WO2011033736A1 - アクリル系粘着テープ - Google Patents
アクリル系粘着テープ Download PDFInfo
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- WO2011033736A1 WO2011033736A1 PCT/JP2010/005443 JP2010005443W WO2011033736A1 WO 2011033736 A1 WO2011033736 A1 WO 2011033736A1 JP 2010005443 W JP2010005443 W JP 2010005443W WO 2011033736 A1 WO2011033736 A1 WO 2011033736A1
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- acrylate
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- adhesive tape
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J7/26—Porous or cellular plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
- C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J2301/302—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 the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
- C09J2433/006—Presence of (meth)acrylic polymer in the substrate
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- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
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- 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
- Y10T428/2848—Three or more layers
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- 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
- Y10T428/2891—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof
Definitions
- the present invention relates to an acrylic pressure-sensitive adhesive. More specifically, the present invention relates to an acrylic pressure-sensitive adhesive tape.
- acrylic pressure-sensitive adhesive tapes having an acrylic pressure-sensitive adhesive layer are excellent in light resistance, weather resistance, oil resistance, etc., adhesive properties such as adhesive strength and cohesive strength, and aging resistance such as heat resistance and weather resistance. It is widely used because of its excellent performance.
- applications of acrylic adhesive tapes include application to low-polar adherends such as polystyrene, ABS, and polycarbonate that are widely used as materials for home appliances and building materials.
- Conventional acrylic pressure-sensitive adhesive tape has a problem of low adhesion to low-polar adherends such as polystyrene, ABS, and polycarbonate.
- low-polar adherends used for home appliances, building materials and the like are required to have high adhesion reliability, and there is a demand for improved adhesion of acrylic adhesive tapes to low-polar adherends.
- the present invention has been made in view of these problems, and an object thereof is to provide an acrylic pressure-sensitive adhesive tape having improved adhesion to a low-polar adherend.
- 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), fine particles (B), and bubbles (C).
- the surface layer contains an acrylic polymer (D) and an acrylic oligomer (E).
- acrylic pressure-sensitive adhesive tape of this aspect it is possible to improve the adhesive force to low-polar adherends such as polystyrene, ABS, and polycarbonate.
- the content of the acrylic oligomer (E) may be 5 to 45% by mass with respect to the acrylic polymer (D). 45 N / 25 mm or more may be sufficient as the adhesive force when peeled in the 90 degree peeling direction after passing for 72 hours after adhere
- the ratio of the thickness of the surface layer to the total thickness of the thickness of the core layer and the surface layer may be 8 to 20%.
- the acrylic polymer (A) and the acrylic polymer (D) may contain (meth) acrylic acid alkyl ester as a main monomer component.
- the acrylic oligomer (E) may have a weight average molecular weight of 2000 to 20000.
- the adhesion of the acrylic pressure-sensitive adhesive tape to the low-polar adherend can be improved.
- FIG. 1 is a schematic cross-sectional view showing a configuration of an acrylic pressure-sensitive adhesive tape 10 according to an embodiment.
- the acrylic pressure-sensitive adhesive tape 10 includes a core layer 20, a surface layer 30a provided on one surface of the core layer 20, and a surface layer 30b provided on the other surface of the core layer.
- the surface layers 30a and 30b are collectively referred to as the surface layer 30.
- the core layer 20 has an adhesive composition and fine particles, and bubbles are formed in the core layer 20.
- each component of the core layer 20 will be described in detail.
- An acrylic polymer (A) is used as the adhesive composition constituting the core layer 20.
- the acrylic polymer (A) contains 50% by mass or more of an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms as a monomer unit.
- alkyl (meth) acrylates having an alkyl group having 1 to 20 carbon atoms can be used alone or in combination of two or more.
- the acrylic polymer (A) can be obtained by polymerizing an alkyl (meth) acrylate together with a polymerization initiator (for example, solution polymerization, emulsion polymerization, UV polymerization).
- the proportion of the alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms is 50% by mass or more, preferably 60% by mass or more, based on the total amount of monomer components for preparing the acrylic polymer (A). It is preferable that it is 70 mass% or more.
- alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) ) Butyl acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate , Heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, (meth) acrylic
- Examples of (meth) acrylic acid esters other than (meth) acrylic acid alkyl esters include alicyclic hydrocarbon groups such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate (meth). Examples thereof include acrylic acid esters, (meth) acrylic acid esters having an aromatic hydrocarbon group such as phenyl (meth) acrylate, and (meth) acrylic acid esters obtained from terpene compound derivative alcohols.
- the acrylic polymer (A) is a monomer component (copolymerization) that can be copolymerized with the alkyl (meth) acrylate, if necessary, for the purpose of modifying cohesion, heat resistance, crosslinkability, etc. Monomer). Therefore, the acrylic polymer (A) may contain a copolymerizable monomer together with the alkyl (meth) acrylate as the main component. As the copolymerizable monomer, a monomer having a polar group can be suitably used.
