WO2012164836A1 - 接着剤組成物及び接着フィルム - Google Patents
接着剤組成物及び接着フィルム Download PDFInfo
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- WO2012164836A1 WO2012164836A1 PCT/JP2012/003066 JP2012003066W WO2012164836A1 WO 2012164836 A1 WO2012164836 A1 WO 2012164836A1 JP 2012003066 W JP2012003066 W JP 2012003066W WO 2012164836 A1 WO2012164836 A1 WO 2012164836A1
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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
- 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
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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
- 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
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
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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
- 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
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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
- 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
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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
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
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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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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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
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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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
- 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
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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
- 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
- C09J2301/314—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
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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
Definitions
- the present invention relates to an adhesive composition and an adhesive film, for example, an adhesive composition and an adhesive film that are suitably used for connection of a signal drawing circuit of a touch panel and a flexible printed circuit.
- anisotropic conductive paste has been used for the connection between the signal extraction circuit of the touch panel and the flexible printed circuit board.
- anisotropic conductive paste improving the uniformity of film thickness has been a problem from the past, and nowadays, as the capacitance type touch panel is increasing, it is required to support connection to fine pitched parts. It has become to.
- a chloroprene type is generally used (for example, Patent Document 1).
- This type is tack-free and has the advantage that it can be stored at room temperature for a short period of time.
- the present inventors are a halogen-free anisotropic conductive paste having excellent adhesive strength, long-term reliability, workability, etc., and an adhesive composition that can be suitably used for connecting the above-described substrates.
- An adhesive composition that can be suitably used for connecting the above-described substrates.
- Have been proposed comprising a polyetheresteramide and a styrene-isobutylene-styrene olefin elastomer (SIBS) (Patent Document 2).
- the base materials and wiring materials of touch panels have also diversified, and adhesives are required to be compatible with these various materials.
- the present invention has been made in view of the above, and an object of the present invention is to provide an adhesive composition that is halogen-free and has improved adhesion to various materials and long-term reliability as compared with the prior art.
- the adhesive composition of the present invention comprises 1 to 100 parts by weight of crystalline polyester and 20 to 110 parts by weight of silica with respect to 100 parts by weight of polyetheresteramide.
- conductive particles can be contained.
- Metal conductive resin balls are preferably used as the conductive particles.
- the crystalline polyester has a molecular weight in the range of 10,000 to 35000, a glass transition point in the range of ⁇ 70 to 30 ° C., and a melting point in the range of 90 to 180 ° C. It is preferable to be within.
- the adhesive film of the present invention is composed of the above adhesive composition.
- an adhesive composition which is halogen-free and has further improved adhesion and long-term reliability compared to the prior art.
- the adhesion with nonpolar materials such as polyethylene terephthalate (hereinafter sometimes abbreviated as PET), which is a part of the touch panel substrate, can be greatly improved.
- FPC flexible printed circuit board
- PTF polymer thick film film
- substrate 2 used in the Example of this invention.
- PTF polymer thick film film
- substrate 2 used in the Example of this invention.
- PTF polymer thick film film
- substrate 2 used in the Example of this invention.
- PTF polymer thick film film
- substrate 2 used in the Example of this invention.
- PTF polymer thick film film
- the polyether ester amide used in the present invention (hereinafter sometimes abbreviated as PEEA) has a melting point of 80 ° C. to 135 ° C. and a melt index of 5 g / 10 min to 100 g / 10 min (190 ° C., 21.18 N). And preferably soluble in a solvent. Conventionally, it has been difficult to form an elastomer film, but the use of a solvent-soluble type polyether ester amide makes it easy to form a thin film.
- polyether ester amide has a structure in which a high melting point (Tm) polyamide is a hard segment and a low melting point or low glass transition point (Tg) polyether or polyester chain is a soft segment.
- Tm high melting point
- Tg low melting point or low glass transition point
- PEEA hard segments include nylon 12 and nylon 6.
