CN105331308B - Thermosetting adhesive composition, thermosetting adhesive sheet, its manufacture method and enhancing flexible printing wiring board - Google Patents
Thermosetting adhesive composition, thermosetting adhesive sheet, its manufacture method and enhancing flexible printing wiring board Download PDFInfo
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- CN105331308B CN105331308B CN201510763270.2A CN201510763270A CN105331308B CN 105331308 B CN105331308 B CN 105331308B CN 201510763270 A CN201510763270 A CN 201510763270A CN 105331308 B CN105331308 B CN 105331308B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4035—Hydrazines; Hydrazides
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- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
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- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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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
- 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
- C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2433/00—Presence of (meth)acrylic polymer
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2463/00—Presence of epoxy resin
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/00013—Fully indexed content
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0277—Bendability or stretchability details
- H05K1/028—Bending or folding regions of flexible printed circuits
- H05K1/0281—Reinforcement details thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention relates to thermosetting adhesive composition, thermosetting adhesive sheet, its manufacture method and enhancing flexible printing wiring board.Thermosetting adhesive composition, it contains acrylic acid series copolymer (A), epoxy resin (B) and hardener for epoxy resin (C).Acrylic acid series copolymer (A) is to form the mass % of (methyl) acrylate monomer (c) 1~10 copolymerization without the mass % of epoxy radicals (methyl) acrylate monomer (a) 65~75, the mass % of acrylonitrile monemer (b) 20~35 and containing epoxy radicals.Hardener for epoxy resin is organic acid dihydrazide particle of 0.5~15 μm of average grain diameter.
Description
The application is Application No. 201080045247.5 (international filing date is on July 26th, 2010), entitled
The national rank of entrance of " thermosetting adhesive composition, thermosetting adhesive sheet, its manufacture method and enhancing flexible printing wiring board "
The divisional application of the PCT application of section
Technical field
The present invention relates to the thermosetting bonding group containing acrylic acid series copolymer, epoxy resin and hardener for epoxy resin
Compound.
Background technology
The polyimide film such as portion of terminal by the flexible printing wiring board comprising polyimide film, glass epoxy resin
Plate, sheet metal liner, to improve its intensity.In this case, strengthen between plate and the polyimides of flexible printing wiring board
Bonding is typically to make to be solidified to be bonded by the heat-curable adhesive layer clamped by them.As this heat-curable adhesive layer,
Widely used in flexible printing wiring board field and mainly include liquid-state epoxy resin, solid epoxy and their curing agent
Epoxide resin adhesive (patent document 1).
But this epoxide resin adhesive exists in normal temperature because the compounding ratio of epoxy resin and curing agent
Problem be present in the problem of curing reaction is slowly carried out in preservation, normal temperature preservation characteristics aspect.Therefore, preserved to improve normal temperature
Characteristic, it is proposed that suppress the use level of epoxy resin, the acrylic acid of main component is correspondingly used as using acrylic acid series polymeric compounds
It is thermosetting adhesive composition (patent document 2, particularly embodiment 2).
Patent document 1：Japanese Unexamined Patent Publication 04-370996 publications
Patent document 2：Japanese Unexamined Patent Publication 2007-9058 publications.
The content of the invention
It is conventional with patent document 1 however, in the case of the acrylic acid series thermosetting adhesive composition of patent document 2
Epoxide resin adhesive is compared, although normal temperature keeping quality improve, if but at normal temperatures preserve up to the several months time, then
In engagement for flexible printed board and resin sheet, metal reinforcing plate or glass epoxy board, then cementability (is peeled off strong
Degree) and reflow soldering heat resistance be likely to decrease, it is desirable to it is improved.
It is an object of the present invention to solves the existing technical problem of the above, there is provided used in the fields such as flexible printed board
In the acrylic acid series thermosetting adhesive composition of bonding, its be can by the resin substrates such as polyimide film and polyimide film,
It is bonded well between metal reinforcing plate or glass epoxy substrate, by that can also be shown well up to the time of several months
Normal temperature preservation characteristics acrylic acid series thermosetting adhesive composition.
As the hardener for epoxy resin of the normal temperature keeping quality for improving epoxide resin adhesive, the present inventor
Eye in due to not readily dissolve in organic solvent, at normal temperatures solid thus will not react with epoxy resin, by heating and
Epoxy resin melting mixing and organic acid dihydrazide of initiation reaction, to coordinating epoxy resin in acrylic acid series copolymer, making
Studied for organic acid dihydrazide of hardener for epoxy resin.Usually as the manufacture method of membranaceous adhesive sheet, adopt
With dissolving, being dispersed in the organic solvents such as MEK, the method for being coated to manufacture by above-mentioned complex, although but existing
The curing agent particle of organic acid dihydrazide not readily dissolves in organic solvent, but in organic solvent can slow mechanism dissolved, institute it is molten
The curing agent of solution also dissolves in the epoxy, therefore the problem of reacted.Based on this viewpoint, find by by organic acid
The average grain diameter of two hydrazides is controlled in specific particle size range, can well be realized with balance and be suppressed organic acid when normal temperature preserves
The dissolving in organic solvent of two hydrazides and the quick progress of heat cure reaction, and then acrylic acid series copolymer is used as, pass through
Using (methyl) acrylate monomer without epoxy radicals of particular range amount, acrylonitrile monemer and (methyl) third containing epoxy radicals
The copolymer of olefin(e) acid ester monomer, above-mentioned purpose can be reached, so as to complete the present application.
