TW201741427A - Adhesive composition - Google Patents

Abstract

An adhesive composition comprises 100 parts by mass of a copolymerized polyester and 0.2 to 15 parts by mass of a curing agent, wherein in the acid component of the copolymerized polyester, the content of isophthalic acid is 30 mol% or more; in the glycol component of the copolymerized polyester, the content of the glycol having a side chain is 30 mol% or more, and the content of the polyalkylene glycol having 2 to 4 carbon atoms in the repeating unit is 1 to 20 mol%; and the softening point of the composition is 90 DEG C or more.

Description

Adhesive composition

The present invention relates to an adhesive composition and a laminate having a layer composed thereof.

A polyester resin represented by polyethylene terephthalate or polybutylene terephthalate is widely used in fibers by utilizing its excellent mechanical strength, thermal stability, hydrophobicity, and chemical resistance. , film, molding materials and other fields.

The polyester resin can obtain a copolymerized polyester resin having various characteristics by changing the kind of the dicarboxylic acid and the diol which are constituent components.

The copolymerized polyester resin generally has excellent adhesion to plastics such as polyester, polycarbonate, and polyvinyl chloride resin, or metals such as aluminum and copper, and is widely used for adhesives and coatings. Cloth, ink adhesive, paint, etc. For example, Patent Document 1 discloses a polyester resin excellent in adhesion to a specific alkanediol.

In addition, since the copolymerized polyester-based adhesive is excellent in characteristics such as electrical insulating properties, flame retardancy, and flexibility (peeling resistance in a curved portion), it is widely used as, for example, a wiring for digital home appliances or automobiles. It is widely used as a flexible flat cable or the like.

The flexible planar cable has two structures in which two insulating films are formed of a base film and an adhesive layer, and are opposed to each other on the adhesive layer side, and are bonded to each other with a wire interposed therebetween. As the base film, a polyethylene terephthalate film is often used, and in the case of a wire, a metal such as copper or copper plated with tin is used.

In particular, in the flexible flat cable used for small-sized home appliances and automotive parts that have been thinned and miniaturized, the heat-resistant nature of the liquid crystal backlight and the CPU cannot be ignored. In addition, since it is also used outside the house, the adhesive constituting the flexible planar cable is also required to have the resistance to maintain the adhesion even if the interface is not peeled off under high temperature and high humidity. Damp heat.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-200041

An object of the present invention is to provide an adhesive composition which is excellent in adhesion to a metal and which has excellent heat resistance and moist heat resistance, and a laminate having a layer formed thereon.

The present inventors have found that a copolymerized polyester having a specific structure is obtained by repeating careful research in order to solve the above problems. The adhesive composition of the crosslinking agent is excellent in adhesion to metals, and has excellent heat resistance and moist heat resistance, and the present invention has been achieved.

That is, the gist of the present invention is as follows.

(1) An adhesive composition comprising 100 parts by mass of a copolymerized polyester and 0.2 to 15 parts by mass of a curing agent, wherein a content of isophthalic acid in an acid component of a copolymerized polyester is 30 mol% or more, The content of the diol having a side chain in the diol component of the copolymerized polyester is 30 mol% or more, and the content of the polyalkylene glycol having 2 to 4 carbon atoms in the repeating unit is 1 to 20 mol%. The softening point of the subsequent composition is 90 ° C or higher.

(2) The adhesive composition according to (1), wherein the polyalkylene glycol contains two or more types, and the number average molecular weight of at least one type is 200 or more.

(3) A laminate comprising a layer composed of the adhesive composition described in (1) or (2).

(4) A flexible planar cable comprising the laminate according to (3).

According to the present invention, it is possible to provide an adhesive composition which has excellent adhesion to metals and which has excellent heat resistance and moist heat resistance. The laminate having the layer composed of the adhesive composition can be used as a constituent member of the flexible planar cable.

The adhesive composition of the present invention contains a copolymerized polyester and a hardener, and has a softening point of 90 ° C or higher, and the copolymerized polyester contains isophthalic acid as an acid component, and contains a diol having a side chain and repeats The unit has a polyalkylene glycol having a carbon number of 2 to 4 as a diol component.

