JP2006057043A - Adhesive composition and laminated body using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition that has excellent adhesion to plastic film and metal and shows excellent extrusion film-forming properties. <P>SOLUTION: The adhesive composition comprises (A) a crystallin polyester having a melting point of 200°C or lower, (B) a thermoplastic resin, and (C) polytetrafluoroethylene and satisfies all of (a) to (c): (a) the amount of (B) the thermoplastic resin is 0.5 to 110 pts.wt., when (A) the crystalline polymer melting at 200°C or lower is used, based on 100 pts.wt.; (b) the amount of (C) the polytetrafluoroethylene is 0.0001 to 10 pts.wt., when (A) the crystalline polymer melting at 200°C or lower is used, based on 100 pts.wt.; (c) the adhesive composition has a melt-viscosity of from 500 dPa s to 50,000 dPa s at 200°C under a shear rate of 50 s<SP>-1</SP>. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an adhesive composition characterized by being excellent in adhesiveness to plastic films and metals and having excellent extrusion film forming properties. Furthermore, it is related with the laminated body using it, a flexible flat cable, and a flexible printed wiring board.

  In electrical and electronic materials, high adhesiveness, environmental stability and easy processability are required for adhesives for bonding other kinds of materials such as metal and plastic. For example, in a flexible printed circuit board (FPC) and a flexible flat cable (FFC), a film substrate and a metal that is a conductor are bonded using an adhesive, and in this case, the adhesive is used for a long time such as repeated bending. Long-term durability that does not cause peeling, environmental reliability under low temperatures of -30 ° C, high temperatures over 100 ° C, and heat and humidity resistance, and easy application and no need for post heat treatment There is a demand for an adhesive having excellent processability. As such an adhesive, a method of dissolving a copolyester in an organic solvent and applying it to a plastic film or metal has been used. However, although such an adhesive has excellent adhesiveness, it is generally amorphous, so that blocking when left at high temperature becomes a problem. Moreover, not only a drying process is required, but also costs are increased in terms of processes and facilities, such as prevention of volatilization of organic solvents. Against this background, in recent years there has been no generation of environmentally hazardous substances and the number of processing steps has been reduced. Therefore, a technique of directly melt extrusion laminating a copolymerized polyester on a plastic film or metal has been widely used. However, since polyester has a low melt tension, it essentially lacks film formability by a T-die. Furthermore, since the polyester usually used as an adhesive has a low molecular weight, when the film is formed by extrusion, the film formation becomes more difficult due to the low viscosity. Therefore, even if it is attempted to form a film using such polyester alone, the film forming property is insufficient, pinholes and thickness unevenness occur in the adhesive layer, and the adhesive strength inherent in the adhesive is fully exhibited. become unable. Furthermore, in applications that require a thinner adhesive layer and cost reduction, such as FFC, it is essential to increase the line speed, but it has been difficult to form a film with conventional adhesives. Even when a large amount of a flame retardant or an inorganic filler is added, the adhesive is required to have sufficient melt tension and melt elongation sufficient to form a film. Even if these problems are solved by reducing the line speed, it is not a practical method because productivity is greatly reduced. In the case of crystalline polyester, it is possible to increase the apparent melt viscosity by increasing the crystallization speed so as to eliminate the dripping or spreading of the adhesive on the adherend or on the adherend. It becomes difficult to achieve both film-forming properties and adhesive properties, such as a decrease in wettability to the body and rapid volume shrinkage, so that the adhesive peels off from the adherend.

  As a conventional technique of an adhesive for plastics and metals, for example, in Patent Document 1, an adhesive containing a polyester resin, an epoxy resin, or a polyethylene resin is used to improve the adhesion to a polyester coated surface applied as a precoated steel sheet. It is disclosed. However, since this adhesive contains a large amount of low molecular weight epoxy in order to improve adhesion, it has a low melt viscosity and cannot maintain the melting characteristics necessary for extrusion film formation. Therefore, when extrusion lamination is performed using this adhesive, pinholes and thickness unevenness occur in the adhesive layer, and the adhesiveness is greatly reduced.

  As an example of improving the polyester resin in order to improve the extrusion film forming property, it is a polyester resin sealing material of Patent Document 2, and branching is performed by copolymerizing a polyester with a trifunctional or higher polycarboxylic acid or polyol as a branching agent. By introducing and increasing the molecular weight, extrusion film-forming properties are imparted. However, when an attempt is made to continuously polymerize a resin having a high molecular weight and a branch introduced in this way, crosslinking by the branching agent proceeds and a gel-like product is generated. When such a resin is extruded, fish eyes and the like are generated at the time of extrusion, and a sufficiently satisfactory extruded film cannot be obtained. Furthermore, in Patent Document 3, it is proposed to blend a polyester having a branched chain with a polyester having no branched chain in order to improve heat-sealability. However, it is essential to use a polyester having a branched chain. The reality is that the productivity, heat sealability, and extrudability are not compatible.

