WO2014157445A1 - 両面粘着シート - Google Patents

両面粘着シート Download PDF

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Publication number
WO2014157445A1
WO2014157445A1 PCT/JP2014/058734 JP2014058734W WO2014157445A1 WO 2014157445 A1 WO2014157445 A1 WO 2014157445A1 JP 2014058734 W JP2014058734 W JP 2014058734W WO 2014157445 A1 WO2014157445 A1 WO 2014157445A1
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WO
WIPO (PCT)
Prior art keywords
sensitive adhesive
pressure
adhesive layer
release film
film
Prior art date
Application number
PCT/JP2014/058734
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English (en)
French (fr)
Japanese (ja)
Inventor
敦史 黒川
雅康 加茂
Original Assignee
リンテック株式会社
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Publication date
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to JP2015508650A priority Critical patent/JP6300788B2/ja
Priority to CN201480013447.0A priority patent/CN105008478B/zh
Priority to KR1020157028990A priority patent/KR102069612B1/ko
Publication of WO2014157445A1 publication Critical patent/WO2014157445A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • 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
    • C09J7/403—Adhesives in the form of films or foils characterised by release liners characterised by the structure of the release feature
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • 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
    • B32B2405/00—Adhesive articles, e.g. adhesive tapes
    • 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
    • B32B2457/00—Electrical equipment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • C09J2301/1242—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape the opposite adhesive layers being different
    • 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

Definitions

  • the present invention relates to a double-sided pressure-sensitive adhesive sheet.
  • An optical functional film such as a polarizing plate is fixed by using a double-sided pressure-sensitive adhesive sheet composed of a member such as a liquid crystal cell and an adhesive. Moreover, such a double-sided adhesive sheet forms an adhesive layer by apply
  • the conventional double-sided pressure-sensitive adhesive sheet has not been able to sufficiently prevent the generation of crushed skin.
  • a part of the pressure-sensitive adhesive layer sticks to one release film, and a pressure-sensitive adhesive layer that is smooth and has a good appearance does not remain on the other release film.
  • a phenomenon called so-called crying separation occurred.
  • the object of the present invention is to prevent both of the generation of wrinkles on the surface of the pressure-sensitive adhesive layer and the transfer phenomenon called so-called crying separation when the roll is wound and stored. It is to provide an adhesive sheet.
  • an adhesive layer comprising a first surface and a second surface; A first release film adhered to the first surface of the pressure-sensitive adhesive layer; A second release film adhered to the second surface of the pressure-sensitive adhesive layer, The peeling force from the pressure-sensitive adhesive layer of the second release film is smaller than the peeling force from the pressure-sensitive adhesive layer of the first release film,
  • the arithmetic average roughness Ra of the surface opposite to the surface in contact with the pressure-sensitive adhesive layer of the first release film and the second release film is 5 to 35 nm, and the maximum protrusion height Rp is 50.
  • a double-sided pressure-sensitive adhesive sheet characterized by being -400 nm.
  • the peel force from the pressure-sensitive adhesive layer of the first release film is X [mN / 25 mm]
  • the peel force from the pressure-sensitive adhesive layer of the second release film is Y [mN / 25 mm].
  • the double-sided pressure-sensitive adhesive sheet according to any one of (1) to (4), wherein the double-sided pressure-sensitive adhesive sheet satisfies the relationship of XY ⁇ 5.
  • the present invention for example, it is used for sticking an optical functional film such as a polarizing plate, and a plurality of minute irregularities are generated on the surface of the pressure-sensitive adhesive layer when stored in a roll shape. It is possible to provide a double-sided pressure-sensitive adhesive sheet capable of preventing the transfer phenomenon referred to as crying separation. Moreover, it becomes possible to provide the double-sided adhesive sheet which can suppress the electric charging at the time of drawing out a blocking and peeling film from a roll.
  • FIG. 1 is a cross-sectional view of the double-sided pressure-sensitive adhesive sheet of the present invention.
  • the double-sided pressure-sensitive adhesive sheet of the present invention is used, for example, for bonding an optical functional film such as a polarizing plate and a member such as a liquid crystal cell.
  • FIG. 1 is a cross-sectional view of the double-sided pressure-sensitive adhesive sheet of the present invention.