That is, thermosetting adhesive composition provided by the invention, it is to contain acrylic acid series copolymer (A), epoxy resin (B)
With the thermosetting adhesive composition of hardener for epoxy resin (C), wherein
The acrylic acid series copolymer (A) be by without the mass % of epoxy radicals (methyl) acrylate monomer (a) 65~75,
The mass % of acrylonitrile monemer (b) 20~35 and containing epoxy radicals the mass % of (methyl) acrylate monomer (c) 1~10 copolymerization form
,
The hardener for epoxy resin is organic acid dihydrazide particle of 0.5~15 μm of average grain diameter.It should illustrate, at this
In specification, " (methyl) acrylic acid " this term refers to " methacrylic acid or acrylic acid ".
In addition, the present invention provides thermosetting adhesive sheet, it is formed on base material film comprising thermosetting bonding combination
What the thermosetting adhesive linkage of thing formed.
Further, the present invention provides manufacture method, and it is the manufacture method of the thermosetting adhesive sheet, and it includes：
The thermosetting adhesive composition of the invention described above is put into organic solvent, makes hardener for epoxy resin (C)
It is scattered on the other hand to make acrylic acid series copolymer (A) and epoxy resin (B) dissolving in organic solvent in organic solvent, by
This prepares the step of thermosetting adhesive linkage formation coating, and
By on thermosetting adhesive linkage formation coatings to base material film, it is dried, is consequently formed thermosetting adhesive linkage
The step of.
The thermosetting adhesive composition of the present invention is by the resin substrates such as polyimide film and polyimide film, glass ring oxygen tree
(preferably more than 15N/cm) is bonded well between the metallic plates such as fat, stainless steel, and is also shown by the time up to the several months
Good film normal temperature preservation characteristics.In addition, after more than 260 DEG C of reflow soldering processing, also showing will not be due to inhaling
Characteristic that is wet and producing expansion.
Embodiment
The thermosetting adhesive composition of the present invention, which contains acrylic acid series copolymer (A), epoxy resin (B) and epoxy resin, to be used
Curing agent (C).
In the present invention, acrylic acid series copolymer (A) is scratched for providing film forming when film is molded, having solidfied material
Property, toughness, it is by without epoxy radicals (methyl) acrylate monomer (a), acrylonitrile monemer (b) and (first containing epoxy radicals
Base) acrylate monomer (c) copolymerization forms.
, can be from suitable for the conventional of field of electrical components as (methyl) acrylate monomer (a) without epoxy radicals
Acrylic acid series heat-curable adhesive in (methyl) acrylate monomer without epoxy radicals for using appropriate selection use,
Such as methyl acrylate, ethyl acrylate, n-propyl, n-butyl acrylate, isobutyl acrylate, propylene can be enumerated
The just own ester of acid, n-octyl, Isooctyl acrylate monomer, 2-EHA, the different nonyl ester of acrylic acid, stearyl acrylate
Ester, methyl methacrylate, EMA, n-BMA, Isobutyl methacrylate, methacrylic acid
Just own ester, n octyl methacrylate, EHMA, 2-Ethylhexyl Methacrylate, the different nonyl of methacrylic acid
Ester, methacrylic acid n-dodecane base ester, methacrylic acid Permethyl 99A base ester, stearyl methacrylate etc..Wherein, preferably
Use butyl acrylate, ethyl acrylate.
Prepare in the whole monomers used during acrylic acid series copolymer (A), (methyl) acrylate list without epoxy radicals
The dosage of body (a), if crossing fundamental characteristics at least reduces, if the trend that heat resistance reduction at most be present is crossed, therefore preferably 65~
75 mass %, more preferably 65~70 mass %.
Acrylonitrile monemer (b) is used to improve heat resistance.
Prepare in the whole monomers used during acrylic acid series copolymer (A), the dosage of acrylonitrile monemer (b), if crossing at least
Heat resistance reduces, and is difficult to dissolve trend in a solvent, therefore preferably 20~35 mass % if crossing at most and existing, more preferably
25~30 mass %.
