CN102027087B - Adhesive film - Google Patents

Adhesive film Download PDF

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Publication number
CN102027087B
CN102027087B CN200980117182.8A CN200980117182A CN102027087B CN 102027087 B CN102027087 B CN 102027087B CN 200980117182 A CN200980117182 A CN 200980117182A CN 102027087 B CN102027087 B CN 102027087B
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China
Prior art keywords
quality
methyl
bonding film
graftomer
tenderizer
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CN200980117182.8A
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Chinese (zh)
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CN102027087A (en
Inventor
斋田诚二
久保幸治
吉村大辅
铃木阳介
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Denka Co Ltd
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Denki Kagaku Kogyo KK
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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
    • 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
    • B32B25/04—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
    • 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
    • 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
    • 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
    • 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]
    • 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
    • B32B25/12—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
    • 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
    • B32B27/30—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
    • 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
    • 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
    • C09J151/04—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
    • 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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  • 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)

Abstract

Disclosed is an adhesive film configured of a base which is composed of a vinyl chloride resin composition and an adhesive layer which is formed on at least one side of the base. The adhesive layer contains an adhesive base agent composed of a natural rubber and/or a styrene-butadiene rubber, a graft polymer obtained by graft-polymerizing a (meth)acrylate having an alkyl group to a natural rubber and/or a styrene-butadiene rubber, and a softening agent. The softening agent is blended in an amount of 0.3-4% by mass relative to the adhesive agent constituting the adhesive layer; the graft polymer is blended in an amount of 10-50 parts by mass per 100 parts by mass of the adhesive base agent; and the graft polymer has a Mooney viscosity of 60-90 Ms 1+4 (100 DEG C).

Description

Bonding film
Technical field
The present invention relates to bonding film, for example, the bonding film that is configured as belt like shape can be preferred for tying up tying up with band, representing the label film of character and figure on the surface of bonding film of the electric wire of the wiring of automobile etc. or cable.
Background technology
Bonding film as the various insulating tapes of the various electric installations for automobile, railway, flyer, boats and ships, house and factory etc., from thering is appropriate flexibility and stretchiness, good and the less expensive reasons in aspect such as flame retardant resistance, physical strength, resistance to heat distorsion, electrical insulating property and shaping processability are set out, and have been coated with the polyvinyl chloride-base bonding film of tackiness agent on a face of the base material that the resin combination that employing wherein contains vinyl chloride resin in use is raw material.
Conventionally, in order to make base material softnessization, and in the base material of bonding film compounding tenderizer.But, As time goes on, the situation that exists tenderizer to move from base material to binder layer.If tenderizer moves to binder layer, tackiness agent is softening, be extruded to the side of Wound product and cause be clamminess (sticky limit), thereby and the cohesive strength of tackiness agent or bounding force reduce and cause bonding film to be peeled off from adherend.In addition,, when from adherend release adhesive film, exist part tackiness agent and tenderizer to remain in the situation on adherend, thereby cause adherend to pollute.
As the binding moving in order to suppress above-mentioned tenderizer, someone has proposed to arrange the bonding film (for example, patent documentation 1 and patent documentation 2) of curing priming paint between soft base material and binder layer.But; the defect of these bonding films is: if protect paste face or the back side of base material (forming the face of paste face) do not carried out to surface treatment without base material barrier film; so; after coiling is for web-like; the surface of the binder layer of the bonding film being superimposed with each other will directly contact with the back side of another bonding film, and tenderizer will move between bonding film thus.Therefore,, if paste face or the back side are not further protected, just there is the problem that can not fully suppress the migration of tenderizer.
Patent documentation 1: Japanese unexamined patent application publication H11-263946
Patent documentation 2: Japanese unexamined patent application publication 2002-146274
Summary of the invention
The object of the present invention is to provide a kind of minimizing tenderizer to be moved to binder layer by base material, there is good bounding force, uncoiling power and confining force, and can reduce the residual bonding film of paste on adherend.
For achieving the above object, main contents of the present invention are following.