  • the double-sided pressure-sensitive adhesive sheet 1 includes a pressure-sensitive adhesive layer 10 having a first surface 101 and a second surface 102, and a first surface provided on the first surface 101 of the pressure-sensitive adhesive layer 10.
  • the release film 11 and the second release film 12 provided on the second surface 102 of the pressure-sensitive adhesive layer 10 are included.
  • the pressure-sensitive adhesive layer 10 does not have anything that becomes a support after the first release film 11 and the second release film 12 have been removed.
  • the double-sided pressure-sensitive adhesive sheet of the present invention is the double-sided pressure-sensitive adhesive sheet 1 having the pressure-sensitive adhesive layer 10, the first release film 11, and the second release film 12, and has the following characteristics.
  • the peeling force from the adhesive layer 10 of the second release film 12 is configured to be smaller than the peeling force from the adhesive layer 10 of the first release film 11, and the first release film 11 and the first release film 11 2 is characterized in that the arithmetic average roughness Ra of the surface opposite to the surface in contact with the adhesive layer 10 of the release film 12 is 5 to 35 nm, and the maximum protrusion height Rp is 50 to 400 nm.
  • the arithmetic average roughness Ra of the surface opposite to the surface in contact with the adhesive layer 10 of the release film 12 is 5 to 35 nm
  • the maximum protrusion height Rp is 50 to 400 nm.
  • the double-sided pressure-sensitive adhesive sheet 1 is rolled up and stored / conveyed, the first surface 101 and the second surface 102 of the pressure-sensitive adhesive layer 10 have minute irregularities (skin skin). ) Can be prevented.
  • the 2nd peeling film 12 is made into the adhesive layer 10 by making the peeling force from the adhesive layer 10 of the 2nd peeling film 12 smaller than the peeling force from the adhesive layer 10 of the 1st peeling film.
  • a part of the pressure-sensitive adhesive layer 10 sticks to the second release film 12, and the phenomenon that the pressure-sensitive adhesive layer in a smooth and good appearance does not remain on the first release film, so-called crying It is possible to prevent the occurrence of a so-called transfer phenomenon.
  • the peeling force from the adhesive layer 10 means the peeling force measured as follows.
  • the peel force was measured in accordance with JIS-Z0237.
  • the double-sided pressure-sensitive adhesive sheet 1 was cut into a width of 25 mm and a length of 200 mm, and the release film was 300 mm / mm in a state where the pressure-sensitive adhesive layer 10 was fixed using a tensile tester. It shall be performed by pulling in the direction of 180 ° at a speed of minutes.
  • the pressure-sensitive adhesive layer 10 has a first surface 101 and a second surface 102.
  • pressure-sensitive adhesives such as acrylic pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, and urethane-based pressure-sensitive adhesives can be used without limitation, but acrylic pressure-sensitive adhesives are preferred.
  • acrylic pressure-sensitive adhesives are preferred.
  • examples of the form of the pressure-sensitive adhesive include solvent type and emulsion type.
  • acrylic adhesives it is preferable to use a (meth) acrylic acid ester copolymer.
  • the acrylic ester copolymer has high transparency and can be suitably used for optical parts. Moreover, the acrylic ester copolymer is excellent in durability.
  • the pressure-sensitive adhesive is an acrylic pressure-sensitive adhesive
  • a polymer mainly comprising a main monomer component that provides tackiness, a comonomer component that provides adhesiveness and cohesive force, a functional group-containing monomer component for improving crosslinking points and adhesion, or It can be composed of a copolymer.
  • main monomer components include ester moieties such as methyl acrylate, ethyl acrylate, butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, cyclohexyl acrylate, benzyl acrylate, and methoxyethyl acrylate.
  • ester moieties such as methyl acrylate, ethyl acrylate, butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, cyclohexyl acrylate, benzyl acrylate, and methoxyethyl acrylate.
  • alkyl methacrylates having 1 to 20 carbon atoms in the alkyl group, and methacrylic acid having 1 to 20 carbon atoms in the alkyl portion of the ester moiety such as butyl methacrylate, 2-ethylhex
  • Examples include acid alkyl esters.
  • Examples of the comonomer component include methyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl acetate, styrene, acrylonitrile, and the like.
  • the functional group-containing monomer component preferably contains at least one of a hydroxyl group, a carboxyl group, and an amino group as a functional group.
  • a hydroxyl group preferably contains at least one of 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid.