(methyl) acrylate monomer (c) containing epoxy radicals is used to react with hardener for epoxy resin, is glued in thermosetting
Connect in the solidfied material of composition and form three-dimensional crosslinking structure.If form three-dimensional crosslinking structure, the moisture-proof of solidfied material and heat-resisting
Property improve, such as even in being bonded and fixed to flexible printing wiring board comprising the solidfied material by thermosetting adhesive composition
The enhancing flexible printing wiring board of reinforced resin sheet material carries out the feelings of more than 260 DEG C of soldering processing (such as reflow soldering processing)
Under condition, it is also possible to prevent to produce the swelling caused by moisture absorption in its portion of being adhesively fixed.As this containing epoxy radicals
(methyl) acrylate monomer (c), can be from the conventional acrylic acid series heat-curable adhesive suitable for field of electrical components
Appropriate selection uses in the monomer used, such as can to enumerate glycidyl acrylate (GA), Glycidyl methacrylate sweet
Grease (GMA) etc..Wherein, from the aspect of obtaining easiness from security, market, preferably using GMA
(GMA)。
Prepare in the whole monomers used during acrylic acid series copolymer (A), (methyl) acrylate monomer containing epoxy radicals
(c) dosage, if crossing heat resistance at least reduces, if the trend that peel strength reduction at most be present is crossed, therefore preferably 1~10 matter
Measure %, more preferably 3~7 mass %.
(methyl) acrylate monomer (a), acrylonitrile monemer (b) described above by without epoxy radicals and containing epoxy radicals
(methyl) acrylate monomer (c) prepare acrylic acid series copolymer, known copolymerization process can be applicable to carry out.
For the acrylic acid series copolymer (A) used in the present invention, the peel strength and resistance to if its weight average molecular weight is too small
Hot reduction, exist if excessive solution viscosity rise, coating be deteriorated trend, therefore preferably have 500000~
700000th, more preferably 550000~650000 weight average molecular weight.
The epoxy resin (B) for forming the thermosetting adhesive composition of the present invention is used to form tridimensional network, makes heat-resisting
Property, cementability are good.
, can be from the conventional epoxy resin thermosetting bonding suitable for field of electrical components as epoxy resin (B)
Appropriate selection uses in the liquid or the epoxy resin of solid-like that are used in agent, for example, can enumerate bisphenol A type epoxy resin,
Bisphenol f type epoxy resin, bisphenol-A D-ring oxygen tree fat, bisphenol-A epoxy resin, phenol novolak type epoxy resin,
Cresol novolak type epoxy resin, polyalkylene polyol (neopentyl glycol etc.) poly epihydric alcohol base ether, four glycidyl group
Diaminodiphenyl-methane, triglycidyl group-para-aminophenol, triglycidyl group-m-aminophenol, four glycidols
Base-m-xylene diamine, phthalic acid 2-glycidyl ester, hexahydrobenzene dicarboxylic acid diglycidyl ester, four hydrogen phthalates two
Ethylene oxidic ester, vinyl cyclohexene dioxide, 3,4- epoxycyclohexylmethyls (3,4- epoxy-cyclohexanes) carboxylate,
Double (3,4- epoxy radicals -6- methylcyclohexylmethyls) adipate esters etc..
The dosage of epoxy resin (B) in the thermosetting adhesive composition of the present invention, if crossing heat resistance at least reduces, if mistake
The trend of cementability reduction at most be present, therefore relative to the mass parts of acrylic acid series copolymer (A) 100, preferably 5~30 mass
Part, more preferably 10~20 mass parts.
In the thermosetting adhesive composition of the present invention, as with from epoxy resin (B) and preparing acrylic acid series copolymer
(A) hardener for epoxy resin (C) of the epoxy reaction of (methyl) acrylate monomer containing epoxy radicals used when, use
Average grain diameter is 0.5~15 μm, preferably 1~5 μm of organic acid dihydrazide particle.It is using the reasons why organic acid dihydrazide,
Because it is solid at normal temperatures, therefore the normal temperature preservation characteristics of thermosetting adhesive composition can be improved.In addition, make organic acid
The reasons why average grain diameter of two hydrazides particles is 0.5~15 μm is, if less than 0.5 μm, in order to be coated with thermosetting bonding group
Compound and when using organic solvent, the possibility rise of organic acid dihydrazide particle dissolving, normal temperature preservation characteristics are likely to decrease,
If being more than 15 μm on the contrary, the coating of thermosetting adhesive composition reduces, additionally due to granularity is big, with acroleic acid polymerization
It is possible to be sufficiently mixed when thing, epoxy resin melting.