In the copolymerized polyester constituting the composition of the adhesive of the present invention, the acid component must contain 30 mol% or more of isophthalic acid, preferably 40 mol% or more, more preferably 50 to 80 mol. ear%. When the content of the terephthalic acid in the acid component is less than 30 mol%, the resulting adhesive composition tends to have a lower adhesiveness and a lower solubility in an organic solvent.

Examples of the acid component other than isophthalic acid include terephthalic acid, naphthalene dicarboxylic acid, succinic acid, adipic acid, sebacic acid, sebacic acid, hexahydroterephthalic acid, and phthalic acid. , 4,4'-dicarboxylic acid biphenyl, sodium 5-sulfonate isophthalate, 5-hydroxy-isophthalic acid, fumaric acid, maleic acid, itaconic acid, mesaconic acid, Coke citrate, 1,3,4-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, oxalic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylate Acid, 2,5-norbornene dicarboxylic acid, and the like. These may use an anhydride as a monomer raw material, or may be used in combination. Among them, from the viewpoint of maintaining heat resistance, terephthalic acid, naphthalene dicarboxylic acid, and hexahydroterephthalic acid are preferably used as the acid component other than isophthalic acid.

In the copolymerized polyester, the diol having a side chain having a diol component must contain 30 mol% or more, preferably 40 mol% or more, more preferably 50 to 80 mol%. Two of the diol components having side chains When the content of the alcohol is less than 30 mol%, the resulting adhesive composition has a decrease in the adhesiveness and a tendency to lower the solubility in an organic solvent. On the other hand, when the content of the diol having a side chain is more than 80 mol%, the adhesive composition tends to have a decrease in adhesion.

Examples of the diol having a side chain include 1,2-propanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-methylpropanediol, and 3-methyl- 1,5-pentanediol, 2-ethyl-2-butylpropanediol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, trimethylolpropane, etc. These can be used in combination. Among them, the diol having a side chain is preferably 2,2-dimethyl-1,3-propanediol (neopentylene glycol) or ethylene oxide of bisphenol A from the viewpoint of improving the adhesion. Adult.

In the copolymerized polyester, the diol component must contain from 1 to 20 mol%, preferably from 3 to 15 mol%, more preferably 4, of the polyalkylene glycol having 2 to 4 carbon atoms in the repeating unit. Up to 10% by mole. When the content of the polyalkylene glycol having 2 to 4 carbon atoms in the repeating unit in the diol component is less than 1 mol%, the heat resistance of the resulting adhesive composition may be lowered. Further, the glass transition temperature of the copolymerized polyester tends to be high, and the adhesion of the resulting adhesive composition is lowered. On the other hand, when the content of the polyalkylene glycol having 2 to 4 carbon atoms in the repeating unit is more than 20 mol%, the obtained adhesive composition has a low softening point and deteriorates heat resistance.

In the case of a polyalkylene glycol having 2 to 4 carbon atoms in the repeating unit, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene is preferred from the viewpoint of adhesion and heat and humidity resistance. Glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol.

As the copolymerized polyester, in the case of a polyalkylene glycol having 2 to 4 carbon atoms in the repeating unit, it is preferred to use a number average molecular weight of 200 or more. Among them, it is more preferred to use a number average molecular weight of 500 to 10,000, and more preferably a number average molecular weight of 800 to 5,000. Polyalkylene glycol having a carbon number of 2 to 4 by using a repeating unit When the number average molecular weight is 200 or more, the heat resistance of the resulting adhesive composition is improved.

Further, as for the copolymerized polyester, the diol component is preferably two or more types of polyalkylene glycol having 2 to 4 carbon atoms in the repeating unit. Thereby, the adhesion of the adhesive composition can be improved. Among them, in the case of using two types, it is preferred to use together polytetramethylene glycol and diethylene glycol, and further preferably, polytetramethylene glycol and triethylene glycol are used in combination.

Examples of the diol component other than the above include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,4- For example, cyclohexanedimethanol or the like may be used in combination of two or more kinds.

