TW201439201A - 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 not C is 800 to 2000 MPa, the storage modulus (E'80) at 80 not C is 0.5 to 2.5 MPa, and the ratio of the storage modulus at 80 not C to the storage modulus at 20 not 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 which is solvent-soluble and which maintains the following characteristics over a wide temperature range.

Materials used for encapsulation of electrical and electronic parts must have electrical insulation from the outside in order to achieve their intended use, and must follow the shape of the electrical and electronic parts without peeling. Further, when the circuit portion or the like assembled in the steering portion of the automobile is repeatedly subjected to bending in a high-heat environment, in order to achieve the purpose of use, it is necessary to have a follow-up characteristic in a wide temperature range.

A polyester having high electrical insulating properties and water resistance is considered to be a very useful material for this purpose. However, a solvent-soluble amorphous resin generally used as an adhesive has low elasticity and cannot withstand repeated bending. On the other hand, in Patent Document 1, an elastic resin composition composed of a polyether segment and a crystalline polyester segment has been proposed, which discloses that it is possible to conform to electricity by copolymerizing a polyether diol having a high molecular weight. Insulation and the like are required while maintaining high elasticity. By this resin composition, a good molded product can be obtained, and the application of the polyester resin composition to general electric and electronic parts is also possible. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 3553559

[The problem that the invention wants to solve]

However, the resin composition disclosed in Patent Document 1 has poor stability after solvent dissolution due to its crystallinity, and the processing method is limited. An object of the present invention is to provide an elastic resin composition (hereinafter also referred to simply as "resin composition") which has good solvent solubility and can maintain the following characteristics over a wide temperature range. [The way to solve the problem]

In order to achieve the above object, the inventors of the present invention have made great efforts to discuss the following inventions. That is, the present invention is an elastomer resin composition which is solvent-dissolved and which maintains the following characteristics over a wide temperature range.

A soluble elastic resin composition comprising a crystalline polyether segment (a) and an amorphous polyester segment (b), characterized by: a storage elastic modulus at 20 ° C when measured at a frequency of 10 Hz (E'20) ) is 800~2000MPa, the storage elastic modulus (E'80) at 80 °C is 0.5~2.5MPa, and the storage elastic modulus at 80 °C is proportional to the storage elastic coefficient at 20 °C (E'80/E' 20) is in the range of 0.025% to 0.25%.

Furthermore, it is preferable to contain 0.05 to 5 parts by weight of the antioxidant (c) containing a phenolic oxygen atom in the molecule, based on 100 parts by weight of the solvent-soluble elastic resin composition.

In addition, the antioxidant (c) containing a phenolic oxygen atom in the molecule is preferably a compound (c1) represented by the formula (1) and/or a compound (c2) represented by the formula (2). General formula (1); (R ₁ and R ₂ are each independently a straight chain having a carbon number of 1 to 4 or a branched alkyl group, or hydrogen. R ₃ is an alkylene group having 1 to 4 carbon atoms. R ₄ is a carbon number of 5 The linear chain of ~10 may also have a branched alkyl group. n represents an integer of 1 to 4). General formula (2); (R ₅ and R ₆ are each independently a straight chain having a carbon number of 1 to 4 or a branched alkyl group, or hydrogen. R ₇ is an alkylene group having 1 to 4 carbon atoms. Each of R ₈ and R ₉ Independently, it is a linear chain having a carbon number of 5 to 10 or a branched alkyl group.

An adhesive composition comprising the solvent-soluble elastic resin composition according to any one of the above. [Effects of the Invention]

The solvent-soluble elastic resin composition of the present invention (hereinafter also referred to simply as "resin composition") has good solvent solubility, excellent solution stability, and can be maintained at a wide temperature range from room temperature (about 20 ° C) to 80 ° C. Sex, followed by heat resistance.