, can be from the organic acid dihydrazide for the curing agent for being used as epoxy resin in the past as this organic acid dihydrazide
It is appropriate to select to use, such as careless acid dihydrazide, acid dihydrazide, amber acid dihydrazide, iminodiacetic acid can be enumerated
Two hydrazides, adipic dihydrazide, the hydrazides of pimelic acid two, the hydrazides of suberic acid two, the hydrazides of azelaic acid two, sebacic dihydrazide, 12
Alkane dicarboxyl acid dihydrazide, the hydrazides of hexadecane dicarboxylic acid two, Malaysia acid dihydrazide, the hydrazides of fumaric acid two, diglycolic acid two
Hydrazides, winestone acid dihydrazide, apple acid dihydrazide, isophthalic dihydrazide, terephthaldehyde's acid dihydrazide, 2,6- naphthoic acids two
Double (Hydrazinocarbonyl the ethyl) -5- isopropyl hydantoins of hydrazides, 4,4 '-bis- hydrazides of benzene two, the hydrazides of 1,4- naphthoic acids two, 1,3-
(ア ミ キ ュ ア VDH (trade name), monosodium glutamate (strain)), the carbohydrazides of 18 carbon diene -1,18- of 7,11- two (ア ミ キ ュ ア UDH
(trade name), monosodium glutamate (strain)), the hydrazides of citric acid three etc..It can be used alone one kind in them or combine two or more next
Use.Wherein, from fusing point is relatively low, curability balance is excellent, be readily available from the aspect of, preferably using adipic dihydrazide
Or the carbohydrazides of 18 carbon diene -1,18- of 7,11- two.
The dosage of hardener for epoxy resin (C) in the thermosetting adhesive composition of the present invention, remained at least not if crossing
The epoxy radicals of reaction, crosslinking are also insufficient, therefore heat resistance, cementability reduce, if crossing at most excessive curing agent unreacted
Still remain, therefore heat resistance be present, the trend that cementability reduces, so relative to acrylic acid series copolymer (A) and asphalt mixtures modified by epoxy resin
The mass parts of total 100 of fat (B), more preferably preferably 4~20 mass parts, 6~15 mass parts.
In the thermosetting adhesive composition of the present invention, in addition to composition described above, effect of the present invention is not being damaged
In the range of, the matal deactivator, defoamer, antirust of the dissolving that will not promote organic acid dihydrazide can be coordinated as needed
Additive known to agent, dispersant etc..
The thermosetting adhesive composition of the present invention can be by using conventional method by acrylic acid series copolymer (A), epoxy
Resin (B), hardener for epoxy resin (C) and other additives are equably mixed to prepare.As its form, can make
Into paste, film, scattered liquid etc..Wherein, consider from viewpoints such as operability when keeping quality, use, preferably with poly- terephthaldehyde
The heat for including the present invention is formed on the base material film such as sour glycol ester film, polyimide film (peeling base) with 10~50 μm of thickness
The mode of the thermosetting adhesive sheet that the thermosetting adhesive linkage of solidity adhesive composition forms uses.It should illustrate, according to need
Lift-off processing can also be implemented to the base material film with organosilicon etc..
The manufacture method of this thermosetting adhesive sheet contains following thermosetting adhesive linkage formation coating preparation step
With thermosetting adhesive linkage forming step.
<Thermosetting adhesive linkage forms and uses coating preparation step>
First, the thermosetting adhesive composition of the present invention is put into suitable to be formed in the organic solvents such as MEK, toluene
Together in the viscosity of rubbing method, make hardener for epoxy resin (C) scattered in organic solvent, on the other hand make acrylic copolymer
Thing (A) and epoxy resin (B) dissolving in organic solvent, thus prepare thermosetting adhesive linkage formation coating.Now, in order to carry
The normal temperature keeping quality of high thermosetting adhesive sheet, preferably at room temperature 70 mass % of whole organic acid dihydrazide particles are with solid
Particulate forms are dispersed in thermosetting adhesive linkage formation coating.
<Thermosetting adhesive linkage forming step>
Then, by bar coater, roll coater etc. by thermosetting adhesive linkage formation coatings on base material film so that dry
Dry thickness is 10~50 μm, is dried by conventional method, is consequently formed thermosetting adhesive linkage.So as to obtain thermosetting
Adhesive sheet.
Thermosetting adhesive composition and thermosetting adhesive sheet described above can be preferably applied to field of electrical components
In.Particularly above-mentioned thermosetting adhesive sheet can be preferably applied to by portion of terminal of flexible printing wiring board etc. with for being formed
The polyethylene terephthalate of its lining, polyimides, glass epoxy resin, stainless steel, aluminium equal thickness are 50 μm~2mm
Enhancing be adhesively fixed with resin sheet, be applicable by this, obtain the portion of terminal of flexible printing wiring board and enhancing resin sheet
Material be adhesively fixed by the thermosetting compound for eliminating the thermosetting adhesive linkage after the base material film of thermosetting adhesive sheet of the present invention and
Into enhancing flexible printing wiring board.
Embodiment
More specific description is carried out to the present invention by the following examples.
