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CN103403121A - Adhesive composition and adhesive film - Google Patents

Adhesive composition and adhesive film Download PDF

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Publication number
CN103403121A
CN103403121A CN2012800107192A CN201280010719A CN103403121A CN 103403121 A CN103403121 A CN 103403121A CN 2012800107192 A CN2012800107192 A CN 2012800107192A CN 201280010719 A CN201280010719 A CN 201280010719A CN 103403121 A CN103403121 A CN 103403121A
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Prior art keywords
binder composition
weight
adhesive composition
solvent
parts
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Granted
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CN2012800107192A
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CN103403121B (en
Inventor
木下淳一
寺田恒彦
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Tatsuta Electric Wire and Cable Co Ltd
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Tatsuta Electric Wire and Cable Co Ltd
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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
    • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
    • C09J177/12—Polyester-amides
    • 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
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/40—Polyamides containing oxygen in the form of ether groups
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—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
    • C09J2301/314—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 layer and/or the carrier being conductive
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Conductive Materials (AREA)
  • Adhesive Tapes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明提供不含卤素并且密合性、长期可靠性与以往相比提高的粘合剂组合物。粘合剂组合物，相对于聚醚酯酰胺100重量份，含有结晶性聚酯1～100重量份和二氧化硅20～110重量份。也能够使本粘合剂组合物中进一步含有导电性粒子而成为导电性糊。The present invention provides an adhesive composition that does not contain halogen and has improved adhesiveness and long-term reliability compared with conventional ones. The adhesive composition contains 1 to 100 parts by weight of crystalline polyester and 20 to 110 parts by weight of silica, based on 100 parts by weight of polyetheresteramide. It is also possible to further contain electroconductive particles in this pressure-sensitive adhesive composition to obtain an electroconductive paste.

Description

Binder composition and bonding film
Technical field
The present invention relates to binder composition and bonding film, relate to the binder composition and the bonding film that are suitable for drawing such as the signal of touch panel circuit and being connected of flexible printed board etc.
Background technology
Draw circuit and being connected of flexible printed board etc. for the signal of touch panel, used the anisotropic conductive paste in the past.Stick with paste for anisotropic conductive, the raising of the homogeneity of thickness is problem up to now, and recently along with the growth trend of the touch panel of capacitance-type, has also required to tackle and being connected of the part of minuteness space.
Stick with paste as anisotropic conductive in the past, generally use chloroprene type (for example patent documentation 1).The type has following strong point: do not glue,, although be short-term, can preserve by normal temperature.
But because the requirement to environmental problem, security in recent years improves, for tackiness agent, not halogen-containing requirement also constantly strengthens.In addition, chloroprene type in the past is because of the difference of purposes, aspect bond strength, long-term reliability, workability, may not satisfy the demand, and particularly, as the binder composition of the connection that is used for substrate, has the not talkative sufficient problem of long-term reliability.
Therefore, the inventor sticks with paste as the not halogen-containing anisotropic conductive of bond strength, long-term reliability, workability etc. also excellence, namely also be suitable for the binder composition of the connection of above-mentioned substrate, proposed to comprise the binder composition (patent documentation 2) of polyether ester amides and vinylbenzene-iso-butylene-polystyrene olefin elastomer (SIBS) etc.
But in recent years, the electronicss such as mobile telephone are large picture hastily, with it, accompanies, and the signal of touch panel is drawn narrow and smallization of bond area that circuit is connected with flexible printed board.However, tackiness agent is required and equal or binding property more than it in the past, so the further raising of the adaptation of tackiness agent becomes the task of top priority.
In addition, follow variedization of electronic products, the base material of touch panel, wiring material be variation also, and tackiness agent is required to tackle these various materials.
The prior art document
Patent documentation
Patent documentation 1: JP 2004-143219 communique
Patent documentation 2: JP 2010-168510 communique
Summary of the invention
The problem that invention will solve
The present invention completes in view of foregoing, and its purpose is to provide and does not conform to halogen and for the adaptation of various materials, the binder composition of long-term reliability further raising compared with the past.
Be used for solving the means of problem
The inventor conducts in-depth research in order to solve above-mentioned problem, found that,, by take specific polyether ester amides as basis, adds certain vibrin, and adaptation can significantly improve, and has completed the present invention.
