WO2015190441A1 - 粘着シート - Google Patents
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- WO2015190441A1 WO2015190441A1 PCT/JP2015/066500 JP2015066500W WO2015190441A1 WO 2015190441 A1 WO2015190441 A1 WO 2015190441A1 JP 2015066500 W JP2015066500 W JP 2015066500W WO 2015190441 A1 WO2015190441 A1 WO 2015190441A1
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- sensitive adhesive
- adhesive sheet
- 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
- 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
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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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- 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
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- 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
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- 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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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- 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
- C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F30/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F30/08—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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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
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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
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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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- 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
- C09J143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
- C09J143/04—Homopolymers or copolymers of monomers containing silicon
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- 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
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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- 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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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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
- 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
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- 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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- 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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- 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
- C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
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- 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
- C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
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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
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- C09J2433/00—Presence of (meth)acrylic polymer
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- C09J2483/00—Presence of polysiloxane
Definitions
- the present invention relates to an adhesive sheet.
- the pressure-sensitive adhesive sheet is used for the purpose of adhering adherends to each other or fixing an article to the adherends by firmly adhering to the adherends.
- the properties required for the pressure-sensitive adhesive sheet vary depending on the application. For example, a pressure-sensitive adhesive sheet in consideration of re-sticking (reworkability) is required in order to prevent the yield from being lowered due to a sticking error. That is, there is a demand for a pressure-sensitive adhesive sheet that exhibits low adhesive strength at the initial stage of application and exhibits high adhesive strength when the adherend is used.
- Patent Documents 1 to 4 Conventionally, in order to satisfy such a change in adhesive force, a method of changing the adhesive force of the adhesive sheet by a method such as heating or ultraviolet irradiation has been used (see Patent Documents 1 to 4).
- the adhesive properties may be different if the material of the adherend is different. Further, depending on the use of the pressure-sensitive adhesive sheet, it may be necessary to re-apply immediately after the pressure-sensitive adhesive sheet has been applied to the adherend, or may need to be re-applied after a while after being applied.
- the present invention has been made in view of such a situation, and the object of the present invention is that rework on the adherend can be performed over a long period of time and the adhesive force necessary for fixing the adherend at a desired timing can be expressed. It is in providing the adhesive sheet which made it possible.
- the pressure-sensitive adhesive sheet has a base material and a pressure-sensitive adhesive layer laminated on at least one side of the base material.
- the pressure-sensitive adhesive layer contains a (meth) acrylic polymer having a weight average molecular weight of 10,000 or more and less than 50,000.
- the adhesive strength after 30 minutes has passed after the adhesive layer is bonded to the ABS plate is 1.0 [N / 20 mm] or less, and 24 hours after the adhesive layer is bonded to the ABS plate.
- the adhesive strength after the lapse is 2.5 [N / 20 mm] or less, the adhesive layer is bonded to the ABS plate, heated at 80 ° C. for 5 minutes, and after 30 minutes at 23 ° C. Is 6.5 [N / 20 mm] or more.
- the (meth) acrylic polymer may contain a monomer having a polyorganosiloxane skeleton as a monomer unit.
- the monomer having a polyorganosiloxane skeleton may be a polyorganosiloxane group-containing monomer having a functional group equivalent of 700 g / mol or more and less than 15000 g / mol represented by the following general formula (1) or (2).
- R 3 is hydrogen or methyl
- R 4 is methyl or a monovalent organic group
- m and n are integers of 0 or more.
- the adhesive layer may contain 100 parts by mass of a polymer having a glass transition temperature of less than 0 ° C. and 0.1 to 20 parts by mass of a (meth) acrylic polymer.
- the present invention it is possible to realize a pressure-sensitive adhesive sheet that can be reworked on an adherend for a long period of time and can develop an adhesive force necessary for fixing the adherend at a desired timing.
- the pressure-sensitive adhesive composition according to the embodiment includes a polymer (A) and a (meth) acrylic polymer (B).
- the polymer (A) is a polymer having a glass transition temperature of less than 0 ° C.
- the polymer (A) is not particularly limited as long as the glass transition temperature is less than 0 ° C., and is generally used as an adhesive such as an acrylic polymer, a rubber polymer, a silicone polymer, a polyurethane polymer, and a polyester polymer.
- Various polymers can be used.
- the polymer (B) is a (meth) acrylic polymer, an acrylic polymer that is easily compatible with the (meth) acrylic polymer and has high transparency is preferable.
- the glass transition temperature (Tg) of the polymer (A) is less than 0 ° C., preferably less than ⁇ 10 ° C., more preferably less than ⁇ 40 ° C., and usually ⁇ 80 ° C. or higher.
- Tg glass transition temperature
- the glass transition temperature is a nominal value described in literatures, catalogs, or the like, or a value calculated based on the following formula (X) (Fox formula).
- Tg is the glass transition temperature (unit: K) of the polymer (A)
- the above formula (X) is a calculation formula when the polymer (A) is composed of n types of monomer components of monomer 1, monomer 2,..., Monomer n.
- glass transition temperature when homopolymer is formed means “glass transition temperature of homopolymer of the monomer”, and may be referred to as a certain monomer (“monomer X”). ) Is the glass transition temperature (Tg) of a polymer formed using only the monomer component. Specifically, “Polymer Handbook” (3rd edition, John Wiley & Sons, Inc, 1989) lists numerical values. In addition, the glass transition temperature (Tg) of the homopolymer which is not described in the said literature says the value obtained by the following measuring methods, for example.
- this homopolymer solution is cast-coated on a release liner and dried to prepare a test sample (sheet-like homopolymer) having a thickness of about 2 mm. Then, about 1 to 2 mg of this test sample is weighed in an aluminum open cell, and a nitrogen atmosphere of 50 ml / min is used using a temperature modulation DSC (trade name “Q-2000”, manufactured by T.A. Instruments Inc.). Under the heating rate of 5 ° C./min, the reversing heat flow (specific heat component) behavior of the homopolymer is obtained.
- a temperature modulation DSC trade name “Q-2000”, manufactured by T.A. Instruments Inc.
- the temperature at the point where the partial curve intersects is the glass transition temperature (Tg) when the homopolymer is used.
- the weight average molecular weight (Mw) of the polymer (A) is, for example, about 50,000 to 5,000,000.
- Mw weight average molecular weight
- the weight average molecular weight (Mw) is less than 50,000, the cohesive force of the pressure-sensitive adhesive is insufficient and the adhesion reliability may be inferior.
- the weight average molecular weight (Mw) exceeds 5,000,000, the fluidity of the pressure-sensitive adhesive is lowered, which may be inferior to an increase in pressure-sensitive adhesive force during heating.
- the acrylic polymer is, for example, a polymer containing 50% by mass or more of (meth) acrylic acid alkyl ester having a linear or branched alkyl group having 1 to 20 carbon atoms as a monomer unit.
- the acrylic polymer may 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 method for obtaining the acrylic polymer is not particularly limited, and various polymerization methods generally used as synthetic methods for acrylic polymers such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and radiation curing polymerization are applied. Thus, the polymer can be obtained.
- the proportion of the (meth) acrylic acid alkyl ester having a linear or branched alkyl group having 1 to 20 carbon atoms is 50% by mass to 99.9% by mass with respect to the total amount of monomer components for preparing the acrylic polymer. %, Preferably 60 mass% to 98 mass%, more preferably 70 mass% to 95 mass%.