Embodiment 1~10, comparative example 1~8
(1) preparation of acrylic acid series copolymer
Prepare the acrylic acid series copolymer for including the monomer shown in Tables 1 and 2.These acrylic acid series copolymers are divided equally again
Son amount is as shown in Table 1 and Table 2.
(2) preparation of heat cure adhesive linkage formation coating
Into resulting acrylic acid series copolymer solution with the compounding ratio of Tables 1 and 2 addition epoxy resin (B) and
As organic acid dihydrazide of hardener for epoxy resin (C), equably mix, thus prepare thermosetting adhesive linkage formation painting
Material is used as thermosetting adhesive composition.The viscosity of resulting coating is measured by Brookfield viscometer, is shown in Tables 1 and 2
In.
(3) manufacture of thermosetting adhesive sheet
By resulting thermosetting adhesive linkage formation coatings in the poly terephthalic acid second for implementing lift-off processing
Diol ester film, dried in 50~130 DEG C of drying oven, form the thermosetting adhesive linkage of 35 μ m-thicks, thus manufactured thermosetting and glue
Contact pin material.
(4) evaluation of the coating of thermosetting adhesive linkage formation coating
When manufacturing above-mentioned thermosetting adhesive sheet, according to coating of the following benchmark to thermosetting adhesive linkage formation coating
Property is evaluated.Resulting evaluation result is as shown in Table 1 and Table 2.
AA：The thickness of bonding agent is homogeneous, texture is not formed in coating, does not also observe the feelings of curing agent particle in appearance
Condition
A：Although not forming texture in coating, but the situation of curing agent particle is observed on film after the drying
B：In the presence of coating texture, thickness also inhomogenous situation
C：Solution forms gel, it is impossible to the situation of coating
(5) evaluation of peel strength
The thermosetting adhesive sheet just obtained is cut into the rectangle (5cm × 10cm) of prescribed level, by the thermosetting
Adhesive linkage is temporarily pasted with the laminating machine for being set as 80 DEG C on the polyimide film (175AH, (strain) カ ネ カ) of 175 μ m-thicks
Afterwards, remove base material film and expose thermosetting adhesive linkage.For the thermosetting adhesive linkage exposed, the 50 of formed objects are overlapped from top
The polyimide film (200H, デ ュ ポン societies) of μ m-thick, under 170 DEG C, 2.0MPa pressure after heating pressurization 60 seconds, 140
DEG C baking oven in kept for 60 minutes.
It is pressed in addition, the thermosetting adhesive linkage for the thermosetting adhesive sheet for being cut into rectangle (5cm × 10cm) is pressed
0.5mm SUS304 plates or thickness 1mm glass epoxy board are carried out after temporarily pasting, and removing base material film exposes thermosetting and glued
Connect layer.For the thermosetting adhesive linkage exposed, from top overlap rectangular 50 μm of thickness polyimide film (5cm ×
10cm), after heating pressurization 60 seconds, kept for 60 minutes in 140 DEG C of baking oven under 170 DEG C, 2.0MPa pressure.
Then, for polyimide film, 90 degree of disbonded tests are carried out with peeling rate 50mm/min, measure is peeled off required
Power.Obtained result is as shown in Table 1 and Table 2.Peel strength is desired for 10N/cm in practical.Additionally, it is desirable to normal temperature preserves 6
The difference of peel strength and the peel strength at initial stage after month is less than -30%.Therefore, situation of the difference less than 2N/cm is denoted as normal temperature
Preservation characteristics are good, bad if being denoted as more than if.
In addition, preserving the thermosetting adhesive sheet of 6 months for normal temperature at 25 DEG C, commenting for same peel strength is carried out
Valency.Obtained result is as shown in Table 1 and Table 2.
[table 1]
[table 2]
<The investigation of the result of Tables 1 and 2>
In the thermosetting adhesive sheet of embodiment 1~7, acrylic acid series copolymer (A) is free from (methyl) third of epoxy radicals
The mass % of olefin(e) acid ester monomer (a) 65~75, the mass % of acrylonitrile monemer (b) 20~35 and (methyl) acrylate containing epoxy radicals
The mass % of monomer (c) 1~10 copolymerization forms, and hardener for epoxy resin is the acyl of organic acid two of 0.5~15 μm of average grain diameter
Hydrazine particle, therefore coating, peel strength at initial stage and normal temperature preservation characteristics are all satisfactory.
It should illustrate, in the thermosetting adhesive sheet of embodiment 8, the weight average molecular weight of acrylic acid series copolymer (A) is 30
Ten thousand, less than the thermosetting adhesive sheet of embodiment 1~7, thus while normal temperature preservation characteristics are good, but overall peel strength
Reduced with heat resistance.
