WO2018143446A1 - Polyester resin composition, adhesive agent, and laminated body - Google Patents

Abstract

This polyester resin composition is characterized by containing 100 parts by mass of a polyester resin (A), 0.1-5 parts by mass of a silane coupling agent (B), and 1-5 parts by mass of an isocyanate compound (C), wherein the polyester resin (A) has a glass transition temperature of -20°C to 30°C and a melting point of 110-150°C.

Description

Polyester resin composition, adhesive and laminate

The present invention relates to a polyester resin composition that has excellent adhesion to polyester films and metals and can be suitably used as an adhesive for flexible flat cables.

Until now, a flexible flat cable (hereinafter sometimes referred to as FFC) in which a conductor having a flat cross section is covered with an electrically insulating synthetic resin film in a sandwich shape has been widely used for internal wiring of electronic devices. In addition, the efficiency of wiring work is improved.

A polyester film has been conventionally used as the electrically insulating synthetic resin film constituting the FFC, and as an adhesive for bonding the electrically insulating synthetic resin film and the conductor, insulating properties and durability are used. Furthermore, polyester-based resins are used from the viewpoint of adhesiveness with an electrically insulating synthetic resin film as a base material.

FFCs that are thin, light, and resistant to miswiring can be modularized in parts and expanded in the car space in the automotive field, so their use in various wiring and parts is increasing. Adopted for fixed wiring such as cockpit and roof internal wiring, and moving part wiring such as steering and back monitor.

Furthermore, FFC is expected to be deployed in the engine room, which becomes a more severe usage environment, as the demand for lighter weight and higher functionality increases. Parts used in the engine room are required to have not only heat resistance but also salt water resistance that can withstand the effects of water entering the engine room and salt entering when traveling near the coast. The adhesive for FFC is also required to have salt water resistance that is less likely to cause a decrease in adhesive strength even under the influence of water and salt.

However, an adhesive composed of a polyester resin composition having such excellent heat resistance and salt water resistance has not been proposed yet. The adhesive composition containing the polyester resin and the curing agent disclosed in Patent Documents 1 and 2 is intended to improve the adhesive strength, is not considered for salt water resistance, and is a salt spray treatment. Later, the adhesive strength was greatly reduced, and the salt water resistance was insufficient.

International Publication No. 2011/129278 JP 2008-150443 A

The present invention solves the above-mentioned problems, and is particularly excellent in adhesiveness to polyester films and metals, and is preferably used as an adhesive for FFC used for internal wiring of electronic equipment. It is an object of the present invention to provide a polyester resin composition having high adhesive strength under high temperature atmosphere, excellent heat resistance, small decrease in adhesive strength after salt spray treatment, and excellent performance in salt water resistance. It is.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the gist of the present invention is the following (1) to (8).
(1) 100 parts by mass of a polyester resin (A), 0.1 to 5 parts by mass of a silane coupling agent (B), and 1 to 5 parts by mass of an isocyanate compound (C),
The polyester resin (A) has a glass transition temperature of −20 to 30 ° C. and a melting point of 110 to 150 ° C.
(2) The polyester resin (A) contains 60 to 90 mol% of terephthalic acid as an acid component and 10 to 50 mol% of an aliphatic dicarboxylic acid having 4 to 15 carbon atoms, and 1,4-cyclohexanedimethanol 25 as a glycol component. The polyester resin composition as described in (1), which contains ˜55 mol%.
(3) The polyester resin composition according to (1) or (2), wherein the silane coupling agent (B) has any one of an amino group, an epoxy group, and an isocyanate group as a terminal group.
(4) The polyester resin composition according to any one of (1) to (3), wherein the isocyanate compound (C) has two or more isocyanate groups in the molecule.
(5) An adhesive comprising the polyester resin composition according to any one of (1) to (4) above.
(6) A laminate comprising a layer containing the polyester resin composition according to any one of (1) to (4) above.

Since the polyester resin composition of the present invention comprises a specific amount of a silane coupling agent and an isocyanate compound in a specific polyester resin, it is particularly excellent in adhesion to polyester films and metals, After bonding, the adhesive strength in a high temperature atmosphere is high and the heat resistance is excellent. Even when the salt spray treatment is performed, the decrease in the adhesive strength is small and the adhesive strength is excellent in salt water resistance. For this reason, products such as FFC using the polyester resin composition of the present invention as an adhesive layer are excellent in heat resistance and salt water resistance, and even when used in harsh environments, problems such as peeling and poor contact are unlikely to occur. It becomes.

Hereinafter, the present invention will be described in detail.
The polyester resin composition of the present invention contains a polyester resin (A), a silane coupling agent (B), and an isocyanate compound (C).