- Examples of the (meth) acrylic acid alkyl ester having a linear or branched alkyl group having 1 to 20 carbon atoms include, for example, 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, (meth) acryl Isopentyl acid, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, (meth) Ison
- Acrylic polymers can be copolymerized with other (meth) acrylic acid alkyl esters as needed for the purpose of modifying cohesion, heat resistance, crosslinkability, etc. Monomer). Therefore, the acrylic polymer may contain a copolymerizable monomer together with the (meth) acrylic acid alkyl ester as the main component. As the copolymerizable monomer, a monomer having a polar group can be suitably used.
- Carboxyl group-containing monomers such as acrylic acid, (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl Hydroxyl group-containing monomers such as hydroxyalkyl (meth) acrylate such as (meth) acrylate; Acid
- (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; Vinyl esters such as vinyl acetate and vinyl propionate; N-vinyl-2-pyrrolidone,
- the copolymerizable monomer By containing 0.01% by mass or more of the copolymerizable monomer, it is possible to prevent the cohesive force of the pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer formed of the acrylic pressure-sensitive adhesive composition from being lowered. Moreover, by making content of a copolymerizable monomer into 40 mass% or less, it can prevent that cohesion force becomes high too much and can improve the tuck feeling in normal temperature (25 degreeC).
- the acrylic polymer may contain a polyfunctional monomer as necessary in order to adjust the cohesive strength of the pressure-sensitive adhesive composition 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.
- a polyfunctional monomer 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 and the number of functional groups, but is 0.01% by mass to 3.0% by mass, preferably 0%, based on the total amount of monomer components for preparing the acrylic polymer. It is added in an amount of 0.02 mass% to 2.0 mass%, more preferably 0.03 mass% to 1.0 mass%.
- the cohesive force of the pressure-sensitive adhesive composition becomes too high, and the initial pressure-sensitive adhesive strength The suppression effect may be reduced.
- the cohesive force of the pressure-sensitive adhesive composition may be reduced, and the increase in the adhesive force during heating may be insufficient.
- a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator (photoinitiator). It can.
- 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, lauroyl peroxide, etc.) Redox polymerization initiators, and the like
- the amount of the thermal polymerization 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. It mix
- the photopolymerization initiator is not particularly limited, and examples thereof include benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, ⁇ -ketol photopolymerization initiators, aromatic sulfonyl chloride photopolymerization initiators, and photoactive initiators.
- 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- 1-one [trade name: Irgacure 651, manufactured by BASF Corporation], anisoin and the like can be mentioned.
- acetophenone photopolymerization initiator for example, 1-hydroxycyclohexyl phenyl ketone [trade name: Irgacure 184, manufactured by BASF], 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 BASF Corp.], 2-hydroxy-2-methyl-1-phenyl-propane- 1-one [trade name: Darocur 1173, manufactured by BASF], methoxyacetophenone, and the like can be given.
- 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 aromatic sulfonyl chloride photopolymerization initiators include 2-naphthalenesulfonyl chloride.
- Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime.
- the benzoin photopolymerization initiator includes, for example, benzoin.
- Examples of the benzyl photopolymerization initiator include benzyl.
- Examples of the benzophenone photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinyl benzophenone, ⁇ -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- T
- 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. In an amount within the range of parts.
- the amount of the photopolymerization initiator used is less than 0.01 parts by mass, the polymerization reaction may become insufficient.
- an ultraviolet-ray may not reach the inside of an adhesive layer because a photoinitiator absorbs an ultraviolet-ray.
- the polymerization rate is lowered, or the molecular weight of the produced polymer is reduced.
- the cohesive force of the adhesive layer formed becomes low by this, and the adhesive force raise at the time of a heating may become inadequate.
- a photopolymerization initiator can be used individually or in combination of 2 or more types.
- the 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. It can also be prepared as.
- a pressure-sensitive adhesive composition is prepared by blending the polymer (B) described later with an acrylic polymer syrup, and this pressure-sensitive adhesive composition is applied to a predetermined coated body and irradiated with ultraviolet rays to complete the polymerization. You can also. That is, the acrylic polymer syrup is a precursor of the polymer (A), and the polymer (B) blended with the acrylic polymer syrup also corresponds to the pressure-sensitive adhesive composition of the present embodiment.
- the (meth) acrylic polymer (B) (hereinafter referred to as “polymer (B)” as appropriate) has a weight average molecular weight of 10,000 or more and less than 50,000.
- the (meth) acrylic polymer preferably contains a monomer having a polyorganosiloxane skeleton as a monomer unit.
- the monomer (B1) having a polyorganosiloxane skeleton constituting the polymer (B) is not particularly limited, and any polyorganosiloxane skeleton-containing monomer can be used. Since the polyorganosiloxane skeleton-containing monomer has a low polarity derived from its structure, it actively promotes the uneven distribution of the polymer (B) on the surface of the adherend, and exhibits light release at the initial stage of bonding. .
- a polyorganosiloxane skeleton-containing monomer represented by the following general formula (1) or (2) can be used.
- examples of the one-end reactive silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. include X-22-174ASX, X-22-2426, X-22-2475, KF-2012, etc. Two or more kinds can be used in combination.
- R 3 is hydrogen or methyl
- R 4 is methyl or a monovalent organic group
- m and n are integers of 0 or more.
- the functional group equivalent of the monomer (B1) having a polyorganosiloxane skeleton constituting the polymer (B) is preferably 700 g / mol or more and less than 15000 g / mol, more preferably 800 g / mol or more and less than 10,000 g / mol. Preferably, it is more preferably 850 g / mol or more and less than 6000 g / mol, and particularly preferably 1500 g / mol or more and less than 5000 g / mol.
- the functional group equivalent of the monomer (B1) having a polyorganosiloxane skeleton is within the above range, the compatibility is moderately lowered, so that the increase in adhesive strength is stable at room temperature, and the adhesive strength during heating is increased. Excellent.
- the functional group equivalent of the monomer (B1) having a polyorganosiloxane skeleton is less than 700 g / mol, light peelability does not appear, and the adhesive strength may not decrease in the initial stage of bonding.
- the functional group equivalent of the monomer having a polyorganosiloxane skeleton is 15000 g / mol or more, the compatibility with the polymer (A) is remarkably deteriorated, and the adhesive force does not decrease at the initial stage of bonding to the adherend. In some cases, the adhesive strength during heating may be poor.
- “functional group equivalent” means the mass of the main skeleton (for example, polydimethylsiloxane) bonded per functional group.
- the title unit g / mol is converted to 1 mol of functional group.
- the functional group equivalent of the monomer having a polyorganosiloxane skeleton is calculated from, for example, the spectrum intensity of 1 H-NMR (proton NMR) obtained by a nuclear magnetic resonance measuring apparatus (NMR).
- the number A of the siloxane structure is known, the number A of the siloxane structure, the number of functional groups, The value obtained by multiplying the ratio (A / B) is the mass of the siloxane structure having a Si— (CH 3 ) 2 bond per functional group, that is, the mass of the main skeleton, and the mass is multiplied by the Avogadro number. The value becomes the functional group equivalent (g / mol).
- the content of the monomer (B1) having a polyorganosiloxane skeleton having a functional group equivalent of 700 g / mol or more and less than 15000 g / mol is 5% by mass or more and 50% by mass or less with respect to all monomer components of the polymer (B). Yes, it is preferably 10% by mass or more and 40% by mass or less, and more preferably 15% by mass or more and 30% by mass or less.
- the content is less than 5% by mass, the adhesive strength may not decrease at the initial stage of bonding. On the other hand, when the content is more than 50% by mass, the adhesive strength during heating may be poor.
