CN1290958C - Adhesive resin composition and use thereof - Google Patents
Adhesive resin composition and use thereof Download PDFInfo
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- CN1290958C CN1290958C CNB038033933A CN03803393A CN1290958C CN 1290958 C CN1290958 C CN 1290958C CN B038033933 A CNB038033933 A CN B038033933A CN 03803393 A CN03803393 A CN 03803393A CN 1290958 C CN1290958 C CN 1290958C
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- adhesive resin
- resin composition
- bonded body
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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
- 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
- C09J7/35—Heat-activated
-
- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/08—Epoxidised polymerised polyenes
-
- 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
- C09J2423/00—Presence of polyolefin
-
- 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
- C09J2463/00—Presence of epoxy resin
Abstract
An adhesive resin composition comprising the following components (A), (B), and (C): (A) an epoxidized olefin resin, (B) a curing agent, and (C) a thermally decomposable foaming agent; an adhesive film made from the composition; an adhesive laminated film produced by laminating a support with the adhesive film; a laminate made by bonding an adherend to an adhesive layer formed by heating the adhesive film; and a method for peeling and recovering the adherend from the laminate by heating the laminate.
Description
Technical field
Bonding bonded body on the binder layer that the present invention relates to comprise the olefin resin that contains epoxy group(ing) and the adhesive resin composition of solidifying agent and thermal degradation type whipping agent, the binding property film that this adhesive resin composition membranization is formed, the adhesive multilayer film that forms supporting folded this binding property film of layers on substrates, obtains and the multilayer body that forms and heat this multilayer body and peel off the method that reclaims bonded body from multilayer body at this binding property film of heating.
Background technology
The multilayer body that obtains by the bonding bonded body of the bonding coat of binding property film is used for automobile parts, tame electrical article, electronic products, office appliance, daily necessities etc. in a large number.Open the spy and also to disclose such content in the clear 64-14235 communique: obtain and strong ground of bonded body adherent multilayer body by a kind of bonding coat, this bonding coat is with ethylene-alpha, the beta-unsaturated carboxylic acid analog copolymer with contain the epoxy group(ing) vinyl copolymer and do to mix after, extrusion moulding and obtaining.
On the other hand, recently, for this bonded body of recirculation (utilizing again), demand reclaims the method for bonded body from multilayer body.
, the result of inventor's investigation, because the bonding coat that above-mentioned spy opens in the multilayer body of putting down in writing in the clear 64-14235 communique has strong bounding force, it is difficult therefore easily peeling off, reclaim bonded body from the non-cohesive bonding coat of this multilayer body.
Summary of the invention
The present invention seeks to, the binding property excellence to bonded body, the while can easily be peeled off bonded body when reclaiming bonded body adhesive resin composition are provided.
The invention provides:
[1] contain following (A), (B) and (C) adhesive resin composition of composition, wherein,
(A): the olefin resin that contains epoxy group(ing)
(B): solidifying agent
(C): thermal degradation type whipping agent;
[2] according to [1] described adhesive resin composition, wherein, (A) composition is the following (a of polymerization
1) and (a
2) and obtain contain the epoxy group(ing) vinyl copolymer,
(a
1) ethene (following (a that often is designated as
1) monomer.)
(a
2) at least a kind of monomer (following (a that often is designated as of from the monomer of representing with the monomer of following general formula (1) expression with following general formula (2), selecting
2) monomer.)
(in the formula, R represents to have the alkyl of the carbon number 2-18 of two keys, also can in conjunction with halogen atom on this alkyl.X represents singly-bound or carbonyl.)
(in the formula, R ' expression has the alkyl of the carbon number 2-18 of two keys, also can in conjunction with halogen atom on this alkyl.)；
[3] according to [1] or [2] described adhesive resin composition, wherein, (A) composition be polymerization not can with epoxy reaction, can with the monomer of ethylene copolymer, above-mentioned (a
1) monomer and above-mentioned (a
2) monomer and the multipolymer that obtains;
[4] according to wantonly 1 described adhesive resin composition of [1]-[3], wherein, (B) composition is the following (b of polymerization
1), (b
2) and (b
3) and the ethylene-alpha that obtains, the beta-unsaturated carboxylic acid analog copolymer,
(b
1) ethene (following (b that often is designated as
1) monomer.)
(b
2) α, beta-unsaturated carboxylic acid and/or α, the beta-unsaturated carboxylic acid acid anhydride (following (b that often is designated as
2) monomer.)