In the thermosetting adhesive sheet of embodiment 9, the weight average molecular weight of acrylic acid series copolymer (A) is 900,000, higher than reality
Apply the thermosetting adhesive sheet of example 1~7, therefore coating texture on the surface of adhesive sheet be present, thickness also heterogeneity, but
Normal temperature preservation characteristics are good.
In the case of the thermosetting adhesive sheet of embodiment 10, because the average grain diameter of organic acid dihydrazide is more than embodiment
1~7 thermosetting adhesive sheet, therefore coating somewhat reduces, normal temperature has good keeping qualities in addition, but overall peel strength
Reduce.Further, since hydrazides particle is excessive, therefore reactivity reduces, and peel strength, heat resistance are insufficient.
On the other hand, in the thermosetting adhesive sheet of comparative example 1, composition (a) in acrylic acid series copolymer is very few, into
Divide (b) excessively, therefore can not be substantially dissolved in organic solvent, produce gelation.
In the thermosetting adhesive sheet of comparative example 2, composition (a) in acrylic acid series copolymer is excessive, composition (b) is very few,
Thus while normal temperature preservation characteristics are good, but peel strength at initial stage is to be unsuitable for the low-level of practicality.
In the thermosetting adhesive sheet of comparative example 3, the composition (c) in acrylic acid series copolymer is very few, thus while normal temperature
Preservation characteristics are good, but peel strength at initial stage is to be unsuitable for the low-level of practicality.
In the thermosetting adhesive sheet of comparative example 4, the composition (c) in acrylic acid series copolymer excessively, thus while normal temperature
Preservation characteristics are good, but peel strength at initial stage is to be unsuitable for the low-level of practicality.
In the thermosetting adhesive sheet of comparative example 5, the average grain diameter of organic acid dihydrazide is excessive, therefore peel strength at initial stage
To be unsuitable for the low-level of practicality.
In the thermosetting adhesive sheet of comparative example 6~8, due to hydroxyl or carboxyl in acrylic acid series copolymer be present, therefore
Normal temperature preservation characteristics are bad.
Embodiment 11
Use embodiment 1~10 and the thermosetting adhesive sheet of comparative example 2~8, as described below, the flexible print of manufacture enhancing
Brush wiring plate.
<Moisture absorption reflow soldering heat-resistance test>
The thermosetting adhesive linkage for the thermosetting adhesive sheet for being cut into rectangle (2cm × 2cm) is used and is set as 80 DEG C
After laminating machine is temporarily pasted on the polyimide film (ア ピ カ Le 175AH, (strain) カ ネ カ) of 175 μ m-thicks, peeling base is removed
Expose thermosetting adhesive linkage.For the thermosetting adhesive linkage exposed, the polyamides that 50 μ m-thicks of formed objects are overlapped from top is sub-
Amine film (カ プ ト Application 200H, デ ュ ポン societies), under 170 DEG C, 2.0MPa pressure after heating pressurization 60 seconds, in 140 DEG C of baking
Kept for 60 minutes in case.Then, it is small that the test film being heating and curing is placed to 96 in 40 DEG C, 90%RH damp and hot baking oven
When.
Make the test film after firm humid heat treatment by being set as the maximum temperature reflow soldering furnace of 260 DEG C × 30 seconds, visually
Test film after observation passes through whether there is the abnormal appearances such as expansion, stripping, and outward appearance is evaluated as into " A " without the situation of exception completely,
It will be observed that the situation that test film somewhat has expansion but had no problem in practicality is evaluated as " B ", it will be observed that test film has hair
The situation of expansion caused by bubble is evaluated as " C ".Obtained result is as shown in Table 3 and Table 4.
[table 3]
[table 4]
The result of moisture absorption reflow soldering heat-resistance test is to use the enhancing of the thermosetting adhesive sheet of embodiment 1~10
Not observing completely in appearance for flexible printing wiring board is abnormal, or observes that test film somewhat has expansion but does not have in practicality
Problem.Especially with embodiment 1~7 thermosetting adhesive sheet enhancing flexible printing wiring board acrylic copolymer-
The balance of epoxy resin-hydrazides cross-linked structure is good, hardly the raw material of remained unreacted, therefore does not observe outward appearance completely
It is abnormal.
On the other hand, in the case of comparative example 2~8, in addition to comparative example 4, after 25 DEG C/6 months, it was observed that experiment
Piece has the expansion caused by foaming.It should illustrate, in the case of comparative example 4, due to for good cross-linked structure, moisture absorption Reflow Soldering
Connect that heat resistance is good, but as described above, peel strength at initial stage is to be unsuitable for the low-level of practicality.
Industrial applicability
The present invention thermosetting adhesive composition and thermosetting adhesive sheet can by the resin substrates such as polyimide film with
It is bonded well between polyimide film, stainless steel plate or glass epoxy substrate, and by the time up to the several months
Show good normal temperature preservation characteristics.In addition, even if carrying out 260 DEG C of reflow soldering processing, will not also be produced due to moisture absorption
Expansion.Therefore, it is useful as the bonding agent in the field of electrical components commonly using polyimide material.
