WO2014141984A1 - Solvent-soluble elastic resin composition - Google Patents

Abstract

Provided is a resin composition which is soluble in solvents and can keep adhesion properties thereof in a wide temperature range. A solvent-soluble elastic resin composition comprising a crystalline polyether segment (a) and an amorphous polyester segment (b), said solvent-soluble elastic resin composition being characterized in that the storage modulus (E'20) at 20˚C is 800 to 2000 MPa, the storage modulus (E'80) at 80˚C is 0.5 to 2.5 MPa, and the ratio of the storage modulus at 80˚C to the storage modulus at 20˚C (i.e., E'80/E'20) is 0.025 to 0.25% as measured at a frequency of 10 Hz.

Description

Solvent-soluble elastic resin composition

The present invention relates to an elastic resin composition that is soluble in a solvent and can retain adhesive properties in a wide temperature range.

In order to achieve the purpose of use, the material used for sealing electrical and electronic parts must have electrical insulation from the outside, and it is necessary to follow the shape of the electrical and electronic parts reliably and not to cause peeling. Is done. In addition, when subjected to repeated bending in a high heat environment such as a circuit portion incorporated in a steering part of an automobile, adhesive characteristics in a wide temperature range are required to achieve the purpose of use.

Polyester with high electrical insulation and water resistance is considered to be a very useful material for this application, but solvent-soluble amorphous resins generally used as adhesives have low elasticity and tend not to withstand repeated bending. there were. On the other hand, Patent Document 1 discloses an elastic resin composition composed of a polyether segment and a crystalline polyester segment. By copolymerizing a polyether glycol having a high molecular weight, conditions such as electrical insulation are disclosed. It is disclosed that high elasticity can be maintained while satisfying the above. With this resin composition, a good molded product can be obtained, and the polyester resin composition can be applied to general electric and electronic parts.

Japanese Patent No. 3553559

However, since the resin composition disclosed in Patent Document 1 is crystalline, the stability after dissolving the solvent is poor, and the processing method is limited. An object of the present invention is to solve the above-mentioned problems, and is an elastic resin composition (hereinafter simply referred to as “resin composition”) that has good solvent solubility and can maintain adhesive properties in a wide temperature range. .) To provide.

In order to achieve the above object, the present inventors have intensively studied and have come up with the following inventions. That is, the present invention is an elastic resin composition having solvent solubility shown below and capable of maintaining adhesive properties in a wide temperature range.

A solvent-soluble elastic resin composition containing a crystalline polyether segment (a) and an amorphous polyester segment (b),
The storage elastic modulus (E'20) at 20 ° C. when measured at a frequency of 10 Hz is 800 to 2000 MPa,
The storage elastic modulus (E'80) at 80 ° C. is 0.5 to 2.5 MPa,
And the ratio of the storage elastic modulus at 80 ° C. to the storage elastic modulus at 20 ° C. (E′80 / E′20) is in the range of 0.025% to 0.25%. Composition.

Furthermore, it is preferable to contain 0.05 to 5 parts by weight of an antioxidant (c) containing phenolic O atoms in the molecule with respect to 100 parts by weight of the solvent-soluble elastic resin composition.

（Ｒ₁、Ｒ₂はそれぞれ独立に炭素数１～４の直鎖または分岐を有しても良いアルキル基、または水素である。Ｒ₃は炭素数１～４のアルキレン基である。Ｒ₄は炭素数５～１０の直鎖または分岐を有しても良いアルキル基である。ｎは１～４の整数を表す。）
一般式（２）；

（Ｒ_５、Ｒ_６はそれぞれ独立に炭素数１～４の直鎖または分岐を有しても良いアルキル基、または水素である。Ｒ_７は炭素数１～４のアルキレン基である。Ｒ_８、Ｒ_９はそれぞれ独立に炭素数５～１０の直鎖または分岐を有しても良いアルキル基である。） Further, the antioxidant (c) containing the phenolic O atom in the molecule is a compound (c1) represented by the general formula (1) and / or a compound (c2) represented by the general formula (2). Preferably there is.
General formula (1);

(R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 4 carbon atoms or hydrogen. R ₃ is an alkylene group having 1 to 4 carbon atoms. R ₄ Is a linear or branched alkyl group having 5 to 10 carbon atoms, n represents an integer of 1 to 4.)
General formula (2);

(R ₅ and R ₆ are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, or hydrogen. R ₇ is an alkylene group having 1 to 4 carbon atoms. R ₈ And R ₉ are each independently an alkyl group having 5 to 10 carbon atoms which may be linear or branched.)