(b
3) vinyl acetate and/or α, the beta-unsaturated carboxylic acid ester (following (b that often is designated as
3) monomer.)；
[5] according to [4] described adhesive resin composition, wherein, (B) the phase antithetical phrase constitutes unitary total 100 weight parts of entire infrastructure of (B) composition in the composition, contains to derive from (b
2) monomeric structural unit 0.01-20 weight part, derive from (b
3) monomeric structural unit 25-70 weight part;
[6] according to wantonly 1 described adhesive resin composition of [1]-[5], wherein, (A) composition contains the above-mentioned (a of polymerization
1) monomer and above-mentioned (a
2) monomer and obtain contain the epoxy group(ing) vinyl copolymer, (B) composition contains the above-mentioned (b of polymerization
1) monomer, above-mentioned (b
2) monomer and above-mentioned (b
3) monomer and the ethylene-alpha that obtains, the beta-unsaturated carboxylic acid analog copolymer, derive from ethene structural unit content the total amount with respect to (A) composition and (B) total 100 weight parts of composition be the 30-75 weight part;
[7] according to wantonly 1 described adhesive resin composition of [1]-[6], wherein, (A) composition is (A)/(B)=90/10-40/60 with (B) weight ratio of composition;
[8] according to wantonly 1 described adhesive resin composition of [1]-[7], wherein, (C) composition is azodicarboamide (a ァ ゾ ジ カ Le ボ Application ァ ミ De);
[9] according to wantonly 1 described adhesive resin composition of [1]-[8], wherein, with respect to (A) composition and (B) total 100 weight parts of composition, (C) composition is the 2-10 weight part;
[10] a kind of binding property film, wantonly 1 described adhesive resin composition of membranization [1]-[9] and forming;
[11] according to [10] described binding property film, wherein, the mixing thing that obtains by mixing this adhesive resin composition of extrusion forming obtains;
[12] according to [10] described binding property film, wherein, with this adhesive resin composition dissolving or be dispersed in the solvent, coating in the plane, dry and obtain;
[13] a kind of adhesive multilayer film forms at wantonly 1 described binding property film of supporting folded [10]-[12] of layers on substrates;
[14], wherein, support that base material is from comprising polyolefinic film, comprising at least a kind that selects the film of demoulding polyethylene terephthalate, the film that comprises cellulose triacetate and the release paper according to [13] described adhesive multilayer film;
[15] a kind of multilayer body comprises wantonly 1 described binding property film of heating [10]-[12] and the binder layer and the bonded body that obtain;
[16] a kind of multilayer body, have binder layer and bonded body, the stacked bonded body of binding property rete one side that forms by adhesive resin composition at membranization [13] or [14] described adhesive multilayer film, less than (C) thus under the temperature of the decomposition temperature of composition this laminate of heating bonding after, peel off and support base material and can obtain;
[17] a kind of multilayer body, have binder layer and bonded body, the stacked bonded body of binding property rete one side that forms by adhesive resin composition at membranization [13] or [14] described adhesive multilayer film, peel off support base material after, heating under less than the temperature of the decomposition temperature of (C) composition, bonding and can obtain;
[18] a kind of multilayer body, have binder layer and bonded body, the stacked bonded body of binding property rete one side that forms by adhesive resin composition at membranization [13] or [14] described adhesive multilayer film, after peeling off the support base material, at a side stacked bonded body different of having peeled off the face of supporting base material, be heated to less than the decomposition temperature of (C) composition and carry out bonding and can obtain with this bonded body; And
[19] a kind of recovery method of bonded body is characterized in that, by heating wantonly 1 described multilayer body of [15]-[18] in decomposition temperature of (C) composition or above temperature, comes to peel off bonded body from multilayer body.
The embodiment of invention
Below explain the present invention.
(A) composition among the present invention is the olefin resin that contains epoxy group(ing), specifically lists: ェ Port Off レ Application De (registered trademark, ダ ィ セ Le chemical industry Co., Ltd. system) etc., the olefin resin that contains carbon-carbon double bond by oxidation produce the olefin resin of epoxy group(ing); Polymerization contains that epoxy group(ing) comprises the monomer of carbon-carbon double bond and resin of forming etc.
Among (A) composition, preferably polymerization contains that epoxy group(ing) comprises the monomer of carbon-carbon double bond and the olefin resin that obtains, the special above-mentioned (a of preferred polymeric
1) monomer and (a
2) monomer and obtain contain epoxy group(ing) vinyl copolymer (the following A1 multipolymer that often is designated as).
Describe the A1 multipolymer in detail, R in the general formula (1) has two keys, particularly has the alkyl of the carbon number 2-18 of the two keys of non-aromatic CC, R ' in the general formula (2) has two keys, particularly has the alkyl of the carbon number 2-18 of the two keys of non-aromatic CC, and the hydrogen atom in all alkyl on the alkyl replaces also passable with halogen atom.
As R and R ', specifically list with the alkyl of following formula (3)-(8) expressions etc.
X in the general formula (1) is Sauerstoffatom and direct bonded singly-bound of R or the carbonyl in the general formula (1).
As (a
2) monomeric concrete example, list glycidyl allyl ether, 2-methacrylic glycidyl ether, vinylbenzene-to unsaturated glycidyl ethers such as glycidyl ethers; Unsaturated glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, glycidyl itoconate etc.
As (a that derives from the A1 multipolymer
2) content of monomeric structural unit, contain whole structural units 100 weight parts of epoxy group(ing) vinyl copolymer with respect to formation, be generally about the 1-30 weight part.When deriving from (a
2) content of monomeric structural unit is 1 weight part or when above, the tendency that has the physical strength of the binding property film that obtains to improve, so preferably, when being 30 weight parts or when following, have as the tendency that contains the package stability excellence of epoxy group(ing) vinyl copolymer, so preferred.
For the A1 multipolymer, enable with the monomer of ethylene copolymer (for not with epoxy reaction, can with the monomer (following (a that often is designated as of ethylene copolymer
3) monomer), promptly with (a
1) monomer and (a
2) the different monomer of monomer) and (a
1) monomer and (a
2) monomer together polymerization also can.In addition, (a
3) monomer do not contain carboxylic acid group and hydroxyl etc. can with the functional group of epoxy reaction.
As (a
3) monomeric concrete example, list the α that methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, methacrylic tert-butyl acrylate and Propenoic acid, 2-methyl, isobutyl ester etc. have the alkyl about carbon number 3-8, the beta-unsaturated carboxylic acid alkyl ester; Vinyl acetate, vinyl butyrate, propionate, trimethylacetic acid vinyl acetate, vinyl laurate, different n-nonanoic acid vinyl acetate, バ one サ チ ッ Network vinyl acetate etc. have the vinyl acetate of the carboxylic acid about carbon number 2-8; Alpha-olefin about carbon number 3-20 such as propylene, 1-butylene, iso-butylene; Diolefins such as divinyl, isoprene, cyclopentadiene; Vinyl compounds such as vinylchlorid, vinylbenzene, vinyl cyanide, methacrylonitrile, acrylamide, Methacrylamide etc.