- Specific examples of the soft segment include aliphatic polyether or aliphatic polyester.
- PEEA is thought to contribute to adhesion with polyimide, nickel-gold plated copper foil, ITO (indium tin oxide), silver paste, etc. of the touch panel.
- PEEA is preferably soluble in a solvent as described above. More specifically, PEEA is preferably soluble in an amine solvent, an alcohol solvent, or a ketone solvent.
- Amine solvents include diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, diisopropylamine, butylamine, isobutylamine, sec-butylamine, tert-butylamine, dibutylamine, diisobutylamine, tributylamine, pentylamine, dipentylamine , Tripentylamine, 2-ethylhexylamine, allylamine, aniline, N-methylaniline, ethylenediamine, propylenediamine, diethylenetriamine, formamide, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N -Methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, 2-pyrrolidone, N-methyl Rupiroridon, .epsilon.-caprolactam, carbamic acid ester and
- alcohol solvent examples include methanol, ethanol, isopropyl alcohol (IPA), benzyl alcohol and the like.
- ketone solvents include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, diisobutyl ketone, acetonyl acetone, mesityl oxide, phorone, isophorone, and cyclohexanone. And methylcyclohexanone.
- polyether ester amide those introduced with a functional group such as —NH 2 or —COOH can be preferably used.
- a functional group such as —NH 2 or —COOH
- the adhesion can be further improved. In that case, it is desirable that the amine value is 20 or less and the acid value is 20 or less. If more functional groups are introduced, there is a risk of incurring problems such as a decrease in peel strength and connection reliability in a moisture-resistant environment.
- PEEA can be produced by a known method, but commercially available products can also be used.
- TPAE series solvent soluble grade, polyether ester amide type
- TPAE series TPAE-12, TPAE-31, TPAE-32, TPAE-826, PA-200, PA-201, etc. can be selected and used suitably.
- These polyether ester amides can be used in a blend of two or more.
- the adhesive composition of the present invention contains a predetermined amount of crystalline polyester.
- “Crystalline polyester” generally means a polyester having a melting point of 80 ° C. or higher.
- crystalline polyester is soluble in a solvent and is gelled at room temperature (25 ° C.) in a state dissolved in a solvent. And a polyester that becomes liquid at 70 ° C. or higher ”.
- the crystalline polyester used in the present invention preferably has a number average molecular weight (Mn) of 10,000 to 35000, a glass transition point (Tg) of ⁇ 70 to 30 ° C., and a melting point of 90 to 180. It is preferable that it is ° C.
- Examples of usable crystalline polyesters include acrylic / polyester hybrid curable resins, blocked isocyanate curable hydroxyl group-containing polyester resins, epoxy resin curable carboxyl group-containing polyester resins, and hydroxyalkylamide curable carboxyl group-containing polyester resins. Can be mentioned. These crystalline polyesters can also be produced by known methods, but commercially available ones can also be used. As a commercially available product, for example, DIC Corporation Fine Dick (registered trademark) series can be used.
- 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, and M-8420 can be preferably used.
- GM-900, GM-913, GM-9200, and GA-5300 can be preferably used.
- Nichigo Polyester (registered trademark) series manufactured by Nippon Synthetic Chemical Industry Co., Ltd. can be used.
- SP-180, SR-100, VR-300, HR-200, Z-1651ML Z-1606ML can be preferably used.
- the content of the polyester resin is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the polyetheresteramide. If the content is less than 1 part by weight, the effect of improving the adhesion cannot be obtained, and if it exceeds 100 parts by weight, the heat resistance may be lowered.
- the content is more preferably 2 parts by weight or more in consideration of the possibility of bubble generation during pressing, and more preferably 40 parts by weight or less in consideration of heat-resistant creep resistance.
- the method for blending the crystalline polyester is not particularly limited.
- a method in which the crystalline polyester is dissolved in a suitable solvent and mixed with PEEA can be used.
