TWI737890B - Polyester resin composition, adhesive and laminate - Google Patents

Abstract

A polyester resin composition of the present invention includes 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), wherein, the polyester resin composition (A) has a glass transition temperature of -20℃ to 30℃, and a melting point of 110 to 150℃.

Description

Polyester resin composition, adhesive and laminate

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

So far, in the internal circuits of electronic equipment, flexible ribbon cables are widely used in which a conductor with a flat cross-section is covered with an electrically insulating synthetic resin film into a sandwich (sandwich) (hereinafter sometimes Called FFC) to make the line work more efficient.

In the electrically insulating synthetic resin film constituting the FFC, polyester film has been used in the past, and the adhesive used to bond the electrically insulating synthetic resin film to the conductor is in terms of insulation, durability, and From the viewpoint of the adhesiveness of the electrically insulating synthetic resin film to the base material, a polyester-based resin is used.

In addition, FFC, which has the characteristics of being thin, light, and not prone to wrong wiring, has been widely used in various wiring or parts in the automotive field because it can modularize parts or expand the space in the car. In the cockpit or roof internal wiring and other fixed wiring, or steering (steering), reverse monitor and other movable part wiring.

In addition, with the increasing demand for light weight and high functionality, FFC is looking forward to the development of an engine room with a more severe use environment. Among the parts used in the engine room, heat resistance is of course required, and salt water resistance that can withstand the influence of water intruding into the engine room or salt intruding when traveling near the coast is also required. In the adhesive for FFC, it also needs to be affected by water or salt, and it is not easy to produce salt water resistance with reduced adhesive strength.

However, an adhesive containing a polyester resin composition having such excellent performance in heat resistance or salt water resistance has not been proposed so far. The adhesive composition containing polyester resin and curing agent disclosed in Patent Documents 1 and 2 aims to increase the adhesive strength, and does not consider salt water resistance. After salt spray treatment, the adhesive strength is greatly reduced, and the salt water resistance Insufficient sex.

[Prior Technical Literature] [Prior Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2011/129278

[Patent Document 2] JP 2008-150443 A

The present invention solves the above-mentioned problems, and its subject is to provide a polyester resin composition having the following properties: especially excellent adhesion to polyester films or metals, and can be suitably used as internal wiring of electronic equipment It is an adhesive for FFC, etc., which has high adhesive force under high temperature environment and excellent heat resistance, and the adhesive force after salt spray treatment has a small decrease and excellent salt water resistance.

In order to solve the above-mentioned problems, the inventors of the present invention continued to conduct intensive research and completed the present invention. That is, the gist of the present invention is the following (1) to (8).

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

(2) The polyester resin composition according to (1), wherein the polyester resin (A) contains 60 to 90 mol% of terephthalic acid and 10 to 50 mol of aliphatic dicarboxylic acid having 4 to 15 carbon atoms % Is the acid component, and contains 25 to 55 mol% of 1,4-cyclohexanedimethanol as the diol component.

(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 described in any one of (1) to (4) above.

(6) A laminate comprising a layer containing the polyester resin composition described in any one of (1) to (4).

The polyester resin composition of the present invention is formed by containing a specific amount of a silane coupling agent and an isocyanate compound in a specific polyester resin, and therefore has the following adhesive properties: especially adhesive properties to polyester films or metals It is excellent and has high adhesive force in a high-temperature environment after bonding and excellent heat resistance, and even if it is subjected to salt water spray treatment, the decrease in adhesive force is small and salt water resistance is excellent. Therefore, products such as FFC using the polyester resin composition of the present invention as an adhesive layer have excellent heat resistance and salt water resistance, and are unlikely to cause problems such as peeling or poor contact even when used in a severe environment.

The present invention will be described in detail below.

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 explained.

The glass transition temperature of the polyester resin (A) must be -20 to 30°C, and among them, it is preferably -10 to 20°C. When the glass transition temperature of the polyester resin (A) is less than -20°C, the elastic modulus at room temperature decreases, so that the adhesive force of the polyester resin composition to the metal is insufficient. On the other hand, when the glass transition temperature of the polyester resin (A) exceeds 30°C, the elastic modulus near room temperature becomes high, and the resin itself becomes too hard, so that the polyester resin composition does not show adhesion to the substrate. sex.

