Classifications

• • 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
  • C09J121/00—Adhesives based on unspecified rubbers
• • 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
  • C09J107/00—Adhesives based on natural rubber
• • 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
  • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
  • B32B25/12—Layered products comprising a layer of natural or synthetic rubber comprising natural rubber
• • 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
  • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
  • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
• • 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
• • 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
  • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
  • C09J109/06—Copolymers with styrene
• • 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
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
  • C09J123/28—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
• • 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
  • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J153/02—Vinyl aromatic monomers and conjugated dienes
  • C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/22—Plastics; Metallised plastics
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/22—Plastics; Metallised plastics
  • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C09J7/245—Vinyl resins, e.g. polyvinyl chloride [PVC]
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
• • C—CHEMISTRY; METALLURGY
  • 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
• • 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
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
• • 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
  • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
  • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber 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
  • B32B2509/00—Household appliances
• • 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
  • B32B2605/00—Vehicles
• • 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
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • 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
  • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
• • 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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• • 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
  • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J151/006—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • 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
  • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J151/04—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to rubbers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
  • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2407/00—Presence of natural rubber
• • 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
  • C09J2427/00—Presence of halogenated polymer
  • C09J2427/006—Presence of halogenated polymer in the substrate
• • 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
  • C09J2451/00—Presence of graft polymer

Definitions

• the present invention relates to an adhesive film, and is suitable for, for example, a binding tape for binding an electric wire / cable such as an automobile wire harness by forming the adhesive film into a tape shape, and a marking film displaying characters and figures on the surface of the adhesive film. Can be used.
• a softening agent is blended with the base material of the adhesive film in order to soften the base material.
• the softener sometimes moved from the base material to the pressure-sensitive adhesive layer with time.
• the pressure-sensitive adhesive softens and is squeezed out to the side of the rolled product, causing stickiness (side stick), and the pressure-sensitive adhesive cohesive force and pressure-sensitive adhesive force decrease.
• the adhesive film peeled off the adherend. Further, when the adhesive film is peeled off, a part of the adhesive and the softening agent remain on the adherend, which may contaminate the adherend.
• Patent Document 1 and Patent Document 2 As an adhesive film that suppresses the migration of such a softener, an adhesive film in which a curable primer is provided between a soft substrate and an adhesive layer has been proposed (for example, Patent Document 1 and Patent Document 2). .
• these pressure-sensitive adhesive films are overlapped when wound in a roll shape unless the adhesive surface is protected with a base material separator or the back surface of the base material is not surface-treated.
• the surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film and the back surface of the other pressure-sensitive adhesive film are in direct contact with each other, and the softening agent moves between the pressure-sensitive adhesive films. Therefore, there is a problem that the movement of the softening agent cannot be sufficiently suppressed unless the glue surface and the back surface are further protected.
• An object of the present invention is to provide a pressure-sensitive adhesive film in which the softening agent is little transferred from the base material to the pressure-sensitive adhesive, has excellent pressure-sensitive adhesive force, unwinding force, and holding power and has little adhesive residue on the adherend.
• a pressure-sensitive adhesive film comprising a base material comprising a vinyl chloride resin composition and a pressure-sensitive adhesive layer formed on at least one side of the base material, wherein the pressure-sensitive adhesive layer comprises (i) natural rubber and / Or an adhesive base agent made of styrene-butadiene rubber, (Ii) a graft polymer obtained by graft polymerizing a natural rubber and / or a styrene-butadiene rubber with a (meth) acrylic acid ester having an alkyl group, and (iii) a softening agent, (A) The softener is blended in an amount of 0.3 to 4% by weight based on the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer.
• the graft polymer is blended in an amount of 10 to 50 parts by mass with respect to 100 parts by mass of an adhesive base agent made of natural rubber and / or styrene-butadiene rubber.
• the (meth) acrylic acid ester having an alkyl group is selected from the group consisting of methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and mixtures thereof (1)
• the pressure-sensitive adhesive film according to (1), wherein the softening agent is diisononyl phthalate.