As (a
3) monomer, wherein, preferred propylene, vinyl acetate, methyl acrylate, ethyl propenoate, n-butyl acrylate, methyl methacrylate.
As (a that derives from the A1 multipolymer
3) content of monomeric structural unit, contain whole structural units 100 weight parts of epoxy group(ing) vinyl copolymer with respect to formation, be generally about the 0-70 weight part, be preferably especially about the 25-60 weight part.Derive from (a when containing
3) during monomeric structural unit, operation when mixing adhesive resin composition is arranged becomes and is easy to tendency, be dissolved in the tendency of organic solvent easily with the A1 multipolymer, so it is preferred, when being 70 weight parts or when following, the tendency that adopts high-pressure free radical method etc. can easily make the A1 multipolymer is arranged, so preferably.
The A1 multipolymer can be any of segmented copolymer, graft copolymer, random copolymers, alternating copolymer, for example enumerates the propylene-ethylene block copolymer grafting (a that sends as an envoy to
2) monomeric multipolymer (No. 2632980 communique of Japanese Patent), make ethene-contain epoxy group(ing) monomer copolymer grafting α, the multipolymer of beta-unsaturated carboxylic acid ester (No. 2600248 communique of Japanese Patent) etc.
Manufacture method as the A1 multipolymer, for example list following method: in the presence of ethene and free radical generating agent, about the 500-4000 normal atmosphere, about 100-300 ℃, appropriate solvent and chain-transfer agent in the presence of or not in the presence of, make the method for the monomer copolymerization that becomes raw material beyond the ethene; In polyethylene, be mixed together the monomer that becomes raw material beyond the ethene, the method for fusion-grafting copolymerization etc. in forcing machine with free radical generating agent.
The A1 multipolymer also can be used such commercially available product by commercially available.As this commercially available product, for example can list: " ボ Application De Off ァ-ス ト CG5001 ", " ボ Application De Off ァ-ス ト E ", " ボ Application De Off ァ-ス ト 20B " etc. " ボ Application De Off ァ-ス ト (registered trademark) " series (Sumitomo Chemical (strain) system is with the ethylene copolymer and the ethylene-dien terpolymer of glycidyl methacrylate), " セ Port Le ジ ョ Application G " series (Sumitomo refine (strain) system), " レ Network ス パ-Le RA " series (Japanese polyolefine (strain) system) etc.
(B) composition that uses among the present invention is the epoxy solidifying agent, for example lists: amines such as aliphatic polyamine, aromatic polyamine; The polymeric amide polyamines that polycarboxylic acid and polyamines is carried out deamination reaction and obtain, polymeric amino acid and the amidess such as polymeric amide that obtain; The polymer that contains carboxylic acid group and anhydride group; Novolak; Potentiality solidifying agent such as Dyhard RU 100, polysulfide, polythiol, two hydrazides, guanidine, imidazoles; Heat or light cationic polymerization starter etc.Also can use 2 kinds or above solidifying agent as (B) composition.
Among solidifying agent, the polymer that contains carboxylic acid group and anhydride group is for preferred, especially preferably with (b
1) monomer, (b
2) monomer and (b
3) monomer polymerization and the ethylene-alpha that obtains, beta-unsaturated carboxylic acid analog copolymer (the following B1 multipolymer that often is designated as).
Further, describe the B1 multipolymer in detail.
As (the b in the B1 multipolymer
2) monomeric α, beta-unsaturated carboxylic acid for example lists the monocarboxylic acid of vinylformic acid, methacrylic acid, butenoic acid, monoalkyl fumarate, monoalkyl maleic acid ester etc.; Methylene radical-1,2,3 in toxilic acid, fumaric acid, methylene-succinic acid, the citraconic acid, 3,6-, dicarboxylic acid such as 6-tetrahydrochysene-cis-phthalic acid etc.In addition, as (b
2) monomeric α, the beta-unsaturated carboxylic acid acid anhydride lists above-mentioned α, the intramolecularly of beta-unsaturated carboxylic acid or intermolecular acid anhydride.
As (b
2) monomer, wherein, preferred vinylformic acid, methacrylic acid, maleic anhydride.
As (the b that derives from the B1 multipolymer
2) content of monomeric structural unit, whole structural units 100 weight parts with respect to constituting the B1 multipolymer are generally about the 0.01-20 weight part, are preferably about the 0.1-15 weight part.When deriving from (b
2) content of monomeric structural unit is 0.01 weight part or when above, the tendency that has the physical strength of the binding property film that obtains to improve, thus preferred, when being 20 weight parts or when following, the tendency as the package stability excellence of B1 multipolymer is arranged, so preferably.
As (the b in the B1 multipolymer
3) monomeric esters of unsaturated carboxylic acids, for example list carbon number and be the α about 3-8, the beta-unsaturated carboxylic acid alkyl ester for example lists methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, methacrylic tert-butyl acrylate and Propenoic acid, 2-methyl, isobutyl ester etc. particularly.
As (the b in the B1 multipolymer
3) monomeric vinyl acetate, for example list the vinyl carboxylates about carbon number 1-20, list vinyl acetate, vinyl butyrate, propionate, trimethylacetic acid vinyl acetate, vinyl laurate, different n-nonanoic acid vinyl acetate, バ one サ チ ッ Network vinyl acetate etc. particularly.
As (b
3) monomer, wherein, preferred vinyl acetate, methyl acrylate, ethyl propenoate, n-butyl acrylate, methyl methacrylate.