  • (Meth) acrylic such as 2-hydroxypropyl, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Acid hydroxyalkyl ester; (meth) acrylic acid monomethylaminoethyl, (meth) acrylic acid monoethylaminoethyl, (meth) acrylic acid monomethylaminopropyl, (meth) acrylic acid monoethylaminopropyl, etc.
  • Alkylaminoalkyl acrylic acid, Methacrylic acid, crotonic acid, maleic acid, itaconic acid, ethylenically unsaturated carboxylic acids such as citraconic acid.
  • the (meth) acrylic acid ester copolymer is not particularly limited with respect to the copolymerization form, and may be any of random, block, and graft copolymers.
  • the (meth) acrylic acid ester-based copolymer those having a mass average molecular weight of 500,000 or more are preferable, those having 600,000 to 2,000,000 are more preferable, and 700,000 to 180 are preferable. It is more preferable to use one of many.
  • the double-sided pressure-sensitive adhesive sheet 1 has sufficient adhesion to the adherend and adhesion durability, and can more effectively prevent the occurrence of floating and peeling.
  • the mass average molecular weight is a value in terms of polystyrene measured by a gel permeation chromatography (GPC) method.
  • the content of units derived from the functional group-containing monomer component is preferably in the range of 0.01 to 10% by mass.
  • the content is 0.01% by mass or more, crosslinking is sufficient due to a reaction with a crosslinking agent described later, and durability is improved.
  • a more preferable content of the unit derived from the functional group-containing monomer component is 0.05 to 7.0% by mass, and a range of 0.2 to 6.0% by mass is particularly preferable.
  • the (meth) acrylic acid ester copolymer (A) one type may be used, or two or more types may be used in combination.
  • an acrylic pressure-sensitive adhesive usually does not have an unsaturated bond in the molecule, so that stability to light and oxygen can be improved. Furthermore, a pressure-sensitive adhesive having quality and characteristics according to the application can be obtained by appropriately selecting the type and molecular weight of the monomer.
  • the pressure-sensitive adhesive layer 10 is prepared by preparing a pressure-sensitive adhesive solution (pressure-sensitive adhesive composition) in which such a pressure-sensitive adhesive is dissolved in an organic solvent, and applying this onto the first release film 11 or the second release film 12. Can be formed.
  • a pressure-sensitive adhesive solution pressure-sensitive adhesive composition
  • Such a pressure-sensitive adhesive composition may be either a crosslinked type that undergoes crosslinking treatment or a non-crosslinked type that does not undergo crosslinking treatment, but a crosslinked type is more preferred.
  • a cross-linked type is used, a pressure-sensitive adhesive layer with better cohesion can be formed.
  • the crosslinking agent used in the crosslinking adhesive composition include isocyanate compounds, epoxy compounds, metal chelate compounds, metal alkoxides, metal salts, amine compounds, hydrazine compounds, and aldehyde compounds.
  • Examples of the organic solvent used for preparing the pressure-sensitive adhesive composition include toluene, xylene, methanol, ethanol, isobutanol, n-butanol, acetone, methyl ethyl ketone, tetrahydrofuran, and ethyl acetate.
  • the concentration of the pressure-sensitive adhesive composition is adjusted so that the solid content is in the range of about 5 to 60% by mass using these organic solvents for the convenience of coating.
  • Coating of the pressure-sensitive adhesive composition to the first release film 11 or the second release film 12 is, for example, a bar coating method, a reverse roll coating method, a knife coating method, a roll knife coating method, a gravure coating method, an air doctor.
  • the coating can be performed by a conventionally known coating method such as a coating method or a doctor blade coating method.
  • the average thickness of the pressure-sensitive adhesive layer 10 is preferably 3 to 30 ⁇ m, more preferably 5 to 28 ⁇ m. Thereby, it can be set as the thinness suitable for using for a thin display.
  • the proportion of the unevenness outside the range of ⁇ 0.2 ⁇ m from the reference surface in the first surface 101 of the pressure-sensitive adhesive layer 10 is preferably 20% or less.
  • the proportion of the unevenness outside the range of ⁇ 0.2 ⁇ m from the reference surface in the second surface 102 of the pressure-sensitive adhesive layer 10 is preferably 20% or less.
  • the first release film 11 is attached to the first surface 101 of the pressure-sensitive adhesive layer 10.
