WO2012011265A1 - 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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- WO2012011265A1 WO2012011265A1 PCT/JP2011/004058 JP2011004058W WO2012011265A1 WO 2012011265 A1 WO2012011265 A1 WO 2012011265A1 JP 2011004058 W JP2011004058 W JP 2011004058W WO 2012011265 A1 WO2012011265 A1 WO 2012011265A1
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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
- 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
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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
- 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
- C09J133/10—Homopolymers or copolymers of methacrylic acid 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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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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
- 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
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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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
- 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
Definitions
- the present invention relates to an adhesive composition excellent in adhesive strength, long-term reliability, workability, etc., and particularly an adhesive composition suitable for application to anisotropic conductive paste and conductive adhesive film, and the same It is related with the adhesive film obtained by these.
- 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 is increasing, it is required to support connection to parts with finer pitches. 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.
- anisotropic conductive film for example, a film mainly composed of a thermosetting resin such as a blend of acrylic rubber and an epoxy resin has been conventionally used for taking out terminals of a liquid crystal display.
- thermosetting resin such as a blend of acrylic rubber and an epoxy resin
- these products have a problem that they cannot be stored at room temperature, a problem that they are poor in insertion / extraction due to tackiness, and a problem that they are more expensive than conventional touch panel materials.
- the present invention has been made in view of the above, and is a halogen-free adhesive composition excellent in adhesive strength, long-term reliability, and workability, and is an anisotropic conductive paste used for connecting substrates. It is an object of the present invention to provide an adhesive composition suitable for application to a medical device.
- it is an adhesive film suitable for use when paste printing is difficult, etc., and can be stored at room temperature, and is excellent in insertion / removal by controlling the tack and advantageous in cost.
- the purpose is to provide.
- the present inventors have added a specific olefin resin based on a specific ether ester amide, and further, if necessary, a urethane resin, a polyester resin, an acrylic resin
- a specific olefin resin based on a specific ether ester amide
- a urethane resin based on a specific ether ester amide
- a polyester resin based on a specific ether ester amide
- an acrylic resin an acrylic resin
- the adhesive composition of the present invention is a styrene-isobutylene-styrene-based olefin elastomer or a styrene-ethylene-butylene-styrene-based olefin elastomer with respect to 100 parts by weight of polyether ester amide (however, the resin solid content, the same applies hereinafter).
- polyether ester amide the same applies hereinafter.
- one or two or more of these maleic anhydride-modified products are contained in a total amount of 1 to 300 parts by weight.
- the adhesive composition of the present invention may further contain a urethane elastomer.
- the content is preferably 10 to 100 parts by weight of the urethane elastomer with respect to 100 parts by weight of the polyetheresteramide. .
- the adhesive composition of the present invention may further contain a polyester resin.
- the content is 1 to 100 parts by weight of the polyester resin with respect to 100 parts by weight of the polyetheresteramide. preferable.
- the adhesive composition of the present invention may further contain an acrylic resin, and the content in that case is 1 to 100 parts by weight of the acrylic resin with respect to 100 parts by weight of the polyetheresteramide. Is preferred.
- the adhesive composition of the present invention may contain an epoxy resin instead of the urethane elastomer, polyester resin, or acrylic resin, or together with the urethane elastomer, polyester resin, or acrylic resin.
- the content is preferably 5 to 50 parts by weight of epoxy resin per 100 parts by weight of polyetheresteramide.
- the adhesive composition of the present invention may further contain conductive particles.
- the adhesive film of the present invention is composed of the above-described adhesive composition of the present invention.
- the adhesive composition of the present invention not only satisfies the halogen-free requirements, but also has excellent adhesive strength, long-term reliability, workability, etc. compared to conventional chloroprene adhesives, and the signal extraction circuit and flexible print for touch panels It is suitable for application to an anisotropic conductive paste used for connection to a substrate.
- the adhesive film obtained using the adhesive composition of the present invention can be stored at room temperature, has excellent insertability and is advantageous in terms of cost.
- 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
- 3 is a plan view showing a connection position between the FPC 1 and the PTF substrate 2.