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, and is preferably a crystalline polyalkylene glycol. It is preferred in terms of heat resistance by the crystallinity. Specific examples thereof include polyethylene glycol (hereinafter also referred to as PEG), polytrimethylene glycol (hereinafter also referred to as PPG), and polytetramethylene glycol (hereinafter also referred to as PTMG). ), etc., but not limited to these. Among them, PTMG is particularly 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, still more 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 imparted with flexibility, and the bending resistance cannot be exhibited. Further, the number average molecular weight of the crystalline polyether segment (a) is preferably 5,000 or less, more preferably 4,000 or less, still more preferably 3,000 or less. When the number average molecular weight exceeds 5,000, there is a tendency that compatibility with other copolymerization components is poor and copolymerization is impossible.

In the present invention, crystallinity refers to a temperature rise of -100 ° C at 20 ° C / min to 300 ° C using a differential scanning calorimeter (DSC), and a clear melting peak is displayed during the temperature rising process.

<Amorphous polyester segment (b)> The amorphous polyester segment (b) is preferably a polyester obtained by polymerizing an acid component and a diol component, and is solvent-soluble in terms of solubility in a solvent. good. Amorphous means that the temperature is raised from -100 ° C to 20 ° C / min to 300 ° C using a differential scanning calorimeter (DSC), and no clear melting peak is displayed during the temperature rising process.

The acid component constituting the amorphous polyester segment (b) used in the present invention is not particularly limited, and is preferably an aromatic dicarboxylic acid. The carbon number of the aromatic dicarboxylic acid is preferably from 8 to 14, more preferably from 9 to 13. When the total acid component of the resin composition is 100 mol%, and 50 mol% or more of the aromatic dicarboxylic acid is contained, the elasticity of the resin composition can be improved, which is preferable, and more preferably 60 mol% or more. More preferably, it is more than 80% by mole, and the best is more than 95% by mole, even if it is 100% by mole. Specific examples of the aromatic dicarboxylic acid are not particularly limited, and are selected from reactivity of one or more acids and diol components selected from the group consisting of terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid. It is good in terms of polymerizability and productivity. The total of the terephthalic acid, the isophthalic acid, and the naphthalene dicarboxylic acid is preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably 80 mol% or more of all the acid components of the resin composition. More preferably, it is 95% by mole or more, and all of the acid components may be composed of one or more acids selected from the group consisting of terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid. In the case of naphthalene dicarboxylic acid, it may be 1,4-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene. Any of the dicarboxylic acids, particularly 2,6-naphthalenedicarboxylic acid, is preferred.

Examples of the other acid component constituting the amorphous polyester segment (b) include an aromatic dicarboxylic acid such as diphenyldicarboxylic acid or sodium isophthalate-5-sulfonate, and cyclohexane. Alicyclic dicarboxylic acid such as carboxylic acid or tetrahydrophthalic anhydride, succinic acid, glutaric acid, adipic acid, sebacic acid, sebacic acid, dodecanedioic acid, dimer acid, hydrogen dimerization a dicarboxylic acid such as an aliphatic dicarboxylic acid such as an acid. When the total acid component of the resin composition is 100 mol%, the copolymerization ratio of the dicarboxylic acid components is preferably less than 50 mol%, more preferably less than 40 mol%, and more preferably It is less than 20% by mole, and the best is less than 5% by mole, even if it is 0% by mole. Further, as the other acid component constituting the amorphous polyester segment (b), a trifunctional or higher polycarboxylic acid such as trimellitic acid or pyromellitic acid can also be used. 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 diol component constituting the amorphous polyester segment (b) used in the present invention is not particularly limited, and is preferably an aliphatic diol and/or an alicyclic diol, particularly a branched aliphatic Alcohol and/or branched alicyclic diols are preferred. The preferred aliphatic carbon number of the branched aliphatic diol and/or the branched alicyclic diol is 4 or more, more preferably 5 or more, still more preferably 6 or more, preferably 20 or less, more preferably 15 or more. Hereinafter, it is more preferably 10 or less, and particularly preferably 8 or less. When the diol component is 100 mol% based on the total diol component of the resin composition, it is preferably 20 mol% or more, more preferably 25 mol% or more, and still more preferably 30 mol% or more. , especially good for more than 40%. Further, it is preferably 99 mol% or less, more preferably 97 mol% or less, still more preferably 95 mol% or less. If it is less than 20% by mole, the solvent solubility may be insufficient. If it exceeds 99% by mole, the storage elastic modulus at 20 ° C may be insufficient because the amount of the crystalline polyether segment (a) is insufficient. (E'20) is a case where the storage elasticity exceeds 2000 MPa, the storage elasticity is too high, and the adhesion is lowered.