In addition, the melting point of the polyester resin (A) must be 110 to 150°C, and among them, it is preferably 120 to 140°C. When the melting point of the polyester resin (A) is less than 110°C or does not have a melting point, the adhesive force of the polyester resin composition in a high-temperature environment may decrease. On the other hand, when the melting point of the polyester resin (A) exceeds 150°C, the fluidity of the polyester resin composition during lamination decreases and the adhesive strength decreases.

When the glass transition temperature and melting point of the polyester resin (A) are in the above-mentioned ranges, it is preferable to set the composition of the polyester resin (A) as follows.

First, when the total amount of the diol component is 100 mol%, the diol component preferably contains 25 to 55 mol% of 1,4-cyclohexanedimethanol, and more preferably contains 35 to 45 mol%. When the content of 1,4-cyclohexanedimethanol is less than 25 mol%, the melting point of the polyester resin (A) will decrease, and as explained in the previous paragraph, the adhesive strength of the polyester resin composition will decrease in a high temperature environment. situation. On the other hand, when the content of 1,4-cyclohexanedimethanol exceeds 55 mol%, the melting point of the polyester resin (A) becomes higher. However, as explained in the previous paragraph, the polyester resin composition will have a resinous effect when laminated. When the fluidity is reduced and the adhesive strength is reduced.

The diol components other than 1,4-cyclohexanedimethanol in the polyester resin (A) include ethylene glycol, 1,4-butanediol, 1,2-propanediol, 1,3-propanediol, Diethylene glycol, triethylene glycol, tetraethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and other aliphatic diols, polyethylene glycol, triethylene glycol Polyalkylene glycols such as ethylene glycol and polytetramethylene glycol, hydroquinone, 4,4'-dihydroxybisphenol, 1,4-bis(β-hydroxyethoxy)benzene, bisphenol A , 2,5-naphthalenediol, and aromatic diols such as diols formed by adding ethylene oxide to these diols. Among them, ethylene glycol, 1,4-butanediol, triethylene glycol, and polytetramethylene glycol are preferred.

Examples of polyols other than diols include trimethylolmethane, trimethylolethane, trimethylolpropane, neopentylerythritol, glycerin, hexanetriol, and the like.

When the total amount of acid components is 100 mol%, the acid component of the polyester resin (A) preferably contains 60 to 90 mol% of terephthalic acid, and more preferably contains 70 to 80 mol%. When 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 crystallinity of the polyester resin (A) decreases and the melting point decreases, resulting in a decrease in adhesiveness of the polyester resin composition in a high temperature environment.

In addition, when the total amount of acid components is 100 mol%, the acid component of the polyester resin (A) preferably contains 10 to 50 mol% of aliphatic dicarboxylic acids having 4 to 15 carbon atoms, and among them, it is preferable to contain 20 to 40 mol%. The content of aliphatic dicarboxylic acids with carbon numbers of 4 to 15 exceeds 50 mol%. As the glass transition temperature of the polyester resin (A) becomes lower, the elastic modulus at high temperatures decreases, resulting in adhesion of the polyester resin composition Insufficient situation. On the other hand, when the content of aliphatic dicarboxylic acids with 4 to 15 carbons is less than 10 mol%, the glass transition temperature of the polyester resin (A) becomes higher, and the elastic modulus near room temperature becomes higher, resulting in The polyester resin composition may decrease its adhesive strength.

The aliphatic dicarboxylic acids with carbon numbers from 4 to 15 include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, twelve Alkanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, etc., can be used alone or in combination of two or more kinds. Among them, adipic acid and sebacic acid are preferred.

Other acid components other than terephthalic acid and aliphatic dicarboxylic acids with 4 to 15 carbons in the polyester resin (A) include isophthalic acid, 5-sulfoisophthalic acid (alkali metal), Aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, or ester-forming derivatives of these, fumaric acid, maleic acid, and itaconic acid Unsaturated aliphatic dicarboxylic acids or ester-forming derivatives of these.

Polycarboxylic acids other than dicarboxylic acids include butane tetracarboxylic acid, pyromellitic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 3,4,3',4' -Biphenyltetracarboxylic acid, and these ester-forming derivatives, etc.

In addition, the polyester resin (A) of the present invention preferably has a hydroxyl value and an acid value as described later.

The hydroxyl value of the polyester resin (A) is preferably from 3 to 20 mgKOH/g, and among them, from 5 to 11 mgKOH/g is preferred. When the hydroxyl value of the polyester resin (A) is less than 3 mgKOH/g, the reaction with the isocyanate compound (C) cannot proceed sufficiently, which may cause the polyester resin composition to have poor adhesion or poor heat resistance. On the other hand, when the hydroxyl value of the polyester resin (A) exceeds 20 mgKOH/g, the curing shrinkage becomes too large, and the adhesive strength of the polyester resin composition may decrease.