That is, binder composition of the present invention,, with respect to polyether ester amides 100 weight parts, contain crystallinity polyester 1～100 weight part and silicon-dioxide 20～110 weight parts.
Also can make binder composition of the present invention contain electroconductive particle., as electroconductive particle, preferably use the washing resin balls.
In binder composition of the present invention, for above-mentioned crystallinity polyester, preferably, molecular weight is in 10000～35000 scope, and second-order transition temperature is in the scope of-70～30 ℃, and fusing point is in the scope of 90～180 ℃.
Bonding film of the present invention is formed by above-mentioned binder composition.
The effect of invention
, according to the present invention, can provide the binder composition of not halogen-containing, adaptation and long-term reliability further raising compared with the past.Especially, can increase substantially adaptation with the nonpolar materials such as polyethylene terephthalate (following sometimes referred to as PET) of a part of material of substrate as touch panel.
Description of drawings
Fig. 1 is for representing the orthographic plan of the flexible printed board (the following FPC that sometimes is abbreviated as) 1 that uses in embodiments of the invention.
Fig. 2 is for representing the orthographic plan of polymer thick film (the following PTF that the sometimes is abbreviated as) substrate 2 that uses in embodiments of the invention.
Fig. 3 for expression test with orthographic plan sample, link position above-mentioned FPC1 and PTF substrate 2.
Fig. 4 is the orthographic plan of the measuring method of expression contact resistance.
Fig. 5 is oblique drawing and the sectional view of the test method of expression 90 degree stripping strengths.
Embodiment
Below binder composition of the present invention is described in detail.
The polyether ester amides that uses in the present invention (following sometimes referred to as PEEA), preferably, fusing point is 80 ℃～135 ℃, melt index is 5g/10 minute～100g/10 minute (190 ℃, 21.18N), and solvable in solvent.In the past, make elastomerics become the film difficulty, but pass through the use of the polyether ester amides of solvent-soluble type, it is easy that filming becomes.
Said in this specification sheets " elastomerics ", refer to have thermoplastic synthetic rubber material.Wherein, the preferred elastomerics that uses the structure with the soft chain segment that comprises the large hard segment of cohesive force and flexibility.Above-mentioned polyether ester amides has uses the polymeric amide of high-melting-point (Tm) as hard segment, the polyethers of low melting point or lower glass transition temperatures (Tg) or the polyester chain structure as soft chain segment of using., as the concrete example of the hard segment of PEEA, can enumerate nylon 12, nylon 6 etc., as the concrete example of soft chain segment, can enumerate aliphatic polyether or aliphatic polyester.
PEEA, think and help to give the adaptation of with the ITO (tin indium oxide) of the polyimide that forms flexible printed board and nickel-Jin plating Copper Foil, touch panel and silver, sticking with paste etc.
PEEA, as mentioned above, preferably dissolve in solvent, more specifically, preferably is dissolvable in water amine series solvent, pure series solvent or ketone series solvent.
as the amine series solvent, can enumerate diethylamine, triethylamine, propylamine, Isopropylamine, dipropyl amine, Diisopropylamine, butylamine, isobutylamine, sec-butylamine, TERTIARY BUTYL AMINE, dibutylamine, diisobutylamine, Tributylamine, amylamine, diamylamine, triamylamine, 2 ethyl hexylamine, allylamine, aniline, methylphenylamine, quadrol, propylene diamine, diethylenetriamine, methane amide, N-METHYLFORMAMIDE, N, dinethylformamide, N, the N-diethylformamide, ethanamide, the N-methylacetamide, N, the N-N,N-DIMETHYLACETAMIDE, the N-methyl propanamide, 2-Pyrrolidone, N-Methyl pyrrolidone, ε-caprolactam, carbamate etc.
, as pure series solvent, can enumerate methyl alcohol, ethanol, Virahol (IPA), benzylalcohol etc.
, as the ketone series solvent, can enumerate acetone, methyl ethyl ketone, 2 pentanone, propione, methyl-n-butyl ketone, methyl iso-butyl ketone (MIBK), 2-heptanone, dipropyl ketone, diisobutyl ketone, methyl ethyl diketone, mesityl oxide, sym.-diisopropylideneacetone, isophorone, pimelinketone, methylcyclohexanone etc.