(1) bonding film, it comprises the base material that contains vinyl chloride resin composition and the binder layer forming at least one face of base material, and wherein, binder layer contains:
(i) bonding base, it contains natural rubber and/or styrene butadiene rubbers;
(ii) graftomer, obtains by having (methyl) acrylate of alkyl and natural rubber and/or styrene butadiene rubbers graft polymerization; And
(iii) tenderizer; And wherein
(A) with respect to the tackiness agent that forms binder layer, the tenderizer of compounding 0.3 quality %-4 quality %;
(B) the bonding base that contains natural rubber and/or styrene butadiene rubbers with respect to 100 mass parts, the graftomer of compounding 10 mass parts-50 mass parts;
(C) mooney viscosity of graftomer is the mooney viscosity of measuring according to JIS K 6300, and it is 60Ms1+4 (100 ℃)-90Ms1+4 (100 ℃).
(2) bonding film as described in above-mentioned (1), wherein, with respect to resinous principle total amount, vinyl chloride resin composition contains vinyl chloride resins more than 50 quality %.
(3) bonding film as described in above-mentioned (1), wherein, graftomer is the polymkeric substance obtaining by the styrene butadiene rubbers of 60 quality %-80 quality % and (methyl) graft polymerization of acrylic ester with alkyl of 20 quality %-40 quality %.
(4) bonding film as described in above-mentioned (1), wherein, (methyl) acrylate that has an alkyl is selected from (methyl) acrylate methyl esters, (methyl) n-butyl acrylate, (methyl) 2-EHA and their mixture.
(5) bonding film as described in above-mentioned (1), wherein, tenderizer is diisononyl phthalate.
(6) bonding film as described in above-mentioned (1), wherein, with respect to the resinous principle total amount of vinyl chloride resin composition, contains the tenderizer of 15 quality %-45 quality % in base material.
According to the present invention, can provide reduce tenderizer by base material to adhesive migration, there is good bounding force, uncoiling power and confining force and can reduce the residual bonding film of paste.
Embodiment
Bonding film of the present invention is the bonding film that comprises the base material that contains vinyl chloride resin composition and the binder layer forming at least one face of base material, wherein above-mentioned binder layer is formed by the tackiness agent that contains tenderizer and graftomer, wherein, described tenderizer is 0.3 quality %-4 quality % with respect to tackiness agent, the polymkeric substance that graftomer obtains by having alkyl (methyl) acrylate and natural rubber and/or styrene butadiene rubbers graft polymerization.
I. base material
The vinyl chloride resin composition that forms base material is not particularly limited, as long as contain vinyl chloride resin as the main component of resinous principle.Vinyl chloride resin is not particularly limited, and is the homopolymer resin for existing known vinylchlorid list polymers, or existing known various copolymer resins.
As above-mentioned copolymer resin, can use existing known copolymer resin, typically illustration: the vinylchlorid of vinyl chloride-vinyl acetate copolymer resin, vinylchlorid-vinyl propionate ester copolymer resin etc. and the copolymer resin of vinyl ester; The vinylchlorid of vinylchlorid-butyl acrylate copolymer resin, vinylchlorid-2-EHA copolymer resin etc. and the copolymer resin of esters of acrylic acid; The vinylchlorid of vinyl chloride-ethylene copolymer resin, VCP resin etc. and the copolymer resin of olefines; Vinyl chloride-acrylonitrile copolymer resin etc.Particularly preferably use homopolymer resin into vinylchlorid list polymers, vinyl chloride-ethylene copolymer resin, vinyl chloride-vinyl acetate copolymer resin etc.In copolymer resin, the content of comonomer is not particularly limited, and can determine according to the specification of quality of shaping processability etc.
Vinyl chloride resin, with respect to the ratio of the resinous principle total amount in vinyl chloride resin composition, for example, is more than 50 quality %, more than being preferably 80 quality %, and 90 quality %-100 quality % more preferably.In addition, can add as required fire retardant, stablizer, antiaging agent, pigment, inorganic filler etc.
As vinyl chloride resin, can preferably use soft vinyl chloride resin.As soft vinyl chloride resin, can be set forth in the vinyl chloride resin that viscosity average polymerization degree is 900-1300 and add the material that appropriate stablizer, tenderizer etc. obtain.If the above-mentioned polymerization degree of vinyl chloride resin is less than 900, there is the situation that base material is soft, thermotolerance reduces.On the other hand, if the above-mentioned polymerization degree surpasses 1300, there is the dispersed variation of the additive of vinyl chloride resin based resin composition, the situation of the flexibility variation of bonding film.The above-mentioned polymerization degree is calculated as follows: 200g resin is dissolved in the oil of mirbane of 50ml, in the thermostatic bath of 30 ℃, use the specific viscosity of this polymers soln of determination of ubbelohde viscometer, then calculate according to JIS K 6720-2.