An adhesive composition containing the solvent-soluble elastic resin composition according to any one of the above.

The solvent-soluble elastic resin composition (hereinafter also simply referred to as “resin composition”) according to the present invention has good solvent solubility, excellent solution stability, and a wide range from room temperature (about 20 ° C.) to 80 ° C. Maintains adhesiveness and adhesive heat resistance in the temperature range.

Hereinafter, the present invention will be described in detail.

<Crystalline polyether segment (a)>
The crystalline polyether segment (a) used in the present invention is not particularly limited, but is preferably mainly crystalline polyalkylene glycol. It is preferable in terms of heat resistance because it is crystalline. Specific examples include polyethylene glycol (hereinafter also referred to as PEG), polytrimethylene glycol (hereinafter also referred to as PPG), polytetramethylene glycol (hereinafter also referred to as PTMG), and the like. It is not limited. Among these, PTMG is preferable from the viewpoint of heat resistance.

The number average molecular weight of the crystalline polyether segment (a) is preferably 230 or more, more preferably 400 or more, and further preferably 800 or more. When the number average molecular weight of the crystalline polyether segment (a) is less than 230, there is a tendency that the resin composition cannot be given flexibility and problems such as inflexibility cannot be exhibited. The number average molecular weight of the crystalline polyether segment (a) is preferably 5000 or less, more preferably 4000 or less, and further preferably 3000 or less. When the number average molecular weight exceeds 5,000, the compatibility with other copolymerization components is poor, and problems such as inability to copolymerize tend to occur.

In the present invention, the term “crystallinity” means that the temperature is raised from −100 ° C. to 300 ° C. at 20 ° C./min using a differential scanning calorimeter (DSC) and shows a clear melting peak in the temperature raising process. .

<Amorphous polyester segment (b)>
The amorphous polyester segment (b) is preferably a polyester obtained by polymerizing an acid component and a glycol component, and is preferably amorphous in terms of solvent solubility. Amorphous means that the temperature is raised from −100 ° C. to 300 ° C. at 20 ° C./min using a differential scanning calorimeter (DSC) and does not show a clear melting peak in the temperature raising process.

The acid component constituting the amorphous polyester segment (b) used in the present invention is not particularly limited, but an aromatic dicarboxylic acid is preferable. The aromatic dicarboxylic acid preferably has 8 to 14 carbon atoms, more preferably 9 to 13 carbon atoms. The aromatic dicarboxylic acid is preferably contained in an amount of 50 mol% or more when the total acid component of the resin composition is 100 mol% in order to improve the elasticity of the resin composition, more preferably 60 mol% or more. It is more preferably at least mol%, particularly preferably at least 95 mol%, and may be 100 mol%. Specific examples of the aromatic dicarboxylic acid include, but are not particularly limited to, one or more acids selected from the group consisting of terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, which have good reactivity with the glycol component, and polymerization. In terms of productivity and productivity. The total of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid is preferably 50 mol% or more, more preferably 60 mol% or more, and more preferably 80 mol% or more in the total acid component of the resin composition. More preferably, it is 95 mol% or more, and the total acid component may be composed of one or more acids selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid. As long as it is naphthalenedicarboxylic acid, any of 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid may be used. Of these, 2,6-naphthalenedicarboxylic acid is preferred.

Other acid components constituting the amorphous polyester segment (b) include diphenyl dicarboxylic acid, aromatic dicarboxylic acid such as 5-sodium sulfisophthalic acid, cyclohexane dicarboxylic acid, and alicyclic dicarboxylic acid such as tetrahydrophthalic anhydride. And dicarboxylic acids such as aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid and hydrogenated dimer acid. The copolymerization ratio of these dicarboxylic acid components is preferably less than 50 mol%, more preferably less than 40 mol%, still more preferably less than 20 mol%, and more preferably 5 mol% when the total acid component of the resin composition is 100 mol%. Less than is particularly preferable, and it may be 0 mol%. Further, as the other acid component constituting the amorphous polyester segment (b), it is possible to use a tri- or higher functional polycarboxylic acid such as trimellitic acid or pyromellitic acid. The copolymerization ratio of the trifunctional or higher polycarboxylic acid is preferably 10 mol% or less, and more preferably 5 mol% or less from the viewpoint of preventing gelation of the resin composition.