, as polyether ester amides, also can preferably use and import-NH 2The product of the ,-functional groups such as COOH.Import suitable functional group by object bonding according to metal, resin etc., can realize the further raising of closing force.In this case, preferably import to become amine value below 20, acid number below 20., if import functional group on the degree more than this, likely cause the stripping strength under the moisture-proof environment, the unfavorable situations such as reduction of connection reliability.
PEEA can adopt known method manufacturing, also can utilize commercially available product.In commercially available product, can use for example TPAE series (solvent soluble grade, polyether ester amides type) of T﹠K TOKA (strain) system.Wherein, can select TPAE-12, TPAE-31, TPAE-32, TPAE-826, PA-200, the PA-201 etc. of TPAE series and use aptly according to purposes.These polyether ester amides also can use blend more than 2 kinds.
The crystallinity polyester that contains specified amount in adhesive composition of the present invention.So-called " crystallinity polyester ", usually, refer to have the polyester of the fusing point more than 80 ℃, in the present invention, refer to " soluble polyester in solvent, be under normal temperature under the state that dissolves in solvent (25 ℃) for gel and becoming the polyester of liquid more than 70 ℃ ".In addition, the crystallinity polyester preferred number average molecular weight (Mn) of using in the present invention is 10000～35000, and preferred glass transition temperature (Tg) is-70～30 ℃, and preferred fusing point is 90～180 ℃., by using such crystallinity polyester, can make with the adaptation of the nonpolar materials such as PET of baseplate material as touch panel and improve.In addition, also can improve the thixotropy of adhesive composition, the bubble while preventing presswork, while applying operation occurs.
, as the example of the crystallinity polyester that can use, can enumerate the mixing cured type resin of acrylic acid series/polyester, the blocked isocyanate curing contains the vibrin of hydroxyl, the vibrin that the epoxy resin cure type contains carboxyl, the vibrin that the hydroxyalkyl amide curing contains carboxyl etc.These crystallinity polyester also can adopt known method manufacturing, also can utilize commercially available product., as commercially available product, can use for example Off ア processed of Dainippon Ink Chemicals イ Application デ ィ シ Network (registered trademark) series.Wherein, can preferably use M-8010, M-8020, M-8021, M-8023, M-8076, M-8100, M-8230, M-8240, M-8250, M-8830, M-8842, M-8860, M-8630M-8961, M-8962, A-239-J, A-239-X, M-8420., as the crystallinity polyester, can preferably use the serial GM-400GM-415 of Toyo Boseki K.K's バ イ processed ロ Application (registered trademark), GM-443, GM-480, GM-900, GM-913, GM-920, GM-925, GM-990, GA-1200, GA-1300, GA-1310, GA-2310, GA-3200, GA-3410, GA-5300, GA-5310, GA-5410, GA-6300, GA-6400,30P.Wherein, can preferably use GM-900, GM-913, GM-9200, GA-5300.In addition, as the crystallinity polyester, also can use the ニ チ processed of the Nippon Synthetic Chemical Industry Co., Ltd go one Port リ エ ス タ one (registered trademark) series, wherein, can preferably use SP-180, SR-100, VR-300, HR-200, Z-1651ML, Z-1606ML.
The content of above-mentioned vibrin, with respect to polyether ester amides 100 weight parts, preferred 1～100 weight part.If content, less than 1 weight part, can't obtain the effect of above-mentioned adaptation raising etc., if surpass 100 weight parts, likely thermotolerance reduces.In addition, if the possibility that the bubble while considering pressurization occurs, content is more preferably more than 2 weight parts, if consider heat-resisting creep properties, more preferably below 40 weight parts.
Fitting method to above-mentioned crystallinity polyester is not particularly limited, and is for example in the situation of solid under normal temperature, can adopt and make the crystallinity polyester be dissolved in suitable solvent, the method for with PEEA, mixing.As solvent, the solvent that can use above-mentioned PEEA to dissolve.On the other hand, be in the situation of liquid under normal temperature, can former state add and stir.
The crystallinity polyester that coordinates, think by be formed on the intermolecular island structure that disperses of PEEA as weighting agent, helps the thixotropy of binder composition to improve.In addition, think melting when heating and pressurizing, help to improve with the adaptation of PET etc.