  • the first release film 11 has a function of protecting the pressure-sensitive adhesive layer 10.
  • the first release film 11 is a laminate in which a first release agent layer 111 and a first base film 112 are sequentially laminated from the side in contact with the pressure-sensitive adhesive layer 10. It is configured.
  • the first base film 112 has a function of imparting physical strength such as rigidity and flexibility to the first release film 11.
  • the material constituting the first base film 112 examples include various synthetic resins.
  • a polyester resin such as polybutylene terephthalate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, and polyethylene terephthalate. It is more preferable to use a resin.
  • the first base film 112 may be a single-layer film or a multilayer film having two or more layers made of the same or different materials. Such a multilayer film may be obtained by laminating films formed in advance through an adhesive layer as necessary, or by coating a resin film forming composition on a film formed in advance. But you can.
  • the resin layer forming composition for forming the resin layer is mainly composed of an epoxy compound, an acrylate compound, a urethane acrylate compound, a polyester compound, etc., and if necessary, a crosslinking agent, a catalyst, and photopolymerization start. And those containing an agent, an ultraviolet absorber and the like.
  • These composition for resin layer formation may have sclerosis
  • the arithmetic average roughness Ra of the outer surface of the first base film 112 is obtained by using the multilayer film in which the resin layer forming composition is coated on the film formed in advance and the resin layer is formed.
  • the maximum protrusion height Rp can be adjusted.
  • the first base film 112 may contain a filler.
  • the filler include silica, titanium oxide, calcium carbonate, kaolin, and aluminum oxide.
  • the thickness of the first base film 112 is not particularly limited, but is preferably 10 to 300 ⁇ m, and more preferably 15 to 200 ⁇ m.
  • the arithmetic average roughness Ra of the surface of the first release film 11 opposite to the surface in contact with the pressure-sensitive adhesive layer 10 is 5 to 35 nm, and more preferably 13 to 30 nm. Thereby, it is possible to more effectively prevent the skin from being generated on the first surface 101 and the second surface 102 of the pressure-sensitive adhesive layer 10 over time after winding the double-sided pressure-sensitive adhesive sheet 1 into a roll. it can.
  • the arithmetic average roughness Ra is less than the lower limit value, the first release film 11 may be blocked over time after the first release film 11 is wound into a roll, or the first release film 11 may be blocked. It is impossible to prevent the release film 11 from being charged when it is fed out from the roll.
  • the wound surface of the pressure-sensitive adhesive layer 10 may be damaged over time on the first surface 101 and the second surface 102 after the double-sided pressure-sensitive adhesive sheet 1 is rolled up. Can not be prevented.
  • the maximum protrusion height Rp on the surface opposite to the surface in contact with the pressure-sensitive adhesive layer 10 of the first release film 11 is 50 to 400 nm, and more preferably 90 to 240 nm.
  • the first release agent layer 111 has a function of imparting peelability to the first release film 11.
  • the first release agent layer 111 is formed by applying a first release agent layer-forming composition containing the first release agent to the surface of the first base film 112 and drying it.
  • the first release agent is not particularly limited, and examples thereof include alkyd compounds, acrylic compounds, silicone compounds, long-chain alkyl group-containing compounds, and fluorine compounds. Among these, as the first release agent, it is preferable to use an alkyd compound, an acrylic compound, a silicone compound, or a long-chain alkyl group-containing compound.
  • an alkyd compound having a crosslinked structure is generally used. Formation of the alkyd compound layer having a crosslinked structure can be performed, for example, by a method in which a layer made of a thermosetting composition containing an alkyd compound, a crosslinking agent, and optionally a curing catalyst is heated and cured.
  • the alkyd compound may be a modified product such as a long-chain alkyl-modified alkyd compound or a silicone-modified alkyd compound.
  • the acrylic compound an acrylic compound having a crosslinked structure is generally used.
  • the acrylic compound may be a modified product such as a long-chain alkyl-modified acrylic compound or a silicone-modified acrylic compound.
  • silicone compounds include silicone compounds having dimethylpolysiloxane as a basic skeleton.
  • examples of the silicone compound include an addition reaction type, a condensation reaction type, an ultraviolet curable type, and an electron beam curable type.
  • the addition reaction type silicone compound has high reactivity and excellent productivity, and has advantages such as little change in peel strength after production and no cure shrinkage compared to the condensation reaction type.