The glycol component constituting the amorphous polyester segment (b) used in the present invention is not particularly limited, but is preferably an aliphatic glycol and / or an alicyclic glycol, and in particular, a branched aliphatic glycol and / or a branched fat. A cyclic glycol is more preferred. The number of carbon atoms of the branched aliphatic glycol and / or the branched alicyclic glycol is 4 or more, more preferably 5 or more, still more preferably 6 or more, preferably 20 or less, more preferably It is 15 or less, more preferably 10 or less, and particularly preferably 8 or less. The glycol component is preferably 20 mol% or more, more preferably 25 mol% or more, still more preferably 30 mol% or more, and more preferably 40 mol% or more when the total glycol component of the resin composition is 100 mol%. Particularly preferred. Moreover, it is preferable that it is 99 mol% or less, 97 mol% or less is more preferable, and 95 mol% or less is further more preferable. If it is less than 20 mol%, the solvent solubility may be insufficient, and if it exceeds 99 mol%, the amount of crystalline polyether segment (a) will be insufficient, so the storage elastic modulus at 20 ° C. (E'20) exceeds 2000 MPa, and the storage elasticity may be too high, resulting in a decrease in adhesion.

Here, the branched aliphatic glycol is an aliphatic glycol having a side chain group having 1 or more carbon atoms in a linear hydrocarbon, and the branched alicyclic glycol is a cyclic carbon of an alicyclic hydrocarbon. Is an alicyclic glycol having a side chain group having 1 or more carbon atoms. Specifically, although not particularly limited, examples of the branched aliphatic glycol include neopentyl glycol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3 -Butanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,2-dimethyl-3-hydroxy Propyl-2 ′, 2′-dimethyl-3-hydroxypropanoate, 2-normalbutyl-2-ethyl-1,3-propanediol, 3-ethyl-1,5-pentanediol, 3-propyl-1,5 -Pentanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 3-octyl-1,5- Nthanediol, 3-phenyl-1,5-pentanediol, 2,5-dimethyl-3-sodium sulfo-2,5-hexanediol and the like. Examples of branched alicyclic glycols include 1,3-bis (Hydroxymethyl) cyclohexane, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxyethyl) cyclohexane, 1,4-bis (hydroxypropyl) cyclohexane, 1,4-bis (hydroxymethoxy) cyclohexane, 1,4-bis (hydroxyethoxy) cyclohexane, 2,2-bis (4-hydroxymethoxycyclohexyl) propane, 2,2-bis (4-hydroxyethoxycyclohexyl) propane, bis (4-hydroxycyclohexyl) methane, 2, 2-bis (4-hydroxycyclohex Sil) propane, 3 (4), 8 (9) -tricyclo [5.2.1.0 ² , ⁶ ] decandimethanol, hydrogenated bisphenol A, ethylene oxide adduct of hydrogenated bisphenol A, hydrogenated bisphenol A These propylene oxide adducts can be used, and these can be used alone or in combination of two or more. Among these, neopentyl glycol is most preferable in terms of improving the solvent solubility of the composition.

The content of the short-chain glycol having 3 or less carbon atoms is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less, when the total glycol component of the resin composition is 100 mol%. 40 mol% or less is particularly preferable. If the amount is too large, the compatibility with the crystalline polyether segment (a) tends to be poor, and the polymerizability tends to deteriorate. Specific examples of the short-chain glycol having 3 or less carbon atoms include, but are not limited to, ethylene glycol, 1,2-propylene glycol, or 1,3-propylene glycol.

Also, linear glycol components having 4 or more carbon atoms can be used. The blending amount of the linear glycol is preferably 20 mol% or less, more preferably 10 mol% or less, further preferably 5 mol% or less, and may be 0 mol%. When there are too many linear glycols, there exists a tendency for a polyester segment (b) to become crystallinity, and solvent solubility may fall.

Further, as a part of the glycol component, a tri- or higher functional polyol such as glycerin, trimethylolpropane, pentaerythritol, etc. may be used, and the content is made 10 mol% or less from the viewpoint of preventing gelation of the resin composition. Preferably, it is more preferably 5 mol% or less. If the amount is too large, the resin composition may be gelled.

<Solvent-soluble elastic resin composition>
The solvent-soluble elastic resin composition according to the present invention contains the crystalline polyether segment (a) and the amorphous polyester segment (b), and has a storage elastic modulus at 20 ° C. (measured at a frequency of 10 Hz). E'20) is 800 to 2000 MPa, storage elastic modulus at 80 ° C. (E′80) is 0.5 to 2.5 MPa, and storage elastic modulus at 80 ° C. relative to storage elastic modulus at 20 ° C. (E'80 / E'20) is a resin composition in the range of 0.025% to 0.25%.