- FIG. It is the perspective view and sectional drawing which show the test method of 90 degree
- 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). It is a polyamide elastomer and is 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.
- a thixo ratio (however, a viscosity ratio (viscosity at 2 rpm / viscosity at 20 rpm) measured by a viscometer PVB-10 manufactured by Toki Sangyo Co., Ltd.) is 2.0 to 6.0, so that it is suitable for printing ( It is excellent in plate removal and stringing.
- “elastomer” refers to a synthetic rubber material having thermoplasticity. Among these, it is preferable to use one having a structure composed of a hard segment having a large cohesive force and a flexible soft segment.
- the 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
- the PEEA hard segment nylon 12, nylon 6, or the like is used.
- As the soft segment aliphatic polyether or aliphatic polyester is used for both.
- PEEA is soluble in a solvent as described above. More specifically, PEEA is soluble in an amine solvent, alcohol solvent or 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 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 inconveniences such as a decrease in peel strength and connection reliability in a moisture-resistant environment.
- PEEA is commercially available, and for example, TPAE series (solvent soluble grade, polyether ester amide type, polyester amide type) manufactured by T & K TOKA Corporation can be used. Among them, TPAE series TPAE-12, TPAE-31, TPAE-32, TPAE-617, TPAE-H471EP, TPAE-826, etc. can be selected and used suitably. These PEEAs can be used in a blend of two or more.
- the styrene-isobutylene-styrene-based olefin elastomer used in the present invention (a fully saturated copolymer consisting of both ends of a polystyrene chain and a polyisobutylene chain between them, hereinafter abbreviated as SIBS) is used as styrene as a hard segment. And a triblock structure obtained by living polymerization of isobutylene and styrene. SIBS has excellent thermal stability due to the main chain being saturated, and has the effect of greatly improving the heat aging resistance of an adhesive composition using the SIBS. As a commercially available product, for example, SIBSTAR (registered trademark) manufactured by Kaneka Corporation can be used.
- styrene-ethylene-butylene-styrene-based olefin elastomer (fully saturated copolymer consisting of polystyrene chains at both ends and an ethylene-butylene chain between the ends; hereinafter abbreviated as SEBS) is also used. It consists of styrene as the hard segment and ethylene-butylene as the soft segment.
- SEBS ethylene-butylene
- H1052, H1053, H1051, H1041, M1943, M1911, M1913, MP10, P1500, etc. manufactured by Toughtech (registered trademark) of Asahi Kasei Chemicals Corporation can be suitably used.
- SEBS When SEBS is used, the effect of improving the heat aging resistance of the adhesive composition due to the excellent thermal stability as in the case of SIBS is obtained, and in addition, SEBS has higher gas permeability than SIBS. In addition, when forming into a film, the solvent is easily removed, so that a higher quality film can be obtained.
- olefin elastomer SIBS or SEBS
- those modified with maleic anhydride can also be suitably used, which makes it possible to improve adhesion to metals, resins, and the like.
- olefin elastomers SIBS or SEBS or their maleic anhydride-modified products
- SIBS or SEBS or their maleic anhydride-modified products can be used alone or in combination of two or more.
- one or two or more of SIBS, SEBS, or these modified maleic anhydrides are blended at a ratio of 1 to 300 parts by weight in total with respect to 100 parts by weight of polyetheresteramide. Is preferred.
- the olefin elastomer within this range, the adhesion to polyethylene terephthalate resin, polyolefin resin or metal and long-term reliability should be improved.
- urethane elastomer (TPU)
- TPU urethane elastomer
- the urethane elastomer is composed of a polyurethane hard segment and a polyester or polyether soft segment, and has a structure in which an isocyanate and a polyol are bonded by a urethane bond.
- polyester polyol examples include adipate, polycaprolactone, and polycarbonate
- polyether polyol examples include polyoxytetramethylene glycol (PTMG).
- isocyanate examples include 4,4'-diphenylmethane diisocyanate (MDI), hydrogenated MDI, isophorone diisocyanate (IPDI), and the like.