In the B1 multipolymer, as deriving from (b
3) content of monomeric structural unit, whole structural units 100 weight parts with respect to constituting the B1 multipolymer are generally the 25-70 weight part, are preferably about the 25-65 weight part.When deriving from (b
3) content of monomeric structural unit is 25 weight parts or when above, operation when mixing adhesive resin composition of the present invention is arranged becomes and is easy to tendency, so it is preferred, in addition, there is the B1 multipolymer to be dissolved in the tendency of organic solvent easily, thus preferred, when being 70 weight parts or when following, the tendency that can adopt high-pressure free radical method etc. easily to make the B1 multipolymer is arranged, so preferred.
Adhesive resin composition of the present invention contains the A1 multipolymer as (A) composition, contains the B1 multipolymer as (B) composition, with respect to (A) composition and (B) total 100 weight parts of composition, derives from as (a
1) monomer and (b
1) the content total amount of structural unit of monomeric ethene is the 30-75 weight part for well.
Manufacture method as the B1 multipolymer, for example list following method: in the presence of ethene and free radical generating agent, about the 500-4000 normal atmosphere, about 100-300 ℃, appropriate solvent and chain-transfer agent in the presence of or not in the presence of, make the method for the monomer copolymerization that becomes raw material beyond the ethene; In polyethylene, be mixed together the ethene monomer that becomes raw material in addition, in forcing machine, make it the method for fusion-grafting copolymerization etc. with free radical generating agent.
The B1 multipolymer also can be used such commercially available product by commercially available." ボ Application ダ ィ Application (registered trademark) " series ((having) firmly changes ァ ト Off ィ Na system), " レ Network ス パ-Le ET " series (Japanese polyolefine (strain) system)), " PRIMACOR " serial (Dow Chemical system) etc. as this commercially available product, for example can list:.
As (A) composition in the adhesive resin composition of the present invention and (B) weight ratio of composition, be generally about (A)/(B)=99/1-40/60.If in this scope, then having becomes with the tendency of (C) the mixing property excellence of composition and membranization is easy to tendency.
In addition, mixing (A) composition and (B) melt flow rate (MFR) (being designated as MFR later on) during composition, is for well under 190 ℃, the condition of 2.16kg load about 5-400g/10 minute.
(C) composition as in the adhesive resin composition of the present invention for example lists the whipping agent that decomposes by heating, specifically lists inorganic foaming agent and organic blowing agent etc.
As inorganic foaming agent, list carbonate cpdss such as sodium bicarbonate, volatile salt, bicarbonate of ammonia, ammonium nitrite; Phosphate compoundss such as Tripyrophosphoric acid acid amides, ammonium polyphosphate, melamine phosphate; Carbonization materials such as starch, Mierocrystalline cellulose, carbohydrate, Dipentaerythritol; Light metals such as magnesium end, aluminium end; Hydride such as sodium borohydride, sodium hydride; Trinitride such as sodiumazide etc.
As organic blowing agent, list azo-compound, dinitrosopentamethylene tetramine, N such as azodicarboamide, Diisopropyl azodicarboxylate, N '-dinitroso-N, N '-nitroso compound, p-toluene sulfonyl hydrazide, p such as dimethyl terephthalamide, hydrazide compounds such as p '-oxygen two (benzol sulfohydrazides), hydrazo carboxamide, p-toluene sulfonyt azide, acetone-to sulphonyl hydrazone, melamine, urea, dicyanamide or the like.
As whipping agent, also can use 2 kinds or above whipping agent.In addition, in whipping agent, preferred organic blowing agent, preferred especially azodicarboamide.
The content of (C) composition in the adhesive resin composition of the present invention with respect to (A) composition and (B) total 100 weight parts of composition, is generally about the 2-10 weight part.When the total amount of (C) composition is 2 weight parts or when above, have to peel off and reclaim bonded body and be easy to tendency from the multilayer body that obtains, be 10 weight parts or following occasion at (C) composition, the stable tendency of bounding force is arranged.In addition, more relatively in the adhesive resin composition occasion high by the content that makes (C) composition to the bounding force of bonded body, can easily peel off bonded body from the multilayer body that obtains.
Adhesive resin composition of the present invention for example is to contain by above-mentioned (A) that obtains, (B) and (C) adhesive resin composition of composition.
In the scope of not damaging effect of the present invention, also can in adhesive resin composition of the present invention, contain additives such as mineral filler, pigment, antioxidant, processing stabilizers, weather resisting agent, thermo-stabilizer, photostabilizer, nuclear agent, lubricant, releasing agent, fire retardant, antistatic agent.
As the manufacture method of adhesive resin composition, for example list following method: with the mixing roll of ラ ボ プ ラ ス ト ミ Le etc. etc., mixing (A), (B) and (C) composition, the additive that further comprises as required, the method that obtains with mixing thing form; This mixing thing through further compacting, carry out extrusion moulding with the T die head processing of single shaft or biaxial extruder etc., is obtained the method for membranaceous adhesive resin composition; With (A), (B) and (C) composition, the additive that further comprises as required be dissolved or dispersed in the organic solvent, obtain the method for aqueous adhesive resin composition; (A) composition of mixed emulsion shape, (B) composition of emulsion form and (C) composition, the additive that further comprises as required obtain being scattered in the method for the adhesive resin composition of the emulsion form in the water, or the like.
Also the adhesive resin composition former state ground that obtains so directly can be used as tackiness agent, but can make binding property film (following this binding property film that is designated as sometimes) by membranization adhesive resin composition of the present invention.This binding property film can for example adopt following method easily to obtain: the method for the mixing thing extrusion forming that mixing adhesive resin composition of the present invention is obtained; Adhesive resin composition of the present invention is dissolved or dispersed in the solvent, in the plane coating, exsiccant method.
The thickness of this binding property film, be generally about 3 μ m or more than, be preferably about 3-200 μ m, be preferably about 10-150 μ m especially.
This binding property film-stack is the adhesive multilayer film (following this adhesive multilayer film that is designated as sometimes) that forms supporting on the base material, since not bonding with the face of supporting base material, be preferred scheme aspect the easness of operation.