The resin composition of the present invention needs to contain a crystalline polyether segment (a) and an amorphous polyester segment (b). The crystalline polyether segment (a) and the amorphous polyester segment (b) Is preferably copolymerized. Further, the resin composition is preferably amorphous. By making the resin composition amorphous, it is possible to maintain adhesive properties over a wide range of temperatures while maintaining stability after dissolving the solvent. Amorphous means that the temperature is raised from −100 ° C. to 300 ° C. at 20 ° C./min using a differential scanning calorimeter (DSC) and does not show a clear melting peak in the temperature raising process.

The content of the crystalline polyether segment (a) in the resin composition of the present invention is preferably 1 mol% or more, preferably 3 mol% or more when the total glycol component of the resin composition is 100 mol%. More preferably, it is 5 mol% or more. Moreover, 80 mol% or less is preferable, 75 mol% or less is more preferable, 70 mol% or less is more preferable, 60 mol% or less is especially preferable. When the content of the crystalline polyether segment (a) is less than 1 mol%, the storage elastic modulus (E′20) at 20 ° C. exceeds 2000 MPa, and sufficient storage elasticity may not be obtained. On the other hand, if it exceeds 80 mol%, the storage elastic modulus (E′80) at 80 ° C. becomes less than 0.5 MPa, and sufficient storage elasticity may not be obtained.

The resin composition of the present invention needs to have a storage elastic modulus (E′20) at 20 ° C. of 800 to 2000 MPa. Preferably it is 900 MPa or more, More preferably, it is 1000 MPa or more, More preferably, it is 1100 MPa or more. Moreover, 1900 MPa or less is preferable, 1800 MPa or less is more preferable, and 1700 MPa or less is more preferable. By satisfying the above range, excellent adhesiveness at 20 ° C. can be exhibited.

The resin composition of the present invention is required to have a storage elastic modulus (E′80) at 80 ° C. of 0.5 to 2.5 MPa. Preferably it is 0.8 MPa or more, More preferably, it is 1.0 MPa or more, More preferably, it is 1.5 MPa or more. Moreover, 2.4 MPa or less is preferable, 2.2 MPa or less is more preferable, and 2.0 MPa or less is more preferable. By satisfying the above range, excellent adhesive heat resistance at 80 ° C. can be exhibited.

In the resin composition of the present invention, the ratio of the storage elastic modulus at 80 ° C. to the storage elastic modulus at 20 ° C. (E′80 / E′20) is in the range of 0.025% to 0.25%. is necessary. Preferably it is 0.03% or more, More preferably, it is 0.05% or more, More preferably, it is 0.1% or more. Moreover, less than 0.25% is preferable, 0.24% or less is more preferable, and 0.23% or less is more preferable. By satisfying the above range, excellent adhesiveness and adhesive heat resistance can be stably expressed in a wide temperature range from 20 ° C to 80 ° C.

The storage elastic modulus of the resin composition of the present invention is measured by the following method. That is, the resin composition is placed on a heat press adjusted to about 200 ° C. via a polyimide film. Hold for about 20 seconds at a pressure of about ² N / mm ² to obtain a sheet sample of about 1 mm thickness. This is cut into a length of about 15 mm (excluding the grip allowance) and a width of about 4 mm, set in a dynamic viscoelasticity measuring device “DVA-200” manufactured by IT Measurement Control Co., Ltd., and measured in a tensile mode. . The measurement condition is that the frequency is fixed at 10 Hz, and scanning is performed from −100 ° C. until the measurement becomes impossible (maximum 250 ° C.) at a heating rate of 4 ° C./min.

Satisfactory solvent solubility and excellent solution stability by satisfying the above blending amount and storage elastic modulus, and good followability to a substrate in a wide temperature range from room temperature (about 20 ° C.) to 80 ° C. It is possible to maintain adhesiveness and adhesive heat resistance.

The lower limit of the number average molecular weight of the resin composition of the present invention is not particularly limited, but is preferably 3,000 or more, more preferably 5,000 or more, and further preferably 7,000 or more. The upper limit of the number average molecular weight is not particularly limited, but is preferably 50,000 or less, more preferably 40,000 or less, and still more preferably 30,000 or less. If the number average molecular weight is less than 3,000, elasticity may be insufficient, and if the number average molecular weight exceeds 50,000, the solvent solubility of the resin composition may be lowered.

The lower limit of the reduced viscosity of the resin composition of the present invention is preferably 0.6 dl / g or more, more preferably 0.7 dl / g or more, and further preferably 0.8 dl / g or more. The upper limit of the reduced viscosity is not particularly limited, but is preferably 1.5 dl / g or less, more preferably 1.4 dl / g or less, and further preferably 1.3 dl / g or less. If the reduced viscosity is less than 0.6 dl / g, the elasticity may be insufficient, and if the reduced viscosity exceeds 1.5 dl / g, the solvent solubility of the resin composition may be lowered.