First, the polyester resin (A) in the present invention will be described.
The polyester resin (A) needs to have a glass transition temperature of −20 to 30 ° C., and particularly preferably −10 to 20 ° C. If the glass transition temperature of the polyester resin (A) is less than −20 ° C., the elastic modulus at ordinary temperature is lowered, so that the polyester resin composition has insufficient adhesion to metal. On the other hand, when the glass transition temperature exceeds 30 ° C., the polyester resin (A) has a high elastic modulus near room temperature, the resin itself becomes too hard, and the polyester resin composition adheres to the adherend. Sex does not appear.

Further, the melting point of the polyester resin (A) is required to be 110 to 150 ° C., and preferably 120 to 140 ° C. among them. When the melting point of the polyester resin (A) is less than 110 ° C. or does not have a melting point, the polyester resin composition has low adhesive strength under a high temperature atmosphere. On the other hand, when the melting point of the polyester resin (A) exceeds 150 ° C., the polyester resin composition has poor fluidity during lamination and low adhesive strength.

In order to set the glass transition temperature and melting point of the polyester resin (A) within the above ranges, the composition of the polyester resin (A) is preferably as follows.
First, the glycol component preferably contains 25 to 55 mol% of 1,4-cyclohexanedimethanol, more preferably 35 to 45 mol%, when the total amount of glycol components is 100 mol%. When the content of 1,4-cyclohexanedimethanol is less than 25 mol%, the polyester resin (A) has a lower melting point, and as described in the above paragraph, the polyester resin composition has an adhesive strength in a high-temperature atmosphere. May decrease. On the other hand, when the content of 1,4-cyclohexanedimethanol exceeds 55 mol%, the polyester resin (A) has a high melting point, but as explained in the above paragraph, the polyester resin composition is The fluidity of the resin may decrease and the adhesive strength may decrease.

In the polyester resin (A), other glycol components other than 1,4-cyclohexanedimethanol include ethylene glycol, 1,4-butanediol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, Aliphatic glycols such as ethylene glycol, tetraethylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, polyalkylene glycols such as polyethylene glycol, triethylene glycol, and polytetramethylene glycol; Hydroquinone, 4,4'-dihydroxybisphenol, 1,4-bis (β-hydroxyethoxy) benzene, bisphenol A, 2,5-naphthalenediol, ethyleneoxy in these glycols There and aromatic glycols such as glycol was added. Of these, ethylene glycol, 1,4-butanediol, triethylene glycol, and polytetramethylene glycol are preferable.
Examples of the polyhydric alcohol other than glycol include trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, hexanetriol and the like.

The acid component of the polyester resin (A) preferably contains 60 to 90 mol% of terephthalic acid, more preferably 70 to 80 mol%, when the total amount of the acid components is 100 mol%. If the content of terephthalic acid exceeds 90 mol%, the solubility of the polyester resin (A) may decrease. On the other hand, when the content of terephthalic acid is less than 60 mol%, the polyester resin (A) has a lower crystallinity and a lower melting point, so that the polyester resin composition may have lower adhesive strength in a high-temperature atmosphere.

Further, the acid component of the polyester resin (A) preferably contains 10 to 50 mol% of an aliphatic dicarboxylic acid having 4 to 15 carbon atoms, particularly 20 to 40 mol, when the total amount of the acid components is 100 mol%. % Content is preferable. When the content of the aliphatic dicarboxylic acid having 4 to 15 carbon atoms exceeds 50 mol%, the polyester resin (A) has a low glass transition temperature and a low elastic modulus at high temperatures. May have insufficient adhesive strength. On the other hand, when the content of the aliphatic dicarboxylic acid having 4 to 15 carbon atoms is less than 10 mol%, the polyester resin (A) has a high glass transition temperature and a high elastic modulus near room temperature. Things may have reduced adhesion.

Examples of aliphatic dicarboxylic acids having 4 to 15 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, and tetradecanedioic acid. And pentadecanedioic acid. Among these, these are used alone or in combination of two or more. Of these, adipic acid and sebacic acid are preferred.

In the polyester resin (A), other acid components other than terephthalic acid and aliphatic dicarboxylic acid having 4 to 15 carbon atoms include isophthalic acid, 5- (alkali metal) sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, Examples thereof include aromatic dicarboxylic acids such as 4,4′-biphenyldicarboxylic acid or ester-forming derivatives thereof, unsaturated aliphatic dicarboxylic acids such as fumaric acid, maleic acid, and itaconic acid, or ester-forming derivatives thereof.
Examples of polyvalent carboxylic acids other than dicarboxylic acids include butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3 ′, 4′-biphenyltetracarboxylic acid, and ester-forming derivatives thereof. Can be mentioned.