- a suitable solvent the solvent which can dissolve PEEA mentioned above can be used.
- PEEA the solvent which can dissolve PEEA mentioned above can be used.
- it when it is liquid at normal temperature, it can be added and stirred as it is.
- the blended crystalline polyester contributes to improvement of thixotropy of the adhesive composition by forming a sea-island structure dispersed like a filler between PEEA molecules. Moreover, it is considered that it melts at the time of hot pressing and contributes to improvement in adhesion to PET or the like.
- the silica is further contained in the adhesive composition of the present invention.
- problems such as generation of bubbles during pressing can be solved. That is, when the melt viscosity of the PEEA resin is low, there are problems that the resin bleeds (resin flow) at the time of adhesion, and bubbles are generated at the time of printing, coating, and pressing. It is considered that these problems can be improved by adjusting the melt viscosity of the resin when an appropriate amount is used.
- silica for example, Admafine series of Admatechs Co., Ltd. and Aerosil (registered trademark) series of Nippon Aerosil Co., Ltd. can be used.
- the silica content is preferably 20 to 110 parts by weight, more preferably 50 to 90 parts by weight, based on 100 parts by weight of the polyetheresteramide.
- the silica content is less than 20 parts by weight, the above-described bubble generation suppressing effect is insufficient, and when it exceeds 110 parts by weight, the heat aging resistance may be lowered.
- the adhesive composition of the present invention can be made into a conductive paste having anisotropic conductivity by adding conductive particles.
- conductive particles metal-coated resin balls are preferably used.
- the metal-coated resin ball is obtained by applying a metal coating to the surface of a spherical resin, and in particular, a core portion made of polymethyl methacrylate (PMMA) and gold-coated through a nickel coating is preferably used. .
- the metal-coated resin ball has an advantage that the particle size distribution is remarkably narrow and the core part is resin, so that it has elasticity and it is difficult to break glass and ITO that are in contact with it.
- specific gravity is small compared with metal powder, it also has the advantage that precipitation in a composition does not occur easily.
- Metal coated resin balls having various particle diameters can be used, but in the present invention, those having an average particle diameter of about 1 to 50 ⁇ m are usually used, and those having an average particle diameter of 10 to 35 ⁇ m can be preferably used. .
- the conductive particles include metal powders such as copper, silver, lead, zinc, iron and nickel, and inorganic powders such as these metal powders and glass powders, nickel, gold, silver, Particles plated with copper or the like can also be used.
- the shape of these conductive particles is not particularly limited, and any shape such as a spherical shape, a scale shape, a potato shape, a needle shape, or an indefinite shape can be used. preferable.
- the size is preferably in the range of an average particle size of 1 to 50 ⁇ m.
- the content of the conductive particles depends on the use of the adhesive composition, but usually it is preferably in the range of 1 to 100 parts by weight with respect to 100 parts by weight of the total resin solid content in the adhesive composition. .
- the silane coupling agent has a reactive functional group and a hydrolyzable group (OR) and improves the dispersibility of the silica, thereby further improving the bubble generation suppression effect due to the silica blending.
- the reactive functional group reacts with a resin component such as PEEA, and the hydrolyzable group is oriented on the surface of the conductive particles, thereby contributing to the suppression of bubble generation.
- the amount used is preferably 0.01 to 20% by weight with respect to silica and conductive particles.
- silane coupling agent commercially available products such as Shin-Etsu Silicone KBM-403 (Shin-Etsu Chemical Co., Ltd.) can be suitably used.
- the adhesive composition of the present invention includes other components that may be used in the adhesive composition, that is, a tackifier, a stabilizer, an antioxidant, a reinforcing agent, a pigment, and an antifoaming agent. Etc. can be further added as needed.
- a kneader such as a planetary kneader may be used, a solvent may be added to the raw material resin, heated, and dissolved and mixed.