The resin composition of the present invention exhibits good solubility in a solvent. Examples of the solvent include aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ketone solvents, ether solvents, and aprotic polar solvents. Specifically, acetone, methyl ethyl ketone (hereinafter, also referred to as “MEK”), toluene, xylene, hexane, heptane, cyclohexane, methylcyclohexane, tetrahydrofuran, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, Solvesso 100 , Solvesso 150, Solvesso 200 and the like, but are not limited thereto. These solvents can be used alone or in combination of two or more. The solubility in these solvents is preferably 20% by weight or more at 25 ° C., more preferably 25% by weight or more, and further preferably 30% by weight or more. Since the solvent solubility is excellent, the processability when an adhesive composition is obtained is improved.

The resin composition of the present invention is stable enough to maintain fluidity even after being stored at 25 ° C. for 8 hours after being dissolved in the solvent so as to be 30% by weight. The resin composition has good adhesive properties at room temperature (about 20 ° C.) and 80 ° C.

The carboxyl group concentration of the resin composition of the present invention is preferably 5 to 60 equivalent / t, more preferably 10 to 55 equivalent / t, and further preferably 15 to 50 equivalent / t. When it is less than 5 equivalents / t, the adhesiveness is lowered, and when it exceeds 60 equivalents / t, the heat resistance may be lowered.

As a method for producing the resin composition of the present invention, a known method can be used. For example, an esterification reaction of a crystalline polyether segment (a) and an amorphous polyester segment (b) at 150 to 250 ° C. Thereafter, a polycondensation reaction is carried out at 230 to 300 ° C. under reduced pressure to obtain a solvent-soluble elastic resin composition. Although it does not specifically limit as a metal catalyst, Ti atom is preferable from a polymeric viewpoint, and specifically, tetrabutyl titanate is especially preferable from a polymeric viewpoint. The amount of the catalyst is not particularly limited, but is preferably 200 ppm to 1000 ppm. If it exceeds 1000 ppm, the environmental resistance may deteriorate.

The resin composition of the present invention may be copolymerized with a tri- or higher functional polycarboxylic acid such as trimellitic anhydride or trimethylolpropane or a polyol, if necessary.

Examples of the method for determining the composition and composition ratio of the resin composition include ¹ H-NMR and ¹³ C-NMR in which a polyester resin is dissolved in a solvent such as deuterated chloroform, and gas chromatography that is measured after methanolysis of the polyester resin. (Hereinafter sometimes abbreviated as methanolysis-GC method). In the present invention, the composition and composition ratio are determined by ¹ H-NMR.

<Antioxidant (c) containing phenolic O atom in molecule>
The antioxidant (c) (hereinafter also simply referred to as “antioxidant (c)”) containing a phenolic O atom in the molecule used in the resin composition of the present invention is an antioxidant having phenol as a basic skeleton. Preferably there is. Specific examples include hindered phenol compounds represented by the following general formula (1) and the following general formula (2). The antioxidant (c) has a function of preventing the crystalline polyether segment (a) from being decomposed by being depolymerized by the catalyst Ti atom and decreasing in elasticity. Therefore, it is particularly effective to use it during the polymerization of the resin composition. Furthermore, it also has an effect of preventing the adhesive force from being reduced due to a decrease in molecular weight when the resin composition is used for a long time in a high temperature environment.

The content of the antioxidant (c) is preferably 0.05 to 5 parts by weight, more preferably 0.08 to 4.5 parts by weight, even more preferably 100 parts by weight of the resin composition. 0.1 to 4 parts by weight. If it is less than 0.05 part by weight, the antioxidant effect cannot be sufficiently exhibited, and if it exceeds 5 parts by weight, it may bleed out from the resin and adversely affect the adhesion.

　Ｒ₁、Ｒ₂はそれぞれ独立に直鎖または分岐を有しても良いアルキル基、または水素であり、アルキル基の好ましい炭素数は１～４であり、より好ましくは２～３である。Ｒ₃はアルキレン基であり、好ましい炭素数は１～４であり、より好ましくは２～３である。Ｒ₄は直鎖または分岐を有しても良いアルキル基であり、好ましい炭素数は５～１０であり、より好ましくは６～９であり、さらに好ましくは７～８である。ｎは１～４の整数である。 <(C1) component>
The component (c1) is preferably a hindered phenol compound represented by the general formula (1).
General formula (1);

R ₁ and R ₂ are each independently an alkyl group which may be linear or branched, or hydrogen, and the alkyl group preferably has 1 to 4 carbon atoms, more preferably 2 to 3 carbon atoms. R ₃ is an alkylene group, preferably having 1 to 4 carbon atoms, more preferably 2 to 3 carbon atoms. R ₄ is an alkyl group which may be linear or branched, and preferably has 5 to 10 carbon atoms, more preferably 6 to 9 carbon atoms, and even more preferably 7 to 8 carbon atoms. n is an integer of 1 to 4.