Moreover, it is preferable that the polyester resin (A) of this invention has a hydroxyl value and an acid value which are mentioned later.
The hydroxyl value of the polyester resin (A) is preferably 3 to 20 mgKOH / g, and more preferably 5 to 11 mgKOH / g. When the polyester resin (A) has a hydroxyl value of less than 3 mgKOH / g, the reaction with the isocyanate compound (C) does not proceed sufficiently, so that the polyester resin composition may be inferior in adhesive strength and heat resistance. On the other hand, when the hydroxyl value of the polyester resin (A) exceeds 20 mgKOH / g, the curing shrinkage increases, so that the polyester resin composition may have a reduced adhesive strength.

The acid value of the polyester resin (A) is preferably 5 mgKOH / g or less, and more preferably 3 mgKOH / g or less. When the acid value of the polyester resin (A) exceeds 5 mgKOH / g, the reaction with the isocyanate compound is accelerated and the solution stability may be lowered.

By changing the polymerization method, polymerization time, etc. of the polyester resin (A), the hydroxyl value and acid value of the polyester resin (A) can be within the above ranges. The inherent viscosity of the polyester resin (A) is preferably 0.52 to 1.00.

In the present invention, the polyester resin (A) and the polyester resin composition may contain an antioxidant as long as the characteristics are not impaired. For example, as a hindered phenol-based antioxidant, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,1,3-tri (4-hydroxy-2 -Methyl-5-tert-butylphenyl) butane, 1,1-bis (3-tert-butyl-6-methyl-4-hydroxyphenyl) butane, 3,5-bis (1,1-dimethylethyl) -4 -Hydroxy-benzenepropanoic acid, pentaerythrityl tetrakis (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3- (1,1-dimethylethyl) -4-hydroxy-5-methyl- Benzenepropanoic acid, 3,9-bis [1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5.5] undecane, 1,3,5-trimethyl-2,4,6-tris (3 ′, 5′-di-t-butyl-4′-hydroxy And benzyl) benzene. As phosphorus antioxidants, 3,9-bis (p-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis ( Octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, tri (monononylphenyl) phosphite, triphenoxyphosphine, isodecylphosphite, iso Decylphenyl phosphite, diphenyl 2-ethylhexyl phosphite, dinonylphenyl bis (nonylphenyl) ester phosphoric acid, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-t-butylphenyl) ) Butane, tris (2,4-di-t-butylphenyl) phosphite, pentaerythritol (2,4-di-t-butylphenyl phosphite), 2,2'-methylenebis (4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, bis (2,6-di-t- Butyl-4-methylphenyl) pentaerythritol diphosphite and the like. As thioether antioxidants, 4,4′-thiobis [2-tert-butyl-5-methylphenol] bis [3- (dodecylthio) propionate], thiobis [2- (1,1-dimethylethyl) -5- Methyl-4,1-phenylene] bis [3- (tetradecylthio) -propionate], pentaerythritol tetrakis (3-n-dodecylthiopropionate), bis (tridecyl) thiodipropionate. An antioxidant may be used independently and may use 2 or more types together.

The polyester resin (A) in the present invention can be synthesized by a conventionally known polyester synthesis method. For example, using an acid component and a glycol component as described above as raw materials and performing an esterification or transesterification reaction at a temperature of 220 to 280 ° C. by a conventional method, a polycondensation catalyst is added, and the pressure is reduced to 5 hPa or less. It can be obtained by performing a polycondensation reaction at a temperature of 230 to 280 ° C., preferably 240 to 260 ° C. Further, depending on the purpose and application, it can also be obtained by a method in which an acid component or a glycol component is added to a polymer obtained by a polycondensation reaction and a depolymerization reaction is performed at a temperature of 220 to 280 ° C. Moreover, the flame retardant and filler which are mentioned later can also be added at the time of polycondensation reaction.

Next, the silane coupling agent (B) will be described.
The polyester resin composition of the present invention needs to contain 0.1 to 5 parts by mass of the silane coupling agent (B) with respect to 100 parts by mass of the polyester resin (A). It is preferable to contain 3.5 parts by mass.
By containing the silane coupling agent (B) in the above range, the polyester resin composition particularly improves the adhesion to the metal surface, improves the adhesion to the metal, and the adhesive strength after the salt spray treatment. The decrease in the resistance is small, and the salt water resistance is excellent.
When the content of the silane coupling agent (B) is less than 0.1 parts by mass, the polyester resin composition has an insufficient effect of improving the adhesion to metal, and the adhesive strength after the salt spray treatment is greatly reduced. On the other hand, when the content of the silane coupling agent (B) exceeds 5 parts by mass, the polyester resin composition has an insufficient effect of improving the adhesion to metal, and the adhesive strength after the salt spray treatment is greatly reduced. Moreover, a polyester resin composition will be inferior to the adhesive force in a high temperature atmosphere. Furthermore, the stability of the solution of the polyester resin composition described later is lowered.