- MDI 4,4'-diphenylmethane diisocyanate
- IPDI isophorone diisocyanate
- Milactolan registered trademark
- P390RSUP, P395SRNAT, P480RSUI, P485RSUI, P490RSUI, P890RSUA, P22MRNAT, P25MRNAT, P26MRNAT, P22SRNAT, and P26SRNAT can be suitably used.
- the urethane elastomer is preferably blended at a ratio of 10 to 100 parts by weight with respect to 100 parts by weight of the polyether ester amide.
- the adhesion can be improved, and the workability when used as a paste can also be improved.
- the polyester resin used in the present invention preferably has a functional group such as a hydroxyl group, a glycidyl group, or an amino group in the structure.
- crystalline polyester can also be used as a polyester resin.
- polyester resin commercially available ones such as Finedic (registered trademark) series manufactured by DIC Corporation can be used. Among them, 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. As the crystalline polyester, Byron (registered trademark) series manufactured by Toyobo Co., Ltd. can be used.
- Byron registered trademark
- GA-6300, GA-3410, GM-913, GM-920, GA-6400, GA-5300, GA-5200, GM-900, and 30P 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 adhesion can also be improved by further using an acrylic resin, and the workability when used as a paste can also be improved.
- the acrylic resin preferably has a functional group such as a hydroxyl group, a glycidyl group, or an amino group in the structure.
- DIC Corporation Fine Dick (registered trademark) series can be used. Among them, A-247S, A-254, A-253, A-229-30, A-244-A, A-249, A-261, A-266, A-241 and A-251 are preferably used. Can do.
- the adhesive composition of the present invention can further contain an epoxy resin.
- Epoxy resins that can be suitably used include those based on bisphenol A, F, S, or AF, and more specifically, for example, product numbers 827, 828, 828EL, 828XA, 834 manufactured by Mitsubishi Chemical Corporation. 801N, 801PN, 802, 811, 813, 816A, 816C, 819, or the like can be used.
- the epoxy resin is preferably blended at a ratio of 5 to 50 parts by weight with respect to 100 parts by weight of the polyetheresteramide. By using within this range, the film strength of the film obtained from the composition can be further improved.
- the epoxy resin can be used in place of the urethane elastomer, polyester resin, or acrylic resin, or can be used together with the urethane elastomer, polyester resin, or acrylic resin.
- the specific aspect of the adhesive composition comprising the above resin components is not particularly limited, for example, in the polyether ester amide having the largest polarity among them, urethane elastomer, polyester resin, or acrylic resin having medium polarity
- urethane elastomer urethane elastomer
- polyester resin polyester resin
- acrylic resin having medium polarity
- adhesion excellent in all of the adhesive strength, long-term reliability, and workability targeted by the present invention An agent composition can be obtained.
- a solvent is added to the resin as a raw material, heated, dissolved and mixed. That's fine.
- 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. Can be used.
- 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. Can be used.
- 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 nitrogen or amide solvent and the ketone solvent are in the range of 0 to 375 parts by weight and the hydrocarbon solvent is in the range of 0 to 125 parts by weight with respect to 100 parts by weight of the resin component. It is preferable that
- the adhesive composition of the present invention can be made into a conductive paste having anisotropic conductivity by adding conductive particles such as metal powder.
- conductive particles include metal powders such as copper, silver, lead, zinc, iron and nickel, or inorganic powders such as these metal powders, plastic powders and glass powders, nickel, gold, silver, copper, etc. It is the particle which plated.
- the shape of the conductive particles is not particularly limited, and any shape such as a true sphere, scale, potato, needle, or indefinite shape can be used.
- 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 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 filler, a reinforcing agent, a pigment, An antifoaming agent etc. can further be added as needed.
- the adhesive film of the present invention can be obtained from any of the above-described adhesive compositions of the present invention.
- the adhesive film of the present invention is not only halogen-free compared to adhesive films that have been used for the same purpose so far. It has the feature of being.
- 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 14, Comparative Examples 1 to 5 The following resin components 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 6 hours at a heating temperature of 85 ° C. and a rotation speed of 50 rpm using a planetary kneader.