Specifically, the component (c1) is thiodiethylene bis [3- (3,5-di-tert-butyl 4-hydroxyphenyl) propionate], octadecyl [3- (3,5-di-tert-butyl 4-hydroxy Phenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], 1,3,5-trimethyl-2, 4,6-tris (3,5-di-tert-butyl-4-hydroxy) benzene, 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ], Triethylene glycol-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 3,3′-thiobi Propionic acid dioctadecyl ester, 2,5,7,8-tetramethyl- (4 ′, 8 ′, 12′-trimethyltridecyl) chroman-6-ol, stearyl-β- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate, 3,9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylfienyl) propionyloxy] ethyl] 2, Examples include, but are not limited to, 4,8,10-tetraoxaspiro (5,5) -undecane.

　Ｒ_５、Ｒ_６はそれぞれ独立に直鎖または分岐を有しても良いアルキル基、または水素であり、アルキル基の好ましい炭素数は１～４であり、より好ましくは２～３である。Ｒ_７はアルキレン基であり、好ましい炭素数は１～４であり、より好ましくは２～３である。Ｒ_８、Ｒ_９はそれぞれ独立に直鎖または分岐を有しても良いアルキル基であり、好ましい炭素数は５～１０であり、より好ましくは６～９であり、さらに好ましくは７～８である。 <(C2) component>
The component (c2) is preferably a hindered phenol compound represented by the general formula (2).
General formula (2);

R ₅ and R ₆ are each independently an alkyl group which may have a straight chain or a branch, or hydrogen, and the alkyl group preferably has 1 to 4 carbon atoms, more preferably 2 to 3 carbon atoms. R ₇ is an alkylene group, preferably having 1 to 4 carbon atoms, more preferably 2 to 3 carbon atoms. R ₈ and R ₉ are each independently an alkyl group which may be linear or branched, and preferably has 5 to 10 carbon atoms, more preferably 6 to 9 carbon atoms, still more preferably 7 to 8 carbon atoms. is there.

Specifically, the component (c2) is tributyl phosphate, tris (2,4-di-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, cyclic neopentanetetraylbis (2,6-di-). tert-butyl-4-methylphenyl) phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-) tert-butylphenyl) pentaerythritol phosphite, bis (2,6-di-tert-butyl-4-methyl-phenyl) pentaerythritol phosphite, 2,2-methylene-bis (4,6-di-tert-butyl) Phenyl) octyl phosphite, tetrakis ( 2,4-di-tert-butylphenyl) -4,4′-biphenylene-diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylene-diphosphonite, etc. However, it is not limited to these.

Only one or more of the antioxidants (c1) can be used, and only one or more of the antioxidants (c2) can be used. Furthermore, antioxidant (c1) and antioxidant (c2) can also be used together.

<Adhesive composition>
The adhesive composition of this invention is a composition which contains the said resin composition and has a resin composition as a main component. The main component means that the resin composition contains 50% by weight or more in the adhesive composition, preferably 60% by weight or more, and more preferably 70% by weight or more. If the amount is too small, good adhesiveness and adhesive heat resistance may not be exhibited. As other components, the components described later can be blended.

<Other components>
In the adhesive composition of the present invention, components other than the resin composition can be blended for the purpose of improving adhesion, flexibility, durability and the like within a range not impairing the effects of the present invention. Specific examples include, but are not limited to, polyesters, polyamides, polyolefins, epoxies, polycarbonates, acrylics, ethylene vinyl acetate, phenols and other resins, isocyanate compounds and curing agents such as melamine, fillers such as talc and mica, carbon black, Examples thereof include pigments such as titanium oxide, antimony trioxide, and brominated polystyrene. The content of these components is preferably 50% by weight or less in the adhesive composition, more preferably 40% by weight or less, and still more preferably 30% by weight or less. If the content exceeds 50% by weight, adhesion to electric / electronic parts and adhesion heat resistance may be reduced.

In order to describe the present invention in more detail, examples and comparative examples are given below, but the present invention is not limited to the examples. In addition, each measured value described in the Example and the comparative example was measured by the following method.