  Furthermore, in patent document 4, polytetrafluoroethylene resin is added to polyester and the favorable film forming property is achieved. However, the resin implemented here could not be used as an adhesive because of its very high melt viscosity, melting point, and glass transition point. When the melt viscosity is high, the wettability with the adherend is very poor and the adhesiveness does not come out. Further, when the melting point is high, not only the workability is lowered, but also the adherend such as a polymer film is melted or deteriorated, so that it is difficult to use. Further, when the glass transition point is high, the resin itself is very hard at room temperature and sufficient adhesive force cannot be obtained. As described above, no adhesive composition has been reported that has both high adhesion to plastics and metals and excellent film-forming properties during extrusion lamination.

JP-A-1-254788 (Claims) Japanese Patent No. 3089650 (Claims) JP-A-6-107924 (Claims) JP 9-12848 PR (Claims)

  The subject of this invention is providing the adhesive composition characterized by having the outstanding adhesiveness with respect to a plastic film or a metal, and having the outstanding extrusion film forming property. Furthermore, it is providing the laminated body using it, a flexible flat cable, and a flexible printed wiring board.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to achieve the above-mentioned problems. That is, this invention relates to the adhesive composition characterized by containing crystalline polyester (A) whose melting | fusing point is 200 degrees C or less, a thermoplastic resin (B), and polytetrafluoroethylene (C). More specifically, the thermoplastic resin (B) is an ethylene-propylene copolymer (B1), a styrene-butadiene copolymer (B2), the melt flow rate at 230 ° C. is less than 1.0 g / min, and The present invention relates to an adhesive composition which is at least one of low density polyethylene (B3) having a density of less than 0.92 g / cm ³ and wherein polytetrafluoroethylene (C) is modified with an acrylic resin. . Furthermore, it is related with the laminated body containing this adhesive composition, a flexible flat cable, and a flexible printed wiring board.

  INDUSTRIAL APPLICABILITY The present invention can provide an adhesive composition characterized by being excellent in adhesiveness to plastic films and metals and having excellent extrusion film forming properties. Furthermore, a laminated body, a flexible flat cable, and a flexible printed wiring board using the same can be provided.

The present invention is an adhesive composition comprising crystalline polyester (A), thermoplastic resin (B), and polytetrafluoroethylene (C).
The crystalline polyester referred to in the present invention is defined as follows. First, a polyester sample is heat-treated at 120 ° C. for 1 hour and left at 25 ° C. for 48 hours. Next, the heat-treated sample is measured using a differential scanning calorimeter (DSC). The measurement condition is that the temperature is raised from −100 ° C. to 300 ° C. at 20 ° C./min in a nitrogen atmosphere, then the temperature is lowered to −100 ° C. at 50 ° C./min, and then from −100 ° C. to 300 ° C. Raise the temperature. In the two temperature raising processes, a polyester having a clear melting point peak in either temperature raising process is referred to as crystalline polyester. An amorphous polyester is one in which no crystal melting peak is observed in any temperature rising process.

  As a constituent component of the crystalline polyester (A) used in the resin composition of the present invention, the following polyvalent carboxylic acids, alkyl esters thereof, or acid anhydrides can be used. Examples of the polyvalent carboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, and 2,2′-diphenyl. Aromatic dicarboxylic acids such as dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, sodium 5-sulfonic acid isophthalic acid, fumaric acid, maleic acid, succinic acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, 1,12 -Aliphatic and alicyclic such as dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, dimer acid Dicarboxylic acid, trimellitic acid, pyromellitic acid, benzophenone teto Carboxylic acid, biphenyltetracarboxylic acid, ethylene glycol bis (anhydrotrimellitate), aromatic polycarboxylic acids such as glycerol tris (anhydrotrimellitate), and the like.

  Examples of the polyol component of the crystalline polyester (A) include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, and 1,2-butanedio- 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, Dipropylene glycol, 2,2,4-trimethyl-1,5-pentanediol, neopentyl hydroxypivalate ester, ethylene oxide adduct and propylene oxide adduct of bisphenol A, hydrogenated bisphenol A Of ethylene oxide and propylene oxide 1,9-nonanediol, 2-methyloctanediol, 1,10-decanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, Examples include dimer diol, polycarbonate glycol, glycerin, trimethylol propane, pentaerythritol, dimethylol butanoic acid, dimethylol propionic acid, and polyether glycol. Moreover, it is preferable to copolymerize polyether glycol as a polyol component of crystalline polyester (A). Polyether glycol copolymer gives moderate flexibility and, unlike other long-chain glycols and long-chain carboxylic acid copolymerization, when used as an adhesive, adhesion due to volume shrinkage during crystallization Deterioration is less likely to occur. Further, since the glass transition point is lowered, the glass transition point is sufficiently flexible even in a low temperature environment in winter, and the adhesiveness in a low temperature environment is good even when used as an adhesive. Furthermore, by copolymerizing polyether glycol, the ester group concentration in the resin is lowered, and the heat and moisture resistance is greatly improved. Polyether glycols include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and copolymers thereof, and those obtained by copolymerizing neopentyl glycol, bisphenol A, and the like with these alkylene glycols. The number average molecular weight of the polyether diol is preferably 400 to 10,000. A preferred lower limit is 600, more preferably 800. Moreover, a preferable upper limit is 4000, More preferably, it is 3000, More preferably, it is 2500. The copolymerization amount of polyether glycol is 1 mol% or more, preferably 2 mol% or more. The upper limit is less than 20 mol%.