Further, examples of the other components constituting the copolymerized polyester include tetrahydrophthalic acid, lactic acid, ethylene oxide, glycolic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, and 4-hydroxybutyric acid. 2-hydroxyisobutyric acid, 2-hydroxy-2-methylbutyric acid, 2-hydroxy oxalic acid, 3-hydroxy oxalic acid, 4-hydroxy oxalic acid, 5-hydroxy oxalic acid, 6-hydroxycaproic acid, 10-hydroxyl hard Hydroxycarboxylic acid such as ester acid, 4-(β-hydroxy)ethoxybenzoic acid, malic acid, and β-propiolactone, β-butyrolactone, γ-butyrolactone, δ-valerolactone, ε An aliphatic lactone such as caprolactone may contain such a substance.

Further, the copolymerized polyester may also copolymerize a monobasic acid or a monohydric alcohol as required. As the monobasic acid, lauric acid, myristic acid, Palmitic acid, stearic acid, oleic acid, linoleic acid, linoleic acid, benzoic acid, p-t-butylbenzoic acid, cyclohexane acid, 4-hydroxyphenyl stearic acid, etc., monohydric alcohol Examples thereof include octanol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, 2-phenoxyethanol, and the like.

The above-mentioned monomers constituting the copolymerized polyester may be used in combination of plural kinds depending on the characteristics to be imparted.

Further, the copolymerized polyester may be used in combination of two or more kinds, and may be phase-separated or uniformly mixed.

The copolymerized polyester has a glass transition temperature of preferably 50 ° C or less, more preferably 40 ° C or less, still more preferably 30 ° C or less. When the glass transition temperature of the copolymerized polyester exceeds 50 ° C, the resulting adhesive composition sometimes lowers the adhesion to the metal.

Further, the glass transition temperature is preferably -40 ° C or higher, more preferably -20 ° C or higher, and still more preferably 0 ° C or higher. When the transfer temperature of the copolymerized polyester glass is less than -40 ° C, the adhesion may be strong and it may be difficult to handle.

The adhesive composition of the present invention must contain a hardener in an amount of from 0.2 to 15 parts by mass, preferably from 0.4 to 10 parts by mass, more preferably from 0.4 to 5.0 parts by mass, per 100 parts by mass of the copolymerized polyester. . By adding a hardener, heat resistance and moist heat resistance can be improved. When the content of the curing agent is less than 0.2 part by mass, the heat resistance and moist heat resistance of the obtained adhesive composition are lowered. On the other hand, when the content exceeds 15 parts by mass, the adhesiveness of the resulting adhesive composition is lowered.

Further, the adhesive composition of the present invention is applied to the adherend 1 by a liquid or paste-like adhesive, and the adherend 2 of the same kind or different kinds is attached. Thereafter, the solvent or water is scattered to cure (harden) the adhesive component to form a layer composed of the adhesive composition. Depending on the application, after the layer 1 composed of the adhesive composition is formed by the adherend 1, heat treatment is performed to cause the adherend 2 to follow (mode 1); and the adherend 1 is formed into a layer composed of the adhesive composition. Thereafter, heat treatment is performed without subjecting the adherend 2 to heat treatment (mode 2). The adhesive composition of the present invention is excellent in adhesion especially in the case of using mode 2. In the case of using mode 1, the content of the hardener is preferably set to 0.4 to 5.0 parts by mass relative to 100 parts by mass of the copolymerized polyester.

Further, the content of the hardener is preferably from 0.2 to 2, more preferably from 0.4 to 1.5, more preferably the total of the functional groups (carboxyl groups, hydroxyl groups) of the copolymerized polyester. 0.5 to 0.9. When the equivalent ratio of the subsequent composition is less than 0.2, the heat resistance is lowered, and when the equivalent ratio exceeds 2, the adhesion is lowered.

The curing agent contains a functional group reactive with a hydroxyl group or a carboxyl group of the copolymerized polyester, and examples thereof include an isocyanate compound, an epoxy compound, and a carbodiimide compound. The oxazoline compound or the like may be appropriately combined, and from the viewpoint of reactivity and handleability, an isocyanate compound is preferably used.

In the case of isocyanate compounds, aromatic diisocyanates such as toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and benzene diisocyanate (XDI), hydrogenated TDI, hydrogenated MDI, hydrogenated XDI, hexamethylene di An aliphatic or alicyclic diisocyanate such as isocyanate (HDI) or isophorone diisocyanate (IPDI), which has both adhesion to metal and heat resistance. it works. Derivatives such as a trimeric isocyanate, a biuret, a polyisocyanate having an adduct structure, or a polymethylene polyphenyl polyisocyanate or a carbodiimide modification may also be used as the diisocyanate.