- Solvents used here include nitrogen or amide solvents such as N-methylpyrrolidone, hydrocarbon solvents such as hexane, heptane, decane, toluene, xylene, cyclohexane, benzyl alcohol, and solvent naphtha, and ketone solvents such as isophorone.
- nitrogen or amide solvents such as N-methylpyrrolidone
- hydrocarbon solvents such as hexane, heptane, decane, toluene, xylene, cyclohexane, benzyl alcohol, and solvent naphtha
- ketone solvents such as isophorone.
- ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, ethyl cellosolve acetate, butyl cellosolve acetate, ether solvents such as ethyl cellosolve, butyl cellosolve, isopropyl cellosolve, t-butyl cellosolve, ethyl carbitol, butyl carbitol, etc. Can do.
- the amount of the solvent used is preferably in the range where the resin solid content concentration of the adhesive composition is 10 to 50% by weight. If the resin solid content concentration is less than 10% by weight, the coating thickness cannot be secured, and if it exceeds 50% by weight, the viscosity becomes too high and printing becomes difficult. Further, in relation to the resin component, the solvent component is preferably in the range of 100 to 450 parts by weight with respect to 100 parts by weight of the resin component.
- the adhesive film of the present invention can be obtained from any of the above-described adhesive compositions of the present invention.
- the method for obtaining an adhesive film from the above adhesive composition is not particularly limited, and the adhesive composition is applied on a support such as release paper to a predetermined thickness by various application methods and dried. Then, it can be obtained by peeling from the release paper or the like. Specifically, if necessary, an adhesive composition mixed with conductive particles is dissolved in an amine solvent or a ketone solvent to obtain a desired viscosity, and can be formed into a film by using a coating machine or the like. .
- the thickness of the adhesive film may be appropriately selected according to the use, but is usually about 10 to 50 ⁇ m.
- desired adhesive strength can be obtained by pressure bonding at a temperature of 100 to 160 ° C. and a pressure of 1 to 4 MPa for about 5 to 15 seconds.
- the present invention when a component is mounted on an FPC on a recent capacitive touch panel, the problem that paste printing after mounting is difficult is solved, and the connection material is transferred by transferring as a film type. It becomes possible to crimp on the touch panel.
- Examples 1 to 7, Comparative Examples 1 to 5 The resin components and silica shown in Table 1 were blended and dispersed at the ratios (weight ratio, resin solid content conversion) shown in the table. Dispersion was performed by kneading for 3 hours using a planetary kneader at a heating temperature of 85 ° C. and a rotation speed of 50 rpm. Details of the resin components and silica shown in Table 1 are as follows.
- PEEA TPAE-32 (T & K TOKA Corporation)
- Crystalline polyester Byron GA-5300 (Toyobo Co., Ltd., Mn: 25000, glass transition point: -2 ° C, melting point: 114 ° C)
- Polyurethane elastomer Milactolan P485RSUI (Nihon Milactolan Corporation)
- SIBS Shibustar 103T (Kaneka Corporation)
- Silica Admafine SO-C2 (Admatechs Corporation)
- Conductive particles Metal-coated resin balls (core: PMMA, first layer: Ni, outermost layer: Au, average particle size 30 ⁇ m) 10 parts by weight
- Solvent isophorone 300 parts by weight butyl cellosolve 50 parts by weight N-methylpyrrolidone 80 parts by weight
- Stabilizer Irganox 1010 (Ciba Specialty Chemicals) 1.3 parts by weight
- the resulting adhesive composition was measured for connection resistance, 90-degree peel strength, and heat aging resistance to evaluate the generation of bubbles during pressing.
- the measurement / evaluation method is as follows. The results are shown in Table 1.
- Samples for testing 90 degree peel strength, connection resistance, heat aging resistance, and heat creep are the flexible printed circuit board (FPC) 1 shown in FIG. 1 and the polymer thick film film (PTF) substrate shown in FIG. As shown in FIG. 3, 2 was connected by interposing an adhesive composition layer so that a part of the upper surface of the PTF substrate 2 was covered with the end portion of the FPC 1.