< tenderizer >
Can be in base material compounding tenderizer so that base material softnessization.Can be not particularly limited for the kind of the tenderizer of base material, can adopt known tenderizer.As an example, can use tackiness agent handbook (Handbook of Adhesives) (Japanese adhesives industry association (Japan Adhesive Tape Manufacturer ' sAssociation), the 3rd edition, the diester of DOP (dioctyl phthalate (DOP)), the DINP (diisononyl phthalate) P-69) recording, DINA (diisononyl adipate), DBP (dibutyl phthalate), TOTM (tri trimellitate (2-ethylhexyl) ester), DIDP (Di Iso Decyl Phthalate) etc.; The aqueous rubber of liquid polyisobutene, liquid isoprene, liquid maleic etc.; The common tenderizer of fragrance same clan treated oil, naphthenic treated oil, olefines oil, Viscotrol C, Yatall MA etc.These tenderizers can be used separately, also can combine two or more and use.The ratio of tenderizer is: with respect to the resinous principle total amount of vinyl chloride resin composition, be preferably 15 quality %-45 quality %, further 15 quality %-30 quality % more preferably.If this tenderizer is less than 15 quality %, there is the situation of base material hardening.On the other hand, if surpass 45 quality %,, when base material is manufactured, sometimes there is the problems such as base material fracture or base material contraction.
The thickness of base material is not particularly limited, and is preferably 10-500 μ m, more preferably 12-200 μ m, more preferably 15-100 μ m.In addition, base material can have the form of individual layer, in addition, also can have the form of multilayer.
Can also as required, to base material, carry out the various processing of back side processing, anti-electrostatic processing, primary coat processing etc.
II. binder layer
Be used to form the tackiness agent of the binder layer in the present invention, contain tenderizer and graftomer, wherein, tenderizer is 0.3 quality %-4 quality % with respect to tackiness agent, the polymkeric substance that graftomer obtains by having (following, referred to as " the SBR ") graft polymerization of alkyl (methyl) acrylate and natural rubber and/or styrene butadiene rubbers.
The bonding base > of <
Tackiness agent contains natural rubber and/or styrene butadiene rubbers is used as bonding base.
Natural rubber is as the base-material of binding compositions and be widely used.SBR is representational conventional rubber, has the characteristics such as good ageing resistance, resistance to creep properties, plasticizer-resistant characteristic.Natural rubber, SBR can be used commercially available product.
As SBR, can use known or habitual SBR.In addition, vinylbenzene and the divinyl ratio as the monomer component in SBR is not particularly limited.Kind and the grade of SBR are not particularly limited, and can use the SBR of various kinds and grade.
< tenderizer >
Tenderizer as can compounding in binder layer, can adopt the above-mentioned known tenderizer identical with spendable material in base material.
The containing ratio of the tenderizer in binder layer is: with respect to tackiness agent, be 0.3 quality %-4 quality %, be preferably 1 quality %-3 quality %.If the containing ratio of tenderizer is less than 0.3 quality %, can not suppress tenderizer and be moved by the base material that contains vinyl chloride resin composition, the cohesive strength of tackiness agent reduces, or, bounding force increases along with the time lapse after fitting, and causes occurring the residual situation of paste when release adhesive film.On the other hand, if the containing ratio of this tenderizer is greater than 4 quality %, exist the initial cohesive strength of the tackiness agent irrelevant with time lapse not enough, cause occurring the residual situation of paste when release adhesive film.By having with above-mentioned specified quantitative, be present in the tenderizer in tackiness agent, can, by the principle of chemical equilibrium, suppress tenderizer from base material to adhesive migration.
The content of the tenderizer in the present invention is measured by following method.
Device name: gas-chromatography (GC NEC company (GC Japan ElectronOptics Laboratories, Ltd.) system)
Test method: by normal hexane, the tackiness agent of bonding film is peeled off, extracted, and be dried and measure at 40 ℃.