- the polymer (B) is selected from the group consisting of a monomer having a polyorganosiloxane skeleton, a (meth) acrylic monomer, a monomer having a polyoxyalkylene skeleton, a (meth) acrylic acid ester monomer, and a copolymerizable monomer. It may be a copolymer with one or more monomers.
- Examples of such (meth) acrylic acid ester monomers 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 (me
- Such (meth) acrylic acid ester monomers can be used alone or in combination of two or more. It is particularly preferable to use methyl methacrylate and / or butyl methacrylate.
- the content of the (meth) acrylic acid ester monomer is preferably 10% by mass or more and 95% by mass or less, and more preferably 20% by mass or more and 90% by mass or less, with respect to all monomer components of the polymer (B). More preferably, it is 30 mass% or more and 85 mass% or less.
- the polymer (B) is obtained by copolymerizing other monomer components (copolymerizable monomers) copolymerizable with (meth) acrylic acid esters in addition to the (meth) acrylic acid ester component units.
- a functional group having reactivity with an epoxy group or an isocyanate group may be introduced. Examples of such 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 in the production of the polymer (B) (copolymerization).
- Carboxyl group-containing monomers such as acrylic acid, (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid;
- 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 glyco
- the weight average molecular weight of the polymer (B) is 10,000 or more and less than 50000, preferably 12000 or more and less than 50000, more preferably 15000 or more and less than 40000, and further preferably 20000 or more and less than 40000. If the weight average molecular weight of the polymer (B) is within the above range, the compatibility is moderately lowered, and therefore, the increase in adhesive force is stable at room temperature, and the adhesive strength during heating is excellent. When the weight average molecular weight of the polymer (B) is 50000 or more, the adhesive strength at the initial stage of bonding does not decrease. Moreover, since it becomes low molecular weight as a weight average molecular weight is less than 10,000, the adhesive force of an adhesive sheet may not raise at the time of a heating.
- the measurement of the weight average molecular weight of the polymer (A) or the polymer (B) can be obtained by polystyrene conversion by gel permeation chromatography (GPC) method. Specifically, it is measured according to the method and conditions described in the examples described later.
- GPC gel permeation chromatography
- the polymer (B) can be produced, for example, by polymerizing the above-described monomers by a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, a suspension polymerization, a bulk polymerization, or the like.
- 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, lauryl mercaptan, t-nonyl mercaptan, t-dodecyl mercaptan, mercaptoethanol, ⁇ -thioglycerol; thioglycolic acid, methyl thioglycolate, Ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate, decyl thioglycolate, dodecyl thioglycolate, ethylene Thi
- the amount of the chain transfer agent used is not particularly limited, but is usually 0.05 to 20 parts by mass, preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the monomer. More preferably, the content is 0.2 to 10 parts by mass.
- the (meth) acrylic-type polymer (B) 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 pressure-sensitive adhesive composition contains the polymer (A) and the polymer (B) described above as essential components.
- the content of the polymer (B) is 0.1 parts by mass or more and 20 parts by mass or less, preferably 0.3 parts by mass to 17 parts by mass, with respect to 100 parts by mass of the polymer (A).
- the amount is preferably 0.4 to 15 parts by mass, and more preferably 0.5 to 12 parts by mass.
- the pressure-sensitive adhesive composition may contain various additives generally used in the field of the pressure-sensitive adhesive composition as optional components in addition to the polymer (A) and the polymer (B) described above.
- optional components include tackifier resins, crosslinking agents, catalysts, plasticizers, softeners, fillers, colorants (pigments, dyes, etc.), antioxidants, leveling agents, stabilizers, preservatives, antistatic agents, etc. Is exemplified.
- Conventionally known additives can be used as such additives.
- a crosslinking agent can be used in addition to the various monomers described above.
- a commonly used crosslinking agent can be used.
- a melamine type crosslinking agent, a metal chelate type crosslinking agent, etc. can be mentioned.
- an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, and a metal chelate-based crosslinking agent can be preferably used. These compounds may be used alone or in combination of two or more.
- examples of the isocyanate-based crosslinking agent include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenyl (meth) diisocyanate, hydrogenated diphenyl (meth) diisocyanate. , Tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenyl (meth) triisocyanate, polymethylene polyphenyl isocyanate, and adducts of these with polyols such as trimethylolpropane.
- a compound having at least one isocyanate group and one or more unsaturated bonds in one molecule specifically, 2-isocyanatoethyl (meth) acrylate may be used as an isocyanate-based crosslinking agent.
- 2-isocyanatoethyl (meth) acrylate may be used as an isocyanate-based crosslinking agent.
- Can do These compounds may be used alone or in combination of two or more.
- 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, trimethylol propane tri Glycidyl ether, diglycidyl aniline, diamine glycidyl amine, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, etc. Can do. These compounds may be used alone or in combination of two or more.
- metal chelate compound examples include aluminum, iron, tin, titanium and nickel as metal components, and acetylene, methyl acetoacetate and ethyl lactate as chelate components. These compounds may be used alone or in combination of two or more.
- the content of the crosslinking agent is preferably 0.01 to 15 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymer (A). preferable.
- content is less than 0.01 mass part, the cohesion force of an adhesive composition may become small and it may be inferior to adhesive reliability.
- content exceeds 15 parts by mass, the cohesive force of the pressure-sensitive adhesive composition is large, the fluidity is lowered, and the pressure-sensitive adhesive force increase during heating may be inferior.
- the pressure-sensitive adhesive composition disclosed herein can further contain a crosslinking catalyst for causing any of the above-described crosslinking reactions to proceed more effectively.
- a crosslinking catalyst for example, a tin-based catalyst (particularly dioctyltin dilaurate) can be preferably used.
- the amount of the crosslinking catalyst is not particularly limited, and can be, for example, about 0.0001 parts by mass to 1 part by mass with respect to 100 parts by mass of the polymer (A). .
- the tackifying resin is not particularly limited.
- rosin tackifying resin terpene tackifying resin, phenol tackifying resin, hydrocarbon tackifying resin, ketone tackifying resin, polyamide tackifying Resin, epoxy tackifying resin, elastomer tackifying resin, etc.
- rosin-based tackifier resins examples include unmodified rosins such as gum rosin, wood rosin and tall oil rosin (raw rosin), and modified rosins modified by polymerization, disproportionation, hydrogenation, etc. Polymerized rosin, stabilized rosin, disproportionated rosin, fully hydrogenated rosin, partially hydrogenated rosin and other chemically modified rosins), and various rosin derivatives.
- rosin derivative examples include: A rosin phenolic resin obtained by thermally polymerizing rosins (unmodified rosin, modified rosin, various rosin derivatives, etc.) by adding phenol with an acid catalyst; Ester compounds of rosin obtained by esterifying unmodified rosin with alcohol (unmodified rosin ester), modified rosins such as polymerized rosin, stabilized rosin, disproportionated rosin, fully hydrogenated rosin, partially hydrogenated rosin, alcohols Rosin ester resins such as modified rosin ester compounds esterified by (polymerized rosin ester, stabilized rosin ester, disproportionated rosin ester, fully hydrogenated rosin ester, partially hydrogenated rosin ester, etc.); An unsaturated fatty acid-modified rosin resin obtained by modifying an unmodified rosin or a modified rosin (polymerized rosin, stabilized rosin, disproportionated rosin,
- terpene-based tackifier resins include terpene resins such as ⁇ -pinene polymers, ⁇ -pinene polymers, and dipentene polymers, and modified terpene resins (phenol modified, aromatic modified, hydrogenated modified). Modified terpene resins such as terpene phenol resins, styrene modified terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, and the like.