This adhesive multilayer film for example can adopt following method to make: stacked with mixing thing form adhesive resin composition of the present invention that obtains and the method for supporting base material by co-extrusion modling; Supporting layers on substrates to fold the method for this binding property film by extrusion moulding; Give the adhesive resin composition of the present invention of coating solution shape such as roller coating machine, doctor knife coaters such as rubber coating, the excellent coating machine of マ ィ ャ one coiling, Kohler coater or emulsion form supporting for example to adopt on the base material contrary roll-coater, photogravure coating machine, little coiling rod coating machine, single face, then adopt exsiccant methods such as heating ventilated drying oven, vacuum drier, or the like.
At this,, for example list polyolefinic films such as comprising polyethylene, polypropylene, 4 methyl 1 pentene copolymer as supporting base material; Release paper; The film that comprises demoulding polyethylene terephthalate; Comprise the film of cellulose triacetate etc.At this, in order to peel off the support base material, release paper and comprise the film of demoulding polyethylene terephthalate, usually, their demoulding treated side contacts with this binding property rete.
Extrusion forming as extrusion moulding, co-extrusion modling etc.; Mixing; Drying etc., the temperature when making this binding property film and this adhesive multilayer film, normally implement these operations and about essential temperature, and, be the temperature of the degree that foams hardly of (C) composition in the adhesive resin composition of the present invention, promptly (C) composition decomposition temperature or following about, specifically be about 100-120 ℃.
Multilayer body among the present invention is the multilayer body of the binder layer (following this binder layer that is designated as sometimes) that obtains and bonded body formation by heating this binding property film.In the occasion of having used this adhesive multilayer film, support base material to be stripped from removal usually.As the manufacture method of concrete multilayer body, for example list following method: at the stacked bonded body of this binding property rete side of this adhesive multilayer film, by heating bonding after, peel off the method for supporting base material; At the stacked bonded body of this binding property rete side of this adhesive multilayer film, peel off the method for supporting the base material post-heating; At the stacked bonded body of this binding property film side of this adhesive multilayer film, peel off support base material after, peeling off the folded bonded body different of the surface layer of supporting base material, and the method that heats with this bonded body, or the like.
Heating temperature when bonding is according to the kind of (C) composition that uses and difference, but is about temperature less than the decomposition temperature of (C) composition, specifically is about 80-150 ℃.When confirming the adherent state that causes by heating, substantially do not cause in the scope that (C) composition decomposes and suitablely to determine this time, but general situation is, is the short period of time when carrying out than higher temperature, is long-time when lower temperature is carried out.In addition, confirm that in advance gelation time, (C) composition under the design temperature of adhesive resin composition of the present invention foams the needed time, also can suit to determine the time of gelation taking place and not causing foaming according to its result.Usually suitably selecting between about 5-60 minute than the temperature of low about 5-20 ℃ of the blowing temperature of (C) composition and setting.When heating, with also can about press pressurization 1-6MPa.
At this, as the material that constitutes bonded body, be can with this binder layer adherent material.For example list inorganicss such as metals such as cellulose-based macromolecular material, gold and silver, copper, iron, tin, lead, silicon, glass, pottery particularly; Melamine is that resin, propenoic methyl carbamate are that resin, ammonia ester are macromolecular materials such as resin, (methyl) acrylic resin, styrene-acrylonitrile based copolymer, polycarbonate-based resin, resol, Synolac, Resins, epoxy, silicone resin etc.
As the material of bonded body, with different 2 kinds or above material mixing, compound also passable.In addition, be by bonding 2 the different occasions that bonded body forms of this binder layer in multilayer body, the material that constitutes 2 bonded bodies both can be the material of identical type, also can be the material of different kind.
In addition, as bonded body, when having when peeling off the high heat resisting temperature of Heating temperature when reclaiming bonded body, so the tendency that has the interface of bonded body and this binder layer to peel off easily is preferably.
The multilayer body that obtains like this can require to peel off the bonded body that reclaims bonded body, for example tame electrical articles such as refrigerator, washing machine, air-conditioning, microwave oven, suction cleaner, TV, battery; Office appliances such as Personal Computer, printer, duplicating machine, landline telephone, portable phone; The daily necessities of the automobile of vibroshock, battery jar etc., furniture, housing structure material etc.; The electronic productses of liquid crystal panel, semi-conductor, printed circuit board (PCB), unicircuit, secondary cell container etc. etc. are gone up and are used.In addition, making electronic productses such as semi-conductor is bonded body, the technology interleaving paper (a binding property protection sheet) in the time of also adhesive multilayer film of the present invention can being used to make.
By heating multilayer body of the present invention, bonded body is easily peeled off, is reclaimed from multilayer body, can supply recirculation (utilizing again).For example, this adhesive multilayer film is used as the occasion of technology interleaving paper, multilayer body is the middle manufacture that technology interleaving paper (heating the binder layer that this binding property film obtains) and goods (bonded body) form, if do not need the technology interleaving paper, just easily peels off the recovery goods by heating.
As the concrete method that reclaims bonded body of peeling off, for example list following method: in baking oven, warm water tank etc., put into multilayer body, according to the decomposition temperature of whipping agent and difference, but usually about 80-300 ℃, preferably about 120-240 ℃ the heating, make (C) foaming thus, thereby peel off the method that reclaims bonded body; To multilayer body irradiation flame, infrared rays, steam, ultrasonic wave, hertzian wave etc., make (C) foaming, thereby peel off the method that reclaims bonded body; Multilayer body is placed on the heating member such as iron plate, make (C) foaming, thereby peel off the method that reclaims bonded body; Or the like.In all case all can suit to make up, determine the temperature and time of enough (C) compositions from the foaming of this binder layer.For example can list in the blowing temperature of (C) composition condition to about+20 ℃, 5-60 minute.