- copolymerizable monomers include 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; (meth) acrylic Hydroxyethyl acid, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxydecyl (meth) acrylate, hydroxy (meth) acrylate Hydroxyl group-containing monomers such as hydroxyalkyl (meth) acrylate such as lauryl and (4-hydroxymethylcyclohexyl) methyl methacrylate; acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; styrene Contains sulfonic
- N- (meth) acryloyloxymethylene succinimide N- (meth) acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-oxyhexamethylene succinimide, etc .
- N -Maleimide monomers such as cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide; N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N- Itacone imide monomers such as 2-ethylhexylitaconimide, N-cyclohexitaconimide, N-laurylitaconimide; vinyl esters such as vinyl acetate and vinyl propionate; N-vinyl-2 -Pyrrolidone, N-methylvinylpyrrolidone
- (Meth) acrylic acid alkoxyalkyl monomers such as sodium vinyl sulfonate; imide group-containing monomers such as cyclohexylmaleimide and isopropylmaleimide Mar; 2-isocyanatoethyl (meth) isocyanate group-containing monomers such as acrylate; fluorine-containing (meth) acrylate; silicon-containing (meth) acrylate.
- sulfonic acid group-containing monomers such as sodium vinyl sulfonate
- imide group-containing monomers such as cyclohexylmaleimide and isopropylmaleimide Mar
- 2-isocyanatoethyl (meth) isocyanate group-containing monomers such as acrylate; fluorine-containing (meth) acrylate; silicon-containing (meth) acrylate.
- the acrylic polymer (A) contains a copolymerizable monomer together with an alkyl (meth) acrylate 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, but usually 0.1 to 30% by mass of the copolymerizable monomer, preferably 0. 0% by weight based on the total amount of monomer components for preparing the acrylic polymer. It can be contained in an amount of 5 to 20% by mass, more preferably 1 to 15% by mass.
- the copolymerizable monomer By containing 0.1% by mass or more of the copolymerizable monomer, it is possible to prevent a decrease in the cohesive force of the acrylic pressure-sensitive adhesive tape or sheet made of the acrylic pressure-sensitive adhesive and to obtain a high shearing force. Moreover, by making content of a copolymerizable monomer into 30 mass% or less, it can prevent that a cohesion force becomes high and can improve the tuck feeling in normal temperature (25 degreeC).
- the acrylic polymer (A) may contain a polyfunctional monomer as necessary in order to adjust the cohesive force of the acrylic pressure-sensitive adhesive to be formed.
- 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 0.01 to 3.0% by mass, preferably based on the total amount of monomer components for preparing the acrylic polymer (A). It is added in an amount of 0.02 to 2.0 mass%, more preferably 0.03 to 1.0 mass%.
- the amount of the polyfunctional monomer used exceeds 3.0% by mass with respect to the total amount of monomer components for preparing the acrylic polymer (A), for example, the cohesive force of the acrylic pressure-sensitive adhesive becomes too high, and adhesion There are cases where the power is reduced. On the other hand, when it is less than 0.01% by mass, for example, the cohesive force of the acrylic pressure-sensitive adhesive 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, and 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 [manufactured by BASF, trade name: Irgacure 651], anisole methyl ether, and the like.
- acetophenone photopolymerization initiator for example, 1-hydroxycyclohexyl phenyl ketone [manufactured by BASF, trade name: Irgacure 184], 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1- [4- ( 2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one [manufactured by BASF, trade name: Irgacure 2959], 2-hydroxy-2-methyl-1-phenyl-propane- Examples thereof include 1-one [manufactured by BASF, trade name: Darocur 1173], methoxyacetophenone, and the like.
- 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
- bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide [manufactured by BASF, trade name: Irgacure 819], bis (2,4,6-trimethylbenzoyl) -2,4-di-n -Butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide [manufactured by BASF, trade name: Lucillin TPO], bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide preferable.
- the amount of the photopolymerization initiator used is not particularly limited, but for example, 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the monomer component for preparing the acrylic polymer (A). Parts, more preferably in an amount in the range of 0.08 to 2 parts by mass.
- the amount of the photopolymerization initiator used when the amount of the photopolymerization initiator used is less than 0.01 parts by mass, the polymerization reaction may be insufficient.
- the amount of the photopolymerization initiator used exceeds 5 parts by mass, the photopolymerization initiator absorbs ultraviolet rays, so that the ultraviolet rays do not reach the inside of the pressure-sensitive adhesive layer, resulting in a decrease in the polymerization rate or the polymer produced.
- the molecular weight is reduced, the cohesive force of the pressure-sensitive adhesive layer is reduced, and when the pressure-sensitive adhesive layer is peeled off from the film, part of the pressure-sensitive adhesive layer remains on the film and the film cannot be reused.
- a photopolymerization initiator can be used individually or in combination of 2 or more types.
- crosslinking agent in addition to the polyfunctional monomer described above.
- 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 etherified melamine
- examples thereof include a metal-based crosslinking agent and a metal chelate-based crosslinking agent.
- an isocyanate-based crosslinking agent or 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 thereof include adducts of diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, and polyols such as trimethylolpropane.