- FPC flexible printed circuit board
- PTF polymer thick film film
- Examples 1, 2, 4, and 7 and Comparative Examples 2, 4, and 5 the paste-like adhesive composition was applied to a film thickness of 28 ⁇ m, and Examples 3, 5, 6, and Comparative Examples 1 and 3 were performed by press-bonding for 15 seconds at a pressure of 130 to 140 ° C. and a pressure of 3 MPa, with an adhesive composition previously formed into an adhesive film having a thickness of 28 ⁇ m.
- ⁇ FPC Nikkan Kogyo Co., Ltd.> Composition: Polyimide 25 ⁇ m / Copper foil 18 ⁇ m Electrode plating: Ni3 ⁇ m / Au0.3 ⁇ m Pitch: 3mm Electrode width (a): 10 mm ⁇ PTF substrate> Polymer: Polyethylene terephthalate (PET) 188 ⁇ m manufactured by Toray Industries, Inc. Silver paste: about 10 ⁇ m * Resist coating on silver paste Pitch: 3mm
- a low resistance meter (manufactured by HIOKI, DC system 3227 milliohm high tester) is used between FPC terminal terminals of FPC / PTF test samples, and ab, bc, cd The connection resistance between them was measured, and the average value was obtained.
- the FPC / PTF test sample was peeled off with a tensile tester (PT-200N manufactured by Minebea Co., Ltd.) at a pulling speed of 50 mm / min and a peeling direction of 90 degrees. It was measured.
- a tensile tester PT-200N manufactured by Minebea Co., Ltd.
- ⁇ Heat aging resistance> As shown in FIG. 3, the FPC 1 and the PTF substrate 2 were connected and held at 80 ° C. for 1000 hours, and then the 90 ° peel strength was measured by the above method. If it is less than 5 N / cm, it shall be x, and if it is 5 N / cm or more, after further holding at 105 ° C. for 1000 hours, a 90 degree peel test is performed in the same manner. If it was less than ⁇ , it was set as ⁇ .
- PET is pasted on the circuit 4 of the flexible printed circuit board (FPC) 1 shown in FIG. 1, pressed at 150 ° C., and bubbles around the conductive particles are confirmed with an optical microscope from the PET surface side. If there was no problem in practical use, it was evaluated as ⁇ , and if there was no problem in practical use, it was evaluated as x.
- FPC flexible printed circuit board
- the adhesive composition of the present invention is used for various applications such as connection of various substrates used in mobile phones, game machines, etc., that is, connection between a liquid crystal panel and a substrate, connection of a membrane switch, connection of terminals of an EL backlight, etc. Can be suitably used.
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- Polymers & Plastics (AREA)
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Abstract