In binder composition of the present invention, further contain silicon-dioxide.By containing the silicon-dioxide of specified amount, the problems such as bubble generation in the time of can solving pressurization.Namely, in the low situation of the melt viscosity of above-mentioned PEEA resin, sometimes produce resin when bonding ooze out (resin flows), presswork the time or produce the such problem of bubble while applying operation, during pressurization, but think by using appropriate silicon-dioxide, carry out the melt viscosity adjustment of resin, thereby improve these problems.
, as silicon-dioxide, for example can use the ア De マ Off ァ イ Application series of (strain) ア De マ テ ッ Network ス, ア work mouth ジ Le (registered trademark) series of Japanese ア work mouth ジ Le (strain).
The content of silicon-dioxide, with respect to polyether ester amides 100 weight parts, preferred 20～110 weight parts, more preferably 50～90 weight parts.If the content of silicon-dioxide is less than 20 weight parts, likely above-mentioned bubble generation inhibition becomes insufficient, if surpass 110 weight parts, likely heat-resistant aging reduces.
The binder composition of the invention described above,, by adding electroconductive particle, can form the conductive paste with anisotropic electroconductibility., as electroconductive particle, preferably use the washing resin balls.
So-called washing resin balls, be to have implemented the product of washing on the surface of spherical resin, especially, preferably uses core to be divided into polymethylmethacrylate (PMMA), via nickel, to apply and implemented the product of golden coating.The washing resin balls is compared with metal powder, and size-grade distribution is narrow significantly,, because core is divided into resin, therefore has elasticity, has the glass that is difficult to make contact, the strong point that ITO destroys.In addition,, because to compare proportion little with metal powder, therefore also has the strong point that the sedimentation in composition is difficult to occur.
The washing resin balls can be utilized the washing resin balls of various particle diameters, in the present invention, usually uses the washing resin balls of median size 1～50 μ m left and right, and then can preferably use the washing resin balls of 10～35 μ m.
, as electroconductive particle, except above-mentioned washing resin balls, can also use the metal powder of copper, silver, lead, zinc, iron, nickel etc., to the particle of the inorganic powder nickel plating such as these metal powders, glass powder, gold and silver, copper etc.Shape to these electroconductive particles is not particularly limited, and can use the shape arbitrarily such as spherical shape, flakey, potato-like, needle-like, indefinite shape, in the purposes of touch panel, preferred spherical shape, with spherical approaching potato-like.The scope of preferred median size 1～50 μ m of size.
The content of electroconductive particle is different because of the purposes of binder composition, usually, with respect to the total resin solid in binder composition, divides 100 weight parts, is preferably in the scope of 1～100 weight part.
In above-mentioned silicon-dioxide, electroconductive particle, preferably add silane coupling agent.Think that silane coupling agent has reactive functional groups and hydrolization group (OR),, by improving the dispersiveness of silicon-dioxide, make above-mentioned silicon-dioxide coordinate the bubble generation inhibition of bringing further to improve.In addition, think that the resinous principles such as reactive functional groups and PEEA react, hydrolization group, at the electroconductive particle surface orientation, occurs thereby also help to suppress bubble.Use its usage quantity of the situation of silane coupling agent, with respect to silicon-dioxide, electroconductive particle, preferred 0.01～20 % by weight.
As silane coupling agent, in commercially available product, can the suitable use シ リ コ of SHIN-ETSU HANTOTAI one Application KBM-403 (Shin-Etsu Chemial Co., Ltd) etc.
In binder composition of the present invention, as required, other compositions that use in binder composition in the time of can further being added with, i.e. tackiness imparting agent (tackifier), stablizer, antioxidant, strengthening agent, pigment, defoamer etc.
In order to obtain binder composition of the present invention, can use for example such mixing roll of planetary mixing roll, add solvent in becoming the resin of raw material, heating, dissolve and mix.
, as the solvent of this moment, can use the ether series solvents such as the ester series solvents such as ketone series solvent, vinyl acetic monomer, N-BUTYL ACETATE, isobutyl acetate, ethyl cellosolve acetate, the butyl cellosolve acetates such as hydrocarbon system solvent, isophorone, ethyl cellosolve, ethylene glycol butyl ether, ispropyl cellosolve, tertiary butyl cellosolve, ethyl carbitol, diethylene glycol monobutyl ether such as the nitrogen such as N-Methyl pyrrolidone system or acid amides series solvent, hexane, heptane, decane, toluene, dimethylbenzene, hexanaphthene, benzylalcohol, solvent naphtha etc.