- a compound having at least one isocyanate group and one or more unsaturated bonds in one molecule may be used as an isocyanate-based crosslinking agent.
- 2-isocyanatoethyl (meth) acrylate or the like may be used as an isocyanate-based crosslinking agent.
- the use of a compound having at least one isocyanate group and one or more unsaturated bonds in one molecule as an isocyanate-based crosslinking agent is preferable in that the effect of the present invention is further exhibited.
- 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 polymerization (acrylic polymer syrup) in which the monomer component is partially polymerized by irradiating a mixture containing the monomer component and the polymerization initiator with ultraviolet rays (UV). ) Can also be prepared.
- the weight average molecular weight (Mw) of the acrylic polymer (A) is, for example, 30000 to 5000000.
- Fine particles (B) examples of the function and effect of the fine particles (B) include an improvement in shear adhesive strength and workability of an acrylic pressure-sensitive adhesive tape or sheet made of an acrylic pressure-sensitive adhesive.
- the fine particles (B) include metal particles such as copper, nickel, aluminum, chromium, iron, and stainless steel, metal oxide particles; carbide particles such as silicon carbide, boron carbide, and nitrogen carbide, aluminum nitride, silicon nitride, boron nitride, and the like.
- Nitride particles 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 polymethyl methacrylate , Phenolic resin, benzoguanamine resin, urea resin, silicone resin, nylon, polyester, polyurethane, polyethylene, polypropylene, polyamide, polyimide and other polymer particles; vinylidene chloride, organic hollow bodies such as acrylic, nylon beads, acrylic beads, silicone Organic spheres such as chromatography's, and the like.
- hollow fine particles can be preferably used.
- hollow inorganic fine particles can be preferably used from the viewpoint of the efficiency and weight of polymerization using an ultraviolet reaction.
- glass balloons such as hollow glass balloons (also referred to as hollow glass microspheres); hollow balloons made of metal compounds such as hollow alumina balloons; porcelain hollow balloons such as hollow ceramic balloons and the like.
- the high-temperature adhesive force can be improved without impairing other properties such as shearing force and holding force.
- hollow glass balloon examples include, for example, trade names “Glass Micro Balloon” (manufactured by Fuji Silysia Chemical Co., Ltd.), 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” (both manufactured by Tokai Kogyo Co., Ltd.), trade name “Syracx Fine Balloon” (Made by Fine Balloon Co., Ltd.) and the like.
- the particle size (average particle size) of the fine particles (B) is not particularly limited, but can be selected from the range of, for example, 1 to 500 ⁇ m, preferably 5 to 200 ⁇ m, and more preferably 10 to 150 ⁇ m.
- the specific gravity of the fine particles (B) is not particularly limited, but is, for example, 0.1 to 1.8 g / cm 3 , preferably 0.2 to 1.5 g / cm 3 , more preferably 0.2 to 0.5. / Cm 3 can be selected.
- the amount of the fine particles (B) used is not particularly limited. For example, if the amount used is less than 10% by volume with respect to the total volume of the core layer, the effect of adding the fine particles is low, whereas 50 Adhesive strength is reduced when the amount used exceeds volume%.
- the acrylic pressure-sensitive adhesive (acrylic pressure-sensitive adhesive tape) can exhibit good adhesion to curved surfaces and uneven surfaces, and also has good resilience resistance. It can be demonstrated.
- the bubbles (C) contained in the core layer are desirably closed-cell type bubbles, but may be mixed with closed-cell type bubbles and open-cell type bubbles.
- 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 an irregular shape on the spherical shape.
- the average bubble diameter (diameter) of the bubbles (C) is not particularly limited, and can be selected from the range of, for example, 1 to 1000 ⁇ m, preferably 10 to 500 ⁇ m, more preferably 30 to 300 ⁇ m.
- the gas component contained in the bubble (C) is not particularly limited, and may be nitrogen, carbon dioxide, argon, or the like. In addition to the inert gas, various gas components such as air can be used.
- a gas for forming bubbles when a polymerization reaction or the like is performed in a state in which a gas for forming bubbles is included, it is important to use a gas that does not inhibit the reaction. Nitrogen can be suitably used as the gas for forming bubbles from the viewpoint of not inhibiting the polymerization reaction and the like, and from the viewpoint of cost.
- the amount of bubbles (C) contained in the core layer is not particularly limited and can be appropriately selected depending on the intended use. For example, it is 5 to 50% by volume, preferably 8 to 40% by volume, based on the total volume of the core layer containing bubbles.
- the mixing amount is less than 5% by volume, the effect of mixing bubbles cannot be obtained, and when it exceeds 50% by volume, bubbles penetrating the core layer enter, and the adhesive performance and appearance are deteriorated.
- the form in which bubbles are formed is not particularly limited.
- the core layer containing bubbles for example, (1) a core layer in which bubbles are formed by using a core layer in which gas components (bubble forming gas) that form bubbles in advance are mixed, 2) By mixing a foaming agent into the core layer, a core layer in a form in which bubbles are formed can be formed.