<Polyester composition>
The composition and composition ratio of the polyester were determined by ¹ H-NMR measurement (proton nuclear magnetic resonance spectroscopy) at a resonance frequency of 400 MHz. The measuring apparatus was an NMR apparatus 400-MR manufactured by VARIAN, and deuterated chloroform was used as a solvent.

<Storage modulus>
A sample of the resin composition was placed on a heat press adjusted to 200 ° C. via a polyimide film (“Kapton (registered trademark)” manufactured by Toray DuPont) and held at a pressure of ² N / mm ² for 20 seconds to hold 1 mm. A sheet sample of thickness was obtained. This was cut into a length of 15 mm (excluding the gripping allowance) and a width of 4 mm, and a sample was set in a dynamic viscoelasticity measuring device “DVA-200” manufactured by IT Measurement Control Co., Ltd., and measured in a tensile mode. The measurement condition was a scan from −100 ° C. until measurement became impossible (maximum 250 ° C.) at a heating rate of 4 ° C./min with the frequency fixed at 10 Hz.

<Solvent solubility test>
When the resin composition is dissolved in a solution of MEK / toluene = 1/4 (weight ratio) (solid content concentration = 30% by weight) and completely dissolved visually, “◯”, insoluble matter remains. “×”.

<Solution stability test>
The solution of the resin composition was allowed to stand at room temperature (about 25 ° C.) for 1 day. After standing still for one day, it was gently tilted, and “○” was indicated when fluidity was visually observed, and “X” when fluidity was not observed.

<Adhesion test>
The sample whose solution stability test was “◯” was applied to a PET film, and then dried at 120 ° C. for 7 minutes to prepare a coating film having a thickness of 60 μm. The coating film was adhered to a tin-plated copper foil whose surface was washed well at 160 ° C. and 3 MPa to prepare an adhesion sample A. At room temperature (about 25 ° C.), the adhesive sample A was peeled off at a rate of 100 mm / min, and the adhesive strength was measured.
Evaluation criteria A: Adhesion strength 25 N / 25 mm or more B: Adhesion strength 20 N / 25 mm or more and less than 25 N / 25 mm Δ: Adhesion strength 15 N / 25 mm or more and less than 20 N / 25 mm X: Adhesion strength 15 N / 25 mm or less

<Adhesion heat resistance test>
The adhesive sample A was kept at 80 ° C. for 5 minutes, peeled T-shaped at a speed of 100 mm / min in an environment of 80 ° C., and the adhesive strength was measured.
Evaluation criteria A: Adhesion strength 25 N / 25 mm or more B: Adhesion strength 20 N / 25 mm or more and less than 25 N / 25 mm Δ: Adhesion strength 15 N / 25 mm or more and less than 20 N / 25 mm X: Adhesion strength 15 N / 25 mm or less

<Production Example of Resin Composition>
In a reaction vessel equipped with a stirrer, a thermometer, and a condenser for distillation, 194 parts by weight of terephthalic acid, 194 parts by weight of isophthalic acid, 161 parts by weight of ethylene glycol, 151 parts by weight of neopentyl glycol, tetrabutyl titanate (as Ti atoms) 270 ppm) and an esterification reaction was carried out at 170-220 ° C. for 3 hours. After completion of the esterification reaction, 300 parts by weight of polytetramethylene glycol “PTMG1000” (manufactured by Mitsubishi Chemical Corporation) having a number average molecular weight of 1000 and hindered phenolic antioxidant “Irganox (registered trademark) 1010” (manufactured by Ciba Geigy) Was added to 0.6 parts by weight, and the temperature was raised to 255 ° C., while the pressure in the system was slowly reduced to 665 Pa at 255 ° C. over 60 minutes. Further, a polycondensation reaction was performed at 133 Pa or less for 60 minutes to obtain a resin composition of Example 1. The composition and physical property values of this resin composition are shown in Tables 1 and 2. In addition, the resin compositions of Examples 2 to 10 and Comparative Examples 1 to 5 were synthesized by the same method as in Example 1. The respective compositions and physical property values are shown in Tables 1 and 2.