  Among the acid components of the crystalline polyester (A), terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, and sebacic acid having high crystallinity are preferably copolymerized. The polyol component of the crystalline polyester (A) includes at least one of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol. It is preferable to contain 50 mol% or more. Furthermore, it is preferable to use two or more components of at least one of these acid components and / or polyols in order to reduce the crystal size and the crystallization strain accompanying crystallization.

  In addition, if necessary, a polybasic acid such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate), glycerin, Addition of polyfunctional glycols such as pentaerythritol, trimethylolpropane, dimethylolbutanoic acid, dimethylolpropionic acid to the extent that gel does not occur during polymerization, or addition during melt-kneading can increase the adhesion due to the increase in functional groups. It is preferable in order to improve and further improve the extrusion film forming property.

  The melting point of the crystalline polyester (A) is 200 ° C. or less. Preferably it is 180 degrees C or less, More preferably, it is 150 degrees C or less. When the melting point exceeds 200 ° C., not only is the workability inferior because a high temperature is required when processing the resin, but also the heat seal temperature becomes too high, making it difficult to use as an adhesive. On the other hand, the lower limit of the melting point is preferably 50 ° C. or higher. When the melting point is less than 50 ° C., the heat resistance is insufficient and blocking may occur at room temperature. The glass transition point of the crystalline polyester (A) is 70 ° C. or lower, preferably 30 ° C. or lower, more preferably 0 ° C. or lower, and most preferably −20 ° C. or lower. In particular, 30 ° C. or lower is preferable for improving the adhesion at room temperature. When the glass transition point exceeds 30 ° C., the elastic modulus in the vicinity of room temperature becomes too high, and the adhesiveness particularly in the room temperature region may be lowered. In addition, in a flexible flat cable or the like that requires high bending resistance due to poor flexibility, peeling may occur between the adhesive and the adherend during bending. Although a minimum is not specifically limited, When the adhesiveness of a high temperature area is considered, it is -100 degreeC or more. Here, the melting point and the glass transition temperature were determined as follows using a differential scanning calorimeter. First, the sample was heat-treated at 120 ° C. for 1 hour and left at 25 ° C. for 48 hours. Thereafter, 5 mg of a measurement sample is placed in an aluminum pan, sealed with a lid, heated from −100 ° C. to 300 ° C. at 20 ° C./min, then lowered to −100 ° C. at 50 ° C./min, and then − Of the two temperature raising processes in which the temperature was raised from 100 ° C. to 300 ° C. at 20 ° C./min, the peak of the melting peak that appeared at a higher temperature was taken as the melting point. The glass transition point is determined by the temperature at the intersection of the base line extension below the glass transition point and the tangent that indicates the maximum slope between the peak rise and the peak apex in the second temperature rise process. It was.

The crystalline polyester (A) used as a constituent component of the resin composition of the present invention preferably has a melt viscosity of 200 dC · s to 50000 dPa · s at a shear rate of 50 s ⁻¹ . More preferably, it is 500 dPa * s-40000 dPa * s, More preferably, it is 1000-30000. If the melt viscosity is less than 100 dPa · s, the compound becomes insufficient due to the difference in melt viscosity from the thermoplastic resin (B) or polytetrafluoroethylene (C), and fluffing occurs. Further, the melt viscosity of the final adhesive composition does not increase sufficiently, and film formation is impossible. On the other hand, when it is 50000 dPa · s or more, the final adhesive composition is not sufficiently wetted to the adherend, and sufficient adhesive force cannot be obtained.

The blend of the thermoplastic resin (B) of the present invention is very effective for improving both the film forming property and the adhesive property when blended with polyester.
As the thermoplastic resin (B), one or more selected from polyolefins such as polyethylene and polypropylene, polystyrene, polyvinyl chloride, polyurethane, silicon, polyester having a composition different from that of the crystalline polyester (A), polyamide and the like are used. It is preferable to do. Among them, when used as an adhesive, since adhesion at room temperature and a low temperature atmosphere is required, the glass transition point of the thermoplastic resin (B) is 30 ° C. or lower, preferably 0 ° C. or lower, more preferably −40. It is below ℃. The lower limit is preferably −100 ° C. or higher. In particular, the Shore A hardness of the thermoplastic resin (B) under the measurement conditions of JIS K 7215 is preferably 60 to 98. More preferably, it is 70-95. When the Shore A hardness is less than 60, the mechanical properties of the final resin composition are lowered. On the other hand, when the Shore A hardness is 98 or more, the final resin composition becomes very hard and the adhesiveness is greatly reduced. There is a case. On the other hand, since the thermoplastic resin (B) having a Shore A hardness of 60 to 98 is moderately flexible, strain energy associated with the progress of crystallization of the crystalline polyester (A) can be effectively reduced. A decrease in adhesive strength over time can also be suppressed.