- the foaming agent is not particularly limited. For example, from a known foaming agent It can be selected appropriately.
- the foaming agent for example, thermally expandable microspheres can be used.
- a thickener In addition to the components described above, a thickener, thixotropic agent, extender, etc. may be added to the core layer 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 antioxidant, an antioxidant, and the like may be added as appropriate. It is not limited to these.
- the component of the surface layer 30 contains the acrylic polymer (D) as an adhesive composition, and the acrylic oligomer (E) as a tackifier resin.
- the acrylic polymer (D) 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) can be prepared by the same polymerization method using the same polymerization initiator as the acrylic polymer (A) constituting the core layer.
- the acrylic oligomer (E) will be described in detail.
- the acrylic oligomer is a polymer having a weight average molecular weight smaller than that of the acrylic polymer (D), functions as a tackifier resin, and has an advantage that polymerization inhibition is unlikely to occur during UV polymerization.
- the amount of the acrylic oligomer (E) added is preferably 5 to 45 parts by mass, more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the acrylic polymer (D). If the acrylic oligomer (E) is added in an amount exceeding 45 parts by mass, the elastic modulus of the surface layer 30 is increased, the adhesion performance at low temperatures may be deteriorated, and the tackiness may not be exhibited even at room temperature. In addition, when the addition amount is less than 5 parts, the effect may not be obtained.
- the acrylic oligomer (E) has a glass transition temperature (Tg) of 20 ° C. or higher, preferably 30 ° C. or higher, more preferably 40 ° C. or higher.
- Tg glass transition temperature
- the glass transition temperature (Tg) is less than 20 ° C., the cohesive strength of the polymer at room temperature or higher is lowered, and the holding performance and high-temperature adhesion performance may be lowered.
- the acrylic oligomer (E) has a weight average molecular weight of 2000 to 20000, preferably 2500 to 15000, and more preferably 3000 to 10,000.
- the molecular weight exceeds 20000, the effect of improving the adhesive performance of the adhesive tape may not be sufficiently obtained. Moreover, since it becomes low molecular weight as it is less than 2000, it may cause the fall of adhesive performance or holding
- the measurement of the weight average molecular weight of the acrylic polymers (A) and (D) and the acrylic oligomer (E) is 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 0.5 ml / min.
- the acrylic oligomer (E) is produced, for example, by polymerizing (meth) acrylic acid ester by a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, a suspension polymerization, a bulk polymerization or the like.
- (meth) acrylic acid esters examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, ( Pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate (Meth) acrylic acid alkyl esters such as cyclohexyl (meth) acrylate and esters of (meth) acrylic acid such as isobornyl (meth) acrylate with alicyclic alcohols, phenyl (meth) acrylate, (meth Name a (meth) acrylic aryl ester such as benzyl
- a monomer unit which comprises an acrylic oligomer (E) a cyclohexyl methacrylate can be used conveniently.
- the acrylic oligomer (E) may be obtained by copolymerizing a monomer having a polymerizable unsaturated bond copolymerizable with the (meth) acrylic acid ester in addition to the above (meth) acrylic acid ester component unit. Is possible.
- Monomers having a polymerizable unsaturated bond copolymerizable with (meth) acrylic acid ester include (meth) acrylic acid, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and propoxy (meth) acrylate.
- Ethyl, alkoxyalkyl (meth) acrylates such as butoxyethyl (meth) acrylate and ethoxypropyl (meth) acrylate; salts such as alkali metal (meth) acrylates; di (meth) acrylates of ethylene glycol , Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (Meth) acrylic Esters, di (meth) acrylic esters of (poly) alkylene glycols such as di (meth) acrylic esters of tripropylene glycol; polyvalent (meth) acrylic acids such as trimethylolpropane tri (meth) acrylic esters Esters; (meth) acrylonitrile; vinyl acetate; vinylidene chloride; vinyl halide compounds such as 2-chloroethyl (meth)
- examples of the acrylic oligomer (E) constituting the surface layer include a copolymer of cyclohexyl methacrylate (CHMA) and isobutyl methacrylate (IBMA), cyclohexyl methacrylate (CHMA) and isobol
- a copolymer of nyl methacrylate (IBXMA), a copolymer of cyclohexyl methacrylate (CHMA) and acryloylmorpholine (ACMO), a copolymer of cyclohexyl methacrylate (CHMA) and diethyl acrylamide (DEAA) has a low polarity coating such as polystyrene. This is preferable in that an acrylic pressure-sensitive adhesive tape having excellent adhesion to the adherend can be provided.
- the composition ratio of the copolymer constituting the acrylic oligomer (E) is 50 to 85% by mass, preferably 55 to 75% by mass of cyclohexyl methacrylate (CHMA), and is isobutyl methacrylate (IBMA) or isobornyl.
- CHMA cyclohexyl methacrylate
- IBMA is isobutyl methacrylate
- Methacrylate (IBXMA), acryloylmorpholine (ACMO), and diethylacrylamide (DEAA) are 15 to 50% by mass and 25 to 45% by mass.