, as the usage quantity of solvent, preferably in the resin solid minute concentration of binder composition, become the scope use of 10～50 % by weight.If the resin solid divides concentration lower than 10 % by weight, can not guarantee coating thickness, if surpass 50 % by weight, excess stickiness uprises, it is difficult that printing becomes.In addition, for the relation with above-mentioned resinous principle, with respect to resinous principle 100 weight parts, the preferred solvent composition is in the scope of 100～450 weight parts.
Bonding film of the present invention can be obtained by above-mentioned of the present invention any binder composition.
The method that is obtained bonding film by above-mentioned binder composition is not particularly limited, can, by binder composition being coated with various coating processes on the supports such as interleaving paper to become the thickness of regulation, after making its drying, from this interleaving paper etc., peels off and obtain.Particularly, can be dissolved in the amine series solvent by the binder composition that will mix as required electroconductive particle, the ketone series solvent becomes required viscosity, use coating machine etc. and membranization.The thickness of bonding film can suitably be selected according to purposes, is generally 10～50 μ m left and right.
In addition, while using bonding film of the present invention, by crimping under 100～160 ℃ of temperature, pressure 1～4MPa, about 5～15 seconds, can obtain required bond strength.
According to the present invention, solved the problem of nearest paste printing difficulty after capacitive touch panel is installed during at the FPC installation parts,, by as membranous type, carrying out transfer printing, connecting material can be crimped on touch panel.
Embodiment
Embodiments of the invention below are shown, and the present invention is not limited by following embodiment.
[embodiment 1～7, comparative example 1～5]
Resinous principle shown in table 1 and silicon-dioxide are coordinated, disperse by the ratio (weight ratio, resin solid are divided conversion) shown in table respectively.Disperse to use planetary mixing roll, under 85 ℃ of heating, revolution 50rpm mixing 3 hours and carry out.The details of the resinous principle shown in table 1 and silicon-dioxide is as described below.
PEEA:TPAE-32 (the T﹠amp of Co., Ltd.; K TOKA)
Crystallinity polyester: バ イ ロ Application GA-5300 (Toyo Boseki K.K, Mn:25000, second-order transition temperature :-2 ℃, fusing point: 114 ℃)
Polyurethane elastomer: ミ ラ Network ト ラ Application P485RSUI (Japanese ミ ラ Network ト ラ Application Co., Ltd.)
SIBS: シ Block ス タ one 103T (the カ ネ カ of Co., Ltd.)
Silicon-dioxide: ア De マ Off ァ イ Application S0-C2 (ア of Co., Ltd. De マ テ Star Network ス)
Composition below adding in above-mentioned resinous principle 100 weight parts (solid is divided conversion), mix the modulating adhesive composition.
Electroconductive particle: washing resin balls (core: PMMA, the 1st layer: Ni, outermost layer: Au, median size 30 μ m) 10 weight parts
Solvent: isophorone 300 weight parts
Ethylene glycol butyl ether 50 weight parts
N-Methyl pyrrolidone 80 weight parts
Stablizer: イ Le ガ ノ Star Network ス 1010 (チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ society) 1.3 weight parts
, for the binder composition that obtains, measure contact resistance, 90 degree stripping strengths, heat-resistant aging, the estimating of the bubble during to pressurization.Mensuration-evaluation method is as described below.Show the result in table 1.
The test sample of 90 degree stripping strengths, contact resistance, heat-resistant aging, heat-resisting creep is by polymer thick film (PTF) substrate 2 shown in the flexible printed board (FPC) 1 shown in the Fig. 1 that will make in the following manner and Fig. 2 as shown in Figure 3, by the mode of top a part of coating of PTF substrate 2, the therebetween connection of layer of binder composition made with the end of FPC1.
Bonding is for embodiment 1,2,4,7 and comparative example 2,4,5, the binder composition of pasty state is coated with to become thickness 28 μ m, for embodiment 3,5,6 and comparative example 1,3, binder composition is made in advance the bonding film of thick 28 μ m, hold them pressurization crimping 15 seconds and carrying out under 130～140 ℃ of crimping temperature, pressure 3MPa.