  • addition reaction type silicone compound examples include two or more alkenyl groups having 2 to 10 carbon atoms such as a vinyl group, an allyl group, a propenyl group, and a hexenyl group at the terminal and / or side chain of the molecule.
  • Organopolysiloxane is mentioned.
  • crosslinking agent and a catalyst it is preferable to use a crosslinking agent and a catalyst in combination.
  • crosslinking agent examples include, for example, organopolysiloxane having hydrogen atoms bonded to at least two silicon atoms in one molecule, specifically, a dimethylhydrogensiloxy group end-capped dimethylsiloxane-methylhydrogensiloxane copolymer. And trimethylsiloxy group end-capped dimethylsiloxane-methylhydrogensiloxane copolymer, trimethylsiloxy group end-capped methylhydrogenpolysiloxane, poly (hydrogensilsesquioxane), and the like.
  • the catalyst fine platinum, fine platinum adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complexes of chloroplatinic acid, white metal compounds such as palladium and rhodium Etc.
  • Examples of the long-chain alkyl group-containing compound include a polyvinyl carbamate obtained by reacting a polyvinyl alcohol polymer with a long-chain alkyl isocyanate having 8 to 30 carbon atoms, or a long-chain alkyl group having 8 to 30 carbon atoms with polyethyleneimine. An alkylurea derivative obtained by reacting isocyanate is used.
  • Fluorine compounds include fluorine silicone compounds and fluorine boron compounds.
  • An additive may be appropriately added to the first release agent composition.
  • the additive include a catalyst, a dye, and a dispersant.
  • the material of the first release agent layer forming composition described above so that the release force of the first release film 11 is greater than the release force of the second release film 12. is appropriately selected.
  • the first release agent composition may appropriately contain a dispersion medium or a solvent in order to bring the viscosity at the time of application to an appropriate range.
  • Preferred examples of the dispersion medium or solvent include aromatic hydrocarbons such as toluene, fatty acid esters such as ethyl acetate, ketones such as methyl ethyl ketone, and organic solvents such as aliphatic hydrocarbons such as hexane and heptane.
  • aromatic hydrocarbons such as toluene
  • fatty acid esters such as ethyl acetate
  • ketones such as methyl ethyl ketone
  • organic solvents such as aliphatic hydrocarbons such as hexane and heptane.
  • the content of the first release agent in the first release agent composition is not particularly limited, but is preferably 0.3 to 10% by mass.
  • gravure coating method for example, gravure coating method, bar coating method, spray coating method, spin coating method, air knife coating method, roll coating method, blade coating method, gate roll coating method, die coating method, etc.
  • a gravure coating method and a bar coating method are preferable, and a bar coating method is particularly preferable.
  • the drying temperature is not particularly limited, but is preferably 100 to 150 ° C., and the drying time is preferably 10 seconds to 1 minute.
  • the thickness of the first release agent layer is preferably from 0.01 to 5 ⁇ m, particularly preferably from 0.03 to 3 ⁇ m.
  • the first release film 11 has an arithmetic average roughness Ra of 5 to 50 nm on the surface in contact with the pressure-sensitive adhesive layer 10 (the outer surface of the first release agent layer 111), and its maximum protrusion height Rp. Is preferably 50 to 1000 nm, the arithmetic average roughness Ra of the surface in contact with the pressure-sensitive adhesive layer 10 is 13 to 50 nm, and the maximum protrusion height Rp is more preferably 120 to 1000 nm. Thereby, when the adhesive layer 10 is formed on the 1st peeling film 11, the surface shape of the 1st surface 101 of the adhesive layer 10 can be made favorable.
  • the proportion of the unevenness outside the range of ⁇ 0.2 ⁇ m from the reference surface on the outer surface of the first release agent layer 111 is 20% or less.
  • the second release film 12 is attached to the second surface 102 of the pressure-sensitive adhesive layer 10.
  • the second release film 12 has a function of protecting the pressure-sensitive adhesive layer 10.
  • the second release film 12 is a laminate in which a second release agent layer 121 and a second base film 122 are sequentially laminated from the side in contact with the pressure-sensitive adhesive layer 10. It is configured.
  • the same material as the first substrate film 112 described in the section of the first release film 11 described above can be used.