- a functional group having reactivity with an epoxy group or an isocyanate group may be introduced.
- functional groups 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 is used when producing an acrylic oligomer (E). Is preferred.
- a chain transfer agent can be used during the polymerization in order to adjust the molecular weight of the acrylic oligomer (E).
- chain transfer agents used include compounds having a mercapto group such as octyl mercaptan, dodecyl mercaptan, t-dodecyl mercaptan; thioglycolic acid, ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, thioglycolic acid t-butyl, 2-ethylhexyl thioglycolate, octyl thioglycolate, decyl thioglycolate, dodecyl thioglycolate, thioglycolate of ethylene glycol, thioglycolate of neopentyl glycol
- the amount of the chain transfer agent to be used is not particularly limited, but usually 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass of the chain transfer agent with respect to 100 parts by mass of the acrylic monomer.
- the content is preferably 0.3 to 10 parts by mass.
- the acrylic oligomer (E) of a suitable molecular weight can be obtained by adjusting the addition amount of a chain transfer agent.
- the acrylic polymer (D) and the acrylic oligomer (E) are essential as components constituting the surface layer, and in order to adjust the cohesive force, crosslinking is performed as necessary.
- An agent can also be used.
- the crosslinking agent the same crosslinking agent as that for the core layer can be appropriately selected and used.
- the ratio of the thickness of the surface layer 30a (or surface layer 30b) to the total thickness of the thickness of the core layer 20 and the surface layer 30a (or surface layer 30b) is preferably 8 to 20%.
- the total thickness of the acrylic pressure-sensitive adhesive tape (the total thickness of the core layer and the surface layer) is 0.4 mm to 4.0 mm, preferably 0.5 mm to 2.5 mm. It is.
- the method for laminating the core layer and the surface layer is not particularly limited, but the following method can be applied.
- 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.
- the acrylic pressure-sensitive adhesive tape described above by providing a multilayer structure in which the surface layer containing the acrylic polymer (D) and the acrylic oligomer (E) and the core layer are laminated, polystyrene, ABS, polycarbonate, etc.
- the adhesive force with respect to a low polarity adherend can be improved.
- the surface layer is provided on both sides of the core layer, but the surface layer may be provided on either side of the core layer.
- Table 1 shows the layer structure and components of the acrylic pressure-sensitive adhesive tapes according to Examples 1 to 9 and Comparative Examples 1 and 2.
- the pressure was reduced at 170 ° C., and the mixture was stirred for 1 hour to remove residual monomers, whereby acrylic oligomer 1 was obtained.
- the weight average molecular weight of the obtained oligomer was 3700.
- Example 1 A method for producing the acrylic pressure-sensitive adhesive tape according to Example 1 will be described.
- Acrylic adhesive composition 1 core layer composition
- Acrylic polymer syrup 1 100 parts by mass
- 1,6-hexanediol diacrylate (0.08 parts by mass)
- a photopolymerization initiator trade name “Irgacure 651” manufactured by BASF, 0.04 parts by mass
- hollow glass microspheres (trade name “Cell Star Z-27” manufactured by Tokai Kogyo Co., Ltd.) were added so as to be 9.5 parts by mass with respect to the partially polymerized monomer syrup.
- a fluorosurfactant trade name “Surflon S-393”, manufactured by Sey Chemical Co., Ltd .
- the adhesive composition precursor is opposed to a stator having a large number of fine teeth on a disk having a through-hole in the center and a stator having teeth, and fine teeth similar to the stator are formed on the disk. Introduced between the teeth on the stator and the teeth on the rotor in a device having a rotor attached thereto, and introducing nitrogen gas into the adhesive composition precursor through the through-hole while rotating the rotor at a high speed Then, air bubbles were mixed into the pressure-sensitive adhesive composition precursor to obtain an acrylic pressure-sensitive adhesive composition 1 for the core layer. In addition, it mixed so that a bubble might be about 20 volume% with respect to the whole volume of the acrylic adhesive composition 1.
- the acrylic pressure-sensitive adhesive composition 1 was applied to a thickness of 550 ⁇ m on the surface of the release-treated surface of a 38 ⁇ m-thick polyester film (polyester release liner) subjected to one-side release treatment using a roll coater. Next, the other side of the applied acrylic pressure-sensitive adhesive composition 1 is pasted so that the surface of the same type of polyester release liner subjected to the release treatment faces the other side of the acrylic pressure-sensitive adhesive composition 1. Combined. Next, ultraviolet irradiation was performed from both sides with a black light lamp with an illuminance of 5 mW / cm 2 for 3 minutes. In this way, a core layer made of an acrylic pressure-sensitive adhesive layer having a thickness of 550 ⁇ m was obtained.
- the acrylic pressure-sensitive adhesive composition 2 described above was applied to a thickness of 50 ⁇ m on the surface of the release film of a 38 ⁇ m thick polyester film (polyester release liner) that had been peeled on one side by a roll coater.
- the other side of the applied acrylic pressure-sensitive adhesive composition 2 is pasted so that the surface of the same type of polyester release liner that has been subjected to the release treatment faces the other side of the acrylic pressure-sensitive adhesive composition 2.