The bonded body of Hui Shouing can easily be peeled off from multilayer body in this wise, even no matter adhere to the material that derives from this binder layer hardly or adhere to the material that derives from this binder layer on this bonded body, also be the degree that can easily peel off from bonded body, can recirculation (utilizing again) this bonded body or easily obtain this bonded body with the goods form.
In addition, bonded bodies such as the metal that is recovered, plastics also can fusion, utilize on the basis of its method moulding again.
Embodiment below is shown, illustrates in greater detail the present invention, but the present invention is not limited to these.Part in the example only otherwise special declaration means weight basis.
(A), (B) and (C) composition used following composition.In addition, MFR (melt flow rate (MFR)) has shown the value of measuring according to JIS K7210 standard under 190 ℃, the condition of 2160g load.
(A) composition
A: " ボ Application De Off ァ-ス ト CG 5001 ", the ethylene-methyl acrylate-glycidyl methacrylate copolymer that Sumitomo Chemical (strain) is made, derive from content 18 weight %, MFR=360g/10 minute of structural unit of glycidyl methacrylate
(B) composition
B:(has) firmly change " ボ Application ダ ィ Application HX8210 ", ethylene-propylene acetoacetic ester-copolymer-maleic anhydride, the content 6 weight % that derive from the structural unit of ethyl propenoate that ァ ト Off ィ Na makes, content 3 weight %, MFR=200g/10 minute of the structural unit that derives from maleic anhydride
(C) composition
C: three associations change into " セ Le マ ィ Network C-121 ", azodicarboamide, 205 ℃ of decomposition temperatures, the median size 10-14 μ m that (strain) makes
(embodiment 1-3 and comparative example 1)
(1): the Production Example of adhesive resin composition
With above-mentioned (A), (B) with (C) add small-sized intermittent type kneader " ラ ボ プ ラ ス ト grinding machine " to (the smart mechanism of (strain) Japan is made made main body: 50C150, mixing machine: R100H) by the weight ratio of table 1 record, under the condition of 100 ℃ of tube design temperatures, with 10rpm after pre-mixing 7 minutes, with 50rpm formal mixing 5 minutes, obtain adhesive resin composition.
(2): the Production Example of adhesive multilayer film
Behind the adhesive resin composition that in (1), obtains with the premolding condition hot pressing of following record, be preheated to stacked above one another SUS plate and fluoro-resin sheet on 100 ℃ the hot plate of thermocompressor, the preform of on this fluoro-resin sheet, placing the polyethylene terephthalate template and obtaining, place the fluoro-resin sheet again, place SUS (stainless steel) plate then, the film condition of molding of following following record carries out hot pressing, obtains the binding property film.
Then, the stripping surface of the manufactured polyethylene terephthalate film of the membranaceous adhesive resin composition and the demoulding " ェ Application Block レ ッ ト SC " (ュ ニ チ カ manufacturing) is overlapped, use laminating machine " VA-700 " (manufacturing of great achievement laminating machine company), at roll temperature: 80 ℃, roller speed: 0.5m/ branch, roller pressure: 4.9 * 10
4Pa (0.5kgf/cm
2, represent reading) condition under carry out heat lamination, obtain (supporting base material: adhesive multilayer film demoulding polyethylene terephthalate film)/(binding property rete).
＜premolding condition 〉
Metal die: 120mm * 120mm * 1mm is thick
The hot plate design temperature: 100 ℃, preheating 10 minutes (toppling over ダ Application ピ Application グ 3 times),
Pressurization: 50kg/cm
2* 1 minute-→ 100kg/cm
2* 1 minute-→ 150kg/cm
2, the cooling 100kg/cm
2* 2 minutes
＜film condition of molding 〉
Template: 150mm * 75mm * 0.1mm is thick,
The hot plate design temperature: 100 ℃, preheating 10 minutes (ダ Application ピ Application グ 3 times),
Pressurization: 50kg/cm
2* 1 minute → 100kg/cm
2* 1 minute → 150kg/cm
2, the cooling 100kg/cm
2* 2 minutes
(3): the Production Example of multilayer body
The adhesive multilayer film that will in (2), obtain cut into 25mm wide after, stacked SUS (stainless steel) or slide glass on the binding property film as bonded body.That is, from following sequential cascade by (support base material)/(binding property rete)/(bonded body).Then, with hand peel off support base material after, behind the stacked polyethylene terephthalate film (PET film) of not implementing following demoulding processing as base material, use heat-sealing trier (ヒ-ト シ-Le テ ス -) (" ヒ-ト シ-Le テ ス -TP-701-B " that テ ス -industry (strain) is made), from excellent at 150 ℃, 9.8 * 10 up and down
4Pa (gauge pressure: 1kgf/cm
2) pressure (base material)/(binding property rete)/(bonded body) heat-sealing 30 clocks that will obtain, obtain multilayer body of the present invention.
In addition, the bonded body of use is face as follows, is shown in table 1 about contained (A)-(C) composition and bonded body in the adhesive resin composition that uses.
＜bonded body 〉
SUS:SUS304 is dull and stereotyped, and 160mm * 65mm * 0.8mm is thick
Slide glass: MATSUNAMI (strain) makes S1126
The thick surface water edge mill of 76mm * 26mm * 1.0mm was handled
＜base material 〉
The PET film: DIAF0IL T600E50-W07 50 μ m are thick
The Port リ ェ ス テ of Mitsubishi Chemical Le Off ィ Le system is made the two sided coatings film
(4) mensuration of bounding force before the heating
After the multilayer body state that will obtain in (3) under the condition of 23 ℃ of temperature, relative humidity 50% is modulated 1 hour, cut 10mm wide * test film of 100mm long (bond length 25mm), under the condition of 23 ℃ of temperature, relative humidity 50%, implemented stripping test for 180 ° with peeling rate 100mm/ second, peel angle.