Among them, toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are preferably used, and these may be used in combination of two or more kinds.

The adhesive composition of the present invention must have a softening point of 90 ° C or higher, preferably 100 ° C or higher, more preferably 110 ° C or higher, and most preferably 120 ° C or higher. When the softening point of the subsequent composition is less than 90 ° C, the heat resistance is lowered. In the case of a flexible planar cable containing an adhesive composition having a reduced heat resistance, in a high-temperature environment, a resin may start to flow and the metal may be peeled off to cause dielectric breakdown. On the other hand, the upper limit of the softening point is preferably set to a temperature at which thermal decomposition of the copolymerized polyester resin does not occur, and is preferably less than 400 °C.

In order to set the softening point of the adhesive composition of the present invention to the above range, it is preferred to set the number average molecular weight of the adhesive composition to 20,000 to 100,000, and preferably, the number average molecular weight is set to 30,000 to 100,000. More preferably, it is set to 40,000 to 100,000. When the number average molecular weight of the subsequent composition is less than 20,000, the softening point is lowered and the heat resistance is liable to lower. On the other hand, when the number average molecular weight of the adhesive composition exceeds 100,000, the adhesiveness tends to decrease, which is not preferable.

Further, in order to set the number average molecular weight of the adhesive composition of the present invention to the above range, it is preferred to set the number average molecular weight of the copolymerized polyester of the present invention to 5,000 to 30,000, preferably Set to 10,000 to 25,000.

The adhesive composition of the present invention may contain a heat stabilizer, an antioxidant, a flame retardant, and the like as needed.

As the heat stabilizer, phosphoric acid, phosphate, dibutylhydroxytoluene [3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionic acid] pentaerythritol can be cited. , 3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionic acid n-octadecyl ester, 3,3',3",5,5',5"-sixth third Base-a, a', a"-(trimethyl-2,4,6-triyl)tri-p-cresol, 1,1,3-parade (2-methyl-4-hydroxy-5-third Butylphenyl)butane, 1,3,5-trimethyl-2,4,6-glucosin (3,5-di-t-butyl-4-hydroxybenzyl)benzene, 3,9-double {2-[3-(3-Tertibutyl-4-hydroxy-5-methylphenyl)propanoxy]-1,1-dimethylethyl}-2,4,8,10- Tetraoxaspiro[5,5]undecane, 1,3,5-gin (4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)isophthalic acid, triethyldi Alcohol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-two third Butyl-4-hydroxyphenyl)propionate], 2,2-thio-divinyl-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], Octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], diethyl[[3,5-bis(1,1-dimethylethyl)- Phosphorus such as 4-hydroxyphenyl]methyl]phosphate or A phenol-resistant thermal stabilizer.

As the antioxidant, a hindered amine compound, dioctylthiodipropionate, di(dodecyl)thiodipropionate, di(dodecyl)stearylthiodipropyl can be cited. Acid ester, distearylthiodipropionate, dimyristylthiodipropionate, dikutylthiodipropionate, di(dodecyl)-β,β'-thio Dibutyrate, distearyl-β,β'-thiodibutyrate, pentaerythritol-indole (dodecylthiopropionate), pentaerythritol-indole (dodecane) Thiothio Acid ester), neopentyl alcohol-indole (dodecyl thiobutyrate), neopentyl alcohol-indole (octadecylthiopropionate), neopentyl alcohol-indole (laurylthio) Propionate), dilauryl-3,3'-thiodipropionate, stearyl-3,3'-thiodipropionate, di(tridecyl)3,3'-sulfur An antioxidant such as bispropionate or hydrazine [methylene-3-(dodecylthio)propionate].

In the case of flame retardants, decabromodiphenyl ether, bis(pentabromophenyl)ethane, tetrabromobisphenol, hexabromocyclododecane, hexabromobenzene, etc., bromide, triphenyl phosphate, trimethyl Phenolic phosphate, 1,3-phenylene bis(diphenyl phosphate), ammonium polyphosphate, polyphosphorus amide, phosphonium phosphate, phosphorus compounds, ginseng (chloroethyl) phosphate, ginseng (dichloropropane) Halogen phosphate, red phosphorus, and three Nitrogen-based flame retardants such as melamine cyanurate and ethylene melamine, tin dioxide, antimony pentoxide, antimony trioxide, and the like.