< graftomer >
Graftomer in the present invention has the good deteriorated resistance to tenderizer of difficult generation adhesion characteristic, and has the effect that tackiness agent cohesive strength that further inhibition causes by tenderizer migration reduces.In addition,, due to (methyl) with alkyl is acrylic ester grafted, be therefore expected to improve the adaptation of various adherends and uncoiling power, and be expected to improve the efficiency of low-temperature processability.The compounding amount of graftomer, the bonding base that contains natural rubber and/or SBR with respect to 100 mass parts, is 10-50 mass parts, is preferably 20-50 mass parts.If graftomer is less than 10 mass parts, exists and be difficult to obtain the situation to the suitable bounding force of various adherends and uncoiling power.On the other hand, if graftomer surpasses 50 mass parts, exist graftomer to become too hard, thus situation about can not use as tackiness agent.
By in the molecular structure of above-mentioned graftomer, have the molecular components that polarity is high ((methyl) acrylate with alkyl) and the low molecular components (natural rubber, SBR) of polarity, this graftomer can be brought into play adaptation and the high uncoiling power that is difficult to the adherend of stickup for bonding film simultaneously.Therefore, need suitably to distribute two kinds of molecular components, thereby in graftomer, (methyl) acrylate with alkyl of the natural rubber of preferred polymeric 60 quality %-80 quality % and/or SBR and 20 quality %-40 quality %.More preferably (methyl) acrylate with alkyl of the natural rubber of polymerization 65 quality %-75 quality % and/or SBR and 25 quality %-35 quality %.
As above-mentioned (methyl) acrylate with alkyl, can enumerate (methyl) methyl acrylate (following, referred to as: " MMA "), (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid n-octyl, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) vinylformic acid undecyl ester, the different undecyl ester of (methyl) vinylformic acid, (methyl) dodecylacrylate, (methyl) vinylformic acid isotridecyl ester, methacrylic acid tetradecyl ester, can use wherein a kind, also can be used in combination wherein two or more.Wherein, preferably use (methyl) methyl acrylate, (methyl) n-butyl acrylate, (methyl) 2-EHA.
The mooney viscosity of the graftomer in the present invention is 60Ms1+4 (100 ℃)-90Ms1+4 (100 ℃), is preferably 70Ms1+4 (100 ℃)-90Ms1+4 (100 ℃).If the mooney viscosity of graftomer is less than 60Ms1+4 (100 ℃), the resistibility of adhesive flow is weakened, can not obtain high cohesive strength.On the other hand, if mooney viscosity surpasses 90Ms1+4 (100 ℃), there is the too high situation of cohesive strength of tackiness agent.As the method for adjusting mooney viscosity, can enumerate known method, and be not particularly limited.For example, can enumerate the method for being plasticated by open roll, closed mixing roll, kneader etc., wherein from being easy to adjust the viewpoint of mooney viscosity, the method for preferably plasticating by open roll.The mensuration of mooney viscosity is carried out based on JIS K-6300.
< additive >
As required, can also be in tackiness agent compounding for example, the various known additives such as the various stablizers of softening agent, UV light absorber, antioxidant etc., tackifier, weighting agent, tinting material, static inhibitor, whipping agent, tensio-active agent.
Consider softening temperature, and each composition between consistency etc., can select tackifying resin to be used as tackifier.Can enumerate, for example, the petroleum resin of terpine resin, Gum Rosin, staybelite resin, coumarone-indene resin, styrene resin, aliphatic category and the alicyclic ring same clan etc., terpene-resol, xylene resin, other aliphatic hydrocarbon resin or aromatic hydrocarbon resin etc.The softening temperature of tackifying resin is 65-170 ℃, is preferably 80-150 ℃.The compounding amount of tackifying resin, is 50-200 mass parts with respect to 100 mass parts tackiness agents, preferably in the scope of 100-150 mass parts.If tackifying resin is very few, exists and can not bring into play to bonding film the situation of high adhesion.On the other hand, when the amount of tackifying resin is too high, there is the too high situation of bounding force of bonding film.
III. bonding film
Bonding film of the present invention, comprises the base material that contains vinyl chloride resin composition and the binder layer forming at least one face of above-mentioned base material.Conventionally, binder layer can only be formed on a face of base material, but also can be formed on two faces.Can, by using the customary ways such as coating method, at least one face of base material, form binder layer and prepare bonding film.In addition, can protect binder layer by peeling off base material (release liner).In addition,, in not damaging the scope of effect of the present invention, bonding film also can have other layer (for example, middle layer, undercoat etc.).