- Polyetheresteramide TPAE-32 made by T & K TOKA SIBS: Kaneka Corporation, Shibustar 103T SEBS: Asahi Kasei Chemicals Corporation, Tuftec M1911 Polyurethane elastomer: manufactured by Nihon Milactolan Co., Ltd., Milactolan P485RSUI Epoxy resin: Mitsubishi Chemical Corporation, 828 Polyester resin: Toyobo Co., Ltd .: Byron GA-5300 Acrylic resin: DIC Corporation, Finedick A-254
- Conductive particles Metal powder (Ni powder, average particle size 35 ⁇ m) 55 parts by weight Solvent: Dimethylformamide (DMF) 180 parts by weight Cyclohexanone 80 parts by weight Toluene 45 parts by weight Filler (talc, average particle size 4-5 ⁇ m) 50 parts by weight Part Tackifier (Arakawa Chemical Industries, Pencel D-125) 30 parts by weight Stabilizer (Ciba Specialty Chemicals, Irganox (registered trademark) 1010) 1.3 parts by weight
- the 90 ° peel strength, connection resistance, and heat aging resistance of the obtained adhesive composition were measured, and coating workability, printing workability, tack-free property, and press workability were evaluated.
- the measurement / evaluation method is as follows. The results are shown in Table 1.
- Samples for testing 90 degree peel strength, connection resistance, and heat aging resistance include a flexible printed circuit board (FPC) 1 shown in FIG. 1 and a polymer thick film film (PTF) board 2 shown in FIG.
- the PTF substrate 2 was formed 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.
- the paste adhesive composition was applied to a film thickness of 35 ⁇ m, and Examples 9, 10, 13, and 14 were applied.
- Comparative Examples 3 and 5 the adhesive composition was previously formed into an adhesive film having a thickness of 35 ⁇ m, and press-pressed for 15 seconds at a pressure of 130 to 140 ° C.
- the adhesive film of Example 9 and the like was formed from the adhesive composition using a coating machine (CED coater manufactured by Inoue Metal Industry Co., Ltd.) at a drying temperature of 110 ° C. and a linear velocity of 10 m / min.
- a coating machine CED coater manufactured by Inoue Metal Industry Co., Ltd.
- ⁇ 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: manufactured by Toray Industries, Inc., polyethylene terephthalate (PET) 188 ⁇ m Silver paste: about 10 ⁇ m * Resist coating on silver paste Pitch: 3mm
- the FPC / PTF test sample was peeled off with a tensile tester (PT-200N manufactured by Minebea Co., Ltd.) at a pulling speed of 100 mm / min and a peeling direction of 90 degrees, and the maximum value at the time of breaking was determined. It was measured.
- a tensile tester PT-200N manufactured by Minebea Co., Ltd.
- a low resistance meter (manufactured by HIOKI, DC method 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.
- ⁇ Printability> The adhesive composition was printed using a screen 80 mesh (Tetron (registered trademark)) so that the dry film thickness (drying temperature 120 ° C., 15 minutes) was maintained at 20 ⁇ 5 ⁇ m. Visual observation was made for the presence of defects such as stringing between the screen and the printed material, stenciling, foaming, and bleeding, and the evaluation was made according to the following criteria: A: There are no defects such as stringing, stenciling, foaming, bleeding, etc., and good printing workability. B: Although there are some defects, it is acceptable, printing workability is somewhat good, C: Defects are remarkable and printing workability is poor.
- ⁇ Tack-free> The adhesive composition was applied to a smooth surface with a thickness of 20 ⁇ 5 ⁇ m, dried at a temperature of 100 ° C. for 15 minutes, and then touched the coating film with a fingertip to examine the presence or absence of tackiness (tackiness), and evaluated according to the following criteria: ; A: Good without tack, B: Slightly good with some tack, C: Tack is noticeable and defective.
- the adhesive composition was applied to a smooth surface with a thickness of 20 ⁇ 5 ⁇ m, dried for 5 minutes at a temperature of 120 ° C., and then visually checked for the presence or absence of blocking (sticking) of the coating and the presence or absence of voids in the coating. Evaluated on the basis of: A: Good without blocking and voids, B: Although there are some voids, there is no blocking, and it is somewhat good. C: There are blocking and voids, which are bad.