Here, the branched aliphatic diol means an aliphatic diol having a side chain group having a carbon number of 1 or more in a linear hydrocarbon; a branched alicyclic diol means an alicyclic hydrocarbon The cyclic carbon has an alicyclic diol having a side chain group having 1 or more carbon atoms. Specifically, it is not particularly limited, and examples of the branched aliphatic diol include neopentyl glycol, 2-methyl-1,3-propanediol, 1,2-butanediol, and 1,3-butylene. Glycol, 2,3-butanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3 -hexanediol, 2,2-dimethyl-3-hydroxypropyl-2',2'-dimethyl-3-hydroxypropionate, 2-n-butyl-2-ethyl-1,3 -propylene glycol, 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-pentanediol, 3-phenyl-1,5-pentanediol, 2,5-dimethyl-3-sodium sulfo-2 , 5-hexanediol, etc.; as a branched alicyclic diol, for example, 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-double ( Hydroxyethoxy)cyclohexane, 2,2-bis(4-hydroxymethoxycyclohexyl)propane, 2,2-bis(4-hydroxyethoxycyclohexyl)propane, bis(4-hydroxycyclohexyl) Methane, 2,2-bis(4-hydroxycyclohexyl)propane, 3(4),8(9)-tricyclo[5.2.1.0 ² , ⁶ ]癸The alkane dimethanol, the hydrogenated bisphenol A, the ethylene oxide adduct of the hydrogenated bisphenol A, the propylene oxide adduct of the hydrogenated bisphenol A, and the like may be used alone or in combination of two or more. Among them, neopentyl glycol is most preferable from the viewpoint of improving the solvent solubility of the composition.

When the content of the short-chain diol having a carbon number of 3 or less is 100 mol% based on the total diol component of the resin composition, it is preferably 70 mol% or less, more preferably 60 mol% or less, and still more preferably It is 50 mol% or less, and particularly preferably 40 mol% or less. If it is too large, the miscibility with the crystalline polyether segment (a) is deteriorated, and the polymerizability tends to be deteriorated. Specific examples of the short-chain diol having 3 or less carbon atoms are not particularly limited, and examples thereof include ethylene glycol, 1,2-propylene glycol, and 1,3-propanediol.

Further, a linear diol component having 4 or more carbon atoms can also be used. The blending amount of the linear diol is preferably 20 mol% or less, more preferably 10 mol% or less, still more preferably 5 mol% or less, and even 0 mol%. When the amount of the linear diol is too large, the polyester segment (b) tends to be crystalline, and the solvent solubility may be lowered.

Further, as a part of the diol component, a trifunctional or higher polyhydric alcohol such as glycerin, trimethylolpropane or pentaerythritol may be used, and from the viewpoint of preventing gelation of the resin composition, it is preferably 10 MoM% or less, more preferably 5 mol% or less. Too much is the case where the resin composition is gelated.

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

The resin composition of the present invention must contain a crystalline polyether segment (a) and an amorphous polyester segment (b), preferably a crystalline polyether segment (a) and the aforementioned amorphous polyester segment. (b) Copolymerization. Further, the resin composition is preferably amorphous. By making the resin composition amorphous, the stability after solvent dissolution can be maintained while maintaining the subsequent characteristics in a wide temperature range. Amorphous means that the temperature is raised from -100 ° C to 20 ° C / min to 300 ° C using a differential scanning calorimeter (DSC), and a clear melting peak is not displayed during the temperature rising process.