  As the thermoplastic resin (B) having such characteristics, it is preferable to use various soft polymers or thermoplastic elastomers. Soft polymers and thermoplastic elastomers include soft polyolefins, olefin elastomers, styrene elastomers, polyvinyl chloride elastomers, nitrile elastomers, polyurethane elastomers, polyester elastomers and polyamides having a composition different from that of the crystalline polyester (A). And elastomers such as elastomers, polybutadiene elastomers, silicone elastomers, fluorine elastomers, 1,2-polybutadiene elastomers, and trans-1,4-polyisoprene elastomers.

  Soft polyolefins and polyolefin-based elastomers need only be relatively flexible, so low density polyethylene, ultra-low density polyethylene, linear low density polyethylene, ethylene propylene elastomer, α-olefin copolymer, ethylene -Non-polar polyolefins such as α-olefin copolymers, and ionomers, dynamically crosslinked thermoplastic polyolefin elastomers, ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, ethylene-vinyl acetate-maleic anhydride Terpolymer, ethylene-ethyl acrylate-maleic anhydride terpolymer, ethylene-glycidyl methacrylate copolymer, ethylene-vinyl acetate-glycidyl methacrylate terpolymer, ethylene-methyl acrylate-methacryl Glycidyl acid ternary Copolymers, resins obtained by grafting and modifying other components on these polyolefin resins, blends with other resins, and the like can be used. Examples of the styrene elastomer include styrene-butadiene copolymer, styrene-butadiene-styrene copolymer, styrene-isoprene copolymer, styrene-isoprene-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, and parts thereof. Examples include hydrogenated products and complete hydrogenated products. Examples of the polyvinyl chloride elastomer include those obtained by adding a plasticizer to polyvinyl chloride having a high degree of polymerization, those obtained by modifying polyvinyl chloride, and blends of these with other resins. Examples of nitrile elastomers include acrylonitrile-butadiene copolymers. Examples of the polyurethane elastomer include polyester polyurethane elastomer, polyether polyurethane elastomer, polycarbonate polyurethane elastomer, polycaprolactone polyurethane elastomer and the like. The polyester elastomer having a composition different from that of the crystalline polyester (A) includes a polyester obtained by copolymerizing a dicarboxylic acid having 6 or more carbon atoms such as adipic acid, sebacic acid, dimer acid, and hexanediol and / or a diol. And polyester polyester elastomers, polyether polyester elastomers, polycaprolactone polyester elastomers, polycarbonate polyester elastomers, and the like. Examples of the polyamide-based elastomer include nylon 12, dimer acid copolymerized polyamide, and polyether polyamide.

  Furthermore, the thermoplastic resin (B) preferably has a carboxyl group and / or a glycidyl group. In the case of having a carboxyl group and / or a glycidyl group, compatibility with the crystalline polyester (A) is improved, micro-layer separation is possible, and film-forming properties are improved. Also, when used as an adhesive, since the thermoplastic resin (B) is uniformly dispersed, the adhesiveness of the resin composition is improved by the stress relaxation effect of the thermoplastic resin (B).

  Moreover, when making extrusion film forming property and adhesiveness compatible, 0.01-100 g / 10min is preferable as a melt flow rate (MFR) in 230 degreeC of a thermoplastic resin (B). If the MFR is 100 or more, the melt viscosity of the resin composition decreases and extrusion film formation becomes impossible. On the other hand, if it is less than 0.01, the fluidity of the thermoplastic resin decreases, and it cannot be sufficiently mixed with the polyester. It may remain as a granular material. More preferable MFR is 0.01 to 30 g / 10 min, and more preferably 0.01 to 5 g / 10 min. By using a polyolefin having an MFR as low as possible within a range where it can be sufficiently kneaded with polyester, the melt characteristics of the polyolefin remarkably appear in the final adhesive composition, and the extrusion film forming property of the adhesive composition can be improved.

As a result of diligent examination regarding the thermoplastic resin (B), as the thermoplastic resin (B), the following three types are particularly improved in adhesion and film forming properties. The first is the case where the thermoplastic resin (B) is an ethylene-propylene copolymer or a modified product thereof. The modified product refers to a product in which a carboxylic acid or a glycidyl group is introduced by copolymerization. In general, it is known that polyethylene and the like are easy to form a film because of higher tension and elongation at the time of melting than polyester. Therefore, improvement of the film forming property of polyester is often studied by blending polyethylene with polyester. However, since high-density polyethylene and the like are usually poorly compatible with polyester, it is difficult to develop film-forming properties due to limitations on the blend amount with polyester. Moreover, since high-density polyethylene has a high degree of crystallinity, the entire adhesive composition becomes hard and is not suitable as an adhesive. On the other hand, when ethylene-propylene copolymer elastomer is used, the polymer blend can be made without any problem even if it is added in the same weight as polyester because of the block structure of ethylene-propylene copolymer elastomer, and the adhesion of polyester is impaired. The film-forming property of the ethylene-propylene elastomer can be imparted to the polyester. The second is the case of hydrogenated styrene-butadiene-styrene copolymer and modified products thereof as the thermoplastic resin (B). The hydrogenated product of styrene-butadiene-styrene copolymer is easy to improve the film-forming property because the melt tension of the polyester can be improved by the addition of a smaller amount than the olefin resin because of its compatibility with the polyester. Third, as the thermoplastic resin (B), a low-density polyethylene having a melt flow rate at 230 ° C. of less than 1.0 g / min and a density of less than 0.92 g / cm ³ and modified products thereof. It is. When an ethylene-α-olefin copolymer having a melt flow rate of 230 ° C. and a melt flow rate of 1.26 kg of 1.0 g / min or less is blended with the polyester, the effect of improving the melt viscosity of the polyester is large. The melt elongation can be improved in a well-balanced manner. The melt flow rate is preferably 0.01 g / min or more, and the density is preferably 0.80 g / cm ³ or more.