Claims (6)
1. thermosetting adhesive composition, it is solidified containing acrylic acid series copolymer (A), epoxy resin (B) and epoxy resin
The thermosetting adhesive composition of agent (C), wherein,
The acrylic acid series copolymer (A) is by without the mass % of epoxy radicals (methyl) acrylate monomer (a) 65~75, propylene
The mass % of nitrile monomer (b) 20~35 and (methyl) acrylate monomer (c) 1~10 mass % copolymerization containing epoxy radicals form,
The hardener for epoxy resin is organic acid dihydrazide particle of 0.5~15 μm of average grain diameter,
The weight average molecular weight of the acrylic acid series copolymer (A) is 550000~700000, (methyl) without epoxy radicals
Acrylate monomer (a) does not contain hydroxyl and free carboxy, and described (methyl) acrylate monomer (c) containing epoxy radicals does not contain
Hydroxyl and free carboxy,
Relative to the mass parts of acrylic acid series copolymer (A) 100, containing the mass parts of epoxy resin (B) 5~30, relative to acrylic acid
The mass parts of total 100 of based copolymer (A) and epoxy resin (B), contain the mass parts of hardener for epoxy resin 4~20.
2. thermosetting adhesive composition as claimed in claim 1, wherein, organic acid dihydrazide is adipic dihydrazide or 7,
The carbohydrazides of 18 carbon diene -1,18- of 11- two.
3. thermosetting adhesive composition as claimed in claim 1 or 2, wherein, the weight average molecular weight of acrylic acid series copolymer (A)
For 650000~700000.
4. thermosetting adhesive sheet, it is that the thermosetting described in comprising any one in claims 1 to 3 is formed on base material film
What the thermosetting adhesive linkage of adhesive composition formed.
5. manufacture method, it is the manufacture method of the thermosetting adhesive sheet described in claim 4, and it includes：
Thermosetting adhesive composition described in any one in claims 1 to 3 is put into organic solvent, makes epoxy resin
It is scattered in organic solvent with curing agent (C), on the other hand it has been dissolved in acrylic acid series copolymer (A) and epoxy resin (B)
In solvent, the step of thus preparing thermosetting adhesive linkage formation coating, and
By on thermosetting adhesive linkage formation coatings to base material film, it is dried, is consequently formed the step of thermosetting adhesive linkage
Suddenly.
6. strengthening flexible printing wiring board, it is the enhancing of the portion of terminal enhancing resin sheet lining of flexible printing wiring board
Flexible printing wiring board, it is the portion of terminal is glued with the enhancing with the thermosetting described in resin sheet has been removed claim 4
What the thermosetting compound of the thermosetting adhesive linkage after the base material film of contact pin material was adhesively fixed.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009-233278 | 2009-10-07 | ||
| JP2009233278A JP5728804B2 (en) | 2009-10-07 | 2009-10-07 | Thermosetting adhesive composition, thermosetting adhesive sheet, method for producing the same, and reinforced flexible printed wiring board |
| CN201080045247.5A CN102549097B (en) | 2009-10-07 | 2010-07-26 | Thermoset bonding composition, thermoset adhesive sheet, its manufacture method and enhancing flexible printing wiring board |
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| CN201080045247.5A Division CN102549097B (en) | 2009-10-07 | 2010-07-26 | Thermoset bonding composition, thermoset adhesive sheet, its manufacture method and enhancing flexible printing wiring board |
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| Publication Number | Publication Date |
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| CN105331308A CN105331308A (en) | 2016-02-17 |
| CN105331308B true CN105331308B (en) | 2017-11-28 |
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| CN201510763270.2A Active CN105331308B (en) | 2009-10-07 | 2010-07-26 | Thermosetting adhesive composition, thermosetting adhesive sheet, its manufacture method and enhancing flexible printing wiring board |
| CN201080045247.5A Active CN102549097B (en) | 2009-10-07 | 2010-07-26 | Thermoset bonding composition, thermoset adhesive sheet, its manufacture method and enhancing flexible printing wiring board |