When the content of the crystalline polyether segment (a) in the resin composition of the present invention is 100 mol% based on the total diol component of the resin composition, it is preferably 1 mol% or more, more preferably 3 mol% or more, and more preferably 5 mol% or more. Further, it is preferably 80 mol% or less, more preferably 75 mol% or less, still more preferably 70 mol% or less, and particularly preferably 60 mol% or less. When the content of the crystalline polyether segment (a) is less than 1 mol%, the storage elastic modulus (E'20) at 20 °C becomes more than 2000 MPa, and sufficient storage elasticity cannot be obtained. In addition, when it exceeds 80 mol%, the storage elastic modulus (E'80) at 80 °C becomes less than 0.5 MPa, and sufficient storage elasticity cannot be obtained.

The resin composition of the present invention must have a storage modulus (E'20) of from 800 to 2,000 MPa at 20 °C. It is preferably 900 MPa or more, more preferably 1000 MPa or more, and still more preferably 1100 MPa or more. Further, it is preferably 1900 MPa or less, more preferably 1800 MPa or less, still more preferably 1700 MPa or less. Excellent adhesion at 20 ° C can be exhibited by conforming to the foregoing range.

The resin composition of the present invention must have a storage modulus (E'80) of from 0.5 to 2.5 MPa at 80 °C. It is preferably 0.8 MPa or more, more preferably 1.0 MPa or more, still more preferably 1.5 MPa or more. Further, it is preferably 2.4 MPa or less, more preferably 2.2 MPa or less, still more preferably 2.0 MPa or less. By following the foregoing range, excellent adhesion resistance can be exhibited at 80 °C.

The resin composition of the present invention has a storage elastic modulus at 80 ° C in a ratio (E'80/E'20) to a storage elastic modulus at 20 ° C of 0.025% to 0.25%. It is preferably 0.03% or more, more preferably 0.05% or more, still more preferably 0.1%. Further, it is preferably less than 0.25%, more preferably 0.24% or less, still more preferably 0.23% or less. By conforming to the foregoing range, it is possible to stably exhibit excellent adhesion or heat resistance in a wide temperature range of 20 ° C to 80 ° C.

The storage elastic modulus of the resin composition of the present invention was measured in accordance with the following method. That is, the resin composition was placed on a hot press adjusted to 200 ° C via a polyimide film. A sheet sample having a thickness of about 1 mm was obtained by holding at a pressure of about 2 N/mm ² for about 20 seconds. This was cut into a length of about 15 mm (excluding the fixed portion) and a width of about 4 mm, and then attached to a dynamic viscoelasticity measuring device "DVA-200" manufactured by IT Keisoku Seigyo Co., Ltd., and measured in a tensile mode. The measurement conditions were such that the frequency was fixed at 10 Hz, and the temperature was swept from −100° C. at a temperature increase rate of 4° C./min until the measurement could not be performed (maximum 250° C.).

By satisfying the aforementioned blending amount and storage elastic modulus, good solvent solubility and excellent solution stability can be exhibited, and since the substrate has good followability from a wide temperature range from room temperature (about 20 ° C) to 80 ° C, The adhesion can be maintained, followed by 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, still more preferably 7,000 or more. Further, 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, still more preferably 30,000 or less. If the number average molecular weight is less than 3,000, the 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, still more preferably 0.8 dl/g or more. Further, the upper limit of the reducing viscosity is not particularly limited, but is preferably 1.5 dl/g or less, more preferably 1.4 dl/g or less, still more preferably 1.3 dl/g or less. If the reduction viscosity is less than 0.6 dl/g, the elasticity may be insufficient. When the reduction 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 to a solvent. The solvent may, for example, be an aromatic hydrocarbon, an aliphatic hydrocarbon, an alicyclic hydrocarbon, a ketone solvent, an ether solvent or an aprotic polar solvent. Specific examples thereof include acetone, methyl ethyl ketone (hereinafter also referred to as "MEK"), toluene, xylene, hexane, heptane, cyclohexane, methylcyclohexane, tetrahydrofuran, and N. - methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylhydrazine, SOLVESSO 100, SOLVESSO 150, SOLVESSO 200, etc., but is not limited thereto. These solvents may be used singly or in combination of two or more. The solubility in the solvent is preferably 20% by weight or more, more preferably 25% by weight or more, still more preferably 30% by weight or more at 25 °C. Since the solvent solubility is excellent, the workability when it is used as an adhesive composition becomes favorable.