  The blending amount of the thermoplastic resin (B) in the present invention is preferably 0.5 to 110 parts by weight, more preferably 10 to 80 parts by weight, most preferably 100 parts by weight of the crystalline polyester (A). 20 to 60 parts by weight. When the thermoplastic resin (B) is less than 0.5 parts by weight, the effect of improving the adhesiveness and film forming property is insufficient. On the other hand, when 110 parts by weight or more of the thermoplastic resin (B) is blended, the crystallinity There is a tendency to cancel out properties such as adhesiveness of the polyester (A). In addition, macro phase separation may adversely affect extrusion film forming properties such as reduction in elongation and surface smoothness.

  The polytetrafluoroethylene (C) used in the present invention is a fluorinated olefin such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, perfluoroalkyl vinyl ether or a perfluoroalkyl (meth) acrylate as a copolymer component. Fluorine-containing alkyl (meth) acrylate can be used.

  Furthermore, in order to improve the dispersibility in the polyester resin (A), it is preferable to use polytetrafluoroethylene modified with an acrylic resin. As a modification method, simple mixing may be used because the dispersibility of polytetrafluoroethylene (C) in the polyester resin (A) may be improved. To further improve dispersibility, random copolymerization of polytetrafluoroethylene and acrylic monomers, block copolymerization, graft copolymerization, polymerization of acrylic resin on the surface of polytetrafluoroethylene powder, surface of polytetrafluoroethylene powder Examples thereof include coating an acrylic resin on the surface, polymer blending, forming a multilayer structure by forming a laminated structure of polytetrafluoroethylene and an acrylic resin, and dispersing polytetrafluoroethylene powder in a liquid acrylic resin. The polytetrafluoroethylene content of polytetrafluoroethylene modified with an acrylic resin is preferably 5% to 99%.

  As monomers for producing the acrylic resin, styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, t-butylstyrene, o-ethylstyrene, p-chlorostyrene, o-chlorostyrene, 2 Aromatic vinyl monomers such as 1,4-dichlorostyrene, p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic acid Butyl, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl acrylate, meta (Meth) acrylic acid ester monomers such as cyclohexyl acrylate; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; α, β-unsaturated carboxylic acids such as maleic anhydride; N-phenylmaleimide, N -Maleimide monomers such as methylmaleimide and N-cyclohexylmaleimide; Glycidyl group-containing monomers such as glycidyl methacrylate; Vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; Vinyl acetate and vinyl butyrate And carboxylic acid vinyl monomers such as ethylene, propylene and isobutylene; and diene monomers such as butadiene, isoprene and dimethylbutadiene. These monomers can be used alone or in admixture of two or more.

  Among these monomers, preferred from the viewpoint of affinity with the polyester resin (A) are aromatic vinyl monomers, (meth) acrylic acid ester monomers, vinyl cyanide monomers. , Α, β-unsaturated carboxylic acid and glycidyl group-containing monomer. Particularly preferred is a monomer containing 10% by weight or more of one or more monomers selected from the group consisting of styrene, butyl acrylate, acrylonitrile, maleic anhydride, and glycidyl methacrylate.

  As polytetrafluoroethylene modified with polytetrafluoroethylene and acrylic resin, Asahi Glass Co., Ltd. FLUON PTFE L grade, G grade, CD grade, AD grade, Mitsubishi Rayon Co., Ltd. Metabrene A3000, Dinion Co., Ltd. Dynamer PPA, Dinion Examples thereof include PTFE, polyflon MPA FA-500, and Algoflon manufactured by Solvay Solexis.

  As the shape when polytetrafluoroethylene (C) is added to the crystalline polyester (A), a pellet form, a powder form, a crystalline polyester (A), a thermoplastic resin (B), and a masterbatch with other resins, A liquid dispersion or the like can be used as long as there is no problem in melt kneading.

  The adhesive composition of the present invention is preferably blended so that the polytetrafluoroethylene component is 0.0001 to 10 parts by weight with respect to 100 parts by weight of the polyester resin (A). More preferably, it is 0.01-5 weight part, More preferably, it is 0.1-3 weight part. If it is less than 0.0001 part by weight, the effect of improving the workability is poor, and if it exceeds 10 parts by weight, the film forming property is deteriorated due to the deterioration of the compatibility with the polyester. Moreover, the surface characteristics of polyester are changed by polytetrafluoroethylene, and the adhesiveness is greatly deteriorated.