The silane coupling agent (B) is preferably a hydrolyzable silane compound represented by the general formula: Y—R—Si—X ₃ . Examples of Y include a vinyl group, an epoxy group, a methacryl group, an isocyanate group, a hydroxy group, an amino group, and a mercapto group. R is a linear or branched alkylene group. Examples of X include an alkoxy group such as a methoxy group or an ethoxy group, a chloro group, an acetoxy group, an oxime group, and an isopropenoxy group. Several X may mutually be same or different. From the viewpoint that excellent salt water resistance can be imparted to the polyester resin composition, Y is preferably an epoxy group, an isocyanate group or an amino group, and more preferably an amino group having a high effect of improving salt water resistance.

Specific examples of the silane coupling agent (B) include vinyltriethoxysilane, vinyltrimethoxysilane, γ- (methacryloyloxypropyl) trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ -Glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N -Β (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane.
Examples of commercially available silane coupling agents (B) include “KBE-903” (3-aminopropyltriethoxysilane) and “KBM-403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. ), “KBE-9007” (3-isocyanatopropyltriethoxysilane).

Next, the isocyanate compound (C) will be described.
The polyester resin composition of the present invention needs to contain 1 to 5 parts by mass of the isocyanate compound (C) with respect to 100 parts by mass of the polyester resin (A). Part.
When the content of the isocyanate compound (C) is less than 1 part by mass, the function of curing the polyester resin composition is insufficient. Therefore, the polyester resin composition is inferior in adhesion to metal and adhesion after salt spray treatment. , Heat resistance decreases. On the other hand, when the content of the isocyanate compound (C) exceeds 5 parts by mass, the polyester resin composition is gelled and fluidity is lowered. As a result, workability at the time of adhesion is lowered and the adhesiveness is inferior. It will be a thing.

In the present invention, the isocyanate compound (C) preferably has 2 or more isocyanate groups in the molecule, and preferably has 3 or more isocyanate groups from the viewpoint of heat resistance.
Specific examples of the isocyanate compound (C) include 2,4- or 2,6-tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, methylene diisocyanate, isopropylene diisocyanate, lysine diisocyanate, 2,2, From 4- or 2,4,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isopropylidene dicyclohexyl-4,4'-diisocyanate, etc. A single isocyanate compound selected from the above, or an adduct comprising the above isocyanate compound selected from one or more, isocyanurｰ To Karada, Byu Retto Karada, are Age is Isoshia Isoshia isocyanurate Karada. Among them, an isocyanurate body having two or more isocyanate groups in the molecule or a polyisocyanate having an aromatic ring is preferable.

As a commercially available isocyanate compound (C) which is an isocyanurate having two or more isocyanate groups in the molecule, “TPA-100” (an isocyanurate of hexamethylene diisocyanate) manufactured by Asahi Kasei is preferable. As a commercially available product of the isocyanate compound (C), which is a polyisocyanate having an acid content, Desmodur RFE (tris (phenylisocyanate) thiophosphate) manufactured by Covestro is preferable.

As described above, the polyester resin composition of the present invention contains a specific amount of a silane coupling agent and a curing agent in a specific polyester resin. After bonding, the adhesive strength in a high temperature atmosphere is high and the heat resistance is excellent. Even when the salt spray treatment is performed, the decrease in the adhesive strength is small, and the adhesive strength is excellent in salt water resistance. For this reason, products such as FFC using the polyester resin composition of the present invention as an adhesive layer are excellent in heat resistance and salt water resistance, and even when used in harsh environments, problems such as peeling and poor contact are unlikely to occur. It becomes.

Furthermore, the polyester resin composition of the present invention preferably contains a flame retardant (D) and a filler (E).
The flame retardant (D) can impart flame retardancy to the polyester resin composition, and is preferably a halogen flame retardant, a nitrogen flame retardant, or a phosphorus flame retardant, and more preferably a halogen flame retardant. preferable.