• the transfer of the softening agent from a base material to an adhesive can be obtained, and the adhesive film which is excellent in adhesive force, unwinding force, and holding power, and has little adhesive residue to a to-be-adhered body can be obtained.
• the pressure-sensitive adhesive film of the present invention is a pressure-sensitive adhesive film composed of a base material made of a vinyl chloride resin composition and a pressure-sensitive adhesive layer formed on at least one side of the base material, and the pressure-sensitive adhesive layer comprises: Contains 0.3 to 4% by mass of a softening agent based on the pressure-sensitive adhesive, and a graft polymer obtained by graft-polymerizing a natural rubber and / or styrene-butadiene rubber with a (meth) acrylic acid ester having an alkyl group. It is formed by the pressure sensitive adhesive.
• the vinyl chloride resin composition constituting the substrate is not particularly limited as long as it contains a vinyl chloride resin as a main component of the resin component.
• the vinyl chloride resin is a homopolymer resin that is a conventionally known homopolymer of vinyl chloride or various conventionally known copolymer resins, and is not particularly limited.
• copolymer resin a conventionally known copolymer resin can be used.
• a copolymer resin of vinyl chloride and vinyl esters such as vinyl chloride-vinyl acetate copolymer resin and vinyl chloride-vinyl propionate copolymer resin; vinyl chloride-butyl acrylate Copolymer resin, copolymer resin of vinyl chloride and acrylate such as vinyl chloride-ethyl acrylate copolymer resin; copolymer resin of vinyl chloride and olefin such as vinyl chloride-ethylene copolymer resin, vinyl chloride-propylene copolymer resin Vinyl chloride-acrylonitrile copolymer resin and the like are typically exemplified.
• a homopolymer resin a vinyl chloride-ethylene copolymer resin, a vinyl chloride-vinyl acetate copolymer resin, or the like, which is a homopolymer of vinyl chloride.
• the content of the comonomer is not particularly limited, and can be determined according to the required quality such as moldability.
• the ratio of the vinyl chloride resin to the total amount of the resin components of the vinyl chloride resin composition is, for example, 50% by mass or more, preferably 80% by mass or more, and more preferably 90-100% by mass.
• a flame retardant, a stabilizer, an antiaging agent, a pigment, an inorganic filler, etc. can be added as needed.
• a soft vinyl chloride resin can be suitably used as the vinyl chloride resin.
• the soft vinyl chloride resin include a vinyl chloride resin having a viscosity average polymerization degree of 900 to 1300 and an appropriate amount of a stabilizer, a softening agent, and the like. If the degree of polymerization of the vinyl chloride resin is less than 900, the substrate may be soft and have low heat resistance. On the other hand, when the degree of polymerization exceeds 1300, the dispersibility of the additive of the vinyl chloride resin-based resin composition may be deteriorated and the flexibility of the pressure-sensitive adhesive film may be deteriorated.
• the degree of polymerization was calculated according to JIS K6720-2 by dissolving 200 g of resin in 50 ml of nitrobenzene, measuring the specific viscosity of this polymer solution in a constant temperature bath at 30 ° C. using an Ubbelohde viscometer.
• a softener can be blended with the base material in order to soften the base material.
• the kind of softening agent that can be used for the substrate is not particularly limited, and a known softening agent can be employed.
• DOP dioctyl phthalate
• DINP diisononyl phthalate
• DINA diisononyl adipate
• DBP dibutyl phthalate
• Dibasic acid esters such as TOTM (tri-2-ethylhexyl trimellitic acid) and DIDP (diisodecyl phthalate)
• liquid rubbers such as liquid polyisobutylene, liquid isoprene and liquid butene
• aromatic process oils, naphthenic process oils Common softeners such as paraffinic oil, castor oil and tall oil can be used.
• the softening agent ratio is preferably 15 to 45% by mass, more preferably 15 to 30% by mass, based on the total amount of the resin components of the vinyl chloride resin composition. If the softening agent is less than 15% by mass, the substrate may be hardened. On the other hand, if it exceeds 45% by mass, troubles such as bending of the substrate or shrinkage of the substrate may occur during the production of the substrate.