(5) add the thermally strippable test
On being heated to 240 ℃ hot plate, be placed on the multilayer body that makes in (3), make bonded body below, carry out heating in 5 minutes after, carry out state observation.Table 1 shows the result.
In addition, following benchmark is followed in judgement.
Zero: bonded body has been separated immediately.
*: can not easily separate bonded body.
Table 1
| Embodiment | Comparative example | |||||
| 1 | 2 | 3 | 1 | |||
| The composition of adhesive resin composition | A (part) | 48.5 | 47.6 | 46.3 | 50 | |
| B (part) | 48.5 | 47.6 | 46.3 | 50 | ||
| C (part) | 3.0 | 4.8 | 7.4 | 0 | ||
| C(phr) *1 | 3 | 5 | 8 | 0 | ||
| Bounding force | SUS (N/10mm) | 10.9 | 15.1 | 14.3 | 16.0 | |
| Glass (N/10mm) | 12.8 | 10.6 | 10.1 | 7.9 | ||
| Add the thermally strippable release surface | ○ ① | ○ ① | ○ ② | × - | ||
* 1: with respect to the C umber of 100 parts of the totals of A and B
1.: the interface peel of bonded body and binder layer
2.: bonded body gathers mixing of peeling off with the interface peel and the interior of binder layer of binder layer
The binding property film that adhesive resin composition moulding of the present invention is obtained has the dry film shape form to processing eases such as keeping, carrying, bonding operations before bonding, and, by adding heat bonding, can become binder layer with excellent bounding force.
Secondly, only heating just easily reduces bounding force separately, peel off and reclaim bonded body, even on the bonded body that has reclaimed, adhere to the tackiness agent that derives from the binding property film hardly or adhere to, also be the degree that can easily peel off from bonded body, this bonded body can recirculation (utilizing again).
Utilize the characteristic of such excellence, multilayer body of the present invention for example can be used in decorative film, plasma displays such as the solder resist, trolley part of tube core bonding pad between electronic part encapsulation material, unicircuit/substrates such as semiconductor-encapsulating material, solar cell and EL (electroluminescent) lamp and the interlayer insulating film between substrate, printed circuit board (PCB).In addition, the technology interleaving paper that also can use when making etc. as semi-conductor.
Claims (19)
1. one kind contains following (A), (B) and (C) adhesive resin composition of composition,
(A): the olefin resin that contains epoxy group(ing)
(B): solidifying agent
(C): thermal degradation type whipping agent,
Wherein, (B) composition is the following (b of polymerization
1), (b
2) and (b
3) and the ethylene-alpha that obtains, the beta-unsaturated carboxylic acid analog copolymer,
(b
1) ethene,
(b
2) α, beta-unsaturated carboxylic acid and/or α, the beta-unsaturated carboxylic acid acid anhydride,
(b
3) vinyl acetate and/or α, the beta-unsaturated carboxylic acid ester, and
With respect to (A) composition and (B) total 100 weight parts of composition, (C) composition is the 2-10 weight part.
2. adhesive resin composition according to claim 1, wherein, (A) composition is the following (a of polymerization
1) and (a
2) and obtain contain the epoxy group(ing) vinyl copolymer,
(a
1) ethene,
(a
2) at least a kind of monomer from the monomer of representing with the monomer of following general formula (1) expression and with following general formula (2), selecting,
In the formula, R represent to have two keys carbon number 2-18 alkyl or combine the alkyl of the carbon number 2-18 with two keys of halogen atom, X represents singly-bound or carbonyl,
In the formula, R ' expression have two keys carbon number 2-18 alkyl or combine the alkyl of the carbon number 2-18 with two keys of halogen atom.
3. adhesive resin composition according to claim 1 and 2, wherein, (A) composition be polymerization not with epoxy reaction, can with the monomer of ethylene copolymer, above-mentioned (a
1) monomer and above-mentioned (a
2) monomer and the multipolymer that obtains.
4. adhesive resin composition according to claim 1, wherein, (B) in the composition with respect to unitary total 100 weight parts of entire infrastructure that constitute (B) composition, contain and derive from (b
2) structural unit 0.01-20 weight part, derive from (b
3) structural unit 25-70 weight part.
5。Adhesive resin composition according to claim 1 and 2, wherein, (A) composition contains the above-mentioned (a of polymerization
1) and above-mentioned (a
2) and obtain contain the epoxy group(ing) vinyl copolymer, (B) composition contains the above-mentioned (b of polymerization
1), above-mentioned (b
2) and above-mentioned (b
3) and the ethylene-alpha that obtains, the beta-unsaturated carboxylic acid analog copolymer, derive from ethene structural unit content the total amount with respect to (A) composition and (B) total 100 weight parts of composition be the 30-75 weight part.
6. adhesive resin composition according to claim 1 and 2, wherein, (A) composition is (A)/(B)=90/10-40/60 with (B) weight ratio of composition.
7. adhesive resin composition according to claim 1 and 2, wherein, (C) composition is an azodicarboamide.
8. adhesive resin composition according to claim 1 and 2, wherein, with respect to (A) composition and (B) total 100 weight parts of composition, (C) composition is the 3-8 weight part.
9. adhesive resin composition according to claim 1 and 2, wherein, with respect to (A) composition and (B) total 100 weight parts of composition, (C) composition is the 3-5 weight part.
10. binding property film, wantonly 1 described adhesive resin composition of membranization claim 1-9 and forming.
11. binding property film according to claim 10, wherein, the mixing thing that obtains by mixing this adhesive resin composition of extrusion forming obtains.
12. binding property film according to claim 10, wherein, with the dissolving of this adhesive resin composition or be dispersed in the solvent, coating in the plane, dry and obtain.