- ultraviolet irradiation was performed from both sides with a black light lamp with an illuminance of 5 mW / cm 2 for 3 minutes. In this way, a surface layer composed of an acrylic pressure-sensitive adhesive layer having a thickness of 50 ⁇ m was obtained.
- Example 2 to 9 The basic production method of the acrylic adhesive tape according to Examples 2 to 9 is the same as that of Example 1. However, each Example was produced according to the components shown in Table 1, the surface layer thickness, and the like. In Examples 2 and 3, the surface layer thickness was 90 ⁇ m and 120 ⁇ m, respectively. The ratio of the thickness of the surface layer to the total thickness of the thickness of the core layer and the thickness of the surface layer is 8%, 15%, and 20% in Examples 1, 2, and 3, respectively. In Examples 4 and 5, the content of the acrylic oligomer (E) was 10 parts by mass and 30 parts by mass, respectively, with respect to the acrylic polymer syrup 2 (100 parts by mass) as the component (D). In Examples 6 to 9, the surface layer has a common thickness of 70 ⁇ m, and the composition ratio of the acrylic polymer (D), the composition of the acrylic oligomer (E), and the crosslinking agent are appropriately changed.
- the acrylic pressure-sensitive adhesive tape according to Comparative Example 1 is a single core layer and does not have a surface layer. Moreover, the acrylic adhesive tape which concerns on the comparative example 2 does not have an acrylic oligomer (E) in a surface layer.
- the adhesive strength (unit: N / 25 mm) to each adherend was measured by peeling the adhesive sheet in a 90 ° peeling direction at a tensile rate of 300 mm / min in an atmosphere of 23 ° C.
- the core layer was exposed and the adhesive force of a core layer and each to-be-adhered body was measured. The measurement results are shown in Table 2.
- Example 4 and 5 it was confirmed that adhesive force increases, so that content of an acrylic oligomer (E) increases.
- Acrylic adhesive tape 20 core layer, 30a, 30b surface layer
- the present invention can be used in the field related to acrylic adhesive tape.
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Abstract
Description
芯層20は、粘着性組成物と、微粒子とを有し、芯層20には気泡が形成されている。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としてアクリル系ポリマー(A)が用いられる。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アルキル(メタ)アクリレートをモノマー単位として50質量%以上含有する。前記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アルキル(メタ)アクリレートを単独でまたは2種以上を組み合わせて用いることができる。アクリル系ポリマー(A)は、重合開始剤とともに、アルキル(メタ)アクリレートを重合(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。
クリル系粘着テープまたはシートの凝集力の低下を防ぎ、高いせん断力を得ることができる。また、共重合性モノマーの含有量を30質量%以下とすることで、凝集力が高くなるのを防ぎ、常温(25℃)でのタック感を向上させることができる。
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種以上組み合わせて使用することができる。
微粒子(B)の作用効果としては、アクリル系粘着剤からなるアクリル系粘着テープまたはシートのせん断接着力や加工性の向上が挙げられる。
芯層が気泡(C)を含有することにより、アクリル系粘着剤(アクリル系粘着テープ)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、良好な耐反発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、増量剤等が芯層に添加されていてもよい。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、酸化防止剤等を適宜添加してもよい。これらに限定されるものではない。
表層30の成分は、粘着性組成物としてのアクリル系ポリマー(D)と、粘着付与樹脂としてのアクリル系オリゴマー(E)とを含む。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。また、アクリル系ポリマー(D)は、芯層を構成するアクリル系ポリマー(A)と同様の重合開始剤を使用し、同様の重合方法にて調製することができる。以下、アクリル系オリゴマー(E)について詳述する。
アクリル系オリゴマーは、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。
アクリル系オリゴマー(E)は、たとえば、(メタ)アクリル酸エステルを、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。