Others may include a conventional lubricant such as a slip agent such as talc or cerium oxide, a pigment such as titanium oxide or carbon black, a filler, an antistatic agent, and a foaming agent.

Next, a method of producing the adhesive composition of the present invention will be described.

In the production of the copolymerized polyester constituting the adhesive composition, the necessary raw materials are put into the reaction tank, and the esterification reaction is carried out at a temperature of 180 ° C or higher for 3 hours or more, and then the polyalkylene glycol is added by a known method. The esterification reaction is carried out. Next, for example, a copolymerization polyester can be obtained by performing a polycondensation reaction at a temperature of 220 to 280 ° C under a reduced pressure of 130 Pa or less until a desired molecular weight is obtained.

In the esterification reaction and the polycondensation reaction, a titanium compound such as tetrabutyl titanate, a metal acetate such as zinc acetate, magnesium acetate or zinc acetate, or an antimony trioxide, a hydroxybutyl tin oxide or a tin octylate may be used. The organotin compound is polymerized. The amount of the catalyst used at this time is preferably 0.1 to 20 × 10 ^-4 mol per mol of the acid component.

Further, after the completion of the above polycondensation reaction, the reaction is carried out by adding a predetermined amount of a polybasic acid component or an anhydride thereof, thereby modifying the terminal hydroxyl group to a carboxyl group, and introducing a carboxyl group into the molecule by a transesterification reaction. Give the appropriate acid price.

Next, a solution having a solid content of about 20 to 60% by mass is prepared by dissolving the copolymerized polyester in a suitable organic solvent, and a curing agent is added to prepare a solution of the adhesive composition. The adhesive composition can be obtained by removing the organic solvent from the solution of the adhesive composition.

Examples of the organic solvent include aromatic solvents such as toluene, xylene, mineral spirits, and Solvesso, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and methanol, ethanol, and isopropanol. An alcohol solvent such as isobutanol, an ester solvent such as ethyl acetate or n-butyl acetate; an acetate solvent such as ceramide acetate or methoxyacetate; or two or more types thereof. A mixed solvent (for example, a mixed solvent of toluene and methyl ethyl ketone) or the like. From the viewpoint of workability and environmental aspects, the organic solvent is preferably methyl ethyl ketone or ethyl acetate having a relatively low boiling point.

The layered system of the present invention has a layer composed of an adhesive composition.

A method of producing a laminate having a layer composed of an adhesive composition (hereinafter sometimes referred to simply as an adhesive layer) by using the adhesive composition of the present invention, and a solution in which an adhesive composition is dissolved in an organic solvent (in Hereinafter, it is sometimes referred to simply as an adhesive solution), which is applied to a substrate film and dried. In the case of the adhesive solution, in the production of the above-mentioned adhesive composition, a solution prepared by adding a curing agent to an organic solvent solution of a copolymerized polyester can be used. In the adhesive solution, the concentration of the solid portion is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more.

By laminating the adhesive solution on the substrate by a known coating method and drying, a laminate in which an adhesive layer is laminated can be obtained. As the coating, for example, a bar coater, a notch wheel coater, a die coater, a roll coater, a reverse roll coater, a gravure coater, a gravure reverse coater can be used. , curtain curtain applicator. The thickness of the adhesive layer can be arbitrarily controlled by the coating method of these applicators. Further, in a plurality of coating methods, it may be applied to a substrate.

The flexible planar cable of the present invention, which comprises the above laminated body, can be produced, for example, by the following method.

In other words, a base film having a thickness of about 20 to 50 μm made of a polyester such as polyethylene terephthalate can be used, and the film can be made to have a dry thickness of about 1 to 50 μm on the film. The coating was dried at 80 to 150 ° C to form a laminate (insulating film) in which an adhesive layer was laminated on the substrate film. A copper wire having a thickness of 20 to 100 μm and a line width of 0.1 to 1 mm is sandwiched between two adhesive layers of an insulating film, and laminated by using a heat sealing machine at a temperature of 150 to 180 ° C and a linear pressure of 20 to 40 N/cm. Sexual flat cable.