The melt viscosity of the adhesive composition of the present invention at 200 ° C. and a shear rate of 50 s ⁻¹ is desirably 500 dPa · s to 50,000 dPa · s. More preferably, it is 1000 dPa * s-40000 dPa * s, More preferably, it is 2000-30000. When the melt viscosity is less than 500 dPa · s, the tension and elongation at the time of melting are insufficient, and pinholes and thickness unevenness occur during extrusion lamination. Further, if it is 50000 dPa · s or more, the fluidity in the extruder is insufficient, so that not only the resin is deteriorated by shearing heat generation but also the wettability to the adherend is poor when used as an adhesive. The nature is bad.

  The resin composition of the present invention may contain an epoxy resin (D) in order to enhance the adhesion with a metal or the like. Examples of the epoxy resin (D) include glycidyl ether types such as bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, novolac glycidyl ether, brominated bisphenol A diglycidyl ether, hexahydrophthalic acid glycidyl ester, dimer acid glycidyl ester, and the like. Glycidyl ester type, triglycidyl isocyanurate, glycidylhindantoin, tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, triglycidylmetaaminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidylmetaxylenediamine, diglycidyltribromoaniline Glycidylamine such as tetraglycidylbisaminomethylcyclohexane Alternatively 3,4-epoxycyclohexylmethyl carboxylate, epoxidized polybutadiene, such as alicyclic or aliphatic epoxides such as epoxidized soybean oil. Among these, in particular, those having good compatibility with the thermoplastic crystalline polyester are preferable in order to greatly improve the adhesive strength.

  The compounding amount of the epoxy resin (D) in the present invention is preferably 0 to 80 parts by weight when the crystalline polyester (A) is 100 parts by weight. If the epoxy resin (D) exceeds 80% by weight, the mechanical properties may be inferior and the adhesion and heat resistance may be lowered.

  Moreover, a flame retardant can be used together with the adhesive composition of the present invention as necessary. Examples of the flame retardant include chlorine-based flame retardants such as perchloropentacyclodecanone, brominated flame retardants such as pentadibromotoluene, brominated phenylmethacrylate, 2,4-dibromophenol, antimony trioxide, and phosphoric acid. Organic phosphorus flame retardants such as esters, phosphoric acid amides, organic phosphine oxides, nitrogen-based flame retardants such as red phosphorus, ammonium polyphosphate, phosphazene, triazine, melamine cyanurate, metal salts such as polystyrene sulfonate alkali metal salts Examples include flame retardants, hydrated metal flame retardants such as aluminum hydroxide and magnesium hydroxide, and other inorganic flame retardants.

  Various additives can be blended in the adhesive composition of the present invention. Additives that are widely used as additives for thermoplastic adhesives such as resins, inorganic fillers, stabilizers, ultraviolet absorbers, and anti-aging agents other than the present invention are within the range not impairing the characteristics of the present invention. Can be added. Furthermore, as resins other than the present invention, phenol resins, phenoxy resins, petroleum resins, hydrogenated petroleum resins, terpene resins, rosins, modified rosins, and the like can be added.

  As the inorganic filler, talc, calcium carbonate, zinc oxide, titanium oxide, clay, bentonant, fumed silica, silica powder, mica and the like are 40 parts by weight or less based on 100 parts by weight of the total amount of the resin composition of the present invention. Can be blended. Other additives include crystal nucleating agents such as various metal salts, coloring pigments, inorganic and organic fillers, tackiness improvers, phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants. , Stabilizers such as quenchers, metal deactivators, copper damage inhibitors, UV absorbers, HALS, hydrolysis stabilizers, silane coupling agents, titanium coupling agents, and the like can also be added.

  As a method for producing the adhesive composition of the present invention, the crystalline polyester (A), thermoplastic resin (B), and polytetrafluoroethylene (C) of the present invention are uniaxially or biaxially screw-type melt kneaded. Or an ordinary thermoplastic resin mixer represented by a kneader type heater. In that case, it is also possible to knead the three components at once or knead the two components in advance and then knead the remaining one component. Further, the kneaded product can be subsequently pelletized by a granulation process or directly applied to an adherend.

  As a method of using the adhesive composition of the present invention as an adhesive, it is preferable that the pellets granulated by the above-described manufacturing method are bonded by a screw type extruder having a die portion called a T-die method or an inflation method. A single piece is molded into a sheet or film, fixed in the middle of the substrate to be laminated and bonded, and then heat-bonded, or the sheet-shaped adhesive is heated and melted on one substrate, and then There is an adhesion method in which one adherend is bonded while being cooled.

  In addition, the pellets are melted by the above-described screw type extruder and directly bonded to the laminate to be laminated, and when one of the adherends is a thermoplastic, the pellets are directly adhered by coextrusion, There is a method in which it is directly applied to one of the adherends and then again bonded by heating. As extrusion temperature, melting | fusing point +10 degreeC-melting | fusing point +100 degreeC are preferable.