  • the arithmetic average roughness Ra of the surface of the second release film 12 opposite to the surface in contact with the pressure-sensitive adhesive layer 10 is 5 to 35 nm, and more preferably 12 to 30 nm. Thereby, when the double-sided pressure-sensitive adhesive sheet 1 is wound up in a roll shape, it is possible to more effectively prevent the skin from being generated on the first surface 101 and the second surface 102 of the pressure-sensitive adhesive layer 10. . On the other hand, if the arithmetic average roughness Ra is less than the lower limit value, the second release film 12 may block over time after the second release film 12 is wound into a roll, or the second release film 12 may be blocked. It is impossible to prevent the release film 12 from being charged when it is fed out from the roll.
  • the wound surface of the pressure-sensitive adhesive layer 10 may be damaged over time on the first surface 101 and the second surface 102 after the double-sided pressure-sensitive adhesive sheet 1 is rolled up. Can not be prevented.
  • the maximum protrusion height Rp on the surface opposite to the surface in contact with the pressure-sensitive adhesive layer 10 of the second release film 12 is 50 to 400 nm, more preferably 120 to 240 nm.
  • the second release agent layer 121 is formed by applying a second release agent layer-forming composition containing the second release agent to the surface of the second base film 122 and drying it.
  • the second release agent it can be appropriately selected from the materials constituting the first release agent described in the section of the first release film.
  • the material of the second release agent layer forming composition described above so that the release force of the second release film 12 is smaller than the release force of the first release film 11. is appropriately selected.
  • the second release agent layer 121 may be a single layer or a plurality of layers of two or more layers, but one layer is preferable for simplifying the operation.
  • the thickness of the second release agent layer 121 is preferably 0.01 to 5 ⁇ m, and more preferably 0.03 to 3 ⁇ m.
  • the second release film 12 has an arithmetic average roughness Ra of 5 to 50 nm on the surface in contact with the pressure-sensitive adhesive layer 10 (the outer surface of the second release agent layer 121), and its maximum protrusion height Rp. Is preferably 50 to 1000 nm, the arithmetic average roughness Ra of the surface in contact with the pressure-sensitive adhesive layer 10 is 13 to 50 nm, and the maximum protrusion height Rp is more preferably 120 to 1000 nm.
  • the proportion of the unevenness outside the range of ⁇ 0.2 ⁇ m from the reference surface on the outer surface of the second release agent layer 121 is 20% or less.
  • Example 1 Preparation of double-sided PSA sheet (Example 1) 1. Preparation of First Release Film A polyethylene terephthalate (PET) film (thickness 38 ⁇ m, arithmetic average roughness Ra: 20 nm, maximum protrusion height Rp: 203 nm) having the same front and back roughness was prepared as a first base film. .
  • PET polyethylene terephthalate
  • the first release agent layer-forming composition A having the following composition was applied with a bar coater so that the thickness after drying was 0.1 ⁇ m. And dried at 120 ° C. for 1 minute to provide a first release agent layer. This obtained the 1st peeling film.
  • Table 1 shows the projection height Rp and the ratio of the unevenness outside the range of ⁇ 0.2 ⁇ m from the reference surface on the first release agent layer side surface of the first release film.
  • first release agent layer-forming composition A Silicone resin solution containing organopolysiloxane with vinyl group and organopolysiloxane with hydrosilyl group (manufactured by Toray Dow Corning Co., Ltd., trade name “BY24-561”, solid content 30% by mass) in terms of solid content 30 parts by mass and 15 parts by mass of solid resin in terms of solid content of MQ resin (made by Toray Dow Corning Co., Ltd., trade name “SD7292”, solid content 71% by mass) having a vinyl group, and solid content concentration in toluene solvent was diluted and mixed so as to be 1.0% by mass.
  • 2 parts by mass of a platinum-based catalyst (trade name “SRX-212”, manufactured by Toray Dow Corning Co., Ltd., solid content: 100% by mass) was added to prepare a first release agent layer forming composition A.
  • Second Release Film A polyethylene terephthalate (PET) film (thickness 38 ⁇ m, arithmetic average roughness Ra: 19 nm, maximum protrusion height Rp: 194 nm) having the same front and back surface roughness was prepared as a second base film. .
  • PET polyethylene terephthalate
  • a second release agent layer-forming composition B having the following composition was applied to one surface of the second base film with a bar coater so that the thickness after drying was 0.1 ⁇ m. And dried at 120 ° C. for 1 minute to provide a second release agent layer.