The obtained laminate and/or flexible planar cable can also be heated and aged at 40 to 80 ° C for about 12 to 96 hours. Furthermore, as needed A primer layer is provided on the insulating film.

[Examples]

The invention will be more specifically described below by way of examples.

1. Using raw materials (1) Polyalkylene glycol

PTMG: polytetramethylene glycol (quantitative average molecular weight 1000)

PEG: polyethylene glycol (quantitative average molecular weight 1000)

TEG: triethylene glycol (molecular weight 150.17)

DEG: diethylene glycol (molecular weight 106.12)

(2) Hardener

TDI: toluene-2,4-diisocyanate/toluene-2,6-diisocyanate (8/2) (containing isocyanate 48%)

TDI-A: toluene diisocyanate adduct (containing isocyanate 13%)

IPDI: isophorone diisocyanate (containing isocyanate 38%)

IPDI-N: isophorone diisocyanate trimer isocyanate (containing isocyanate 12%)

HDI: hexamethylene-1,6-diisocyanate (containing isocyanate 50%)

HDI-N: hexamethylene-1,6-diisocyanate trimer isocyanate (containing isocyanate 22%)

(3) Organic solvents

Solvent 1: toluene / methyl ethyl ketone (8 / 2 (mass ratio)) mixed solvent

Solvent 2: methyl ethyl ketone

Solvent 3: ethyl acetate

2. Determination method (1) Composition of copolymerized polyester

Using a NMR measuring apparatus (JNM-LA400 type manufactured by JEOL Ltd.), ¹ H-NMR measurement was carried out, and the composition was determined from the peak intensities of the respective copolymer components. For the determination of the solvent, deuterated trifluoroacetic acid was used.

(2) The number average molecular weight of the copolymerized polyester and the adhesive composition

The number average molecular weight was determined by a GPC analyzer (a liquid delivery unit LC-10ADvp type manufactured by Shimadzu Corporation and an ultraviolet-visible spectrophotometer SPD-6AV type, detection wavelength: 254 nm, solvent: tetrahydrofuran, in terms of polystyrene). . When the subsequent composition was not dissolved in tetrahydrofuran and the number average molecular weight could not be measured, it was shown to be "insoluble".

(3) Glass transition temperature (Tg) of copolymerized polyester

The glass transition temperature (external glass transition start temperature) was determined in accordance with JIS-K7121 using an input compensation type differential scanning calorimeter (Diamond DSC manufactured by PerkinElmer Co., Ltd.).

(4) Softening point

The laminate obtained in the examples and the comparative examples was heat-treated at 50 ° C for 96 hours, and then subjected to a thermomechanical analyzer (TMA manufactured by TA Instruments), and the softening point was measured in accordance with JIS-K7196 to evaluate the heat resistance.

(5) Adhesiveness (adjoining 1)

The laminate obtained in the examples and the comparative examples was heat-treated at 50 ° C for 96 hours, and then the rolled copper foil was superposed on the adhesive composition layer of the laminate, and the above rolls were 170 ° C, a linear pressure of 40 N/cm, and a speed of 1 m / Minute condition Layer, making layer 1 .

A sample having a width of 15 mm was prepared from the obtained laminated body 1, and a T-type peeling test was performed at 20 ° C, and the peel strength was measured to evaluate the adhesion 1.

(adhesive 2)

On the adhesive composition layer of the laminate obtained in the examples and the comparative examples, the rolled copper foil was overlaid, and the above rolls were laminated at 170 ° C, a linear pressure of 40 N/cm, and a speed of 1 m/min, and then subjected to lamination at 50 ° C for 96 hours. The laminate 2 is produced by heat treatment.

A sample having a width of 15 mm was prepared from the obtained laminate 2, and a T-peel test was performed at 20 ° C, and the peel strength was measured to evaluate the adhesion 2 .

In addition, in any of the evaluations of the adhesions 1 and 2, if the peel strength is 13 N/15 mm or more, it is judged that there is no problem in practical use and it is acceptable.