  The adhesive composition of the present invention exhibits strong adhesion to any of plastic, metal, fiber, glass, ceramic, wood and paper. It is especially effective for bonding plastic film and metal. The plastic film can be used for various barrier films including polyester films such as polyethylene terephthalate, nylon films, polyvinyl chloride films, polyethylene films, polypropylene films, polystyrene films, polylactic acid films, and ethylene-vinyl alcohol films. Moreover, as a metal, it can use for copper, tin plating copper, aluminum, a steel plate, stainless steel, etc.

  In the adhesive composition of the present invention, this resin alone can be used as a film, but a non-adherent and an adhesive can be laminated. Examples of the structure include an adherend / adhesive, an adherend / adhesive / adherent, and those obtained by further superimposing these structures.

  In particular, since the adhesive composition of the present invention has high adhesion reliability and easy processability, it is effective as an adhesive for electronic materials and the like. As an electronic material, the use to a flexible flat cable and a flexible printed wiring board is especially effective. Although it does not specifically limit as a use site | part, It can use as adhesion | attachment between an insulating film and a conductor, adhesion | attachment of a cover film, adhesion | attachment of a reinforcement board, adhesion | attachment for multilayering.

  In order to describe the present invention in more detail, examples are given below, but the present invention is not limited to the examples. In the examples, “parts” means “parts by weight”. In addition, the measured value described in the Example is measured by the following method.

Resin composition: The resin was dissolved in deuterated chloroform and quantified by ¹ H-NMR.

Melt viscosity: Measured using a flow tester manufactured by Shimadzu Corporation using a capillary having a diameter of 1 mm and a length of 10 mm under the conditions of 200 ° C. and a shear rate of 50 s ⁻¹ .

Melting point and glass transition temperature: First, the sample was heat-treated at 120 ° C. for 1 hour and left at 25 ° C. for 48 hours. Thereafter, using a differential scanning calorimeter manufactured by Seiko Instruments Inc., 5 mg of a measurement sample was put in an aluminum pan, sealed by pressing a lid, and heated to −100 ° C. to 300 ° C. at 20 ° C./min. The temperature is lowered to −100 ° C. at 50 ° C./min and subsequently raised from −100 ° C. to 300 ° C. at 20 ° C./min. The peak of the melting peak that appeared was taken as the melting point. The glass transition point is determined by the temperature at the intersection of the base line extension below the glass transition point and the tangent that indicates the maximum slope between the peak rise and the peak apex in the second temperature rise process. It was.

<Synthesis Example of Crystalline Polyester (A)>
In a reaction vessel equipped with a stirrer, a thermometer, and a condenser tube for distillation, 130 parts of terephthalic acid, 37 parts of isophthalic acid, 124 parts of ethylene glycol, 0.04 mol% of antimony trioxide with respect to the acid component, and finally Sodium acetate was added so that the amount of Na was 10 ppm with respect to the amount of resin, and the esterification reaction was carried out at 180 to 240 ° C. under pressure for 3 hours. After completion of the esterification reaction, the temperature of the reaction system was raised from 240 ° C. to 260 ° C., while the pressure inside the system was gradually reduced to 500 Pa over 60 minutes. Further, a polycondensation reaction was performed at 130 Pa or less for 2 hours to obtain a crystalline polyester (A-1). As a result of NMR analysis, the crystalline polyester (A-1) has a composition of 78 mol% terephthalic acid, 22 mol% isophthalic acid, and 100 mol% ethylene glycol, a melt viscosity of 15000 dPa · s, and a glass transition temperature of 70. The melting point was 190 ° C.

<Synthesis Example of Crystalline Polyester (A-2 to B-2)>
The crystalline polyester resin (B-2) was obtained in the same manner as in Synthesis Example 1. However, for crystalline polyesters (A-2), (A-3), (A-4), and (B-1) whose compositions were changed, 0.06 mol% of tetrabutyl titanate as an acid component was used as a catalyst. The esterification reaction was carried out at normal pressure without pressure. In addition, when polytetramethylene glycol is included as a copolymerization component, after completion of esterification, Irganox 1330 (manufactured by Ciba Specialty Chemicals Co., Ltd.), an antioxidant, is 0.1 wt% with respect to the amount of resin after the completion of polymerization. Then, polycondensation was performed.

<Example 1>
100 parts of crystalline polyester (A-1), 50 parts of ethylene-propylene copolymer (Exelen EP3721 manufactured by Sumitomo Chemical Co., Ltd.), 3 parts of Dinion PTFE (manufactured by Dinion) at 200 ° C. with a twin screw extruder Kneaded. The obtained adhesive is placed on a 50 μm biaxially stretched PET film using an extruder (manufactured by Plastic Giken) with a screw diameter of 30 mmφ and a T die width of 200 mm so that the adhesive thickness becomes 30 μm at a temperature of 200 ° C. To obtain an adhesive tape. The following evaluation was performed using this adhesive tape.