Abbreviations in the table are as follows.
TPA: terephthalic acid, IPA: isophthalic acid, SA: sebacic acid, NDCA: 2,6-naphthalenedicarboxylic acid, EG: ethylene glycol, NPG: neopentyl glycol, BD: 1,4-butanediol, 2MG: 2-methyl 1,3-propanediol, PTMG1000: polytetramethylene ether glycol 1000, PEG2000: polyethylene glycol 2000, PTXG1000: poly (tetramethylene ether glycol-neopentyl glycol) 1000

　酸化防止剤（ｉｉ）：式（４）で表されるイルガノックス（登録商標）１１３５、チバガイギー社製。
式（４）

　酸化防止剤（ｉｉｉ）：式（５）で表されるイルガノックス（登録商標）２９５、チバガイギー社製。
式（５）

　酸化防止剤（ｉｖ）：式（６）で表されるラスミット（登録商標）ＬＧ、第一工業製薬社製。
式（６）

The following were used as the antioxidant (c).
Antioxidant (i): Irganox (registered trademark) 1010 represented by formula (3), manufactured by Ciba Geigy Corporation.
Formula (3)

Antioxidant (ii): Irganox (registered trademark) 1135 represented by formula (4), manufactured by Ciba Geigy Corporation.
Formula (4)

Antioxidant (iii): Irganox (registered trademark) 295 represented by formula (5), manufactured by Ciba Geigy Corporation.
Formula (5)

Antioxidant (iv): Rasmit (registered trademark) LG represented by formula (6), manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
Formula (6)

<Evaluation of resin composition>
Example 1
The resin composition of Example 1 was subjected to <solvent solubility test>, <solution stability test>, <adhesion test>, and <adhesion heat resistance test>.

Examples 2 to 9
Using the resin compositions of Examples 2 to 9, the same test as in Example 1 was performed. The evaluation results are shown in Table 2.

Comparative Examples 1-5
The same test as in Example 1 was performed using Comparative Examples 1-5. The evaluation results are shown in Table 2.

Examples 1 to 9 satisfied the claims, and all the results of <solvent solubility test>, <solution stability test>, <adhesion test>, and <adhesion heat resistance test> were satisfactory. On the other hand, since the component (b) is a crystalline polyester, the comparative example 1 does not dissolve in the solvent and the <solvent solubility test> is poor. Since the comparative example 2 does not use the antioxidant which contains a phenolic O atom in a molecule | numerator in (c) component, superposition | polymerization becomes bad and <adhesion heat resistance test> is bad. Comparative Example 3 does not contain the component (a), and the <adhesion test> is poor. Comparative Example 4 does not contain the component (a), and since the component (b) is a crystalline polyester, it does not dissolve in the solvent, and the <solvent solubility test> is poor. In Comparative Example 5, since the component (a) is an amorphous polyether, it was dissolved before reaching 80 ° C. during storage elastic modulus measurement, and the storage elastic modulus at 80 ° C. could not be measured. Moreover, <adhesion heat resistance test> is poor.

The resin composition of the present invention has solvent solubility, excellent handling properties, can maintain adhesive properties in a wide temperature range, and is excellent in durability against high temperature environmental loads and high temperature high humidity environmental loads. Accordingly, it is suitable for various applications such as automobiles, communications, computers, home appliances, flexible flat cables, electronic components, switches having a printed circuit board, and sensors.

Claims (4)

A solvent-soluble elastic resin composition containing a crystalline polyether segment (a) and an amorphous polyester segment (b),
The storage elastic modulus (E'20) at 20 ° C. when measured at a frequency of 10 Hz is 800 to 2000 MPa,
The storage elastic modulus (E'80) at 80 ° C. is 0.5 to 2.5 MPa,
And the ratio of the storage elastic modulus at 80 ° C. to the storage elastic modulus at 20 ° C. (E′80 / E′20) is in the range of 0.025% to 0.25%. Composition. The solvent-soluble elasticity according to claim 1, further comprising 0.05 to 5 parts by weight of an antioxidant (c) containing phenolic O atoms in the molecule with respect to 100 parts by weight of the solvent-soluble elastic resin composition. Resin composition. The antioxidant (c) containing the phenolic O atom in the molecule is the compound (c1) represented by the general formula (1) and / or the compound (c2) represented by the general formula (2). The solvent-soluble elastic resin composition according to claim 2.
General formula (1);

(R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 4 carbon atoms or hydrogen. R ₃ is an alkylene group having 1 to 4 carbon atoms. R ₄ Is a linear or branched alkyl group having 5 to 10 carbon atoms, n represents an integer of 1 to 4.)
General formula (2);

(R ₅ and R ₆ are each independently a linear or branched alkyl group having 1 to 4 carbon atoms or hydrogen. R ₇ is an alkylene group having 1 to 4 carbon atoms. R ₈ And R ₉ are each independently an alkyl group having 5 to 10 carbon atoms which may be linear or branched.) An adhesive composition containing the solvent-soluble elastic resin composition according to any one of claims 1 to 3.