In addition, the acid value of the polyester resin (A) is preferably 5 mgKOH/g or less, and among them, it is 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 may become faster and the stability of the solution may decrease.

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 set to the above-mentioned ranges. Also, it is preferable to set the inherent viscosity of the polyester resin (A) to 0.52 to 1.00.

In the present invention, the polyester resin (A) and the polyester resin composition may contain antioxidants within a range that does not impair their characteristics. For example, hindered phenol-based antioxidants include 1,3,5-ginseng (3,5-di-tert-butyl-4-hydroxybenzyl) trimeric isocyanate, 1,1,3-tris(4-hydroxybenzyl) -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-phenylpropionic acid, pentaerythrityl tetrakis(pentaerythrityl tetrakis( 3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 3-(1,1-dimethylethyl)-4-hydroxy-5-methyl-phenylpropionate, 3,9-bis[ 1,1-Dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxa Spiro[5.5]undecane, 1,3,5-trimethyl-2,4,6-ginseng (3',5'-di-tertiarybutyl-4'-hydroxybenzyl)benzene, etc. Phosphorus antioxidants include 3,9-bis(p-nonylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (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, tris(monononylphenyl) phosphite, triphenoxyphosphine, isodecyl phosphite, isodecyl phenylene Phosphate, diphenyl 2-ethylhexyl phosphite, dinonyl phenyl bis (nonyl phenyl) phosphoric acid, 1,1,3-gins (2-methyl-4-di-tridecane) Phosphite-5-tert-butylphenyl)butane, ginseng(2,4-di-tert-butylphenyl) phosphite, neopentyl erythritol bis(2,4-di-tert-butyl) Phenyl phosphite), 2,2'-methylene bis(4,6-di-tert-butylphenyl) 2-ethylhexyl phosphite, bis(2,6-di-tert-butyl- 4-methylphenyl) neopentylerythritol diphosphite and the like. Examples of thioether antioxidants include 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], neopentylerythritol (3-n-dodecylthiopropionate), bis(tridecyl)thiodipropionate. Antioxidants can be used alone or in combination of two or more kinds.

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

Next, the silane coupling agent (B) will be explained.

The polyester resin composition of the present invention must 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), and preferably contains 0.3 to 3.5 parts by mass.

By containing the silane coupling agent (B) in the above range, the polyester resin composition has the following properties: especially the adhesion to the metal surface is improved, the adhesion to the metal is improved, and the adhesion after the salt spray treatment is improved The reduction 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 effect of improving the adhesion of the polyester resin composition to metals is insufficient, and the adhesion after the salt spray treatment is also greatly reduced. On the other hand, when the content of the silane coupling agent (B) exceeds 5 parts by mass, the effect of improving the adhesion of the polyester resin composition to metals is insufficient, and the adhesion after the salt spray treatment is also greatly reduced. In addition, the adhesive strength of the polyester resin composition in a high-temperature environment may deteriorate. In addition, the stability of the solution of the polyester resin composition described later may decrease.

The silane coupling agent (B) is preferably a hydrolyzable silane compound represented by the general formula: Y-R-Si-X3. Examples of Y include a vinyl group, an epoxy group, a methacrylic group, an isocyanate group, a hydroxyl group, an amino group, and a sulfhydryl group. R is a linear or branched alkylene group. Examples of X include alkoxy groups such as methoxy groups and ethoxy groups, chloro groups, acetoxy groups, oxime groups, and isopropenoxy groups. A plurality of Xs may be the same or different from each other. 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 among them, an amino group having a high salt water resistance improvement effect is more preferable.

Specific examples of the silane coupling agent (B) include: vinyl triethoxy silane, vinyl trimethoxy silane, γ-(methacryloxypropyl) trimethoxy silane, β-(3,4) -Epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxy propyl trimethoxy silane, γ-glycidoxy propyl methyl diethoxy silane, γ-hydrosulfanyl propyl Trimethoxysilane, γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(N-vinylbenzylamino Ethyl)-γ-aminopropyl trimethoxysilane.

Commercial products of the silane coupling agent (B) include, for example, "KBE-903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM-403" (3-glycidoxypropane). Trimethoxysilane), "KBE-9007" (3-isocyanate propyl triethoxysilane).