PET adhesiveness: The adhesive surface of the adhesive tape and a 50 μm biaxially stretched PET film were combined and bonded using a roll laminator manufactured by Tester Sangyo Co., Ltd. The lamination was performed at a temperature of 200 ° C., a pressure of 0.3 mPa, and a speed of 0.5 m / min. After laminating, it is allowed to stand at room temperature for 1 week to sufficiently crystallize the adhesive layer, and then a tensile test is performed in an atmosphere of 25 ° C. using RTM100 manufactured by Toyo Baldwin Co., Ltd., at a pulling speed of 50 mm / min. T-type peel adhesion was measured.

Tin-plated copper adhesion: The adhesive surface of the adhesive tape and tin-plated copper (thickness 50 μm, width 1 mm) were laminated in the same manner as described above. After laminating, it is allowed to stand at room temperature for 1 week to sufficiently crystallize the adhesive layer, and then a tensile test is performed in an atmosphere of 25 ° C. using an RTM100 manufactured by Toyo Baldwin Co., Ltd. The 180 degree peel adhesion was measured.

Film forming property: The case where the adhesive layer formed from the T-die extruder did not have tears, pinholes or thickness unevenness was rated as “◯”, and the case where tears, pinholes or thickness unevenness occurred was rated as “X”.

<Examples 1-5, Comparative Examples 1-6>
In the same manner, Examples 2 to 5 and Comparative Examples 1 to 6 were prepared and evaluated. The results are shown in Table 2. However, Comparative Example 1 is a comparative example in which the melting point of the polyester exceeds 200 ° C., and extrusion lamination was performed at 260 ° C. in particular.

  It turns out that the adhesive composition of this invention has favorable adhesiveness with respect to PET and tin plating copper, and film forming property is also favorable.

  On the other hand, as seen in Table 2, in Comparative Example 1, the crystalline polyester (A) had a high melting point, so that the PET substrate was deformed. Further, since the melting was insufficient at an adhesion temperature of about 200 ° C., the adhesion was not exhibited. In Comparative Example 2, since the melt viscosity at 200 ° C. of the adhesive composition exceeds 50000 dPa · s, the wettability with the adherend is very poor and the adhesive force is low. In Comparative Example 3, since the thermoplastic resin (B) is not included, the crystal relaxation of the polyester (A) is not sufficient and the adhesive strength is low. In the system of Comparative Example 4 containing no polytetrafluoroethylene, the adhesiveness was good, but the film-forming property was insufficient, pinholes were generated, and the thickness of the adhesive layer varied. In Comparative Example 5, since the thermoplastic resin (B) was excessively added, the adhesiveness was greatly lowered. In Comparative Example 6, since polytetrafluoroethylene was excessively added, not only the adhesiveness was significantly lowered, but the compatibility with polyester was very poor and the film-forming property was insufficient.

  INDUSTRIAL APPLICABILITY The present invention can provide an adhesive composition characterized by being excellent in adhesiveness to plastic films and metals and having excellent extrusion film forming properties. Furthermore, a laminated body, a flexible flat cable, and a flexible printed wiring board using the same can be provided.

Claims (13)

It consists of a crystalline polyester (A) having a melting point of 200 ° C. or lower, a thermoplastic resin (B), and polytetrafluoroethylene (C), and satisfies all of the following (a) to (c): Adhesive composition.
(A) When crystalline polyester (A) whose melting | fusing point is 200 degrees C or less is made into 100 weight part, 0.5-110 weight part of thermoplastic resins (B) are contained.
(B) When 100 parts by weight of crystalline polyester (A) having a melting point of 200 ° C. or less is contained, 0.0001 to 10 parts by weight of polytetrafluoroethylene (C) is contained.
(C) The melt viscosity at 200 ° C. and a shear rate of 50 s ⁻¹ of the adhesive composition is 500 dPa · s to 50,000 dPa · s.   The adhesive composition according to claim 1, wherein the crystalline polyester (A) has a glass transition point of 30 ° C. or less.   The adhesive composition according to claim 1 or 2, wherein the glass transition point of the thermoplastic resin (B) is 30 ° C or lower.   4. The adhesive composition according to claim 1, wherein the Shore A hardness of the thermoplastic resin (B) under the measurement conditions of JIS K 7215 is 60 to 98. 5.   The adhesive composition according to any one of claims 1 to 4, wherein the thermoplastic resin (B) is an ethylene-propylene copolymer.   The adhesive composition according to any one of claims 1 to 4, wherein the thermoplastic resin (B) is a styrene-butadiene copolymer. The melt flow rate at 230 ° C of the thermoplastic resin (B) is less than 1.0 g / min, and the density is less than 0.92 g / cm ³ , and the low density polyethylene is characterized in that it is a low density polyethylene. The adhesive composition according to any one of the above.   The adhesive composition according to any one of claims 1 to 7, wherein the thermoplastic resin (B) has a carboxyl group and / or a glycidyl group.   The adhesive composition according to claim 1, wherein the polytetrafluoroethylene (C) is modified with an acrylic resin.   Furthermore, an epoxy resin (D) is contained, The adhesive composition in any one of Claims 1-9 characterized by the above-mentioned.   The laminated body using the adhesive composition in any one of Claims 1-10.   The flexible flat cable using the adhesive composition in any one of Claims 1-10.   The flexible printed wiring board using the adhesive composition in any one of Claims 1-10.