치의 제조방법 |
JP2008047558A (ja) * | 2006-08-10 | 2008-02-28 | Nitto Denko Corp | 反り抑制ウエハ研削用粘着シート |
US20100075132A1 (en) * | 2006-12-07 | 2010-03-25 | 3M Innovative Properties Company | Blends of block copolymer and acrylic adhesives |
JP5118880B2 (ja) * | 2007-05-08 | 2013-01-16 | 日東電工株式会社 | 粘着剤組成物及びそれを用いた粘着製品、ディスプレイ |
JP5095279B2 (ja) * | 2007-07-06 | 2012-12-12 | 日東電工株式会社 | 車両用塗膜面接着用粘着シート |
-
2010
- 2010-03-25 JP JP2010070369A patent/JP5502543B2/ja active Active
-
2011
- 2011-03-18 EP EP11758991.1A patent/EP2551315B1/en not_active Not-in-force
- 2011-03-18 WO PCT/JP2011/001618 patent/WO2011118180A1/ja active Application Filing
- 2011-03-18 CN CN201180015846.7A patent/CN102822292B/zh not_active Expired - Fee Related
- 2011-03-18 KR KR1020127027680A patent/KR101353747B1/ko active IP Right Grant
-
2012
- 2012-09-12 US US13/611,501 patent/US20130011672A1/en not_active Abandoned
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5686979A (en) * | 1979-12-17 | 1981-07-15 | Hitachi Chem Co Ltd | Photosensitive self-adhesive or adhesive composition |
JPS58118872A (ja) * | 1982-01-11 | 1983-07-15 | Hitachi Chem Co Ltd | 放射線硬化型感圧性接着剤組成物 |
JPH06207151A (ja) | 1993-01-08 | 1994-07-26 | Sekisui Chem Co Ltd | アクリル系感圧接着剤組成物及び両面テープ |
JPH11504054A (ja) | 1995-04-20 | 1999-04-06 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | 粘着付与アクリル接着剤 |
JP2008174648A (ja) * | 2007-01-19 | 2008-07-31 | Toray Fine Chemicals Co Ltd | 接着剤組成物 |
JP2010184979A (ja) * | 2009-02-10 | 2010-08-26 | Nitta Ind Corp | 感温性粘着テープ |
Non-Patent Citations (1)
Title |
---|
See also references of EP2551315A4 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015146312A1 (ja) * | 2014-03-26 | 2015-10-01 | ニッタ株式会社 | 仮固定用両面粘着テープおよびそれを用いた被加工物の仮固定方法 |
Also Published As
Publication number | Publication date |
---|---|
EP2551315A4 (en) | 2013-10-30 |
KR20130008055A (ko) | 2013-01-21 |
EP2551315B1 (en) | 2014-12-31 |
EP2551315A1 (en) | 2013-01-30 |
CN102822292B (zh) | 2015-04-01 |
US20130011672A1 (en) | 2013-01-10 |
CN102822292A (zh) | 2012-12-12 |
JP2011202013A (ja) | 2011-10-13 |
JP5502543B2 (ja) | 2014-05-28 |
KR101353747B1 (ko) | 2014-01-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5502543B2 (ja) | アクリル系粘着テープ | |
WO2012026118A1 (ja) | アクリル系粘着剤組成物、アクリル系粘着剤層およびアクリル系粘着テープ | |
JP5634803B2 (ja) | アクリル系粘着テープ | |
US8828539B2 (en) | Acrylic pressure-sensitive adhesive, acrylic pressure-sensitive adhesive layer and acrylic pressure-sensitive adhesive tape or sheet | |
EP2572803B1 (en) | Acrylic pressure-sensitive adhesive composition, acrylic pressure-sensitive adhesive layer, and acrylic pressure-sensitive adhesive tape | |
WO2011118179A1 (ja) | アクリル系粘着剤組成物およびアクリル系粘着テープ | |
JP6067826B2 (ja) | アクリル系粘着剤層およびアクリル系粘着テープ | |
EP2385090B1 (en) | Acrylic pressure-sensitive adhesive tape | |
WO2011118181A1 (ja) | アクリル系粘着剤組成物およびアクリル系粘着テープ | |
JP2012149179A (ja) | 光学用アクリル系粘着剤組成物および光学用アクリル系粘着テープ | |
JP2013018163A (ja) | 接合体および接合体の製造方法 | |
WO2011118182A1 (ja) | アクリル系粘着テープ | |
JP6403186B2 (ja) | 粘着剤層、粘着シート、及び、粘着剤層の製造方法 | |
JP2015160905A (ja) | 粘着剤層、粘着シート、及び、粘着剤層の製造方法 | |
JP2016041817A (ja) | アクリル系粘着テープ | |
JP2013079361A (ja) | アクリル系粘着テープ | |
JP5730382B2 (ja) | アクリル系粘着剤組成物およびアクリル系粘着テープ | |
JP2013079362A (ja) | アクリル系粘着剤組成物、アクリル系粘着剤層およびアクリル系粘着テープ | |
WO2013150563A1 (ja) | 粘着テープおよびテープロール | |
JP5616259B2 (ja) | 粘着テープおよびテープロール |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180015846.7 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11758991 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20127027680 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011758991 Country of ref document: EP |