Next, the isocyanate compound (C) will be explained.

The polyester resin composition of the present invention must contain 1 to 5 parts by mass of the isocyanate compound (C) relative to 100 parts by mass of the polyester resin (A), and preferably 1.5 to 3.5 parts by mass.

When the content of the isocyanate compound (C) is less than 1 part by mass, the effect of hardening the polyester resin composition is insufficient, resulting in poor adhesion of the polyester resin composition to metals or after salt spray treatment, and heat resistance Sexual decrease. 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 reduced, so the workability during bonding is reduced and the adhesiveness is poor.

In the present invention, the isocyanate compound (C) preferably has two or more isocyanate groups in the molecule, and among them, from the viewpoint of heat resistance, it preferably has three or more isocyanate groups.

Specific examples of the isocyanate compound (C) include: selected from 2,4- or 2,6-toluene diisocyanate, xylylene diisocyanate (xylylene diisocyanate), 4,4'-diphenylmethane diisocyanate, Methyl diisocyanate, isopropylidene diisocyanate, lysine diisocyanate (lysine diisocyanate), 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, 1,6-hexa Isocyanates such as methylene diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isopropylidene dicyclohexyl-4,4'-diisocyanate, etc. A monomer of the compound; or an adduct containing one or more of the above isocyanate compounds, a trimeric isocyanate body, and a biuret body. Among them, a melamine isocyanate body having two or more isocyanate groups in the molecule, or a polyisocyanate having an aromatic ring is preferred.

A commercially available product of the isocyanate compound (C) of a melamine isocyanate body having two or more isocyanate groups in the molecule is preferably "TPA-100" (trimeric isocyanate product of hexamethylene diisocyanate) manufactured by Asahi Kasei Co., Ltd. A commercially available product of the isocyanate compound (C) of a polyisocyanate having an aromatic ring is preferably Desmodur RFE (ginseng (phenyl isocyanate) phosphorothioate) manufactured by Covestro.

As mentioned above, since the polyester resin composition of the present invention is formed by containing a specific amount of silane coupling agent and hardener in a specific polyester resin, it has the following adhesive properties: especially for polyester films or metal The adhesiveness is excellent, and the adhesive force after the bonding is high in a high-temperature environment, and the heat resistance is excellent, and the decrease in the adhesive force even after the salt spray treatment is applied is small, and the salt water resistance is excellent. Therefore, products such as FFC using the polyester resin composition of the present invention as an adhesive layer have excellent heat resistance and salt water resistance, and are unlikely to cause problems such as peeling or poor contact even when used in severe environments.

Furthermore, the polyester resin composition of the present invention preferably contains a flame retardant (D) or a filler (E).

The flame retardant (D) is one that can impart flame retardancy to the polyester resin composition, preferably a halogen-based flame retardant, a nitrogen-based flame retardant, or a phosphorus-based flame retardant, and among them, a halogen-based flame retardant is more preferred Agent.

、伸乙基雙(四溴苯二甲醯)亞胺、伸乙基雙(五溴苯基)、聚溴苯基茚烷、溴化聚苯乙烯、TBBA聚碳酸酯、溴化聚伸苯基醚、聚五溴苯甲基丙烯酸酯等溴系化合物，或[2,2-雙(氯甲基)-1,3-丙二基]雙氧雙膦酸肆(2-氯乙基)酯([2,2-bis(chloromethyl)-1,3-propanediyl]bisoxybisphosphonic acid tetrakis(2-chloroethyl))、磷酸參(1-甲基-2-氯乙基)酯、磷酸2,2-雙(溴甲基)-3-氯丙基=雙[2-氯-1-(氯乙基)乙基]酯等氯系化合物。 Halogen-based flame retardants include: hexabromocyclododecane, bis(dibromopropyl)tetrabromo-bisphenol A, bis((dibromopropyl)tetrabromo-bisphenol S, ginseng (dibromopropyl) ) Trimeric isocyanate, ginseng (tribromoneopentyl) phosphate, decabromodiphenyl ether, brominated epoxy resin, bis(pentabromophenyl) ethane, ginseng (tribromophenoxy) three

, Ethylene bis (tetrabromophthalimide) imine, Ethylene bis (pentabromophenyl), polybromophenyl indane, brominated polystyrene, TBBA polycarbonate, brominated polyphenylene Bromine compounds such as base ether, polypentabromobenzyl methacrylate, or [2,2-bis(chloromethyl)-1,3-propanediyl]dioxybisphosphonic acid (2-chloroethyl) Ester ([2,2-bis(chloromethyl)-1,3-propanediyl]bisoxybisphosphonic acid tetrakis(2-chloroethyl)), ginseng phosphate (1-methyl-2-chloroethyl) ester, phosphoric acid 2,2-bis (Bromomethyl)-3-chloropropyl=chlorine compounds such as bis[2-chloro-1-(chloroethyl)ethyl] ester.