In the resin composition of the present invention, after the solvent is dissolved in an amount of 30% by weight, it can be stabilized to maintain fluidity even after being stored at 25 ° C for 8 hours, and the resin composition after storage is stored in the chamber. Both temperature (about 20 ° C) and 80 ° C are good.

The carboxyl group concentration of the resin composition of the present invention is preferably from 5 to 60 equivalents/t, more preferably from 10 to 55 equivalents/t, still more preferably from 15 to 50 equivalents/t. If it is less than 5 equivalent/t, there is a case where the adhesion is lowered, and if it exceeds 60 equivalents/t, the heat resistance is lowered.

As a method for producing the resin composition of the present invention, a known method can be employed, for example, after the esterification reaction between the crystalline polyether segment (a) and the amorphous polyester segment (b) at 150 to 250 ° C The polycondensation reaction is carried out at 230 to 300 ° C while reducing the pressure, whereby a solvent-soluble elastic resin composition can be obtained. The metal catalyst is not particularly limited, but is preferably a Ti atom from the viewpoint of polymerizability. Specifically, tetrabutyl titanate is particularly preferable from the viewpoint of polymerizability. The amount of the catalyst is not particularly limited, but is preferably 200 ppm to 1000 ppm, and when it exceeds 1000 ppm, the environmental resistance is deteriorated.

The resin composition of the present invention may be copolymerized with a trifunctional or higher polycarboxylic acid or a polyhydric alcohol such as benzene trimellitic anhydride or trimethylolpropane.

As a method of determining the composition and composition ratio of the resin composition, for example, ¹ H-NMR or ¹³ C-NMR in which a polyester resin is dissolved in a solvent such as heavy hydrogen chloroform, by methanol solution in a polyester resin (methanolysis) The quantitative determination by gas chromatography (hereinafter also referred to as methanol solution-GC method). In the present invention, the composition and composition ratio are determined by ¹ H-NMR.

<Antioxidant (c) containing a phenolic oxygen atom in the molecule> The antioxidant (c) (hereinafter also referred to as "antioxidant (c)") containing a phenolic oxygen atom in the molecule of the resin composition of the present invention, It is preferably an antioxidant having a phenol in the basic skeleton. Specifically, it is not limited, and examples thereof include a hindered phenol compound represented by the following formula (1) or the following formula (2). The antioxidant (c) has a function of preventing the crystalline polyether segment (a) from depolymerizing and decomposing due to the catalyst Ti atom and reducing the elasticity. Therefore, it is particularly effective to use in the polymerization of the resin composition. Further, it has an effect of avoiding a decrease in the molecular weight caused by a decrease in molecular weight when the resin composition is continuously used for a long period of 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, still more preferably 0.1 to 4 parts by weight, per 100 parts by weight of the resin composition. 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 be bleed out from the resin, which may adversely affect the adhesion.

<(c1) component> The component (c1) is preferably a hindered phenol compound represented by the formula (1). General formula (1); R ₁ and R ₂ are each independently a linear or branched alkyl group, or hydrogen; and the alkyl group preferably has a carbon number of from 1 to 4, more preferably from 2 to 3. The R ₃ is an alkyl group, and preferably has a carbon number of from 1 to 4, more preferably from 2 to 3. The R ₄ chain may be a straight chain or may have a branched alkyl group, and preferably has a carbon number of 5 to 10, more preferably 6 to 9, and still more preferably 7 to 8. n is an integer from 1 to 4.