Description
表1に示した樹脂成分及びシリカをそれぞれ表に示した比率(重量比、樹脂固形分換算)で配合し、分散させた。分散はプラネタリー混練機を使用し、加温85℃、回転数50rpmで、3時間混練することにより行った。表1に示した樹脂成分及びシリカの詳細は以下の通りである。
結晶性ポリエステル:バイロンGA-5300(東洋紡績株式会社、Mn:25000、ガラス転移点:-2℃、融点:114℃)
ポリウレタンエラストマー:ミラクトランP485RSUI(日本ミラクトラン株式会社)
SIBS:シブスター103T(株式会社カネカ)
シリカ:アドマファインSO-C2(株式会社アドマテックス)
導電性粒子:金属コーティング樹脂ボール(芯部:PMMA、第1層:Ni、最外層:Au、平均粒径30μm) 10重量部
溶剤:イソホロン 300重量部
ブチルセロソルブ 50重量部
N-メチルピロリドン 80重量部
安定剤:イルガノックス1010(チバ・スペシャルティケミカルズ社) 1.3重量部
構成:ポリイミド 25μm/銅箔 18μm
電極メッキ:Ni3μm/Au0.3μm
ピッチ:3mm
電極幅(a):10mm
<PTF基板>
ポリマー:東レ(株)製ポリエチレンテレフタレート(PET) 188μm
銀ペースト:約10μm
*銀ペースト上にレジスト塗工
ピッチ:3mm
図4に示すように、FPC/PTF試験用サンプルのFPC端末端子間で、低抵抗計(HIOKI製、直流方式 3227ミリオームハイテスタ)を使用して、a-b、b-c、c-d間の接続抵抗をそれぞれ測定し、平均値を求めた。
図5に示すように、上記FPC/PTF試験用サンプルを引張試験機(ミネベア株式会社製 PT-200N)で、引張速度50mm/min、剥離方向90度にて剥離し、破断時の最大値を測定した。
図3に示すようにFPC1とPTF基板2とを接続して80℃で1000時間保持した後、上記方法により90度ピール強度を測定した。5N/cm未満ならば×とし、5N/cm以上のものについては、さらに105℃で1000時間保持した後、同様にして90度ピール試験を行い、5N/cm以上であれば○、5N/cm未満であれば△とした。
図3に示すようにFPC1とPTF基板2とが接続したものをエアオーブン中に吊るし、FPC1に600gの重りを付けた後、1℃/90秒で加熱していき、FPC1とPTF基板2とが接着箇所で分離する温度を計測した。80℃以上であれば○、60℃以上80℃未満であれば△、60℃未満であれば×とした。
図1に示したフレキシブルプリント基板(FPC)1の回路4上に、188μmのPETを貼り付け、150℃でプレスし、PET面側から光学顕微鏡で導電性粒子周りの気泡を確認し、気泡がなければ○とし、気泡が若干認められるが実用上問題がない場合は△とし、気泡が認められるため実用上問題がある場合は×とした。
2……ポリマー厚膜フィルム(PTF)基板
3……接着剤組成物(ペースト又はフィルム)
4……回路
Claims (5)
- ポリエーテルエステルアミド100重量部に対し、結晶性ポリエステル1~100重量部、及びシリカ20~110重量部を含有してなる接着剤組成物。
- 導電性粒子をさらに含有することを特徴とする、請求項1に記載の接着剤組成物。
- 前記導電性粒子が金属コーティング樹脂ボールであることを特徴とする、請求項2に記載の接着剤組成物。
- 前記結晶性ポリエステルが、数平均分子量が10000~35000の範囲内であり、ガラス転移点が-70~30℃の範囲内であり、かつ融点が90~180℃の範囲内であることを特徴とする、請求項1~3のいずれか1項に記載の接着剤組成物。
- 請求項1~4のいずれか1項に記載の接着剤組成物からなる接着フィルム。
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Cited By (3)
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US20160340562A1 (en) * | 2014-02-10 | 2016-11-24 | Nitto Denko Corporation | Adhesive resin composition, adhesive tape, adhesive tape with substrate, and composite article |
JP2018048286A (ja) * | 2016-09-23 | 2018-03-29 | 日亜化学工業株式会社 | 導電性接着剤および導電性材料 |
JP2019026821A (ja) * | 2017-08-03 | 2019-02-21 | トラス カンパニー リミテッドTruss Co.,Ltd | 導電性粘着テープ |
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JP6785856B2 (ja) * | 2016-06-30 | 2020-11-18 | タツタ電線株式会社 | 生体用電極、及び生体用電極の形成方法 |
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CN103403121A (zh) | 2013-11-20 |
KR101812370B1 (ko) | 2017-12-26 |
TW201302948A (zh) | 2013-01-16 |
CN103403121B (zh) | 2015-08-05 |
JPWO2012164836A1 (ja) | 2015-02-23 |
TWI496856B (zh) | 2015-08-21 |
JP5675975B2 (ja) | 2015-02-25 |
KR20140020861A (ko) | 2014-02-19 |
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