(6) Heat and humidity resistance

The layered body 2 produced by the method described in the above-mentioned (5) of the above-mentioned (5) was subjected to a constant temperature and humidity chamber (Model No. LH-30-13M manufactured by Nakatsu Scientific Machinery Co., Ltd.) at a temperature of 85 ° C and a relative humidity of 85%. The condition was maintained for 1000 hours and subjected to a wet heat treatment.

A sample having a width of 15 mm was prepared from the laminate 2 after the wet heat treatment, and a T-peel test was performed at 20 ° C to measure the peel strength to evaluate the moist heat resistance. When the peeling strength is 6 N/15 mm or more, it is judged that there is no problem in practical use and it is acceptable.

(7) Heat resistance

A sample having a width of 15 mm was prepared from the laminate 2 produced by the method described in the above-mentioned (5), and a T-peel test was performed at 80 ° C. The heat resistance was evaluated by peeling strength. When the peeling strength is 3 N/15 mm or more, it is judged that there is no problem in practical use and it is acceptable.

Example 1

In order to make the acid component 50 mol% of terephthalic acid and 50 mol% of isophthalic acid, and to make the diol component into 44% by mole of ethylene glycol, 50% by mole of neopentyl glycol, and the number average The molecular weight of 1000 polybutanediol (PTMG) 5 mol%, diethylene glycol (DEG) 1 mol% of the way, the raw materials are put into the esterification reaction tank, with a stirrer of the anchor wing, while stirring at 100 rpm Esterification was carried out by performing esterification at 250 ° C for 5 hours under a controlled pressure of 0.25 MPa. Thereafter, the mixture was transferred to a polycondensation tank, and the polymerization catalyst was introduced. The pressure was gradually reduced to 1.3 hPa for 60 minutes, and the polycondensation reaction was carried out at 250 ° C until a predetermined molecular weight was reached to obtain a copolymerized polyester A. The obtained copolymerized polyester A coefficient had an average molecular weight of 20,000, a hydroxyl value of 5 mgKOH/g, and a glass transition temperature of 15 °C.

100 parts by weight of the copolymerized polyester A was dissolved in a mixed solvent of toluene/methyl ethyl ketone (8/2 (mass ratio)) (solvent 1) so that the solid content concentration became 30% by mass, and a hardener was added ( TDI) 0.6 parts by mass to prepare a solution of the adhesive composition.

The solution was applied onto a rolled copper foil (film thickness: 30 μm) using a bar coater, and heat-treated at 120 ° C for 1 minute to obtain a laminate in which a binder composition layer having a dry film thickness of 20 μm was laminated on the copper foil.

Examples 2 to 3

The polymerization time at the time of performing the polycondensation reaction using the esterification change was adjusted in such a manner as to achieve the number average molecular weight shown in Table 1. The same procedure as in Example 1 was carried out to obtain a copolymerized polyester B and a copolymerized polyester C.

A solution of the adhesive composition was obtained in the same manner as in Example 1 except that the obtained copolymerized polyesters B and C were used, and the amount of the curing agent (TDI) was changed to that shown in Table 1. Then, in the same manner as in Example 1, a laminate was obtained.

Examples 4 to 16, Comparative Examples 4 to 7

In addition to changing the composition of the copolymerized polyester to as shown in Tables 1, 2 and 4, and using the esterification to change the polymerization time at the time of the polycondensation reaction, the number average molecular weight is as shown in Tables 1, 2, and 4. Other than the value, the same procedure as in Example 1 was carried out to obtain a copolymerized polyester D to P, R to U.

A solution of the adhesive composition was obtained in the same manner as in Example 1 except that the obtained copolymerized polyesters D to P and R to U were used. Then, in the same manner as in Example 1, a laminate was obtained.

Example 17

The same procedure as in Example 1 was carried out except that the copolymerized polyester A (80 parts by mass) obtained in Example 1 and the copolymerized polyester R (20 parts by mass) obtained in Comparative Example 4 were used as the copolymerized polyester. A solution of the composition of the adhesive is obtained. Then, in the same manner as in Example 1, a laminate was obtained.

Examples 18 to 19

A solution of the adhesive composition was obtained in the same manner as in Example 1 except that the solvent type at the time of obtaining the solution of the adhesive composition was changed to that shown in Table 3. Then, in the same manner as in Example 1, a laminate was obtained.