Specific examples of the component (c1) include thiodivinyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] and octadecyl [3- (3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-t-butyl) 4-hydroxyphenyl)propanamine], 1,3,5-trimethyl-2,4,6-paran (3,5-di-t-butyl-4-hydroxy)benzene, 1,6- Hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], triethylene glycol-bis-3-(3-tert-butyl-4-hydroxyl -5-methylphenyl)propionate, di-octadecyl 3,3'-thiobispropanoate, 2,5,7,8-tetramethyl-(4',8',12' -trimethyltridecyl)chroman-6-ol, stearyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3,9-double [1 ,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoxy]ethyl]2,4,8,10-tetraoxa Snail (5,5)-undecane, but is not limited thereto.

<(c2) component> The component (c2) is preferably a hindered phenol compound represented by the formula (2). General formula (2); R ₅ and R ₆ are each independently a linear or branched alkyl group or hydrogen; and the alkyl group preferably has a carbon number of from 1 to 4, more preferably from 2 to 3. R ₇ is an alkyl group; preferably, the carbon number is from 1 to 4, more preferably from 2 to 3. R ₈ and R ₉ are each independently a linear or branched alkyl group; preferably, the carbon number is 5 to 10, more preferably 6 to 9, and still more preferably 7 to 8.

Specific examples of the component (c2) include tributyl phosphate, ginseng (2,4-dibutylphenyl) phosphite, distearyl pentaerythritol diphosphite, and cyclopentane tetrayl. Bis(2,6-di-t-butyl-4-methylphenyl)phosphite, decyl phenyl phosphite, ginseng (2,4-di-t-butylphenyl) phosphite, Distearyl pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol phosphite, bis(2,6-di-t-butyl-4-methyl-phenyl)pentaerythritol Phosphite, 2,2-methylene-bis(4,6-di-t-butylphenyl)octyl phosphite, hydrazine (2,4-di-t-butylphenyl)-4,4 '-Extended biphenyl-diphosphinate, bismuth (2,4-di-t-butylphenyl)-4,4'-biphenyl-diphosphinate, etc., but is not limited thereto.

One type or two or more types of the above-mentioned antioxidants (c1) may be used, and only one type or two or more types of the above-mentioned antioxidants (c2) may be used. Further, an antioxidant (c1) and an antioxidant (c2) may be used in combination.

<Adhesive Composition> The adhesive composition of the present invention contains a composition of the above resin composition and a resin composition as a main component. The main component is a resin composition containing 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more. If it is too small, there is a case where it is impossible to exhibit good adhesion and heat resistance. As other components, the components described later can be blended.

<Other constituent components> In the adhesive composition of the present invention, components other than the resin composition may be blended in order to improve adhesion, flexibility, durability, and the like without impairing the effects of the present invention. The specific example is, for example, a resin such as polyester, polyamide, polyolefin, epoxide, polycarbonate, acrylic, ethylene vinyl acetate or phenol, or a hardener such as an isocyanate compound or melamine. Fillers such as talc or mica, pigments such as carbon black and titanium oxide, antimony trioxide, brominated polystyrene, and the like. The content of the components is preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 30% by weight or less. When the content exceeds 50% by weight, there is a concern that the adhesion to the electric and electronic parts and the subsequent heat resistance are lowered. [Examples]

In order to explain the present invention in further detail, the following examples and comparative examples are given, but the present invention is not limited by the examples. Moreover, each measurement system described in the examples and the comparative examples was measured by the following method.

<Polyester Composition> The composition and composition ratio of the polyester were measured by ¹ H-NMR measurement (proton-type nuclear magnetic resonance spectrometry) at a resonance frequency of 400 MHz. For the measurement apparatus, NMR apparatus 400-MR manufactured by VARIAN Co., Ltd. was used, and the solvent used was dihydrochloroform.