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| CN201080045247.5A Active CN102549097B (en) | 2009-10-07 | 2010-07-26 | Thermoset bonding composition, thermoset adhesive sheet, its manufacture method and enhancing flexible printing wiring board |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP5728804B2 (en) |
| KR (1) | KR101702694B1 (en) |
| CN (2) | CN105331308B (en) |
| HK (2) | HK1169135A1 (en) |
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| JP5770995B2 (en) * | 2010-12-01 | 2015-08-26 | デクセリアルズ株式会社 | Thermosetting resin composition, thermosetting adhesive sheet, and method for producing thermosetting adhesive sheet |
| KR101374365B1 (en) * | 2010-12-27 | 2014-03-17 | 제일모직주식회사 | Adhesive composition for semiconductor, adhesive film comprising the same |
| JP5946688B2 (en) * | 2011-04-26 | 2016-07-06 | 積水化学工業株式会社 | Post-curing tape and joining member joining method |
| JP6239223B2 (en) * | 2011-11-18 | 2017-11-29 | 大日本印刷株式会社 | Adhesive composition and adhesive sheet using the same |
| CN102585745A (en) * | 2012-02-21 | 2012-07-18 | 绵阳艾萨斯电子材料有限公司 | Frame sealing adhesive, and preparation method and application thereof |
| JP5978782B2 (en) * | 2012-06-06 | 2016-08-24 | デクセリアルズ株式会社 | Thermosetting adhesive composition, thermosetting adhesive sheet and reinforced flexible printed wiring board |
| JP5842736B2 (en) * | 2012-06-06 | 2016-01-13 | デクセリアルズ株式会社 | Thermosetting resin composition, thermosetting adhesive sheet, and method for producing thermosetting adhesive sheet |
| CN103509509A (en) * | 2013-01-16 | 2014-01-15 | 上海都为电子有限公司 | Room-temperature fast-curing single-component anaerobic adhesive for silicon block cutting |
| JP6429103B2 (en) * | 2013-06-19 | 2018-11-28 | 大日本印刷株式会社 | Adhesive composition and adhesive film using the same |
| JP6243764B2 (en) | 2014-03-18 | 2017-12-06 | デクセリアルズ株式会社 | Method for manufacturing flexible mounting module body |
| JP6542526B2 (en) * | 2014-11-12 | 2019-07-10 | デクセリアルズ株式会社 | Thermosetting adhesive composition, and thermosetting adhesive sheet |
| CN107109161B (en) * | 2014-11-12 | 2019-07-02 | 迪睿合株式会社 | Thermocurable binding compositions |
| JP6517032B2 (en) * | 2015-02-06 | 2019-05-22 | デクセリアルズ株式会社 | Thermosetting adhesive composition, and thermosetting adhesive sheet |
| KR101949632B1 (en) | 2015-03-26 | 2019-02-18 | 데쿠세리아루즈 가부시키가이샤 | Method for manufacturing flexible mounting module body |
| SG11201706433WA (en) * | 2015-03-31 | 2017-09-28 | Toray Industries | Resin film for electronic component, resin film for electronic component provided with protective film, and semiconductor device and method for manufacturing same |
| ES2754201T3 (en) | 2015-05-25 | 2020-04-16 | Antolin Grupo Ing Sa | Vehicle Roof Trim Manufacturing Process |
| CN106867435B (en) * | 2015-12-11 | 2019-03-08 | 华烁科技股份有限公司 | A kind of flexible printed circuit polyimides stiffening plate modified acrylic ester adhesion agent and its application |
| JP6721325B2 (en) * | 2015-12-14 | 2020-07-15 | デクセリアルズ株式会社 | Thermosetting adhesive sheet and method for manufacturing semiconductor device |
| JP7074033B2 (en) * | 2018-11-22 | 2022-05-24 | 三菱ケミカル株式会社 | Adhesive layer, adhesive sheet and laminate |
| JP7447565B2 (en) * | 2020-03-10 | 2024-03-12 | 三菱ケミカル株式会社 | Adhesive compositions, adhesives, adhesive sheets and laminates |
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- 2010-07-26 KR KR1020127009008A patent/KR101702694B1/en active IP Right Grant
- 2010-07-26 CN CN201510763270.2A patent/CN105331308B/en active Active
- 2010-07-26 WO PCT/JP2010/062492 patent/WO2011043119A1/en active Application Filing
- 2010-07-26 CN CN201080045247.5A patent/CN102549097B/en active Active
- 2010-08-12 TW TW099126891A patent/TWI565772B/en active
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| CN101522751A (en) * | 2006-10-06 | 2009-09-02 | 日立化成工业株式会社 | Liquid resin composition for electronic part sealing and electronic part apparatus utilizing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101702694B1 (en) | 2017-02-06 |
| HK1169135A1 (en) | 2013-01-18 |
| KR20120092594A (en) | 2012-08-21 |
| HK1221481A1 (en) | 2017-06-02 |
| CN105331308A (en) | 2016-02-17 |
| CN102549097A (en) | 2012-07-04 |
| TW201113340A (en) | 2011-04-16 |
| TWI565772B (en) | 2017-01-11 |
| CN102549097B (en) | 2015-12-02 |
| JP2011079959A (en) | 2011-04-21 |
| WO2011043119A1 (en) | 2011-04-14 |
| JP5728804B2 (en) | 2015-06-03 |
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