• the thickness of the substrate is not particularly limited, and is preferably 10 to 500 ⁇ m, more preferably 12 to 200 ⁇ m, and still more preferably 15 to 100 ⁇ m.
• the base material may have a single layer form or may have a multiple layer form.
• the substrate may be subjected to various treatments such as back treatment, antistatic treatment, and undercoating treatment as necessary.
• the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer in the present invention comprises 0.3 to 4% by mass of a softening agent, natural rubber and / or styrene-butadiene rubber (hereinafter referred to as “SBR”). And a graft polymer obtained by graft polymerization of an (meth) acrylic acid ester having an alkyl group.
• SBR styrene-butadiene rubber
• the adhesive contains natural rubber and / or styrene-butadiene rubber as an adhesive base.
• Natural rubber is widely used as a base for adhesive compositions.
• SBR is a typical general-purpose rubber and is excellent in aging resistance, creep resistance, plasticizer resistance, and the like. Commercial products can be used for natural rubber and SBR.
• SBR publicly known or commonly used SBR can be used.
• the ratio of styrene and butadiene as monomer components in SBR is not particularly limited.
• the type or grade of SBR is not particularly limited, and various types or grades of SBR can be used.
• the softening agent that can be blended in the pressure-sensitive adhesive layer the above-mentioned known softening agents can be employed in the same manner as can be used for the substrate.
• the content of the softening agent in the pressure-sensitive adhesive layer is 0.3 to 4% by mass, preferably 1 to 3% by mass with respect to the pressure-sensitive adhesive.
• the content of the softener is less than 0.3% by mass, the migration of the softener from the base material made of the vinyl chloride resin composition cannot be suppressed, and the cohesive strength of the pressure-sensitive adhesive is reduced, or the pasting time The adhesive strength increases with time, and adhesive residue may occur when the adhesive film is peeled off.
• the initial adhesive may have insufficient cohesive strength regardless of the elapsed time, and adhesive residue may be generated when the adhesive film is peeled off.
• the softener is present in the pressure sensitive adhesive in the specific amount, the transition of the softener from the base material to the pressure sensitive adhesive can be suppressed by the principle of chemical equilibrium.
• the softener content in the present invention is measured by the following method.
• Device name Gas Chromatography (GC JEOL Ltd.) Test method: The pressure-sensitive adhesive of the pressure-sensitive adhesive film is peeled off and extracted with normal hexane and dried at 40 ° C. for measurement.
• the graft polymer in the present invention is excellent in softening agent resistance that hardly causes deterioration of adhesive properties, and also has an effect of further suppressing a decrease in adhesive cohesive force due to migration of the softening agent. Moreover, since the (meth) acrylic acid ester having an alkyl group is grafted, adhesion to various adherends and unwinding force can be improved, and efficiency of workability at low temperatures can be improved.
• the blended amount of the graft polymer is 10 to 50 parts by mass, preferably 20 to 50 parts by mass with respect to 100 parts by mass of the adhesive base agent made of natural rubber and / or SBR.
• the graft polymer is less than 10 parts by mass, appropriate adhesion and rewinding force to various adherends may not be obtained. On the other hand, if the graft polymer exceeds 50 parts by mass, the graft polymer may become too hard to be used as an adhesive.
• the graft polymer has both a highly polar constituent molecule ((meth) acrylate ester having an alkyl group) and a low polar constituent molecule (natural rubber, SBR) in the molecular structure of the graft polymer. Adhesion to an adherend that is difficult to adhere as an adhesive film and high unwinding force can be exhibited. Therefore, since both constituent molecules need to be appropriately distributed, in the graft polymer, natural rubber and / or SBR is 60 to 80% by mass, and (meth) acrylic acid ester having an alkyl group is 20 to 40% by mass. It is preferable to polymerize so that. More preferably, it is preferable to polymerize 65 to 75% by mass of natural rubber and / or SBR and 25 to 35% by mass of (meth) acrylic acid ester having an alkyl group.