- phenolic tackifying resins include condensates of various phenols (eg, phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcin, etc.) with formaldehyde (eg, alkylphenolic resin, xyleneformaldehyde). Resin), a resol obtained by addition reaction of the phenols and formaldehyde with an alkali catalyst, and a novolak obtained by a condensation reaction of the phenols and formaldehyde with an acid catalyst.
- formaldehyde eg, alkylphenolic resin, xyleneformaldehyde
- hydrocarbon tackifying resins include: Aliphatic hydrocarbons such as aliphatic hydrocarbon resins [olefins and dienes having 4 to 5 carbon atoms (olefins such as butene-1, isobutylene, pentene-1; dienes such as butadiene, 1,3-pentadiene, isoprene, etc.) Polymers, etc.] Aliphatic cyclic hydrocarbon resin [A so-called “C4 petroleum fraction” or “C5 petroleum fraction” is obtained by cyclization and dimerization and then polymerized, and a cyclodiene compound (cyclopentadiene, diene) Cyclopentadiene, ethylidene norbornene, dipentene, etc.) polymers or hydrogenated products thereof, and the following aromatic hydrocarbon resins and alicyclic hydrocarbon resins obtained by hydrogenating aromatic rings of aliphatic / aromatic petroleum resins, etc.
- Aliphatic hydrocarbons such as aliphatic hydrocarbon resin
- Aromatic hydrocarbon resins polymers of vinyl group-containing aromatic hydrocarbons having 8 to 10 carbon atoms (such as styrene, vinyltoluene, ⁇ -methylstyrene, indene, methylindene)]
- Examples include aliphatic / aromatic petroleum resins (such as styrene-olefin copolymers), aliphatic / alicyclic petroleum resins, hydrogenated hydrocarbon resins, coumarone resins, coumarone indene resins, and the like.
- polymerized rosin esters examples include trade names “Pencel D-125”, “Pencel D-135”, “Pencel D-160”, “Pencel KK”, and “Pencel” manufactured by Arakawa Chemical Industries, Ltd. C ”and the like are exemplified, but not limited thereto.
- terpene phenolic resins that can be preferably used include trade names “YS Polystar S-145”, “YS Polystar G-125”, “YS Polystar N125”, and “YS Polystar U-115” manufactured by Yashara Chemical Co., Ltd. Examples include, but are not limited to, trade names “TAMANOL 803L” and “TAMANOL 901” manufactured by Arakawa Chemical Industries, Ltd., and “Sumilite Resin PR-12603” manufactured by Sumitomo Bakelite Co., Ltd.
- Adhesive layer and adhesive sheet Then, the structure of the adhesive sheet which has an adhesive layer containing the adhesive composition which has the above-mentioned composition is demonstrated.
- the pressure-sensitive adhesive layer can be a cured layer of the pressure-sensitive adhesive composition. That is, the pressure-sensitive adhesive layer can be formed by applying the pressure-sensitive adhesive composition to a suitable support (for example, coating / coating) and then appropriately performing a curing treatment. When performing 2 or more types of hardening processes (drying, bridge
- a pressure-sensitive adhesive composition using a partial polymer (acrylic polymer syrup) typically, as the curing treatment, a final copolymerization reaction is performed (the partial polymer is subjected to a further copolymerization reaction). A complete polymer is formed).
- Application and coating of the pressure-sensitive adhesive composition can be carried out using a conventional coater such as a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray coater, etc. it can.
- the pressure-sensitive adhesive composition may be directly applied to the support to form a pressure-sensitive adhesive layer, or the pressure-sensitive adhesive layer formed on the release liner may be transferred to the support.
- the pressure-sensitive adhesive layer has a solvent-insoluble component ratio of 20.0 mass% to 99.0 mass%, preferably 30.0 mass% to 90.0 mass%. If the solvent-insoluble component ratio is less than 20.0% by mass, the cohesive force may be insufficient, resulting in poor adhesion reliability. If the solvent-insoluble component ratio exceeds 99.0% by mass, the cohesive force becomes too high. In some cases, the increase in adhesive strength during heating may be insufficient. In addition, the evaluation method of a solvent insoluble component rate is mentioned later.
- the thickness of the pressure-sensitive adhesive layer is not particularly limited, but usually good adhesiveness can be realized by setting it to 3 ⁇ m to 200 ⁇ m, preferably 5 ⁇ m to 150 ⁇ m.
- the thickness of the pressure-sensitive adhesive layer is less than 3 ⁇ m, the increase in the pressure-sensitive adhesive force during heating may be inferior.
- the thickness of the pressure-sensitive adhesive layer exceeds 200 ⁇ m, the effect of suppressing the pressure-sensitive adhesive force immediately after bonding becomes insufficient. There is.
- FIG. 1 is a side view of the pressure-sensitive adhesive sheet 10 according to the present embodiment.
- the pressure-sensitive adhesive sheet 10 shown in FIG. 1 includes a base material 12 and a pressure-sensitive adhesive layer 14 that is laminated on one side of the base material 12 and is a pressure-sensitive adhesive composition.
- the pressure-sensitive adhesive sheet 10 is provided with such a pressure-sensitive adhesive layer fixedly on at least one surface of the substrate 12, that is, without intention to separate the pressure-sensitive adhesive layer 14 from the substrate 12.
- the concept of the pressure-sensitive adhesive sheet referred to here may include what are called pressure-sensitive adhesive tapes, pressure-sensitive adhesive films, pressure-sensitive adhesive labels, and the like. Further, it may be cut into a suitable shape, punched out, or the like according to the intended use.
- the pressure-sensitive adhesive layer is not limited to those formed continuously, and may be a pressure-sensitive adhesive layer formed in a regular or random pattern such as a dot shape or a stripe shape.
- the support for example, Polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / vinyl acetate copolymer, ethylene / ethyl acrylate copolymer
- Polyolefin films such as polymers, ethylene / vinyl alcohol copolymers, polyester films such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyacrylate films, polystyrene films, nylon 6, nylon 6,6, partially aromatic polyamides, etc.
- Plastic films such as polyamide film, polyvinyl chloride film, polyvinylidene chloride film, polycarbonate 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.
- the support may be released with a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, silica powder, etc., and antifouling treatment, acid treatment, alkali treatment, primer treatment. Further, easy adhesion treatment such as corona treatment, plasma treatment, and ultraviolet treatment can be performed.
- the thickness of the support can be appropriately selected depending on the purpose, but is generally about 5 ⁇ m to 200 ⁇ m (typically 10 ⁇ m to 100 ⁇ m).
- silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent release with silica powder and antifouling treatment, acid treatment, alkali treatment, primer treatment, Anti-adhesive treatment such as corona treatment, plasma treatment and ultraviolet treatment, coating type, kneading type, vapor deposition type and the like can also be carried out.
- a release liner can be bonded to the surface of the pressure-sensitive adhesive layer for the purpose of protecting the pressure-sensitive adhesive surface as necessary.
- the material constituting the release liner includes paper and plastic film, but a plastic film is preferably used because of its excellent surface smoothness.
- the film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer, and for example, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer. Examples thereof include a coalesced film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.
- the thickness of the release liner is usually about 5 ⁇ m to 200 ⁇ m, preferably about 10 ⁇ m to 100 ⁇ m. It is preferable for it to be in the above-mentioned range, since it is excellent in workability for bonding to the pressure-sensitive adhesive layer and workability for peeling from the pressure-sensitive adhesive layer.