Examples of halogen flame retardants include hexabromocyclododecane, bis (dibromopropyl) tetrabromo-bisphenol A, bis ((dibromopropyl) tetrabromo-bisphenol S, tris (dibromopropyl) isocyanurate, tris (tribromoneopentyl) phosphate, Decabromodiphenylene oxide, brominated epoxy resin, bis (pentabromophenyl) ethane, tris (tribromophenoxy) triazine, ethylenebis (tetrabromophthal) imide, ethylenebispentabromophenyl, polybromophenylindane, brominated polystyrene Bromine compounds such as TBBA polycarbonate, brominated polyphenylene oxide, polypentabromobenzyl acrylate, and [2,2-bis (chloromethyl) -1,3 Propanediyl] bisoxybisphosphonic acid tetrakis (2-chloroethyl), tris (1-methyl-2-chloroethyl) phosphate, 2,2-bis (bromomethyl) -3-chloropropyl phosphate bis [2-chloro-1 phosphate Chlorinated compounds such as-(chloroethyl) ethyl].

Nitrogen-based flame retardants include aliphatic amine compounds, aromatic amine compounds, triazine, melamine, benzoguanamine, methylguanamine, nitrogen-containing heterocyclic compounds such as cyanuric acid, cyanide compounds, aliphatic amides, aromatic amides, urea, thio Examples include urea.

Examples of the phosphorus-based flame retardant include polyphosphate-based, phosphinate-based, phosphate ester-based, condensed phosphate ester-based, and phosphazene-based flame retardants.

What is added as a filler (E) contains various additives, such as a flame retardant adjuvant for improving the flame retardance of said flame retardant, antioxidant, a heat stabilizer, and a pigment. Examples of the flame retardant aid include antimony trioxide, zinc stannate, and zinc borate. As the antioxidant, hindered phenol compounds and phosphorus-based antioxidants are preferable. Examples of the heat stabilizer include phosphoric acid. Examples of the pigment include titanium oxide and carbon black. Examples of other fillers include swellable clay minerals, silica, alumina, and glass beads.
The filler (E) can be used alone or in combination of two or more.

A filler (E) can improve the adhesive force with respect to the polyester film and metal of the polyester resin composition of this invention by acting as a filler in a polyester resin composition.
Accordingly, even when the flame retardant (D) is used, it is preferable to select one having such an action or one that does not inhibit, and among them, it is preferable to use a halogen flame retardant.

When the flame retardant (D) and filler (E) are included in the polyester resin composition of the present invention, the total amount thereof is preferably 20 to 80% by mass in the polyester resin composition, and more preferably 30 to It is preferable that it is 75 mass%.
When the content is less than 20% by mass, the action as a filler becomes insufficient, and the polyester resin composition tends to have a reduced adhesive force to a polyester film or metal. On the other hand, when these contents exceed 80% by mass, the polyester resin composition has a tendency that the adhesive force to the polyester film or metal tends to decrease because the resin content decreases.

The polyester resin composition of the present invention can be used as an adhesive. When used as an adhesive, the polyester resin composition of the present invention is preferably used after being dissolved in an organic solvent. The organic solvent is not particularly limited as long as it dissolves the polyester resin composition of the present invention. Aromatic solvents such as benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, 1, 2 -Chlorine solvents such as dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene and dichlorobenzene, ester solvents such as ethyl acetate, isophorone and γ-butyrolactone, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone Solvents, diethyl ether, ethyl cellosolve, butyl cellosolve, tetrahydrofuran, 1,4-dioxane and other ether solvents, methanol, ethanol, n-propanol, isopropanol, n-butanol and other alcohol solvents, n-butane, isobutane Examples thereof include aliphatic hydrocarbon solvents such as n-pentane, n-hexane, n-heptane, n-octane and nonane, and alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane. Among them, methylene chloride, toluene Methyl ethyl ketone is preferred. The organic solvent may be used alone or in combination of two or more.

In the adhesive in which the polyester resin composition is dissolved in an organic solvent, the content (solid content concentration) of the polyester resin composition is preferably 10 to 40% by mass, and more preferably 20 to 30% by mass. More preferred. When the solid content concentration of the polyester resin composition is higher than 40% by mass, the adhesive may have reduced solution stability, whereas the adhesive having a solid content concentration of less than 10% by mass is the thickness of the adhesive layer. When increasing the amount, it is necessary to increase the amount of coating and the number of coatings, which may result in poor work efficiency and reduced productivity.