• alkyl (meth) acrylic acid esters include methyl (meth) acrylate (hereinafter abbreviated as “MMA”), ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) Acrylate, undecyl (meth) acrylate, isoundecyl (meth) acrylate, dodecyl (meth) acrylate, isotridecyl (meth) acrylate, tetradecyl (meth)
• the Mooney viscosity of the graft polymer in the present invention is 60 to 90 Ms1 + 4 (100 ° C.), preferably 70 to 90 Ms1 + 4 (100 ° C.).
• the Mooney viscosity of the graft polymer is less than 60 Ms1 + 4 (100 ° C.)
• the resistance to the fluidity of the pressure-sensitive adhesive is weak, and a high cohesive force may not be obtained.
• the Mooney viscosity exceeds 90 Ms1 + 4 (100 ° C.)
• the cohesive force of the pressure-sensitive adhesive may become too high.
• the method for adjusting the Mooney viscosity includes known methods, and is not particularly limited.
• mastication using an open roll a Banbury mixer, a kneader, or the like can be mentioned.
• the method of mastication with an open roll is preferable because the Mooney viscosity can be easily adjusted.
• the Mooney viscosity is measured based on JIS K-6300.
• additives for the adhesive, various additives as required, for example, various stabilizers such as plasticizers, ultraviolet absorbers, antioxidants, tackifiers, fillers, colorants, antistatic agents, foaming agents, surface active agents Various known additives such as an agent may be blended.
• the tackifier resin used for the tackifier can be selected in consideration of the softening point, compatibility with each component, and the like.
• terpene resin, rosin resin, hydrogenated rosin resin, chroman indene resin, styrene resin, aliphatic and alicyclic petroleum resin, terpene-phenol resin, xylene resin, other aliphatic hydrocarbon resins Or an aromatic hydrocarbon resin etc. can be mentioned.
• the softening point of the tackifying resin is 65 to 170 ° C, preferably 80 to 150 ° C.
• the compounding amount of the tackifier resin is in the range of 50 to 200 parts by mass, preferably 100 to 150 parts by mass with respect to 100 parts by mass of the adhesive. If the amount of tackifying resin is too small, the pressure-sensitive adhesive film may not be able to exhibit high adhesive strength. On the other hand, when there are too many tackifying resins, the adhesive force of an adhesive film may become too high.
• the pressure-sensitive adhesive film of the present invention includes a base material made of a vinyl chloride resin composition and a pressure-sensitive adhesive layer formed on at least one surface of the base material.
• the pressure-sensitive adhesive layer is formed only on one side of the substrate, but may be formed on both sides.
• the pressure-sensitive adhesive film can be produced by forming a pressure-sensitive adhesive layer on at least one surface of a substrate using a conventional method such as a coating method.
• the pressure-sensitive adhesive layer may be protected by a peeling substrate (peeling liner).
• the adhesive film may have another layer (for example, intermediate
• the means for forming the substrate is not particularly limited, but the above-mentioned various materials are used by conventional melt-kneading and various mixing devices (single- or twin-screw extruder, roll, Banbury mixer, various kneaders, etc.). Then, the components are mixed so that they are uniformly dispersed, and the mixture is formed into a base material by a calendering machine and cut into a desired tape width.
• a roll arrangement method in calendar molding for example, a known method such as L-type, reverse L-type, and Z-type can be adopted, and the roll temperature is usually set in the range of 150 to 200 ° C, preferably 160 to 180 ° C. .
• the means for applying the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer to the substrate is not particularly limited.
• a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, A spray coater can be used.
• the thickness of the pressure-sensitive adhesive layer after drying can be appropriately selected within the range that does not impair the pressure-sensitive adhesiveness and handleability.
• the thickness of the pressure-sensitive adhesive layer is, for example, 5 to 100 ⁇ m, preferably 10 to 50 ⁇ m. If it is thinner than this, the adhesive force and the unwinding force may be reduced. On the other hand, if it is thicker than this, the coating performance may be deteriorated, and adhesive residue may easily occur.