- release and antifouling treatment with a silicone, fluorine, long chain alkyl or fatty acid amide release agent, silica powder, etc., coating type, kneading type, vapor deposition An antistatic treatment such as a mold can also be performed.
- the adhesive sheet according to the present embodiment has a low adhesive force and can be reworked immediately after being bonded to an adherend, and the adhesive force does not increase so much over time at room temperature. Therefore, rework is possible even when the pressure-sensitive adhesive sheet is left on the adherend for a long time (for example, several minutes to several days). That is, the pressure-sensitive adhesive sheet according to the present embodiment needs to be re-attached not only after re-attaching to the adherend but also after inspection for a long time after being attached to the adherend. It is possible to easily cope with the case. Therefore, the pressure-sensitive adhesive sheet according to the present embodiment can be applied to various processes and uses in which the time for which the pressure-sensitive adhesive sheet is left attached to the adherend is different. Moreover, since it can be reapplied for a long time, the manufacturing yield can be improved.
- the pressure-sensitive adhesive sheet according to the present embodiment has a low pressure-sensitive adhesive strength at room temperature (for example, 23 ° C., 50% RH) before heating, but the pressure-sensitive adhesive strength is several times to several tens by heating. Since it can be doubled, it has the property of high adhesion reliability.
- a general thermosetting tape requires heating at 50 to 200 ° C. for about 30 seconds to 5 hours.
- the heating temperature of the pressure-sensitive adhesive sheet according to the present embodiment is, for example, less than 150 ° C., preferably 100 ° C. or less, more preferably 80 ° C. or less.
- the heating time is, for example, less than 1 hour, preferably 30 minutes or less, more preferably 10 minutes or less, and still more preferably 5 minutes or less.
- the adhesive strength after aging of the adhesive sheet and the adhesive strength after heating can also be evaluated by a 180 ° peeling adhesive strength test when peeling is performed at a tensile speed of 300 mm / min and a peeling angle of 180 °.
- the 180 ° peel adhesion test is measured according to the method and conditions described in the examples described later.
- the pressure-sensitive adhesive sheet of the present embodiment has a low adhesive strength so that it can be reworked for a long time from the initial stage of pasting, and can be stored for a long time.
- the degree of freedom of handling of the pressure-sensitive adhesive sheet in a manufacturing method of an electronic device or the like including a step of bonding the pressure-sensitive adhesive sheet to the adherend Increase.
- optical applications such as adhesion of optical films used in image display devices such as liquid crystal displays, plasma displays, and organic EL displays, as bonding materials for members in mobile devices and other electric and electronic devices, It can be suitably used as a bonding material for various members in home appliances and the like.
- ((Meth) acrylic polymer as other (B) component) (Meth) acrylic polymers 2 and 3 (meth) acrylic polymers, except that the monomer composition, the type of solvent, and the mass parts of the chain transfer agent were added as described in Table 1. 1 was prepared.
- the weight average molecular weight of the polymer was measured using a GPC apparatus (HLC-8220 GPC, manufactured by Tosoh Corporation). The measurement conditions were as follows, and the molecular weight was determined by standard polystyrene conversion.
- Example 1 (Preparation of adhesive composition) After adding 100 parts by weight of the (meth) acrylic polymer 1 described above, 7 parts by weight of the (meth) acrylic polymer 1 described above, and 3 parts by weight of coronate L as a crosslinking agent, these were mixed uniformly. Thus, a pressure-sensitive adhesive composition (1) was prepared.
- the pressure-sensitive adhesive composition (1) is applied to a release-treated surface of a polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) and heated at 110 ° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 20 ⁇ m. Formed. Next, a 25 ⁇ m thick polyethylene terephthalate film was bonded to the surface of the pressure-sensitive adhesive layer to prepare a pressure-sensitive adhesive sheet.
- a polyester film trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.
- Each of the pressure-sensitive adhesive sheets of Examples 2 to 5 and 7 includes 100 parts by mass of the polymer (A) described in Table 2, the polymer (B) described in Table 1, the tackifying resin and the crosslinking agent described in Table 2.
- Each pressure-sensitive adhesive sheet of Comparative Examples 1 to 3 was prepared by the same method as in Example 1 except that the polymer (A) shown in Table 2 was used, and the pressure-sensitive adhesive composition was prepared in the same manner as in Example 1. It was.
- Example 6 Preparation of adhesive layer After adding 5 parts by mass of (meth) acrylic polymer 2 and 0.1 part by weight of TMPTA to 100 parts by mass of (meth) acrylic polymer 2, these are uniformly mixed to obtain an adhesive composition. Obtained.
- the pressure-sensitive adhesive composition described above was applied to the release surface of a 38 ⁇ m thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Plastics 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: Diafoil MRE, manufactured by Mitsubishi Plastics Co., Ltd.), one surface of which is peeled off with silicone, is applied to the surface of the applied pressure-sensitive adhesive composition. Covered side by side. Thereby, the application layer (adhesive layer) of the adhesive composition was shielded from oxygen.
- the coating layer 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) for 360 seconds using a chemical light lamp (manufactured by Toshiba Corporation). To obtain an adhesive layer sheet. Thereafter, one polyester film was peeled off, and a 25 ⁇ m-thick polyethylene terephthalate film was bonded to prepare an adhesive sheet.
- Test method [Constant load peeling] What cut
- an ABS plate product name: ABS-N-WN
- ABS-N-WN product name: ABS-N-WN
- isopropyl alcohol was prepared.
- the other release liner (polyester film) of the pressure-sensitive adhesive sheet was peeled off, and the 2 kg roller was reciprocated once to attach the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet to the ABS plate.
- the other end of the pressure-sensitive adhesive sheet is peeled off at a speed of 300 mm / min in a peeling direction of 180 degrees, and the adhesive strength (resistance force) to the adherend at that time ) (Unit: N / 20 mm).
- the initial condition adhesive strength is 1.0 or lower, the adhesive strength after 24 hours is 2.5 or lower, and the adhesive strength after heating is 6.5 or higher.
- the initial condition adhesive strength is 1.5 or less, the adhesive strength after 24 hours is 3.5 or less, and the adhesive strength after heating at 80 ° C. for 5 minutes is 6.0 or more. )
- the adhesive strength in the initial condition is greater than 1.5, the adhesive strength after 24 hours is greater than 3.5, and the adhesive strength after heating is less than 6.0, it was defined as defective (x).
- Table 3 shows the measurement results of the 180 ° peeling adhesive strength.
- Example 6 At the time of measuring the shear storage elastic modulus described below, those except for Example 6 were obtained by applying a pressure-sensitive adhesive to a polyester film and bonding the polyester film to the pressure-sensitive adhesive layer. In Example 6, the thing before bonding polyethylene terephthalate was used. [Measurement of shear storage modulus] The shear storage modulus was determined by dynamic viscoelasticity measurement. A pressure-sensitive adhesive sheet was laminated to prepare a laminate (laminated pressure-sensitive adhesive layer) having a thickness of about 1.5 mm, and used as a measurement sample.
- the measurement sample was ⁇ 20 to The shear storage elastic modulus was calculated by measuring in the temperature range of 100 ° C.
- the shear storage modulus of the pressure-sensitive adhesive layer according to each example is 7.4 ⁇ 10 4 to 1.4 ⁇ 10 5 Pa before and after the heat treatment at 80 ° C. for 5 minutes. is there.
- the rate of change in the shear storage modulus before and after heating at 80 ° C. for 5 minutes is 1.0 to 1.3 times.