  • Table 1 shows the protrusion height Rp and the ratio of the unevenness outside the range of ⁇ 0.2 ⁇ m from the reference surface on the surface of the second release film on the second release agent layer side.
  • Second release agent layer-forming composition B 100 parts by mass of silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name “KS847H”, solid content concentration 30% by mass) and 1 part by mass of a platinum-based catalyst (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name “CAT-PL50T”, solid content)
  • the second release agent layer forming composition B having a solid content concentration of 1% by mass was prepared by diluting with 100% by mass of toluene.
  • a part of the obtained solution was subjected to GPC measurement, and production of a polymer (A) having a mass average molecular weight of 1.6 million was confirmed.
  • 100 parts by mass (solid content) of the polymer (A) 0.15 parts by mass of a polyisocyanate-based crosslinking agent (trade name “Takenate D-110N”, solid content concentration 75% by mass, manufactured by Mitsui Chemicals), and silane
  • a coupling agent (“KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd., solid content concentration: 100% by mass
  • toluene was added as a solvent to adjust the solid content to 15% by mass.
  • An adhesive composition A was prepared.
  • the mass average molecular weight is a value in terms of polystyrene measured by a gel permeation chromatography (GPC) method.
  • Example 2 A double-sided PSA sheet was prepared in the same manner as in Example 1 except that the second release film was obtained as follows.
  • PET polyethylene terephthalate
  • the resin layer forming composition A is applied to the outer surface of the PET film with a bar coater, heated and dried at 150 ° C. for 40 seconds to cure the resin material, and the thickness is 0.6 ⁇ m.
  • a second substrate film was produced by forming a resin layer.
  • the thickness after drying the second release agent composition B on the surface (PET film side) opposite to the side on which the resin layer is formed in the second base film is 0.1 ⁇ m.
  • a second release film was prepared by coating with a bar coater and drying at 120 ° C. for 1 minute to provide a second release agent layer.
  • Table 1 shows the protrusion height Rp and the ratio of the unevenness outside the range of ⁇ 0.2 ⁇ m from the reference surface on the surface of the second release film on the second release agent layer side.
  • Example 3 A double-sided PSA sheet was produced in the same manner as in Example 2 except that the thickness of the resin layer of the second base film was 0.8 ⁇ m.
  • Example 4 A double-sided PSA sheet was prepared in the same manner as in Example 2 except that the thickness of the resin layer of the second base film was 0.5 ⁇ m.
  • Example 5 Except for changing the second base film of the second release film to a polyethylene terephthalate (PET) film (thickness 38 ⁇ m, arithmetic average roughness Ra: 32 nm, maximum protrusion height Rp: 230 nm) with the same roughness on both sides Produced a double-sided PSA sheet as in Example 1.
  • PET polyethylene terephthalate
  • the second base film of the second release film is a polyethylene terephthalate (PET) film (thickness 38 ⁇ m, surface on the second release agent layer side with different roughness on the front and back surfaces (arithmetic average roughness Ra: 40 nm, maximum (Projection height Rp: 900 nm), except for the surface opposite to the second release agent layer (arithmetic average roughness Ra: 19 nm, maximum projection height Rp: 194 nm)), the same as in Example 1 A double-sided PSA sheet was prepared.
  • PET polyethylene terephthalate
  • Example 7 The second substrate film of the second release film was changed to a polyethylene terephthalate (PET) film (thickness 38 ⁇ m, arithmetic average roughness Ra: 15 nm, maximum protrusion height Rp: 131 nm) having the same front and back roughness. Except for the above, a double-sided PSA sheet was prepared in the same manner as in Example 1.
  • PET polyethylene terephthalate
  • the first base film of the first release film and the second base film of the second release film are made of a polyethylene terephthalate (PET) film (thickness: 38 ⁇ m, arithmetic average roughness Ra: 10 nm).
  • PET polyethylene terephthalate
  • a double-sided PSA sheet was prepared in the same manner as in Example 1 except that the maximum protrusion height Rp was changed to 93 nm.
  • the first base film of the first release film and the second base film of the second release film are made of a polyethylene terephthalate (PET) film (thickness: 38 ⁇ m, arithmetic average roughness Ra: 40 nm).
  • PET polyethylene terephthalate
  • a double-sided PSA sheet was prepared in the same manner as in Example 1 except that the maximum protrusion height Rp was changed to 535 nm.