13. an adhesive multilayer film forms at wantonly 1 described binding property film of supporting the folded claim 10-12 of layers on substrates.
14. adhesive multilayer film according to claim 13 wherein, supports that base material is from comprising polyolefinic film, comprising at least a kind that selects the film of demoulding polyethylene terephthalate, the film that comprises cellulose triacetate and the release paper.
15. a multilayer body is included in the binder layer and the bonded body that obtain less than wantonly 1 the described binding property film of heating claim 10-12 under the temperature of the decomposition temperature of (C) composition.
16. multilayer body, have binder layer and bonded body, the stacked bonded body of binding property rete one side that forms by adhesive resin composition at membranization claim 13 or 14 described adhesive multilayer films, less than (C) thus under the temperature of the decomposition temperature of composition this laminate of heating bonding after, support base material and can obtain by peeling off.
17. multilayer body, have binder layer and bonded body, at the adhesive resin composition of membranization claim 13 or 14 described adhesive multilayer films and the stacked bonded body of binding property rete one side that forms, peel off support base material after, by heating under less than the temperature of the decomposition temperature of (C) composition, bonding and can obtain.
18. multilayer body, have binder layer and bonded body, at the adhesive resin composition of membranization claim 13 or 14 described adhesive multilayer films and the stacked bonded body of binding property rete one side that forms, after peeling off the support base material, at a side stacked bonded body different of having peeled off the face of supporting base material, undertaken bonding and can obtain by being heated to less than the temperature of the decomposition temperature of (C) composition with this bonded body.
19. the recovery method of a bonded body is characterized in that, by wantonly 1 described multilayer body that decomposition temperature or above temperature at (C) composition heat claim 15-18, peels off bonded body from multilayer body.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002030739 | 2002-02-07 | ||
| JP30739/2002 | 2002-02-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1628163A CN1628163A (en) | 2005-06-15 |
| CN1290958C true CN1290958C (en) | 2006-12-20 |
Family
ID=27677911
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038033933A Expired - Fee Related CN1290958C (en) | 2002-02-07 | 2003-02-03 | Adhesive resin composition and use thereof |
Country Status (5)
| Country | Link |
|---|---|
| KR (1) | KR20040088052A (en) |
| CN (1) | CN1290958C (en) |
| AU (1) | AU2003208099A1 (en) |
| TW (1) | TWI263666B (en) |
| WO (1) | WO2003066771A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI422601B (en) * | 2007-11-29 | 2014-01-11 | Sumitomo Chemical Co | Thermosetting resin composition |
| JP6068236B2 (en) * | 2013-04-02 | 2017-01-25 | 富士フイルム株式会社 | Laminated film, back sheet for solar cell module, and solar cell module |
| CN103627336A (en) * | 2013-05-14 | 2014-03-12 | 苏州邦立达新材料有限公司 | Pressure sensitive adhesive tape and preparation method thereof |
| CN104497905A (en) * | 2014-12-11 | 2015-04-08 | 安徽明讯新材料科技股份有限公司 | Low-viscosity protective film and preparation method thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5614574A (en) * | 1979-07-16 | 1981-02-12 | Hitachi Chem Co Ltd | Self-adhesive or adhesive tape |
| JPS6414235A (en) * | 1987-07-08 | 1989-01-18 | Showa Denko Kk | Crosslinked ethylenic copolymer mixture |
| JPH0543855A (en) * | 1991-08-13 | 1993-02-23 | Nippon Synthetic Chem Ind Co Ltd:The | Releasable self-adhesive composition |
| JP2970963B2 (en) * | 1991-08-14 | 1999-11-02 | 日東電工株式会社 | Peelable pressure-sensitive adhesive and adhesive member thereof |
| JP2898480B2 (en) * | 1992-09-14 | 1999-06-02 | 日東電工株式会社 | Heat-peelable adhesive and adhesive member |
| JPH07133472A (en) * | 1993-11-11 | 1995-05-23 | Sekisui Chem Co Ltd | Adhesive composition |
| JPH107719A (en) * | 1996-06-28 | 1998-01-13 | Mitsui Petrochem Ind Ltd | Modifier comprising olefin-polar monomer copolymer |
| JP2002069422A (en) * | 2000-08-30 | 2002-03-08 | Toyo Chem Co Ltd | Thermally foamed type pressure sensitive adhesive and its pressure sensitive adhesion member |
| JP4703833B2 (en) * | 2000-10-18 | 2011-06-15 | 日東電工株式会社 | Energy ray-curable heat-peelable pressure-sensitive adhesive sheet and method for producing cut pieces using the same |
| JP2002146326A (en) * | 2000-11-02 | 2002-05-22 | Three M Innovative Properties Co | Adhesive sheet |
| JP2002249744A (en) * | 2001-02-26 | 2002-09-06 | Sekisui Chem Co Ltd | Photocurable adhesive composition, adhesive and method for peeling the same |
-
2003
- 2003-01-30 TW TW092102301A patent/TWI263666B/en not_active IP Right Cessation
- 2003-02-03 CN CNB038033933A patent/CN1290958C/en not_active Expired - Fee Related
- 2003-02-03 WO PCT/JP2003/001044 patent/WO2003066771A1/en active Application Filing
- 2003-02-03 AU AU2003208099A patent/AU2003208099A1/en not_active Abandoned
- 2003-02-03 KR KR10-2004-7012015A patent/KR20040088052A/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| CN1628163A (en) | 2005-06-15 |
| KR20040088052A (en) | 2004-10-15 |
| AU2003208099A1 (en) | 2003-09-02 |
| WO2003066771A1 (en) | 2003-08-14 |
| TWI263666B (en) | 2006-10-11 |
| TW200401019A (en) | 2004-01-16 |
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