- the above-mentioned pressure-sensitive adhesive layer had a shear storage elastic modulus of 23 ° C. and a shear storage elastic modulus after heating at 80 ° C. for 5 minutes determined by dynamic viscoelasticity measurement at a shear strain of 1 Hz.
- X10 4 to 1.0 ⁇ 10 6 Pa is preferable, 2.0 ⁇ 10 4 to 6.0 ⁇ 10 5 Pa is more preferable, and 5.0 ⁇ 10 4 to 3.0 ⁇ 10. More preferably, it is 5 Pa.
- the change rate of the shear storage modulus before and after heating at 80 ° C. for 5 minutes is preferably 2.0 times or less, more preferably 1.0 to 2.0 times, and more preferably 1.0 to 2.0 times.
- the ratio is more preferably 1.8 times, particularly preferably 1.0 to 1.5 times, and most preferably 1.0 to 1.3 times.
- the polydimethylsiloxane skeleton of the (meth) acrylic polymer (B) forms a weak adhesive interface with the adherend in the initial stage of pasting (bonding), and lowers the initial adhesive strength. It is considered that the adhesive force gradually increases as the polydimethylsiloxane chain of the (meth) acrylic polymer (B) separates from the interface over time. In addition, when heated, the polydimethylsiloxane chain that has received external energy is more likely to move, and the adhesive force is considered to increase significantly by leaving the interface. Further, since the (meth) acrylic polymer (B) has a (meth) acrylic skeleton, it has good compatibility with the polymer (A), so that it is not contaminated (transferred) to the adherend after peeling.
- the pressure-sensitive adhesive sheet according to the present embodiment may be produced using an acid-less acrylic polymer.
- a pressure-sensitive adhesive sheet with reduced defects (such as metal corrosion) due to the acid monomer can be realized.
- the adhesive sheet according to the present embodiment can obtain a strong adhesive force by heating at a relatively low temperature of about 80 ° C. for a short time (several minutes). Moreover, since the shear storage elastic modulus of the pressure-sensitive adhesive layer before and after heating does not change greatly in the pressure-sensitive adhesive sheet according to the present embodiment, even if the adherend on which the pressure-sensitive adhesive sheet is bonded is dropped, peeling due to cracking of the pressure-sensitive adhesive layer Is less likely to occur and the drop impact resistance is improved.
- Adhesive sheet 10 Adhesive sheet, 12 Substrate, 14 Adhesive layer
- the present invention relates to an adhesive sheet.
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Abstract
Description
ポリマー(A)は、ガラス転移温度が0℃未満のポリマーである。ポリマー(A)は、ガラス転移温度が0℃未満であれば特に限定されず、アクリル系ポリマー、ゴム系ポリマー、シリコーン系ポリマー、ポリウレタン系ポリマー、ポリエステル系ポリマー等の粘着剤として一般的に用いられる各種ポリマーを用いることができる。特に重合体(B)が(メタ)アクリル系重合体の場合には、(メタ)アクリル系重合体と相溶し易く透明性が高いアクリル系ポリマーが好適である。
[式(X)中、Tgはポリマー(A)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質量分率を表す。]
上記式(X)は、ポリマー(A)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。
以下にポリマー(A)の好適な具体例であるアクリル系ポリマーについて詳述する。
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2-ヒドロキシブチル、(メタ)アクリル酸3-ヒドロキシプロピル、(メタ)アクリル酸4-ヒドロキシブチル、(メタ)アクリル酸6-ヒドロキシヘキシル、(メタ)アクリル酸8-ヒドロキシオクチル、(メタ)アクリル酸10-ヒドロキシデシル、(メタ)アクリル酸12-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ヒドロキシル基含有モノマー;
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;
酢酸ビニル、プロピオン酸ビニル等のビニルエステル類;
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含有モノマー;
(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、(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;
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;
アクリロイルモルホリン;
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、ジシクロペンタニル(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、フェノキシエチル(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。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。
(メタ)アクリル系重合体(B)(以下、適宜「重合体(B)」と称する。)は、重量平均分子量が10000以上50000未満であることを特徴とする。前記(メタ)アクリル系重合体は、ポリオルガノシロキサン骨格を有するモノマーをモノマー単位として含むことが好ましい。
モノマー混合物の官能基当量(g/mol)=(モノマー1の官能基当量×モノマー1の配合量+モノマー2の官能基当量×モノマー2の配合量+・・・+モノマーnの官能基当量×モノマーnの配合量)/(モノマー1の配合量+モノマー2の配合量+・・・+モノマーnの配合量)
(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C1-20アルキルエステル[好ましくは(メタ)アクリル酸C1-10アルキルエステル、さらに好ましくは(メタ)アクリル酸C1-6アルキルエステル、特に好ましくは(メタ)アクリル酸C2-6アルキルエステル];
(メタ)アクリル酸ジシクロペンタニル、(メタ)アクリル酸イソボルニル、(メタ)アクリル酸1-アダマンチルのような脂環式炭化水素基を有する(メタ)アクリル酸エステル;