Examples 20 to 23, Comparative Examples 1 to 2

A solution of the adhesive composition was obtained in the same manner as in Example 1 except that the amount of the curing agent added to the copolymerized polyester A was changed to those shown in Tables 3 and 4. Then, in the same manner as in Example 1, a laminate was obtained.

Example 24, Comparative Example 3

A solution of the adhesive composition was obtained in the same manner as in Example 1 except that the amount of the curing agent to the copolymerized polyester B was changed to those shown in Tables 3 and 4. Then, in the same manner as in Example 1, a laminate was obtained.

Example 25

The same as in Example 1, except that the composition of the copolymerized polyester was changed as shown in Table 3, and the polymerization time at the time of performing the polycondensation reaction was changed by using the esterification so that the number average molecular weight reached the value shown in Table 3. Copolymerized polyester Q was obtained by application.

A solution of the adhesive composition was obtained in the same manner as in Example 1 except that the amount of the curing agent added to the copolymerized polyester Q was changed to that shown in Table 3. Then, in the same manner as in Example 1, a laminate was obtained.

Examples 26 to 28

A solution of the adhesive composition was obtained in the same manner as in Example 1 except that the type and amount of the curing agent when the solution of the adhesive composition was obtained were changed to those shown in Table 3. Then, in the same manner as in Example 1, a laminate was obtained.

Examples 29 to 32

A solution of the adhesive composition was obtained in the same manner as in Example 1 except that two types of curing agents were used in the case of obtaining a solution of the adhesive composition, and the type and the amount of addition were changed to those shown in Table 4. Then, in the same manner as in Example 1, a laminate was obtained.

The characteristics of the copolymerized polyester, the adhesive composition, and the laminate obtained in the examples and the comparative examples are shown in Tables 1 to 4.

Since the adhesive composition obtained in each of Examples 1 to 32 is a member which satisfies the requirements of the present invention, it has excellent adhesion to metals and is excellent in heat resistance and moist heat resistance. Accordingly, the laminate obtained by using these adhesive compositions was excellent in the evaluation results of these properties.

The adhesive composition of Comparative Example 1 had a softening point as low as 55 ° C because the content of the hardener was as small as 0.1 part by mass, and was also inferior in heat resistance.

In the adhesive composition of Comparative Example 2, since the content of the curing agent was as large as 15.7 parts by mass, it was inferior in adhesion.

The adhesive composition of Comparative Example 3 was inferior in heat resistance because the number average molecular weight was as low as 16,000 and the softening point was as low as 85 °C.

The adhesive composition of Comparative Example 4, since the content of the polyalkylene glycol having 2 to 4 carbon atoms of the repeating unit in the diol component of the copolymerized polyester is as low as 0.5 mol%, and further, copolymerization polymerization Since the glass transition temperature of the ester is as high as 65 ° C, it is inferior in adhesion and heat and humidity resistance.

In the adhesive composition of Comparative Example 5, since the content of the polyalkylene glycol having 2 to 4 carbon atoms of the repeating unit in the diol component of the copolymerized polyester is as high as 25 mol%, the softening point becomes As low as 80 ° C, and is poor heat resistance.

In the adhesive composition of Comparative Example 6, since the content of neopentyl glycol having a side chain diol in the copolymerized polyester was as little as 20 mol% in the diol component, the composition of the adhesive of Comparative Example 7 The content of isophthalic acid in the copolymerized polyester is as little as 20 mol% in the acid component, so both are poor in adhesion. Further, any of the adhesive compositions is inferior in solubility to an organic solvent.

Claims (4)

An adhesive composition comprising 100 parts by mass of a copolymerized polyester and 0.2 to 15 parts by mass of a hardener, wherein the content of isophthalic acid in the acid component of the copolymerized polyester is 30 mol% or more, copolymerization polymerization The content of the polyalkylene glycol having a side chain diol content of 30 mol% or more and the repeating unit carbon number of 2 to 4 in the ester diol component is 1 to 20 mol%, and the adhesive composition The softening point of the substance is above 90 °C. The adhesive composition according to claim 1, wherein the polyalkylene glycol contains two or more kinds, and the number average molecular weight of at least one type is 200 or more. A laminate comprising a layer composed of an adhesive composition as described in claim 1 or 2. A flexible planar cable comprising the laminate according to claim 3 of the patent application.