- the film thickness was measured by polishing a film that was embedded in a resin and polishing it to reveal a cross section in the thickness direction of the film, observing the cross section with a CCD camera, and measuring the thickness dimension.
- A Standard deviation less than 3 ⁇ m
- B Standard deviation of 3 ⁇ m or more and less than 5 ⁇ m
- C Standard deviation of 5 ⁇ m or more and less than 7 ⁇ m
- D Standard deviation of 7 ⁇ m or more.
- the adhesive composition of the present invention is suitable as a paste or an adhesive film for various uses such as connection of various substrates, 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 used.
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Abstract
Description
表1に示した以下の樹脂成分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、6時間混練することにより行った。
SIBS:株式会社カネカ製、シブスター103T
SEBS:旭化成ケミカルズ株式会社製、タフテックM1911
ポリウレタンエラストマー:日本ミラクトラン株式会社製、ミラクトランP485RSUI
エポキシ樹脂:三菱化学株式会社製、828
ポリエステル樹脂:東洋紡績株式会社製:バイロンGA-5300
アクリル樹脂:DIC株式会社製、ファインディックA-254
溶剤:ジメチルホルムアミド(DMF) 180重量部
シクロヘキサノン 80重量部
トルエン 45重量部
充填材(タルク、平均粒径4~5μm) 50重量部
粘着性付与剤(荒川化学工業株式会社製、ペンセルD-125) 30重量部
安定剤(チバ・スペシャルティケミカルズ社製、イルガノックス(登録商標)1010) 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:東レ株式会社製、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、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100mm/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5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。
80℃で1000時間保持した後に、上記方法により90度ピール強度を測定し、次の基準で評価した:
A:5N/cm以上、B:5N/cm未満。
スクリーン80メッシュ(テトロン(登録商標))を使用し、乾燥膜厚(乾燥温度120℃、15分間)が20±5μmを維持する様に、接着剤組成物の印刷を実施した。目視により、スクリーンと印刷物間の糸引き、版ぬけ、泡かみ、にじみ等の不具合の有無を観察し、次の基準で評価した;
A:糸引き、版ぬけ、泡かみ、にじみ等の不具合がなく、印刷作業性良好、
B:不具合が若干あるが、許容範囲であり、印刷作業性やや良好、
C:不具合が顕著にあり、印刷作業性不良。
接着剤組成物を平滑面に厚さ20±5μmで塗布し、温度100℃で15分間乾燥後、塗膜に指先で触れて、粘着の有無(タック性)を調べ、次の基準で評価した;
A:タックがなく、良好、
B:タックが若干あり、やや良好、
C:タックが顕著にあり、不良。
コンスタントヒータ方式プレス機(株式会社大橋製作所製、HBM-10)を使用して、圧着温度130~140℃、圧力3MPa、時間15秒でプレス圧着し、目視により、樹脂流れ、ボイド等の不具合の有無を観察し、次の基準で評価した;
A:不具合がなく、プレス作業性良好、
B:不具合が若干あるが、許容範囲であり、プレス作業性やや良好、
C:不具合が顕著にあり、プレス作業性不良。
接着剤組成物を平滑面に厚さ20±5μmで塗布し、温度120℃で5分間乾燥後、塗膜のブロッキング(くっつき)の有無及び塗膜中のボイドの有無を目視で判断し、次の基準で評価した;
A:ブロッキングもボイドもなく良好、
B:ボイドは若干あるが、ブロッキングはなく、やや良好、
C:ブロッキングもボイドもあり、不良。
実施例9,10,13,14及び比較例3については、接着剤組成物を平滑面に塗布、乾燥して、厚さ35μmのフィルムを形成し、それぞれコーティング幅300mmの幅方向3点(左、中心、右)において長手方向10cmごとに10回(n=30)膜厚を測定し、以下の基準により評価した。膜厚測定は、フィルムを樹脂に埋めて硬化したものを研磨することによりフィルムの厚み方向の断面をあらわにし、その断面をCCDカメラで観察して、厚み寸法を測定することにより行った。