The method that forms base material is not particularly limited, use habitual melting mixing etc. or various compounding device (single shaft or biaxial extruder, roll, closed mixing machine, various kneaders etc.) by above-mentioned various material mixing, so that each composition is dispersed, by calendering formation machine, making this mixture forming is again base material, is then cut into the bandwidth of expectation.Roll arrangement mode in calendering formation machine can adopt, for example, the known modes such as L-type, anti-L-type, Z-type, in addition, roller temperature is set in 150-200 ℃ conventionally, preferably sets at 160-180 ℃.
The applying adhesive that forms binder layer is not particularly limited in the method for base material, for example can use, intaglio plate roll coater, reverse roll coater, roller are licked formula coating machine, are immersed roll coater, rod coater, scraper type coating machine, Bracewell coater.The dried thickness of binder layer can suitably be selected in the scope of not damaging binding property and operability, and the thickness of binder layer is for example 5-100 μ m, is preferably 10-50 μ m.If than above-mentioned thin thickness, bounding force and uncoiling power reduce.On the other hand, if thicker than above-mentioned thickness,, easily there is paste residual in coating property variation sometimes.
Bonding film of the present invention, can be coiled as the state of web-like or the self adhesive tape of form (being coiled the bonding film into web-like) for web-like manufactures to have by coiling, in the situation that coiling is not for web-like, can be manufactured adhesive sheet.
When bonding film is formed to self adhesive tape, by the back side at bonding film (not forming the face of paste face) coating stripper, so that back side processing layer to be set, even self adhesive tape is coiled into web-like, still can further guarantee to prevent the tenderizer migration between bonding film.Similarly, by making the release surface of release liner and the Surface Contact of binder layer, stacked, between the surface of the binder layer of a bonding film and the back side of another bonding film, insert release liner, can further guarantee thus to prevent the tenderizer migration between bonding film.
embodiment
Below, based on embodiment and comparative example, the invention will be further described, but the present invention is not limited to these embodiment.
The material using in embodiment is as follows respectively.
The polymerization degree 1100), TH-1300 (ocean ethene company (Taiyo Enbi Co., Ltd.) system: the polymerization degree 1300) (1) vinyl chloride resin: TH-1000 (ocean ethene company (Taiyo Enbi Co., Ltd.) system:
(2) tenderizer: DINP (DIC company system)
(3) tackifier: c5c9 class petroleum resin (Exxon chemical company (ExxonChemical Co., Ltd.) system, 94 ℃ of softening temperatures)
(4) stablizer: Ca-Zn class stablizer (marshy land chemical company (MizusawaIndustrial Chemicals, Ltd.) system)
(5) properties-correcting agent: MB S (MBS-multipolymer) (Japan SYnthetic Rubber Co. Ltd (Japan Synthetic Rubber Co., Ltd.) system)
(6) graftomer obtaining by MMA and natural rubber graft polymerization: MEGAPOLY30 (ASIATIC company system: the graftomer obtaining by the MMA of 30 quality % and the natural rubber graft polymerization of 70 quality %)
(7) graftomer obtaining by MMA and natural rubber graft polymerization: MEGAPOLY50 (ASIATIC company system: the graftomer obtaining by the MMA of 50 quality % and the natural rubber graft polymerization of 50 quality %)
(8) graftomer obtaining by MMA and SBR graft polymerization: SGMM-30 (Deuki Kagaku Kogyo Co., Ltd (Denki Kagaku Kogyo Co., Ltd.) system: the graftomer obtaining by the MMA of 30 quality % and the SBR graft polymerization of 70 quality %)
(9) by butyl methacrylate and SBR graft polymerization arrive graftomer: SGBM-30 (Deuki Kagaku Kogyo Co., Ltd (Denki Kagaku KogyoCo., Ltd.) system: the graftomer obtaining by the butyl methacrylate of 30 quality % and the SBR graft polymerization of 70 quality %)
(10) graftomer obtaining by butyl acrylate and SBR graft polymerization: SGBA-30 (Deuki Kagaku Kogyo Co., Ltd (Denki Kagaku Kogyo Co., Ltd.) system: the graftomer obtaining by the butyl acrylate of 30 quality % and the SBR graft polymerization of 70 quality %)
Table 1
Figure BPA00001255105700111
Table 2
Figure BPA00001255105700121
In table 1, table 2, " initial adhesion power " is measured according to JIS Z 0237.By bonding film be placed on Temperature Setting be 23 ± 2 ℃, humidity be set as indoor 24 hours of the evaluation test of 50 ± 5%RH above after, thereby make the roll reciprocating rolling of 2000g 2 times bonding film is attached to various adherends (SUS (stainless steel), PE (polyethylene), PVC (polyvinyl chloride), PET (polyethylene terephthalate)), after 30 minutes, measure 180 degree stripping strengths (N/10mm).1N/10mm is good above.