Next, the laminated body of this invention is demonstrated.
The laminate of the present invention includes a layer containing the polyester resin composition of the present invention (hereinafter sometimes referred to as an adhesive layer). Especially, it is preferable that it is the laminated body laminated | stacked in order of the film layer / adhesion layer / metal layer, Furthermore, it is a laminated body laminated | stacked in order of the film layer / adhesive layer / metal layer / adhesive layer / film layer. Preferably there is.
The resin constituting the film layer is preferably a polyester such as polyethylene terephthalate (PET), polybutylene terephthalate, or polyethylene naphthalate. Polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyarylate, polyamide, polyolefin, polyethersulfone, polysulfone Resins such as polystyrene and methacryl may be used.
The metal layer is preferably a layer in which a plurality of metal wires serving as conductors are arranged. Examples of the metal constituting the conductor include copper, iron, aluminum, etc., and the conductor includes tin, zinc, and the like. For example, tinplate, or a chemical conversion treatment product such as zinc phosphate or chromate may be used.

As a method for producing the laminate of the present invention, an adhesive containing the polyester resin composition of the present invention is applied between a film layer and a metal layer, and then heat sealing, roll bonding, thermocompression bonding and the like are conventional. A method in which the solvent is removed and bonded by a known method is suitable.

Hereinafter, the present invention will be described specifically by way of examples.
The measurement and evaluation methods for each characteristic value in the examples were performed as follows.
(1) Composition of polyester resin ¹ H-NMR was measured with an ECZ400R type NMR apparatus manufactured by JEOL Ltd. and obtained from the peak integrated intensity ratio of protons of each copolymer component in the obtained chart.

(2) Inherent viscosity (ηinh) of polyester resin
Relative viscosity measured at a concentration of 0.5 g / dl and a temperature of 25 ° C. using a mixed solution of phenol / 1,1,2,2-tetrachloroethane = 50/50 (mass ratio) using an Ubbelohde viscosity tube Based on (ηrel), it was calculated by the following formula and expressed in units of dl / g.
Inherent viscosity (ηinh) = ln (ηrel) / c
ηrel: relative viscosity, c: concentration (g / dl)

(3) Acid value of polyester resin In accordance with JIS K-0070, 0.5 g of a sample was dissolved in 25 ml of dioxane, and titrated with 0.1N-KOH using cresol red as an indicator. Using the titrated value, the mg number of KOH consumed for neutralization was converted per 1 g of the polyester resin, and the acid value was determined.

(4) Hydroxyl value of polyester resin According to JIS K-0070, 3 g of sample was dissolved in 50 ml of pyridine by heating under reflux, acetic anhydride was acetylated solution, and cresol red-thymol blue was used as an indicator, 0.5N hydroxylation. Titrated with potassium methanol solution. Using the titrated value, the number of mg of KOH required to neutralize acetic acid bonded to a hydroxyl group was converted per 1 g of the polyester resin, and the hydroxyl value was determined.

(5) Glass transition temperature (Tg), melting point (Tm)
Using a differential scanning calorimeter (Diamond DSC) manufactured by PerkinElmer, the temperature was increased at a rate of 20 ° C./min.

(6) Solution stability The solution viscosity of the obtained adhesive was measured using a B-type rotational viscometer, and the stability was evaluated by changes over time. After preparation, the solution viscosity of the adhesive when allowed to stand for 1 hour was defined as viscosity 1 immediately after dissolution. Thereafter, the adhesive was stored sealed at 23 ° C. for 24 hours, and the solution viscosity 2 of the adhesive was similarly measured using a B-type rotational viscometer. The ratio of viscosity 2 to viscosity 1 immediately after dissolution was evaluated in two steps according to the following criteria.
○: Viscosity 2 is 1.0 times or more of viscosity 1 and less than 1.3 times ×: Viscosity 2 is 1.3 times or more of viscosity 1

(7) Adhesiveness with nickel-plated copper (adhesive strength with conducting wire)
The obtained adhesive is applied on a PET film (thickness 30 μm) (coating thickness 100 μm), dried at 150 ° C. for 3 minutes, and further treated at 50 ° C. for 72 hours. A laminate 1 in which an adhesive layer having a thickness of 30 μm made of the composition was laminated was produced.
On the adhesive layer surface of the obtained laminate 1, five nickel-plated copper wires (thickness 0.035 mm, width 0.3 mm, length 150 mm) were laminator (SA-1010 manufactured by Tester Sangyo Co., Ltd.) at intervals of 1 to 2 mm. ) To obtain a laminate 2 laminated in the order of PET film / adhesive layer / nickel-plated copper wire under the conditions of a temperature of 180 ° C., a linear pressure of 40 N / cm, and a speed of 1.0 m / min.
The obtained laminate 2 was tested with an autograph AG-2 manufactured by Shimadzu Corporation at a tensile rate of 300 mm / min in an atmosphere of 23 ° C., and a 180 ° peel adhesive strength (peel adhesive strength 1) was obtained. It was measured.