、三聚氰胺、苯胍

(benzoguanamine)、甲基胍胺、三聚氰酸等含氮雜環化合物、氰化合物、脂肪族醯胺、芳香族醯胺、尿素、硫脲等。 Nitrogen-based flame retardants include: aliphatic amine compounds, aromatic amine compounds, three

, Melamine, benzoguanidine

(benzoguanamine), methylguanamine, cyanuric acid and other nitrogen-containing heterocyclic compounds, cyanide compounds, aliphatic amides, aromatic amides, urea, thiourea, etc.

Examples of phosphorus-based flame retardants include flame retardants such as polyphosphate-based, phosphonate-based, phosphate ester-based, condensed phosphate ester-based, and phosphazene-based flame retardants.

What is added as a filler (E) also includes various additives such as flame retardant additives for improving the flame retardancy of the above flame retardant, or antioxidants, heat stabilizers, and pigments. Examples of the flame retardant auxiliary agent include antimony trioxide, zinc stannate, and zinc borate. The antioxidant is preferably a hindered phenol compound or a phosphorus antioxidant. Examples of heat stabilizers include phosphoric acid. Examples of pigments include titanium oxide and carbon black. Other fillers include swelling clay minerals, silica, alumina, glass beads, and the like.

The filler (E) can be used alone or in combination of two or more types.

When the filler (E) functions as a filler in the polyester resin composition, the adhesion of the polyester resin composition of the present invention to the polyester film or metal can be improved.

Therefore, even when the flame retardant (D) is used, it is preferable to select one that has such an effect or does not hinder such an effect. Among them, halogen-based flame retardants are preferable.

When the flame retardant (D) or filler (E) is contained in the polyester resin composition of the present invention, the total amount of these is preferably 20 to 80% by mass in the polyester resin composition, and among them, preferably It is 30 to 75% by mass.

When the content is less than 20% by mass, the effect as a filler is insufficient, and the adhesion of the polyester resin composition to the polyester film or metal tends to decrease. On the other hand, when the content exceeds 80% by mass, the polyester resin composition has a reduced resin content, so the adhesive force to the polyester film or metal tends to decrease.

烷等醚系溶劑、甲醇、乙醇、正丙醇、異丙醇、正丁醇等醇系溶劑、正丁烷、異丁烷、正戊烷、正己烷、正庚烷、正辛烷、壬烷等脂肪族烴系溶劑、環戊烷、環己烷等脂環族烴系溶劑等，其中，較佳為二氯甲烷、甲苯、甲基乙基酮。有機溶劑可單獨使用或混合複數種而使用。 The polyester resin composition of the present invention can be used as an adhesive. When used as an adhesive, it is preferable to dissolve the polyester resin composition of the present invention in an organic solvent and use it. The organic solvent is not particularly limited as long as it can dissolve the polyester resin composition of the present invention. Examples include aromatic solvents such as benzene, toluene, and xylene, dichloromethane, chloroform, carbon tetrachloride, Chlorine-based solvents such as 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, and dichlorobenzene, and ester-based solvents such as ethyl acetate, isophorone, and γ-butyrolactone , Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketone solvents, diethyl ether, ethyl cellosolve, butyl cellosolve, tetrahydrofuran, 1,4 -two

Ether solvents such as alkane, methanol, ethanol, n-propanol, isopropanol, n-butanol and other alcoholic solvents, n-butane, isobutane, n-pentane, n-hexane, n-heptane, n-octane, nonane Aliphatic hydrocarbon solvents such as alkanes, alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane, etc. Among them, dichloromethane, toluene, and methyl ethyl ketone are preferred. The organic solvent can be used alone or in combination of plural kinds.

In the adhesive obtained by dissolving the polyester resin composition in an organic solvent, the content (solid concentration) of the polyester resin composition is preferably 10 to 40% by mass, and more preferably 20 to 30% by mass. When the solid content of the polyester resin composition is higher than 40% by mass, the solution stability of the adhesive may decrease. On the other hand, if the solid content of the adhesive is less than 10% by mass, it is necessary to increase the adhesive layer. At the time of thickness, the coating amount or the number of coatings must be increased, which may result in poor work efficiency and reduced productivity.