In table 1, table 2, " rheological parameters' change with time to SUS bounding force " measured according to JIS Z0237.By bonding film be placed on Temperature Setting be 23 ± 2 ℃, humidity be set as indoor 24 hours of the evaluation test of 50 ± 5%RH above after, thereby the roll that makes 2000g is attached at SUS 304 steel plates by bonding film reciprocal 2 times, and measures 180 degree stripping strengths (N/10mm) after 30 minutes, after 1 month.In addition, by bonding film be placed on Temperature Setting for indoor 24 hours of the evaluation test of-20 ± 2 ℃ above after, thereby make the roll reciprocating rolling of 2000g 2 times bonding film is attached to SUS 304 steel plates, and after 30 minutes, measure 180 degree stripping strengths (N/10mm).All that 1N/10mm is above for good.
In table 1, table 2, " confining force " measured according to JIS Z 0237.By bonding film rest on Temperature Setting be 23 ± 2 ℃, humidity be set as indoor 24 hours of the evaluation test of 50 ± 5%RH above after, use SUS 304 steel plates as adherend, and the bonding film of 20mm * 20mm be attached to surface of steel plate.Then, under the atmosphere of 40 ℃, on gravity direction, apply the load of 500g, under the condition more than n=3, measure weight lowering time (minute).The numerical value of above-mentioned table is mean value.300 minutes is good above.
In table 1, table 2, " uncoiling power " is measured according to JIS Z 0237.By bonding film rest on Temperature Setting be 23 ± 2 ℃, humidity be set as indoor 24 hours of the evaluation test of 50 ± 5%RH above after, under the condition more than n=3, measure with the speed of 15.8m/ minute about numerical value during 3 second of bonding film uncoiling.The numerical value of above-mentioned table is mean value.The scope of 6-8N/10 minute is good.
In table 1, table 2, " SUS peels off " measured according to JIS G 4305.By bonding film be placed on Temperature Setting be 23 ± 2 ℃, humidity be set as indoor 24 hours of the evaluation test of 50 ± 5%RH above after, bonding film is pressed on to SUS 304 steel plates, the tacky state of visual observation after initial 30 minutes, after 7 days, and with following standard, its quality is evaluated.Compression method is as follows: according to JIS K 6253, use the roll of 200g, with the pressing speed reciprocating rolling of 5mm/s 1 time.
Good: not peel off
Bad: to peel off a little
In table 1, table 2, " SUS paste is residual " measured according to JIS G 4305.By bonding film rest on Temperature Setting be 23 ± 2 ℃, humidity be set as indoor 24 hours of the evaluation test of 50 ± 5%RH above after, bonding film is pressed on to SUS 304 steel plates, after initial 30 minutes, after 1 month, with the speed of 300mm/ minute, to 180 ° of directions, bonding film is peeled off, the surface of SUS 304 steel plates after visual observation is peeled off, and with following standard, its quality is evaluated.Compression method is as follows: according to JIS K 6253, use the roll of 200g, with the pressing speed of 5mm/s reciprocal for 1 time.