(8) Adhesive strength with nickel-plated copper after salt spray treatment The laminate 2 produced in the same manner as (7) above is subjected to salt spray treatment for 72 hours according to the method prescribed in JIS Z2371, and dried for 24 hours. A laminate 3 was obtained. The laminate 3 was measured for 180 ° peel adhesive strength (peel adhesive strength 2) in the same manner as in (7).

(9) Retention rate of peel adhesion after salt spray treatment The retention rate of peel adhesion after salt spray treatment was calculated by the following formula. For laminates having a peel adhesive strength 2 of less than 0.01 N / 0.3 mm, the retention rate of the peel adhesive strength was not calculated and indicated as “-” in the table.
Peel adhesive strength retention (%) = [(Peel adhesive force 2) / (Peel adhesive force 1)] × 100

(10) Adhesiveness with nickel-plated copper (high temperature atmosphere (85 ° C))
The laminate 2 produced in the same manner as in the above (7) was tested using an autograph AG-2 manufactured by Shimadzu Corporation under an atmosphere of 85 ° C. and a tensile speed of 300 mm / min. Was measured.

(11) Adhesiveness with polyester film A PET film (thickness of 30 μm) is applied to the surface of the laminate 1 produced in the same manner as in (7) above using a laminator (SA-1010 manufactured by Tester Sangyo Co., Ltd.) Bonding was performed under the conditions of a temperature of 180 ° C., a linear pressure of 40 N / cm, and a speed of 1.0 m / min to obtain a laminate 4 laminated in the order of PET film / adhesive layer / PET film.
A test piece having a width of 25 mm was prepared from the obtained laminate 4 and tested using a Autograph AG-2 manufactured by Shimadzu Corporation under a 23 ° C atmosphere at a tensile rate of 50 mm / min. The force was measured. In addition, the test piece which became material destruction in the peeling test was set as the pass.

The following were used as raw materials for the polyester resin composition.
[Polyester resin (A-1)]
In the esterification reactor, 60.4 parts by mass of polybutylene terephthalate, 17.5 parts by mass of terephthalic acid, 29.9 parts by mass of adipic acid, 33.6 parts by mass of 1,4-cyclohexanedimethanol, triethylene The esterification reaction was carried out at a temperature of 215 ° C. for 4 hours by charging 42.0 parts by mass of glycol and 0.12 parts by mass of Irganox 1010 (manufactured by BASF). After the obtained esterified product was transferred to a polycondensation reaction tank, 0.03 parts by mass of tetrabutyl titanate was added as a polycondensation catalyst. Subsequently, the pressure in the reaction system is gradually reduced to 0.4 hPa in 90 minutes, and a polycondensation reaction is performed at 245 ° C. for 7 hours. A polyester resin (A-1) having a glass transition temperature of −5 ° C. and a melting point of 140 ° C. Got.

[Synthesis of polyester resins (A-2) to (A-17)]
A polyester resin was obtained in the same manner as the polyester resin (A-1), except that the amount of components charged into the esterification reactor was changed so that the polyester resin had the composition shown in Table 1.

Table 1 shows the compositions and characteristic values of the obtained polyester resins (A-1) to (A-17).

〔Silane coupling agent〕
B-1: 3-aminopropyltrimethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.)
B-2: 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
B-3: 3-isocyanatopropyltriethoxysilane (KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd.)

[Isocyanate compound]
C-1: Polyisocyanate of hexamethylene diisocyanate (TPA-100 manufactured by Asahi Kasei Corporation)
C-2: 4,4-diphenylmethane diisocyanate (manufactured by Kanto Chemical Co., Inc.)
C-3: 2,4- / 2,6-toluene diisocyanate [80/20 mixture] (Coronate T-80 manufactured by Tosoh Corporation)
C-4: Tris (phenyl isocyanate) thiophosphate (Desmodur RFE manufactured by Covestro)

Flame retardant: bis (pentabromophenyl) ethane (SAYTEX 8010, manufactured by Albemarle)
Flame retardant aid: antimony trioxide (manufactured by Yamanaka Sangyo)
Pigment: Titanium oxide (Fuji Titanium Industry Co., Ltd.)
Filler: Silica (Aerosil R972 manufactured by Nippon Aerosil Co., Ltd.)