  • PET polyethylene terephthalate
  • the resin layer forming composition A is applied to the outer surface of the PET film with a bar coater, heated and dried at 150 ° C. for 40 seconds to cure the resin material, and the thickness is 0.6 ⁇ m.
  • a second substrate film was produced by forming a resin layer.
  • the thickness of the second release agent composition B after drying is 0.1 ⁇ m on the surface (PET film side) opposite to the surface on which the resin layer is formed in the second base film.
  • a second release film was prepared by coating with a bar coater and drying at 120 ° C. for 1 minute to provide a second release agent layer.
  • Comparative Example 4 A double-sided PSA sheet was prepared in the same manner as Comparative Example 2 except that the thickness of the release agent layer of the second release film was 0.6 ⁇ m.
  • the surface of the adhesive layer side of the first release film and the second release film used in the double-sided adhesive sheet of each example and comparative example and the surface of the base film side (opposite to the surface in contact with the adhesive layer)
  • the arithmetic average roughness Ra and the maximum protrusion height Rp of the side surface were measured according to JIS B 0601-1994 using a surface roughness measuring instrument SV3000S4 (stylus type) manufactured by Mitutoyo Corporation.
  • the proportion of the unevenness outside the range of ⁇ 0.2 ⁇ m from the reference surface on the surface of the pressure-sensitive adhesive layer side of the first release film and the second release film used in the double-sided pressure-sensitive adhesive sheet of each Example and Comparative Example is Using the optical interference type surface shape observation device “Wyko NT-1100” [Veeco Co., Ltd.], stitching was performed at 2.5 magnifications in the VSI mode, and the obtained surface shape image in the range of 4 ⁇ 4 mm To binarize the image with a portion outside the range of ⁇ 0.2 ⁇ m from the reference surface and a portion within the range of ⁇ 0.2 ⁇ m, and the unevenness of the portion outside the range of ⁇ 0.2 ⁇ m from the reference surface The area ratio was calculated.
  • the peel strength of the first release film and the second release film with respect to the PSA layer is in accordance with JIS-Z0237.
  • the measurement was performed by pulling the first release film or the second release film in the 180 ° direction at a speed of 300 mm / min with the pressure-sensitive adhesive layer fixed using a tensile tester.
  • the double-sided adhesive sheet of each Example and each comparative example is a reference surface about each of the 1st surface (1st peeling film side) and 2nd surface (2nd peeling film side) of an adhesive layer.
  • the area occupancy ratio of the irregularities outside the range of ⁇ 0.2 ⁇ m was measured. If the surface of the pressure-sensitive adhesive layer is smooth, the value is close to 0%.
  • stitching was performed at 2.5 magnifications in the VSI mode.
  • the double-sided pressure-sensitive adhesive sheet of the present invention was free from appearance defects because it was prevented from being crushed. Moreover, the double-sided adhesive sheet of this invention was excellent in the peelability of each peeling film, blocking resistance, and antistatic property. Moreover, the double-sided pressure-sensitive adhesive sheet of the present invention prevents the occurrence of a transfer phenomenon called crying separation. On the other hand, satisfactory results were not obtained in the comparative example.
  • the double-sided pressure-sensitive adhesive sheet of the present invention comprises a pressure-sensitive adhesive layer comprising a first surface and a second surface, a first release film adhered to the first surface of the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive.
  • a second release sheet adhered to the second surface of the layer, and the release force of the second release film from the adhesive layer is the adhesive of the first release film.
  • An arithmetic average roughness Ra of the surface opposite to the surface in contact with the pressure-sensitive adhesive layer of the first release film and the second release film is smaller than the peel force from the layer, and is 5 to 35 nm; and
  • the maximum protrusion height Rp is 50 to 400 nm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
PCT/JP2014/058734 2013-03-28 2014-03-27 両面粘着シート WO2014157445A1 (ja)

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JP2019059203A (ja) * 2017-09-28 2019-04-18 東レフィルム加工株式会社 離型フィルムおよびそれを用いた積層体
JP2020132811A (ja) * 2019-02-25 2020-08-31 日東電工株式会社 積層シートのロール体
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TWI579364B (zh) 2017-04-21
JPWO2014157445A1 (ja) 2017-02-16
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CN105008478A (zh) 2015-10-28
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