アクリル系オリゴマー(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が、この中で、チオグリコール酸類を好適に使用することができる。
芯層20の厚さと表層30a(または表層30b)の厚さの総厚に対する比は表層30a(または表層30b)の厚さの比率の好ましい範囲は8~20%である。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の総厚(芯層の厚さと表層の厚さの合計)は、0.4mm~4.0mm、好ましくは、0.5mm~2.5mmである。
芯層と表層とを積層する方法は特に限定されないが、以下に示す方法を適用することができる。
(1)表層および芯層を別々に硬化させた後、芯層の上に表層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(または芯層)に芯層(または表層)を塗工した後、芯層(または表層)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(または芯層)に芯層(または表層)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、芯層ともに一括塗工が可能である。
何ら限定されるものではない。
2EHA:2-エチルヘキシルアクリレート
AA:アクリル酸
CHMA:シクロヘキシルメタクリレート
IBMA:イソブチルメタクリレート
IBXMA:イソボルニルメタクリレート
ACMO:アクリロイルモルフォリン
DEAA:ジエチルアクリルアミド
AOI:2-イソシアナトエチルアクリレート カレンズAOI(昭和電工社製)
HDDA:1,6-ヘキサンジオールジアクリレート
TMPTA:トリメチロールプロパン トリアクリレート
2-エチルヘキシルアクリレート(90質量部)およびアクリル酸(10質量部)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」BASF社製、0.05質量部)と光重合開始剤(商品名「イルガキュア184」BASF社製、0.05質量部)とを配合した後、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、一部が重合した組成物(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(94質量部)およびアクリル酸(6質量部)から構成される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」BASF社製、0.07質量部)と光重合開始剤(商品名「イルガキュア184」BASF社製、0.07質量部)とを配合した後、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、一部が重合した組成物(アクリル系ポリマーシロップ2)を得た。
シクロヘキシルメタクリレート(CHMA、60質量部)、イソブチルメタクリレート(IBMA、40質量部)、チオグリコール酸(4.0質量部)を配合した後、窒素ガスを吹き込んで溶存酸素を除去した。次いで、90℃まで昇温したところで、パーヘキシルO(日油株式会社製、0.005質量部)、パーヘキシルD(日油株式会社製、0.01質量部)を混合した。さらに、90℃で1時間攪拌後、1時間かけて150℃まで昇温し、150℃で1時間攪拌した。次いで、1時間かけて170℃まで昇温し、170℃で60分間攪拌した。
実施例1に係るアクリル系粘着テープの作製方法について説明する。
(アクリル系粘着性組成物1(芯層用組成物)の調製)
上述したアクリル系ポリマーシロップ1(100質量部)に、1,6-ヘキサンジオールジアクリレート(0.08質量部)、および光重合開始剤(商品名「イルガキュア651」BASF社製、0.04質量部)を添加した後、さらに、該部分重合モノマーシロップに対して9.5質量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。
上述したアクリル系ポリマーシロップ2(100質量部)に対して、2-イソシアナトエチルアクリレート(0.08質量部)、上記で得たアクリル系オリゴマー1(20質量部)を配合し、表層用のアクリル系粘着性組成物2を得た。
アクリル系粘着性組成物1をロールコーターにて片面剥離処理された厚さ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)の剥離処理された面上に厚さ550μmとなるように塗布した。次いで、塗布されたアクリル系粘着性組成物1のもう片方の面に、同種のポリエステル製剥離ライナーの剥離処理された面がアクリル系粘着性組成物1のもう片方の面と対向するように貼り合わせた。次いで、照度5mW/cm2のブラックライトランプにて3分間両面から紫外線照射を行った。このようにして厚さ550μmのアクリル系粘着剤層からなる芯層を得た。
上述したアクリル系粘着性組成物2をロールコーターにて片面剥離処理された厚さ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)の剥離処理された面上に厚さ50μmとなるように塗布した。次いで、塗布されたアクリル系粘着性組成物2のもう片方の面に、同種のポリエステル製剥離ライナーの剥離処理された面がアクリル系粘着性組成物2のもう片方の面に対向するように貼り合わせた。次いで、照度5mW/cm2のブラックライトランプにて3分間両面から紫外線照射を行った。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。
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、それぞれの粘着面どうしを貼り合わせることにより実施例1に係るアクリル系粘着テープを得た。
実施例2~9に係るアクリル系粘着テープの基本的な作製方法は実施例1と同様である。ただし、表1に示す成分、表層厚み等に従って各実施例を作製した。実施例2、3では、表層厚みをそれぞれ90μm、120μmとした。芯層の厚さと表層の厚さを合わせた総厚に対する表層の厚さの比率は、実施例1、2、3でそれぞれ、8%、15%、20%となっている。実施例4、5では、アクリル系オリゴマー(E)の含有量を(D)成分としてのアクリル系ポリマーシロップ2(100質量部)に対して、それぞれ10質量部、30質量部とした。実施例6~9では、表層厚みを70μmで共通とし、表層のアクリル系ポリマー(D)の組成比、アクリル系オリゴマー(E)の組成、架橋剤が適宜変えられている。
比較例1に係るアクリル系粘着テープは芯層単体であり、表層を備えていない。また、比較例2に係るアクリル系粘着テープは、表層中にアクリル系オリゴマー(E)を有していない。
[90°剥離試験]
被着体として、SUS304BA板、アルミニウム板、PMMA板、ABS板、ポリカーボネート板、ポリスチレン板を用意した。各実施例および比較例2のアクリル系粘着テープについて、芯層側の剥離ライナーを剥がし、厚み130μmのアルミニウムフィルムを裏打ちしたアクリル系粘着テープを23℃の雰囲気下30分放置した後、もう片方の剥離フィルムを剥がし表層を露出させ、各被着体に5kgローラー片道で圧着させた後、23℃、50%RHで72時間エージングした。エージング後、23℃の雰囲気下、90°剥離方向に引張速度300mm/分にて、粘着シートを剥離することにより各被着体に対する粘着力(単位:N/25mm)を測定した。比較例1のアクリル系粘着テープについては、芯層を露出させて、芯層と各被着体との接着力を測定した。測定結果を表2に示す。
Claims (6)
- 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)と微粒子(B)と気泡(C)とを含み、
前記表層は、アクリル系ポリマー(D)とアクリル系オリゴマー(E)とを含むことを特徴とするアクリル系粘着テープ。 - 前記アクリル系オリゴマー(E)の含有量が前記アクリル系ポリマー(D)100質量部に対して5~45質量部である請求項1に記載のアクリル系粘着テープ。