(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;
アクリロイルモルホリン、ジメチルアクリルアミド、ジエチルアクリルアミド、ジメチルアミノプロピルアクリルアミド、イソプロピルアクリルアミド、ヒドロキシエチルアクリルアミド等のアミド基含有ビニルモノマー;
N-ビニル-2-カプロラクタム等のN-ビニルカプロラクタム等のラクタム系モノマー;
等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モノマーは単独であるいは2種以上を組み合わせて使用することができる。 特にメタクリル酸メチルおよび/またはメタクリル酸ブチルを用いることが好ましい。(メタ)アクリル酸エステルモノマーの含有量は、重合体(B)の全モノマー成分に対して10質量%以上95質量%以下であることが好ましく、20質量%以上90質量%以下であることがより好ましく、30質量%以上85質量%以下であることがさらに好ましい。
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)オキシアルキレンのジ(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、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;
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、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;
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;
(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;
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;
(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;
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)アクリル酸エステルと共重合させることができる。
粘着剤組成物は、上述したポリマー(A)、および重合体(B)を必須成分として含有する。重合体(B)の含有量は、ポリマー(A)100質量部に対して、0.1質量部以上20質量部以下であるが、好ましくは0.3質量部~17質量部であり、より好ましくは0.4質量部~15質量部であり、さらに好ましくは、0.5質量部~12質量部である。本重合体(B)を20質量部を超えて添加すると、本実施の形態に係る粘着剤組成物で形成した粘着剤層の加熱後の粘着力の低下を引き起こす。また、重合体(B)の添加量が0.1質量部より少ない場合は、被着体貼り合わせ時の粘着力抑制効果が弱く、リワークができない不具合が生じる場合がある。
前記ロジン誘導体としては、例えば、
ロジン類(未変性ロジン、変性ロジンや、各種ロジン誘導体など)にフェノールを酸触媒で付加させ熱重合することにより得られるロジンフェノール系樹脂;
未変性ロジンをアルコール類によりエステル化したロジンのエステル化合物(未変性ロジンエステル)や、重合ロジン、安定化ロジン、不均化ロジン、完全水添ロジン、部分水添ロジンなどの変性ロジンをアルコール類によりエステル化した変性ロジンのエステル化合物(重合ロジンエステル、安定化ロジンエステル、不均化ロジンエステル、完全水添ロジンエステル、部分水添ロジンエステルなど)などのロジンエステル系樹脂;
未変性ロジンや変性ロジン(重合ロジン、安定化ロジン、不均化ロジン、完全水添ロジン、部分水添ロジンなど)を不飽和脂肪酸で変性した不飽和脂肪酸変性ロジン系樹脂;
ロジンエステル系樹脂を不飽和脂肪酸で変性した不飽和脂肪酸変性ロジンエステル系樹脂;
未変性ロジン、変性ロジン(重合ロジン、安定化ロジン、不均化ロジン、完全水添ロジン、部分水添ロジンなど)、不飽和脂肪酸変性ロジン系樹脂や不飽和脂肪酸変性ロジンエステル系樹脂におけるカルボキシル基を還元処理したロジンアルコール系樹脂;
未変性ロジン、変性ロジンや、各種ロジン誘導体等のロジン系樹脂(特に、ロジンエステル系樹脂)の金属塩などが挙げられる。
脂肪族系炭化水素樹脂[炭素数4~5のオレフィンやジエン(ブテン-1、イソブチレン、ペンテン-1等のオレフィン;ブタジエン、1,3-ペンタジエン、イソプレン等のジエンなど)などの脂肪族炭化水素の重合体など]、
脂肪族系環状炭化水素樹脂[いわゆる「C4石油留分」や「C5石油留分」を環化二量体化した後重合させた脂環式炭化水素系樹脂、環状ジエン化合物(シクロペンタジエン、ジシクロペンタジエン、エチリデンノルボルネン、ジペンテンなど)の重合体又はその水素添加物、下記の芳香族系炭化水素樹脂や脂肪族・芳香族系石油樹脂の芳香環を水素添加した脂環式炭化水素系樹脂など]、
芳香族系炭化水素樹脂[炭素数が8~10であるビニル基含有芳香族系炭化水素(スチレン、ビニルトルエン、α-メチルスチレン、インデン、メチルインデンなど)の重合体など]、
脂肪族・芳香族系石油樹脂(スチレン-オレフィン系共重合体など)、脂肪族・脂環族系石油樹脂、水素添加炭化水素樹脂、クマロン系樹脂、クマロンインデン系樹脂などが挙げられる。
続いて、上述の組成を有する粘着剤組成物を含む粘着剤層を有する粘着シートの構造について説明する。
ポリエチレン、ポリプロピレン、ポリ-1-ブテン、ポリ-4-メチル-1-ペンテン、エチレン・プロピレン共重合体、エチレン・1-ブテン共重合体、エチレン・酢酸ビニル共重合体、エチレン・エチルアクリレート共重合体、エチレン・ビニルアルコール共重合体などのポレオレフィンフィルム、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレートなどのポリエステルフィルム、ポリアクリレートフィルム、ポリスチレンフィルム、ナイロン6、ナイロン6,6、部分芳香族ポリアミドなどのポリアミドフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルム、ポリカーボネート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。
2-エチルヘキシルアクリレート(2EHA)95質量部、アクリル酸(AA)5質量部、および重合溶媒として酢酸エチル200質量部を撹拌羽根、温度計、窒素ガス導入管、冷却器を備えた4つ口フラスコに投入した。そして、60℃にて窒素雰囲気下で2時間撹拌した後、熱重合開始剤としてアゾビスイソブチロニトリル0.2質量部を投入し、60℃で6時間反応を行った。得られたポリマーの重量平均分子量は110万であった。
2-エチルヘキシルアクリレート(2EHA)94質量部、アクリル酸(AA)6質量部、光重合開始剤(商品名:イルガキュア184、BASF社製)0.05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)0.05質量部を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質量%の部分重合物(アクリル系ポリマーシロップ)を得た。
2-エチルヘキシルアクリレート(2EHA)29質量部、ブチルアクリレート(BA)68質量部、アクリル酸(AA)3質量部、4-ヒドロキシブチルアクリレート0.05質量部、および重合溶媒としてトルエン150質量部を撹拌羽根、温度計、窒素ガス導入管、冷却器を備えた4つ口フラスコに投入した。そして、60℃にて窒素雰囲気下で2時間撹拌した後、熱重合開始剤としてアゾビスイソブチロニトリル0.1質量部を投入し、60℃で6時間反応を行った。得られたポリマーの重量平均分子量は45万であった。
2-エチルヘキシルアクリレート(2EHA)96質量部、ヒドロキシエチルアクリレート(HEA)4質量部、および重合溶媒として酢酸エチル150質量部を撹拌羽根、温度計、窒素ガス導入管、冷却器を備えた4つ口フラスコに投入した。そして、60℃にて窒素雰囲気下で2時間撹拌した後、熱重合開始剤としてアゾビスイソブチロニトリル0.2質量部を投入し、60℃で6時間反応を行った。得られたポリマーの重量平均分子量は55万であった。
トルエン100質量部、メチル(メタ)クリレート(MMA)40質量部、ブチル(メタ)クリレート(BMA)20質量部、2-エチルヘキシル(メタ)クリレート(2-EHMA)20質量部、官能基当量が900g/molのポリオルガノシロキサン骨格含有(メタ)クリレートモノマー(商品名:X-22-174ASX、信越化学工業株式会社製)8.7質量部、官能基当量が4600g/molのポリオルガノシロキサン骨格含有(メタ)クリレートモノマー(商品名:KF-2012、信越化学工業株式会社製)11.3質量部および連鎖移動剤としてチオグリコール酸メチル0.51質量部を撹拌羽根、温度計、窒素ガス導入管、冷却器、滴下ロートを備えた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時間撹拌した後、熱重合開始剤としてアゾビスイソブチロニトリル0.2質量部を投入し、70℃で2時間反応させた後に、熱重合開始剤としてアゾビスイソブチロニトリル0.1質量部を投入し、続いて80℃で5時間反応させた。得られた(メタ)アクリル系重合体1の重量平均分子量は20000であった。
(メタ)アクリル系重合体2、3の各重合体については、モノマー組成、溶剤の種類、連鎖移動剤の質量部を表1に記載の要領で添加したこと以外、(メタ)アクリル系重合体1と同様にして作製した。
・MMA:メチルメタクリレート Tg105℃
・BMA:ブチルメタクリレート Tg20℃
・2EHMA:2-エチルヘキシルメタクリレート Tg-10℃