• the pressure-sensitive adhesive film of the present invention can be produced as a pressure-sensitive adhesive tape (pressure-sensitive adhesive film wound in a roll shape) having a state or form wound in a roll shape by winding in a roll shape. When it is not wound into a roll, it can be produced as an adhesive sheet. When the adhesive film is formed on the adhesive tape, the adhesive film can be wound into a roll by applying a release agent on the back surface (non-glue surface) of the adhesive film and providing a back treatment layer. The movement of the softener between them can be prevented more reliably.
• the release liner is interposed between the surface of the pressure-sensitive adhesive layer of one pressure-sensitive adhesive film and the back surface of the other pressure-sensitive adhesive film by laminating the surface of the pressure-sensitive adhesive layer with the release surface of the release liner in contact with each other. The movement of the softener between the adhesive films can be prevented more reliably.
• peeling was measured according to JIS G 4305. After leaving the adhesive film in the evaluation test chamber set at a temperature of 23 ⁇ 2 ° C. and a humidity of 50 ⁇ 5% RH for 24 hours or more, the adhesive film is pressure-bonded to the SUS304 steel plate, 30 minutes after the initial, and 7 days later. The wearing state was visually observed, and the superiority or inferiority was evaluated according to the following criteria.
• the crimping method was performed in one reciprocation at a crimping speed of 5 mm / s using a 200 g roller according to JIS K 6253. Good: No peeling
• adheresive residue was measured in accordance with JIS G 4305. After the adhesive film is allowed to stand for 24 hours or more in an evaluation test chamber set to a temperature of 23 ⁇ 2 ° C. and a humidity of 50 ⁇ 5% RH, the adhesive film is pressure-bonded to a SUS304 steel plate, 30 minutes after the initial, and one month later. The adhesive film was peeled off at a rate of 300 mm / min in the 180 ° direction, and the surface of the SUS304 steel plate after peeling was visually observed, and the superiority or inferiority was evaluated according to the following criteria. The crimping method was performed in one reciprocation using a 200 g roller according to JIS K 6253 at a crimping speed of 5 mm / s. Good: No glue residue Bad: There is glue residue
• Example 1 100 parts by mass of a vinyl chloride resin having a polymerization degree of 1100 (TH-1000 manufactured by Taiyo PVC Co., Ltd.), 25 parts by mass of DINP (manufactured by DIC) as a softening agent, C5C9 petroleum resin (manufactured by Esso Chemical Co., Ltd.) as a tackifier , Softening point 94 ° C.) 10 parts by mass, 2 parts by mass of MBS (manufactured by Nippon Synthetic Rubber) as a modifier, 2 parts by mass of a Ca—Zn stabilizer (manufactured by Mizusawa Chemical) as a stabilizer, St acid ( 0.2 parts by mass of Nippon Oil & Fats Co., Ltd.
• DINP manufactured by DIC
• C5C9 petroleum resin manufactured by Esso Chemical Co., Ltd.
• Softening point 94 ° C. 10 parts by mass
• MMA manufactured by Kaneka Chemical Co., Ltd.
• a Henschel mixer 2 parts by mass of MMA (manufactured by Kaneka Chemical Co., Ltd.) were mixed with a Henschel mixer, and a sheet having a thickness of 120 ⁇ m was formed by calendering (roll temperature: 145 to 180 ° C.).
• a sheet obtained by winding the sheet at a specified length (20 m) was annealed at 120 ° C. for 8 hours to obtain a substrate.
• Example 2 A pressure-sensitive adhesive film was produced in accordance with Example 1 except that the composition of the pressure-sensitive adhesive and the substrate was variously changed as shown in Table 1.
• Example 6 A pressure-sensitive adhesive film was produced according to Example 1 except that the composition of the pressure-sensitive adhesive was variously changed as shown in Table 2.
• the initial adhesive strength (30 minutes after application) on various adherends is excellent. Further, even when the adhesive strength with SUS is changed with time (from 30 minutes to 1 month, a low temperature of ⁇ 20 ° C.), high adhesive strength is maintained. From these facts, it can be seen that an adhesive film with a small amount of softener transfer from the base material to the adhesive, excellent adhesive force, unwinding force and holding force and less adhesive residue on the adherend can be easily obtained. .

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Adhesive Tapes (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Laminated Bodies (AREA)

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• 2009
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