Good: not exist paste residual
Bad: to exist paste residual
embodiment 1
(i) vinyl chloride resin that is 1100 by Henschel mixer by the 100 mass parts polymerization degree (ocean ethene company (Taiyo Enbi Co., Ltd.) system, TH-1000), 25 mass parts are as the DINP (DIC company system) of tenderizer, 10 mass parts are as c5c9 class petroleum resin ((the Exxon Chemical Co. of Exxon chemical company of tackifier, Ltd.) system, 94 ℃ of softening temperatures), 2 mass parts are as MBS ((the Japan Synthetic Rubber Co. of Japan SYnthetic Rubber Co. Ltd of properties-correcting agent, Ltd.) system), 2 mass parts are as Ca-Zn class stablizer ((the Mizusawa Industrial Chemicals of marshy land chemical company of stablizer, Ltd.) system), 2 mass parts St acid (Nof Corp. (NOF Corporation) system) 0.2 mass parts, MMA ((the Kanegabuchi Chemical IndustriesCo. of Zhong Yuan chemical company, Ltd.) system) mix, by calendering formation (roller temperature is 145-180 ℃), forming thickness is the sheet material of 120 μ m.Length according to the rules (20m) is coiled this sheet material, and under the condition of 120 ℃, resulting materials is carried out annealing for 8 hours and obtain base material.
(ii) (the YasuharaChemical company system of the terpine resin using 100 mass parts as tackifying resin; YS resin PX-1000), 2 mass parts are dissolved in as ageing-resistant 4-ethyl-6-tert.-butyl phenol (the Antage W-500 processed of chemical industrial company of Kawaguchi) base-material that toluene is made 30% mass ratio, then gained base-material are blended in to graftomer (the ASIATIC company system that 100 mass parts natural rubbers (mooney viscosity=45), 20 mass parts obtain the natural rubber of MMA graft polymerization to the 70 quality % of 30 quality %; MEGAPOLY30) in the mixture of the DINP of (mooney viscosity=80), 2 quality % (DIC company system), obtain thus tackiness agent.
(iii) utilize reverse roll coater coating adhesive on a face of base material, via drying process, form binder layer (dried thickness is 20 μ m), then be cut into the band shape of wide 25mm, thereby obtain bonding film.
embodiment 2-9
Except as shown in table 1, the composition of tackiness agent and base material is carried out various changes, according to embodiment 1, manufacture bonding film.
comparative example 1-6
Except as shown in table 2, the composition of tackiness agent is carried out various changes, according to embodiment 1, manufacture bonding film.
As indicated in table 1,2, according to the present invention, the initial adhesion power (pasting after 30 minutes) of various adherends (SUS, PE, PVC, PET) is all good.In addition, even about to the rheological parameters' change with time of SUS bounding force (from initial 30 minutes after 1 month, the low temperature of-20 ℃), still maintained high bounding force.From the above, can easily be reduced tenderizer from base material to adhesive migration, there is good bounding force, uncoiling power and confining force, and can reduce the residual bonding film of paste on adherend.

Claims (6)

1. a bonding film, it comprises the base material that contains vinyl chloride resin composition and the binder layer forming at least one face of described base material, and described binder layer contains:
(i) bonding base, it contains natural rubber and/or styrene butadiene rubbers;
(ii) graftomer, it obtains by having (methyl) acrylate of alkyl and natural rubber and/or styrene butadiene rubbers graft polymerization; And
(iii) tenderizer; And wherein
(A) with respect to the tackiness agent that forms binder layer, the described tenderizer of compounding 0.3 quality %-4 quality %;
(B) the bonding base that contains natural rubber and/or styrene butadiene rubbers with respect to 100 mass parts, the described graftomer of compounding 10 mass parts-50 mass parts;
(C) mooney viscosity of described graftomer is the mooney viscosity of measuring according to JIS K6300, and it is 60Ms1+4 (100 ℃)-90Ms1+4 (100 ℃),
With respect to the resinous principle total amount of described vinyl chloride resin composition, the softening dosage in base material is 15 quality %-45 quality %.
2. bonding film according to claim 1, wherein, the graftomer that graftomer obtains by having alkyl (methyl) acrylate and styrene butadiene rubbers graft polymerization.
3. bonding film according to claim 1, wherein, with respect to resinous principle total amount, described vinyl chloride resin composition contains vinyl chloride resins more than 50 quality %.
4. bonding film according to claim 1, wherein, described graftomer is the polymkeric substance that (methyl) graft polymerization of acrylic ester with alkyl by the styrene butadiene rubbers of 60 quality %-80 quality % and 20 quality %-40 quality % obtains.
5. bonding film according to claim 1, (methyl) acrylate wherein, with alkyl is selected from (methyl) methyl acrylate, (methyl) n-butyl acrylate, (methyl) 2-EHA and their mixture.
6. bonding film according to claim 1, wherein, described tenderizer is diisononyl phthalate.
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