＜FPC: two Star カ Application industry (strain) systems 〉
Form: polyimide 25 μ m/ Copper Foil 18 μ m
Layer electrodes: Ni3 μ m/Au0.3 μ m
Spacing: 3mm
Electrode wide (a): 10mm
＜PTF substrate 〉
Polymkeric substance: east beautiful (strain) polyethylene terephthalate processed (PET) 188 μ m
Silver is stuck with paste: about 10 μ m
* paste painting erosion resistant agent at silver
Spacing: 3mm
＜contact resistance 〉
As shown in Figure 4, between FPC end end of FPC/PTF test with sample, use low ohmmeter (HIOKI system, direct current mode 3227 ミ リ are a system Ha イ テ ス タ), measure respectively the contact resistance between a-b, b-c, c-d, obtain mean value.
＜90 degree stripping strengths 〉
As shown in Figure 5, above-mentioned FPC/PTF test is peeled off the maximum value when mensuration ruptures with draw speed 50mm/ minute, direction of delaminate 90 degree with tensile testing machine (ミ ネ ベ ア PT-200N processed of Co., Ltd.) with sample.
＜heat-resistant aging 〉
As shown in Figure 3 FPC1 is connected connection with the PTF substrate, after keeping 1000 hours under 80 ℃, adopts aforesaid method to measure 90 degree stripping strengths.If less than 5N/cm, be designated as *,, for the sample more than 5N/cm, further after keeping 1000 hours under 105 ℃, similarly carry out 90 degree stripping tests,, if be more than 5N/cm, be designated as zero,, if less than 5N/cm, be designated as Δ.
＜heat-resisting creep 〉
The product that as shown in Figure 3 FPC1 is connected with PTF substrate 2 is hung in air oven, after the counterweight of FPC1 with upper 600g,, with heating in 1 ℃/90 seconds, measures the temperature that FPC1 and PTF substrate 2 separate in bond site.If be more than 80 ℃, be designated as zero, if be more than 60 ℃ less than 80 ℃, be designated as Δ, if, less than 60 ℃, be designated as *.
The generation of the bubble during＜pressurization 〉
On the circuit 4 of the flexible printed board shown in Fig. 1 (FPC) 1, paste the PET of 188 μ m, pressurization under 150 ℃, confirm electroconductive particle bubble on every side from PET face side with opticmicroscope, if without bubble, be designated as zero, find some bubbles but be designated as Δ in the situation of no problem in practical, owing to finding bubble, therefore be designated as in in-problem situation in practical *.
[table 1]
Figure BPA0000176910520000111
Utilize possibility on industry
Binder composition of the present invention can be adapted at the connection of the various substrates that use in mobile telephone, game machine etc., namely being connected of liquid crystal panel and substrate, the connection of membrane switch, EL terminal backlight the various uses such as connection in use.
The explanation of Reference numeral
1...... flexible printed board (FPC)
2...... polymer thick film (PTF) substrate
3...... binder composition (sticking with paste or film)
4...... circuit

Claims (5)

1.粘合剂组合物，相对于聚醚酯酰胺100重量份，含有结晶性聚酯1～100重量份和二氧化硅20～110重量份。1. An adhesive composition comprising 1 to 100 parts by weight of crystalline polyester and 20 to 110 parts by weight of silica, based on 100 parts by weight of polyetheresteramide. 2.权利要求1所述的粘合剂组合物，其特征在于，还含有导电性粒子。2. The adhesive composition according to claim 1, further comprising conductive particles. 3.权利要求2所述的粘合剂组合物，其特征在于，上述导电性粒子为金属涂覆树脂球。3. The adhesive composition according to claim 2, wherein the conductive particles are metal-coated resin balls. 4.权利要求1～3的任一项所述的粘合剂组合物，其特征在于，上述结晶性聚酯的数均分子量为10000～35000的范围内，玻璃化转变温度为-70～30℃的范围内，并且熔点为90～180℃的范围内。4. The adhesive composition according to any one of claims 1 to 3, wherein the crystalline polyester has a number average molecular weight in the range of 10,000 to 35,000 and a glass transition temperature of -70 to 30 °C, and the melting point is within the range of 90-180 °C. 5.粘合膜，其由权利要求1～4的任一项所述的粘合剂组合物形成。5. An adhesive film formed from the adhesive composition according to any one of claims 1 to 4.
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