Next, the laminate of the present invention will be explained.

The laminated system of the present invention includes a layer containing the polyester resin composition of the present invention (hereinafter sometimes referred to as an adhesive layer). Among them, it is preferably a laminate formed in the order of thin film layer/adhesive layer/metal layer, and more preferably a laminate formed in the order of thin film layer/adhesive layer/metal layer/adhesive layer/thin film layer body.

The resin constituting the film layer is preferably polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate and other polyesters, and may also be polyvinyl chloride or polyvinylidene dicarboxylate. Resins such as vinyl chloride, polycarbonate, polyacrylate, polyamide, polyolefin, polyether, polystyrene, methacrylic acid, etc.

The metal layer is preferably a layer formed by arranging a plurality of metal wires as conductors. The metals constituting the conductors may include copper, iron, aluminum, etc., and the conductors may be those formed by plating tin, zinc, etc., For example, tin plate, or chemical conversion treatment products such as zinc phosphate and chromate.

As far as the method of producing the laminate of the present invention is concerned, the following method is suitable: the adhesive containing the polyester resin composition of the present invention is applied between the film layer and the metal layer, followed by heat sealing and roller bonding , Heat pressure bonding and other conventionally known methods to remove the solvent and make it adhere.

(Example)

The following examples illustrate the present invention in detail.

The measurement and evaluation methods of each characteristic value in the examples are carried out in the following manner.

(1) Composition of polyester resin

¹ H-NMR was measured with an ECZ400R type NMR apparatus manufactured by JEOL Ltd., and it was determined from the peak integral intensity ratio of the protons of each copolymer component in the obtained graph.

(2) Inherent logarithmic viscosity of polyester resin (η inh)

Use Ubbelohde’s viscosity tube, and use a mixture of phenol/1,1,2,2-tetrachloroethane=50/50 (mass ratio) as the solvent. The relative viscosity (η rel) is calculated by the following formula, and the unit is expressed as dl/g.

Inherent logarithmic viscosity (η inh)=ln(η rel)/c

Hrel: relative viscosity, c: concentration (g/dl)

(3) Acid value of polyester resin

烷，以甲酚紅(cresol red)作為指示劑並以0.1N-KOH進行滴定。使用該滴定得到的值，將中和時消粍之KOH的mg數換算成每1g的聚酯樹脂，而求出酸值。 According to JIS K-0070, 0.5g of the sample is dissolved in 25ml of

The alkane was titrated with cresol red as an indicator and 0.1N-KOH. Using the value obtained by this titration, the number of mg of KOH in the neutralization was converted into 1 g of the polyester resin to obtain the acid value.

(4) Hydroxyl value of polyester resin

According to JIS K-0070, 3g of the sample was heated and refluxed and dissolved in 50ml of pyridine, acetic anhydride was used as the acetylation solution, cresol red-thymol blue was used as the indicator, and 0.5N potassium hydroxide The methanol solution is titrated. Using the value obtained by this titration, the number of mg of KOH required for the neutralization of the acetic acid bound to the hydroxyl group was converted into 1 g of the polyester resin to obtain the hydroxyl value.

(5) Glass transition temperature (Tg), melting point (Tm)

A differential scanning calorimeter (Diamond DSC) manufactured by Perkin Elmer was used for the measurement at a temperature increase rate of 20°C/min.

(6) Solution stability

The solution viscosity of the resulting adhesive was measured with a B-type rotary viscometer, and the stability was evaluated by changes over time. The viscosity of the solution of the adhesive after being left to stand for 1 hour after preparation was set as the viscosity 1 immediately after dissolution. Then, the adhesive was sealed and stored at 23° C. for 24 hours, and the viscosity of the adhesive solution 2 was measured with a B-type rotary viscometer in the same manner. The ratio of viscosity 2 to viscosity 1 immediately after dissolution was evaluated in two stages according to the following criteria.

○: Viscosity 2 is 1.0 times or more and less than 1.3 times of viscosity 1

×: Viscosity 2 is 1.3 times or more of Viscosity 1.

(7) Adhesion to nickel-plated copper (adhesion to wires)

The resulting adhesive was coated (coating thickness 100μm) on a PET film (thickness 30μm), dried at 150°C for 3 minutes, and then treated at 50°C for 72 hours to produce a PET film laminated with a polyester resin composition The laminated body 1 of the adhesive layer with a thickness of 30 μm is constructed.