<Storage Elasticity Coefficient> A resin composition sample was placed on a hot press machine adjusted to 200 ° C via a polyimide film ("Kapton (registered trademark)" manufactured by Toray-Du Pont Co., Ltd.) at 2 N/ A pressure of mm ² was maintained for 20 seconds to obtain a sample of a sheet having a thickness of 1 mm. After the cutting was performed to a length of 15 mm (excluding the fixed portion) and a width of 4 mm, the sample was attached to a dynamic viscoelasticity measuring device "DVA-200" manufactured by IT Keisoku Seigyo Co., Ltd., and measured in a tensile mode. The measurement conditions were such that the frequency was fixed at 10 Hz, and the temperature was swept from −100° C. at a temperature increase rate of 4° C./min until the measurement could not be performed (maximum 250° C.).

<Solvent Solubility Test> The resin composition was dissolved in a solution (solid content concentration: 30% by weight) of MEK/toluene = 1/4 (weight ratio), and it was visually confirmed that it was evaluated as "○" when completely dissolved, and when the residue was not dissolved, it was evaluated. It is "╳".

<Solution Stability Test> The solution of the aforementioned resin composition was allowed to stand at room temperature (about 25 ° C) for 1 day. After standing for 1 day, it was slanted smoothly, and it was confirmed by visual observation that if the fluidity was observed as "○", if the fluidity was not observed, it was rated as "╳".

<Adhesion test> The sample having the solution stability test described above as "○" 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 tin-plated copper foil which had been sufficiently cleaned on the surface was subjected to the above-mentioned coating film at 160 ° C and 3 MPa to prepare a sample A. At room temperature (about 25 ° C), the following sample A was subjected to T-peeling at a speed of 100 mm/min, and the subsequent strength was measured. Evaluation criteria ◎: Subsequent strength of 25N/25mm or more ○: Subsequent strength of 20N/25mm or more, less than 25N/25mm △: Subsequent strength of 15N/25mm or more, less than 20N/25mm ╳: Subsequent strength is less than 15N/25mm

<Continuation of heat resistance test> After the sample A was kept at 80 ° C for 5 minutes, T-peeling was performed at a rate of 100 mm/min in an environment of 80 ° C, and the bonding strength was measured. Evaluation criteria ◎: Subsequent strength of 25N/25mm or more ○: Subsequent strength of 20N/25mm or more, less than 25N/25mm △: Subsequent strength of 15N/25mm or more, less than 20N/25mm ╳: Subsequent strength is less than 15N/25mm

<Production Example of Resin Composition> 194 parts by weight of terephthalic acid, 194 parts by weight of isophthalic acid, 161 parts by weight of ethylene glycol, and pentylene were added to a reactor equipped with a stirrer, a thermometer, and a cooler for distillation. 151 parts by weight of a diol and tetrabutyl titanate (270 ppm in terms of Ti atoms) were subjected to an esterification reaction at 170 to 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 1,000 and a hindered phenolic antioxidant "IRGANOX (registered trademark) 1010" (Ciba-Geigy) were placed. After 0.6 parts by weight of the company, the temperature was raised to 255 ° C. On the other hand, the pressure was gradually reduced in the inside of the system, and the treatment was carried out at 255 ° C for 60 minutes to 665 Pa. Then, a polycondensation reaction was further carried out at 133 Pa or less for 60 minutes to obtain a resin composition of Example 1. The composition and physical properties of this resin composition are shown in Tables 1 and 2. Further, the resin compositions of Examples 2 to 10 and Comparative Examples 1 to 5 were synthesized in the same manner as in Example 1. The respective compositions and physical properties are shown in Tables 1 and 2.

【Table 1】

【Table 2】

The abbreviation in the table is 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: polymethylene ether glycol 1000, PEG2000: polyethylene glycol 2000, PTXG1000: poly(methylene ether glycol-neopentethylene Alcohol) 1000

The antioxidant (c) uses the following. Antioxidant (i): IRGANOX (registered trademark) 1010 represented by the formula (3), manufactured by Ciba-Geigy Co., Ltd. Formula (3) Antioxidant (ii): IRGANOX (registered trademark) 1135 represented by the formula (4), manufactured by Ciba-Geigy Co., Ltd. Formula (4) Antioxidant (iii): IRGANOX (registered trademark) 295 represented by the formula (5), manufactured by Ciba-Geigy Co., Ltd. Formula (5) Antioxidant (iv): LASMIT (registered trademark) LG represented by the formula (6), manufactured by Daiichi Kogyo Co., Ltd. Formula (6)

<Evaluation of Resin Composition> Example 1 For the resin composition of Example 1, <solvent solubility test>, <solution stability test>, <adhesion test>, and <continuation heat resistance test> were carried out.