・X-22-174ASX:ポリオルガノシロキサン骨格含有メタクリレートモノマー 官能基当量が900g/mol 信越化学工業社製
・KF-2012:ポリオルガノシロキサン骨格含有メタクリレートモノマー 信越化学工業社製 官能基当量が4600g/mol
重合体の重量平均分子量は、GPC装置(東ソー社製、HLC-8220GPC)を用いて測定を行った。測定条件は下記の通りであり、標準ポリスチレン換算により分子量を求めた。
・サンプル濃度:0.2wt%(テトラヒドロフラン(THF)溶液)
・サンプル注入量:10μl
・溶離液:THF
・流速:0.6ml/min
・測定温度:40℃
・カラム:
サンプルカラム;TSKguardcolumn SuperHZ-H(1本)+TSKgel SuperHZM-H(2本)
リファレンスカラム;TSKgel SuperH-RC(1本)
・検出器:示差屈折計(RI)
(粘着剤組成物の調製)
上述した(メタ)アクリル系ポリマー1を100質量部に、上述した(メタ)アクリル系重合体1を7質量部、架橋剤としてコロネートLを3質量部を添加した後、これらを均一に混合して粘着剤組成物(1)を調製した。
上記粘着剤組成物(1)を、ポリエステルフィルム(商品名:ダイアホイルMRF、三菱樹脂株式会社製)の剥離処理面に塗布し、110℃2分間加熱して、厚さ20μmの粘着剤層を形成した。次いで、上記粘着剤層の表面に、厚さ25μmのポリエチレンテレフタラートフィルムを貼り合せて粘着シートを作製した。
実施例2~5,7の各粘着シートは、表2に記載のポリマー(A)100質量部と、表1に記載の重合体(B)と、表2に記載の粘着付与樹脂および架橋剤と、を表2に示す配合で用いたこと以外は実施例1と同様に粘着剤組成物を調整し、実施例1と同様の方法により作製された。比較例1~3の各粘着シートは、表2に記載のポリマー(A)を用いたこと以外は実施例1と同様に粘着剤組成物を調整し、実施例1と同様の方法により作製された。
(粘着剤層の作製)
(メタ)アクリル系ポリマー2が100質量部に対して(メタ)アクリル系重合体2を5質量部、TMPTAを0.1部添加した後、これらを均一に混合して、粘着剤組成物を得た。
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:ダイアホイルMRF、三菱樹脂株式会社製)の剥離処理面に、上述した粘着剤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、塗布された粘着剤組成物の表面に、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:ダイアホイルMRE、三菱樹脂株式会社製)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、粘着剤組成物の塗布層(粘着剤層)を酸素から遮断した。このようにして得られた塗布層に、ケミカルライトランプ(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秒間照射して重合させ、粘着剤層シートを得た。その後、片方のポリエステルフィルムを剥離し、厚さ25μmのポリエチレンテレフタラートフィルムを貼り合せて粘着シートを作製した。
溶剤不溶成分率(ゲル分率)は、粘着剤組成物を、0.1gサンプリングして精秤(浸漬前の質量)し、これを約50mlの酢酸エチル中に室温(20~25℃)で1週間浸漬したのち、溶剤(酢酸エチル)不溶分を取り出し、該溶剤不溶分を130℃で2時間乾燥した後、秤量(浸漬・乾燥後の質量)して、溶剤不溶成分率算出式「溶剤不溶成分率(質量%)=[(浸漬・乾燥後の質量)/(浸漬前の質量)]×100」を用いて、算出した。溶剤不溶成分率の測定結果を表2に示す。
[定荷重剥離]
各実施例、および各比較例に係る粘着シートを幅10mm、長さ60mmのサイズ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2.0mmのABS板(品名:ABS-N-WN)を用意した。そして、粘着シートの他方の剥離ライナー(ポリエステルフィルム)を剥がし、2kgローラーを一往復させてABS板に粘着シートの粘着面を貼り付けた。
各実施例、および各比較例に係る粘着シートを20mm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2.0mmのABS板と、トルエンにて清浄化したSUS(430BA板)を用意した。そして、粘着シートの他方の剥離ライナー(ポリエステルフィルム)を剥がし、2kgローラーを往復させてABS板、SUS(430BA板)に粘着シートの粘着面を貼り付けた。
各実施例、および各比較例に係る粘着シートを幅20mm、長さ50mmのサイズに切断したものを試験片とした。そして、粘着シートの他方の剥離ライナー(ポリエステルフィルム)を剥がし、イソプロピルアルコールで清浄化した厚さ1.0mmのガラス板に、2kgローラーを1往復にて、粘着シートの粘着面を貼り付けた。その後、23℃、50%RHの環境下に24時間経過後、剥離可能かどうか評価した。容易に剥離できる場合を良好(○)とし、剥離できず被着体が破壊される場合を不良(×)とした。リワーク性評価の結果を表3に示す。
[せん断貯蔵弾性率の測定]
せん断貯蔵弾性率は、動的粘弾性測定により求めた。粘着シートを積層して、厚さ約1.5mmの積層体(積層粘着剤層)を作製し、測定サンプルとした。その測定サンプルを、動的粘弾性測定装置(装置名「ARES」、(ティー・エイ・インスツルメント社製)を用いて、周波数1Hz、昇温速度5℃/分の条件で、-20~100℃の温度範囲で測定して、せん断貯蔵弾性率を算出した。各実施例および各比較例に係る粘着シートを80℃で5分加熱する前後での23℃のせん断貯蔵弾性率の測定結果を表3に示す。
Claims (14)
- 基材と、
前記基材の少なくとも片側に積層されている粘着剤層と、を有する粘着シートであって、
前記粘着剤層は、重量平均分子量が10000以上50000未満である(メタ)アクリル系重合体を含み、
該粘着剤層をABS板に対して貼り合わせてから30分間経過後の粘着力が1.0[N/20mm]以下であり、
該粘着剤層をABS板に対して貼り合わせてから24時間経過後の粘着力が2.5[N/20mm]以下であり、
該粘着剤層をABS板に対して貼り合わせてから80℃で5分間加熱し、23℃で30分間経過後の粘着力が6.5[N/20mm]以上である、
ことを特徴とする粘着シート。 - 前記(メタ)アクリル系重合体は、ポリオルガノシロキサン骨格を有するモノマーをモノマー単位として含む請求項1に記載の粘着シート。
- 前記粘着剤層は、
ガラス転移温度が0℃未満のポリマー100質量部と、
前記(メタ)アクリル系重合体0.1~20質量部と、
を含むことを特徴とする請求項1乃至3のいずれか1項に記載の粘着シート。 - 前記粘着剤層は、さらに架橋剤を含むことを特徴とする請求項1乃至4のいずれか1項に記載の粘着シート。
- 前記粘着剤層は、80℃で5分加熱する前後のせん断貯蔵弾性率の変化率が2.0倍以下であることを特徴とする請求項1乃至5のいずれか1項に記載の粘着シート。
- 前記粘着剤層は、80℃で5分加熱する前後のせん断貯蔵弾性率の変化率が1.0~1.3倍であることを特徴とする請求項1乃至5のいずれか1項に記載の粘着シート。
- 前記ガラス転移温度が0℃未満のポリマーは、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50質量%以上含有するポリマーであることを特徴とする請求項4に記載の粘着シート。
- 前記ガラス転移温度が0℃未満のポリマーは、炭素数6~10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50質量%以上含有するポリマーであることを特徴とする請求項4に記載の粘着シート。
- 前記(メタ)アクリル系重合体の重量平均分子量が15000以上40000未満であることを特徴とする請求項1乃至9のいずれか1項に記載の粘着シート。
- 前記ポリオルガノシロキサン基含有モノマーの官能基当量が1500g/mol以上5000g/mol未満であることを特徴とする請求項3に記載の粘着シート
- 前記(メタ)アクリル系重合体は、ポリオルガノシロキサン骨格を有するモノマーと、(メタ)アクリル酸エステルモノマーとの共重合体であることを特徴とする請求項2乃至11のいずれか1項に記載の粘着シート。
- 前記(メタ)アクリル系重合体を構成する(メタ)アクリル酸エステルモノマーは、(メタ)アクリル酸C1-6アルキルエステルであることを特徴とする請求項12に記載の粘着シート。
- 前記(メタ)アクリル酸エステルモノマーの含有量は、前記(メタ)アクリル系重合体を構成する全モノマー成分に対して10質量%以上95質量%以下であることを特徴とする請求項12または13に記載に記載の粘着シート。
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US10738221B2 (en) | 2020-08-11 |
CN106459692B (zh) | 2018-03-20 |
JPWO2015190441A1 (ja) | 2017-04-20 |
US20170081557A1 (en) | 2017-03-23 |
JP5951153B2 (ja) | 2016-07-13 |
KR20170021912A (ko) | 2017-02-28 |
KR20160130315A (ko) | 2016-11-10 |
CN106459692A (zh) | 2017-02-22 |
KR101740211B1 (ko) | 2017-05-25 |
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