Example 1
20 parts by weight of polyester resin (A-1), 48 parts by weight of dichloromethane, 9.6 parts by weight of toluene, and 2.4 parts by weight of methyl ethyl ketone were charged into a 100 mL glass bottle containing glass beads having a diameter of 2 mm, and a metal cap. And then completely dissolved with a high speed ball mill (Rocking Mill RM-50) manufactured by Seiwa Giken at 23 ° C. for 1 hour.
Next, 80 parts by mass of the above solution is filled with 10 parts by mass of bis (pentabromophenyl) ethane as a flame retardant, 7.2 parts by mass of antimony trioxide as a flame retardant aid, and 2 parts by mass of titanium oxide as a pigment. As a material, 0.8 part by mass of silica was charged, and dispersed at 23 ° C. for 1 hour using the same ball mill.
Further, 0.2 part by mass of the silane coupling agent (B-1) and 0.62 part by mass of the isocyanate compound (C-1) were added to the above solution, and the mixture was stirred and mixed at 23 ° C. for 30 minutes in the same ball mill. And the adhesive agent which is a solution of the polyester resin composition containing a polyester resin, a silane coupling agent, and an isocyanate compound was obtained.

Examples 2 to 29, Comparative Examples 1 to 14
Except for changing the type of polyester resin, the silane coupling agent, the type of isocyanate compound and 100 parts by mass of the polyester resin, and the mass parts of the flame retardant and filler are as shown in Tables 2-3. In the same manner as in Example 1, an adhesive that was a solution of the polyester resin composition was produced.

Tables 2-3 show the compositions and evaluation results of the polyester resin compositions obtained in Examples 1-29 and Comparative Examples 1-14.

As is apparent from Tables 2 to 3, the adhesives using the polyester resin compositions obtained in Examples 1 to 29 are excellent in adhesion to metal and maintain adhesion after salt spray treatment. The rate was high and the salt water resistance was excellent.

On the other hand, in the polyester resin compositions of Comparative Examples 1 to 3, the content of the silane coupling agent is less than 0.1 parts by mass with respect to 100 parts by mass of the polyester resin. The adhesive strength was inferior, and the adhesive strength retention after the salt spray treatment was inferior. In the polyester resin composition of Comparative Example 4, the content of the silane coupling agent exceeds 5 parts by mass with respect to 100 parts by mass of the polyester resin. It was inferior in stability.
Since the polyester resin composition of Comparative Example 5 has an isocyanate compound content of less than 1 part by mass with respect to 100 parts by mass of the polyester resin, the resulting adhesive is insufficiently cured and has an adhesive strength in a high-temperature atmosphere. However, it was inferior in heat resistance and inferior in adhesion to metal. In the polyester resin compositions of Comparative Examples 6 to 7, the content of the isocyanate compound exceeds 5 parts by mass with respect to 100 parts by mass of the polyester resin, and gelation occurs. The adhesive strength was inferior.
Since the polyester resin composition of Comparative Example 8 has a glass transition temperature of less than −20 ° C., the obtained adhesive has a low elastic modulus at room temperature and is inferior in adhesive strength to metal. It was. In the polyester resin composition of Comparative Example 9, since the glass transition temperature of the resin exceeded 30 ° C., the elastic modulus at room temperature was high, and the adhesive strength with metal was inferior.
The polyester resin composition of Comparative Example 10 does not have a melting point of the resin and is amorphous, and the polyester resin composition of Comparative Example 11 is obtained because the melting point of the resin is less than 110 ° C. All the adhesives had low adhesive strength in a high temperature atmosphere and were inferior in heat resistance.
Since all of the polyester resin compositions of Comparative Examples 12 to 14 had a melting point of the resin that was too high, in Comparative Example 12, the fluidity of the resin during lamination was lowered and the adhesive strength was poor. No. 14 did not dissolve in the solvent, and an adhesive could not be obtained.

Claims (6)

100 parts by mass of the polyester resin (A), 0.1 to 5 parts by mass of the silane coupling agent (B), and 1 to 5 parts by mass of the isocyanate compound (C),
The polyester resin (A) has a glass transition temperature of −20 to 30 ° C. and a melting point of 110 to 150 ° C. The polyester resin (A) contains 60 to 90 mol% of terephthalic acid as an acid component and 10 to 50 mol% of an aliphatic dicarboxylic acid having 4 to 15 carbon atoms, and 25 to 55 mol% of 1,4-cyclohexanedimethanol as a glycol component. The polyester resin composition according to claim 1, comprising: The polyester resin composition according to claim 1 or 2, wherein the silane coupling agent (B) has any one of an amino group, an epoxy group, and an isocyanate group as a terminal group. The polyester resin composition according to any one of claims 1 to 3, wherein the isocyanate compound (C) has two or more isocyanate groups in the molecule. An adhesive comprising the polyester resin composition according to any one of claims 1 to 4. A laminate comprising a layer containing the polyester resin composition according to any one of claims 1 to 4.