Examples 2 to 9 The same tests as in Example 1 were carried out using the resin compositions of Examples 2 to 9. The evaluation results are shown in Table 2.

Comparative Examples 1 to 5 The same tests as in Example 1 were carried out using Comparative Examples 1 to 5. The evaluation results are shown in Table 2.

Examples 1 to 9 were in compliance with the scope of the patent application, and the results in <Solvent Soluble Test>, <Solution Stability Test>, <Next Test>, and <Continuous Heat Resistance Test> were all good. On the other hand, in the comparative example 1, the component (b) was a crystalline polyester, and it was not dissolved in a solvent, and <solvent solubility test> was inadequate. In the component (c) of Comparative Example 2, the antioxidant having a phenolic oxygen atom in the molecule was not used, so that the polymerizability was not good, and the <heat resistance test> was not preferable. Comparative Example 3 did not contain the component (a), and <subsequent test> was poor. In Comparative Example 4, the component (a) was not contained, and the component (b) was a crystalline polyester, so that it was not dissolved in a solvent, and the <solvent solubility test> was not preferable. Since the component (a) in Comparative Example 5 is an amorphous polyether, it was dissolved before reaching 80 ° C in the measurement of the storage elastic modulus, and the storage elastic modulus at 80 ° C could not be measured. Moreover, <the heat resistance test> is not good. [Industrial use]

The resin composition of the present invention is solvent-soluble and excellent in workability, and can maintain the following characteristics in a wide temperature range, and is excellent in durability against high-temperature environmental load or high-temperature high-humidity environmental load. Therefore, it can be suitably used for various flexible flat cables or electronic parts for automobiles, communication, computers, and home appliances, switches having switches for printed boards, sensors, and the like.

no

Claims (4)

A solvent-soluble elastic resin composition comprising a crystalline polyether segment (a) and an amorphous polyester segment (b), characterized by: a storage elastic modulus (E' at 20 ° C when measured at a frequency of 10 Hz 20) is 800~2000MPa, the storage elastic modulus (E'80) at 80 °C is 0.5~2.5MPa, and the storage elastic modulus at 80 °C is proportional to the storage elastic coefficient at 20 °C (E'80/E '20) is in the range of 0.025% to 0.25%. The solvent-soluble elastic resin composition of claim 1 further contains an antioxidant (c) having a phenolic oxygen atom in the molecule, and the content of the antioxidant (c) is 100% by weight relative to the solvent-soluble elastic resin composition. The serving is 0.05 to 5 parts by weight. The solvent-soluble elastic resin composition according to the second aspect of the invention, wherein the antioxidant (c) having a phenolic oxygen atom in the molecule is the compound (c1) and/or the formula (2) represented by the formula (1). a compound represented by (c2); formula (1); (R ₁ and R ₂ are each independently a linear chain having 1 to 4 carbon atoms or a branched alkyl group, or hydrogen; R ₃ is an alkylene group having 1 to 4 carbon atoms; and R ₄ is a carbon number of 5 a straight chain of ~10 or may also have a branched alkyl group; n represents an integer from 1 to 4; formula (2); (R ₅ and R ₆ are each independently a straight chain having a carbon number of 1 to 4 or a branched alkyl group or hydrogen; R ₇ is an alkylene group having 1 to 4 carbon atoms; and R ₈ and R ₉ are each independently Independently, it is a linear chain having a carbon number of 5 to 10 or a branched alkyl group. An adhesive composition comprising the solvent-soluble elastic resin composition according to any one of claims 1 to 3.