A:標準偏差3μm未満、
B:標準偏差3μm以上、5μm未満、
C:標準偏差5μm以上、7μm未満、
D:標準偏差7μm以上。
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)
Claims (7)
- ポリエーテルエステルアミド100重量部に対し、
スチレン-イソブチレン-スチレン系オレフィンエラストマー、スチレン-エチレン-ブチレン-スチレン系オレフィンエラストマー及びこれらの無水マレイン酸変性物のうちの1種又は2種以上を総量で1~300重量部含有してなる
ことを特徴とする接着剤組成物。 - 前記ポリエーテルエステルアミド100重量部に対し、
さらにウレタンエラストマーを10~100重量部含有してなる
ことを特徴とする、請求項1に記載の接着剤組成物。 - 前記ポリエーテルエステルアミド100重量部に対し、
さらにポリエステル樹脂を1~100重量部含有してなる
ことを特徴とする、請求項1に記載の接着剤組成物。 - 前記ポリエーテルエステルアミド100重量部に対し、
さらにアクリル樹脂を1~100重量部含有してなる
ことを特徴とする、請求項1に記載の接着剤組成物。 - 前記ポリエーテルエステルアミド100重量部に対し、
さらにエポキシ樹脂を5~50重量部含有してなる
ことを特徴とする、請求項1~4のいずれか1項に記載の接着剤組成物。 - 導電性粒子をさらに含有する
ことを特徴とする、請求項1~5のいずれか1項に記載の接着剤組成物。 - 請求項1~6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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CN201180025117.XA CN102906211B (zh) | 2010-07-23 | 2011-07-15 | 导电性粘合剂组合物及导电性粘合膜 |
KR1020127029990A KR101741292B1 (ko) | 2010-07-23 | 2011-07-15 | 접착제 조성물 및 접착 필름 |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2014511029A (ja) * | 2012-03-27 | 2014-05-01 | エイブルスティック・(シャンハイ)・リミテッド | コンデンサ用導電性コーティングおよびそれを用いたコンデンサ |
JP2015110769A (ja) * | 2013-11-07 | 2015-06-18 | 東洋インキScホールディングス株式会社 | 導電性接着剤、導電性接着シート、配線デバイス、および配線デバイスの製造方法 |
WO2016017473A1 (ja) * | 2014-07-31 | 2016-02-04 | 東亞合成株式会社 | 接着剤層付き積層体、並びに、これを用いたフレキシブル銅張積層板及びフレキシブルフラットケーブル |
JP2016040370A (ja) * | 2012-06-29 | 2016-03-24 | タツタ電線株式会社 | 導電性接着剤組成物、導電性接着フィルム、接着方法及び回路基板 |
WO2024009969A1 (ja) * | 2022-07-06 | 2024-01-11 | 東亞合成株式会社 | 接着剤組成物、ボンディングフィルム、接着剤組成物層付き積層体、積層体、及び、電磁波シールドフィルム |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6152319B2 (ja) | 2013-08-09 | 2017-06-21 | 日東電工株式会社 | 粘着剤組成物、粘着テープ又はシート |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61108676A (ja) * | 1984-10-16 | 1986-05-27 | アトケム | 熱可塑性エラストマ−及びポリエ−テル‐アミドを主成分とする接着性組成物とその使用 |
JPS6386781A (ja) * | 1986-09-30 | 1988-04-18 | Sekisui Chem Co Ltd | 異方導電性接着シ−ト |
JPH04231083A (ja) * | 1990-06-01 | 1992-08-19 | Salomon Sa | スキー板の構成部材 |
JPH093323A (ja) * | 1995-06-19 | 1997-01-07 | Taisei Plus Kk | 熱融着性に優れた熱可塑性弾性体組成物 |
JP2001354938A (ja) * | 2000-06-12 | 2001-12-25 | Toray Ind Inc | 半導体装置用接着剤組成物およびそれを用いた接着剤シート、半導体接続用基板ならびに半導体装置 |
WO2010084722A1 (ja) * | 2009-01-26 | 2010-07-29 | タツタ システム・エレクトロニクス株式会社 | 接着剤組成物 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7015284B2 (en) * | 2004-01-06 | 2006-03-21 | The Goodyear Tire & Rubber Company | Thermoplastic elastomer composition |