Using a laminate machine (SA-1010 manufactured by Tester Sangyo), the nickel-plated copper wire (thickness 0.035mm, width 0.3mm, length 150mm) under the conditions of a temperature of 180°C, a line pressure of 40N/cm, and a speed of 1.0m/min Five laminates were attached to the adhesive layer of the obtained laminate 1 at an interval of 1 to 2 mm to obtain a laminate 2 laminated in the order of PET film/adhesive layer/nickel-plated copper wire.

Using the universal testing machine AG-2 manufactured by Shimadzu Corporation, the resulting laminate 2 was tested at a tensile speed of 300 mm/min under an environment of 23° C., and the 180° peeling adhesive force (peeling adhesive force 1) was measured.

(8) Adhesion to nickel-plated copper after salt water spray treatment

The layered body 2 produced in the same manner as in the above (7) was subjected to a salt spray treatment for 72 hours in accordance with the method specified in JIS Z2371, and dried for 24 hours to obtain a layered body 3. With respect to the laminate 3, the 180° peel adhesive force (peel adhesive force 2) was measured in the same manner as in (7).

(9)Retention rate of peeling adhesive force after salt spray treatment

The retention rate of the peeling adhesive force after the salt spray treatment was calculated according to the following formula. In addition, the retention rate of the peeling adhesive force was not calculated for the laminate with the peeling adhesive force 2 of less than 0.01 N/0.3 mm, and it was described as "-" in the table. Retention rate of peeling adhesive force (%)=[(peeling adhesive force 2)/(peeling adhesive force 1)]×100

(10) Adhesion to nickel-plated copper (under high temperature environment (85°C))

Using the universal testing machine AG-2 manufactured by Shimadzu Corporation and in an environment of 85°C, the laminate 2 produced in the same manner as in (7) above was tested at a tensile speed of 300 mm/min, and the 180° peeling adhesion was measured. force.

(11) Adhesion to polyester film

Using a laminator (SA-1010 manufactured by Tester Sangyo), the PET film (thickness 30μm) was laminated on the conditions of a temperature of 180°C, a linear pressure of 40N/cm, and a speed of 1.0m/min in the same manner as in (7) above The adhesive layer of the laminated body 1 produced is laminated in the order of PET film/adhesive layer/PET film to obtain a laminated body 4.

A test piece with a width of 25 mm was prepared from the obtained laminate 4, and the test was performed using the universal testing machine AG-2 manufactured by Shimadzu Corporation at a tensile speed of 50 mm/min under an environment of 23° C., and the T-type peeling adhesive force was measured. . In addition, in the peeling test, the test piece exhibiting material destruction was judged as a pass.

As the raw material of the polyester resin composition, the following were used.

〔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, and triethylene were added to the esterification reactor. 42.0 parts by mass of alcohol and 0.12 parts by mass of Irganox 1010 (manufactured by BASF Corporation) were subjected to esterification reaction at a temperature of 215°C for 4 hours. After transferring the obtained esterified product to the polycondensation reaction tank, 0.03 parts by mass of tetrabutyl titanate (Tetrabutyl titanate) was added as a heavy condensation catalyst. Then, the pressure in the reaction system was gradually reduced to 0.4 hPa within 90 minutes, and the polycondensation reaction was carried out at 245°C for 7 hours to obtain a polyester resin (A-1) having a glass transition temperature of -5°C and a melting point of 140°C. ).

[Synthesis of polyester resins (A-2) to (A-17)]

The polyester resin was obtained by the same method as the polyester resin (A-1) except that the amount of the components added to the esterification reactor was changed so as to be the polyester resin of the composition shown in Table 1.

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

〔Silicane 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-isocyanate propyltriethoxysilane (KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd.)

〔Isocyanate compound〕

C-1: Polyisocyanate body of hexamethylene diisocyanate (TPA-100 manufactured by Asahi Kasei Corporation)

C-2: 4,4-Diphenylmethane diisocyanate (manufactured by Kanto Chemical Co., Ltd.)

C-3: 2,4-/2,6-toluene diisocyanate [80/20 mixture] (Coronate T-80 manufactured by Tosoh)

C-4: Ginseng (phenyl isocyanate) phosphorothioate (Desmodur RFE manufactured by Covestro)

Flame retardant: bis(pentabromophenyl)ethane (SAYTEX8010 manufactured by Albemarle)

Flame retardant additives: Antimony trioxide (manufactured by Yamanaka Sangyo Co., Ltd.)