- 被着体となるポリスチレンに接着後、72時間経過した後の90°剥離方向に引張速度300mm/分で剥離したときの粘着力が45N/25mm以上である請求項1または2に記載のアクリル系粘着テープ。
- 前記芯層の厚さと前記表層の厚さとを合わせた総厚に対する前記表層の厚さの比率が8~20%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。
- 前記アクリル系ポリマー(A)およびアクリル系ポリマー(D)は、(メタ)アクリル酸アルキルエステルを単量体主成分とする請求項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。
- 前記アクリル系オリゴマー(E)の重量平均分子量が2000~20000である請求項1乃至5のいずれか1項に記載のアクリル系粘着テープ。
Priority Applications (3)
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US13/496,355 US20120177901A1 (en) | 2009-09-16 | 2010-09-03 | Acrylic pressure-sensitive tape |
EP10816851.9A EP2479229A4 (en) | 2009-09-16 | 2010-09-03 | ACRYLIC ADHESIVE STRIP |
CN2010800414740A CN102498183A (zh) | 2009-09-16 | 2010-09-03 | 丙烯酸类粘合带 |
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JP2009214836 | 2009-09-16 | ||
JP2009-214836 | 2009-09-16 | ||
JP2010197868A JP5634803B2 (ja) | 2009-09-16 | 2010-09-03 | アクリル系粘着テープ |
JP2010-197868 | 2010-09-03 |
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US (1) | US20120177901A1 (ja) |
EP (1) | EP2479229A4 (ja) |
JP (1) | JP5634803B2 (ja) |
KR (1) | KR20120073231A (ja) |
CN (1) | CN102498183A (ja) |
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WO2012128294A1 (ja) * | 2011-03-24 | 2012-09-27 | リンテック株式会社 | 粘着剤、及び粘着シート |
EP2537903A3 (en) * | 2011-06-22 | 2013-01-23 | Nitto Denko Corporation | Optical double-sided pressure-sensitive adhesive sheet |
WO2013150563A1 (ja) * | 2012-04-04 | 2013-10-10 | 日東電工株式会社 | 粘着テープおよびテープロール |
US20160376470A1 (en) * | 2013-07-09 | 2016-12-29 | Nitto Denko Corporation | Pressure-sensitive adhesive sheet and use thereof |
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IN2015DN03074A (ja) | 2012-10-09 | 2015-10-02 | Avery Dennison Corp | |
JP2014114397A (ja) * | 2012-12-11 | 2014-06-26 | Nitto Denko Corp | 粘着剤組成物および粘着シート |
US9605189B2 (en) | 2013-07-09 | 2017-03-28 | Nitto Denko Corporation | Pressure-sensitive adhesive composition |
CN104298381B (zh) * | 2013-07-17 | 2017-07-11 | 宸鸿科技(厦门)有限公司 | 触控面板、应用于触控面板之光学匹配胶及前述制造方法 |
WO2015129903A1 (ja) * | 2014-02-25 | 2015-09-03 | 住友化学株式会社 | 粒状接着剤 |
JP6470523B2 (ja) | 2014-08-08 | 2019-02-13 | 日東電工株式会社 | 粘着シート |
MX2017010047A (es) | 2015-02-05 | 2017-12-18 | Avery Dennison Corp | Conjuntos de etiquetas para entornos adversos. |
JP6456723B2 (ja) * | 2015-02-25 | 2019-01-23 | マクセルホールディングス株式会社 | 粘着テープ |
WO2018118767A1 (en) | 2016-12-22 | 2018-06-28 | Avery Dennison Corporation | Convertible pressure sensitive adhesives comprising urethane (meth) acrylate oligomers |
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KR102443691B1 (ko) * | 2020-09-29 | 2022-09-15 | 주식회사 연우 | 카메라 렌즈 공정용 점착테이프 및 이의 제조방법 |
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- 2010-09-03 JP JP2010197868A patent/JP5634803B2/ja not_active Expired - Fee Related
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US20160376470A1 (en) * | 2013-07-09 | 2016-12-29 | Nitto Denko Corporation | Pressure-sensitive adhesive sheet and use thereof |
US9896606B2 (en) * | 2013-07-09 | 2018-02-20 | Nitto Denko Corporation | Pressure-sensitive adhesive sheet and use thereof |
Also Published As
Publication number | Publication date |
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EP2479229A1 (en) | 2012-07-25 |
JP5634803B2 (ja) | 2014-12-03 |
KR20120073231A (ko) | 2012-07-04 |
US20120177901A1 (en) | 2012-07-12 |
CN102498183A (zh) | 2012-06-13 |
JP2011084732A (ja) | 2011-04-28 |
EP2479229A4 (en) | 2014-06-18 |
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