JP5236187B2 (ja) * | 2005-08-26 | 2013-07-17 | 株式会社クラレ | 熱可塑性エラストマー組成物およびその複合成形体 |
JP4435253B2 (ja) * | 2008-03-26 | 2010-03-17 | 住友ゴム工業株式会社 | インナーライナーおよび空気入りタイヤ |
-
2011
- 2011-07-15 KR KR1020127029990A patent/KR101741292B1/ko active IP Right Grant
- 2011-07-15 WO PCT/JP2011/004058 patent/WO2012011265A1/ja active Application Filing
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- 2011-07-15 JP JP2011540991A patent/JP5002074B2/ja active Active
- 2011-07-20 TW TW100125646A patent/TWI496863B/zh active
-
2013
- 2013-07-12 HK HK13108218.4A patent/HK1181065A1/xx unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61108676A (ja) * | 1984-10-16 | 1986-05-27 | アトケム | 熱可塑性エラストマ−及びポリエ−テル‐アミドを主成分とする接着性組成物とその使用 |
JPS6386781A (ja) * | 1986-09-30 | 1988-04-18 | Sekisui Chem Co Ltd | 異方導電性接着シ−ト |
JPH04231083A (ja) * | 1990-06-01 | 1992-08-19 | Salomon Sa | スキー板の構成部材 |
JPH093323A (ja) * | 1995-06-19 | 1997-01-07 | Taisei Plus Kk | 熱融着性に優れた熱可塑性弾性体組成物 |
JP2001354938A (ja) * | 2000-06-12 | 2001-12-25 | Toray Ind Inc | 半導体装置用接着剤組成物およびそれを用いた接着剤シート、半導体接続用基板ならびに半導体装置 |
WO2010084722A1 (ja) * | 2009-01-26 | 2010-07-29 | タツタ システム・エレクトロニクス株式会社 | 接着剤組成物 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014511029A (ja) * | 2012-03-27 | 2014-05-01 | エイブルスティック・(シャンハイ)・リミテッド | コンデンサ用導電性コーティングおよびそれを用いたコンデンサ |
JP2016040370A (ja) * | 2012-06-29 | 2016-03-24 | タツタ電線株式会社 | 導電性接着剤組成物、導電性接着フィルム、接着方法及び回路基板 |
JP2015110769A (ja) * | 2013-11-07 | 2015-06-18 | 東洋インキScホールディングス株式会社 | 導電性接着剤、導電性接着シート、配線デバイス、および配線デバイスの製造方法 |
WO2016017473A1 (ja) * | 2014-07-31 | 2016-02-04 | 東亞合成株式会社 | 接着剤層付き積層体、並びに、これを用いたフレキシブル銅張積層板及びフレキシブルフラットケーブル |
CN106536658A (zh) * | 2014-07-31 | 2017-03-22 | 东亚合成株式会社 | 带粘合剂层的层叠体以及使用其的柔性覆铜层叠板及柔性扁平线缆 |
US10875283B2 (en) | 2014-07-31 | 2020-12-29 | Toagosei Co., Ltd. | Adhesive layer-equipped laminate, and flexible copper-clad laminate sheet and flexible flat cable using same |
WO2024009969A1 (ja) * | 2022-07-06 | 2024-01-11 | 東亞合成株式会社 | 接着剤組成物、ボンディングフィルム、接着剤組成物層付き積層体、積層体、及び、電磁波シールドフィルム |
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JP5002074B2 (ja) | 2012-08-15 |
CN102906211B (zh) | 2014-11-05 |
TWI496863B (zh) | 2015-08-21 |
TW201207066A (en) | 2012-02-16 |
KR101741292B1 (ko) | 2017-05-29 |
JPWO2012011265A1 (ja) | 2013-09-09 |
CN102906211A (zh) | 2013-01-30 |
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