Pigment: Titanium oxide (manufactured by Fuji Titanium Industry Co., Ltd.)

Filler: Silicon oxide (Aerosil R972 manufactured by Japan Aerosil Corporation)

Example 1

Add 20 parts by mass of polyester resin (A-1), 48 parts by mass of dichloromethane, 9.6 parts by mass of toluene, and 2.4 parts by mass of methyl ethyl ketone into a 100 mL glass bottle containing glass beads with a diameter of 2 mm, After being sealed with a metal cap, it was completely dissolved at 23°C for 1 hour using a high-speed ball mill (Rocking Mill RM-50) manufactured by Seiwa Giken.

Next, add 10 parts by mass of bis(pentabromophenyl)ethane as a flame retardant, 7.2 parts by mass of antimony trioxide as a flame retardant auxiliary, and 2 parts by mass of titanium oxide as a pigment to 80 parts by mass of the above solution. And 0.8 parts by mass of silica as a filler, and disperse it with the same ball mill at 23°C for 1 hour.

In addition, 0.2 parts by mass of silane coupling agent (B-1) and 0.62 parts by mass of isocyanate compound (C-1) were added to the above solution, and the same ball mill was used to stir and mix at 23° C. for 30 minutes to obtain a polyester-containing resin , Silicone coupling agent and isocyanate compound polyester resin composition solution adhesive.

Examples 2 to 29, Comparative Examples 1 to 14

Except that the type of polyester resin, the type of silane coupling agent, the type of isocyanate compound, and the parts by mass relative to 100 parts by mass of the polyester resin, and the parts by mass of the flame retardant and filler are changed to those shown in Tables 2 to 3. Otherwise, in the same manner as in Example 1, a solution adhesive of the polyester resin composition was produced.

The compositions and evaluation results of the polyester resin compositions obtained in Examples 1 to 29 and Comparative Examples 1 to 14 are shown in Tables 2 to 3.

From the results in Tables 2 to 3, it can be seen that the adhesives using the polyester resin compositions obtained in Examples 1 to 29 have excellent adhesion to metals, and have a high adhesion retention rate after the salt spray treatment is applied. Excellent salt water resistance.

On the other hand, in the polyester resin compositions of Comparative Examples 1 to 3, since the content of the silane coupling agent is less than 0.1 parts by mass relative to 100 parts by mass of the polyester resin, the resulting adhesive has poor adhesion to metals, and The adhesion retention rate after the salt spray treatment is poor. In the polyester resin composition of Comparative Example 4, the content of the silane coupling agent was more than 5 parts by mass relative to 100 parts by mass of the polyester resin. Therefore, the resulting adhesive had poor adhesion to metals and poor solution stability.

In the polyester resin composition of Comparative Example 5, the content of the isocyanate compound is less than 1 part by mass relative to 100 parts by mass of the polyester resin. Therefore, the resulting adhesive is insufficiently hardened, has low adhesive force in a high-temperature environment, and has poor heat resistance. , The adhesion to metal is poor. The polyester resin compositions of Comparative Examples 6 to 7 had an isocyanate compound content of more than 5 parts by mass relative to 100 parts by mass of the polyester resin, which resulted in gelation. Therefore, the fluidity during lamination was reduced and the adhesion to metal Poor power.

In the polyester resin composition of Comparative Example 8, since the glass transition temperature of the resin did not reach -20°C, the resulting adhesive had a low elastic modulus at room temperature and poor adhesion to metals. In the polyester resin composition of Comparative Example 9, since the glass transition temperature of the resin exceeds 30°C, its elastic modulus at room temperature becomes high, and its adhesion to metals is poor.

The polyester resin composition of Comparative Example 10 does not have the melting point of the resin and exhibits amorphousness, and the polyester resin composition of Comparative Example 11 has a resin melting point of less than 110°C. Therefore, the resulting adhesive is exposed to a high temperature environment. The lower adhesive force is low and the heat resistance is poor.

In the polyester resin compositions of Comparative Examples 12 to 14, the melting points of these resins were all too high. Therefore, in Comparative Example 12, the fluidity of the resin during lamination was reduced and the adhesive force was poor. In Comparative Examples 13 to 14, , Is not dissolved in the solvent, and the adhesive cannot be obtained.

Claims (5)

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