JP6754119B2 - Resin composition, coating film and laminate using it - Google Patents

Description

The present invention relates to a resin composition composed of a plurality of types of synthetic resins, a coating film formed by using the resin composition, and a laminate containing the coating film.

In general, a polyester resin having a low glass transition temperature (for example, −50 to 50 ° C.) has excellent adhesiveness, so that a polyester resin having a high glass transition temperature (for example, 40 to 150 ° C.) adheres as an adhesive. Due to its excellent properties, it is used as a conductive paste and coating agent for automobile parts and electrical and electronic parts.

In recent years, the polyester resin has been exposed to a high temperature environment by being used around the headlights of automobiles and in automobiles in automobile parts applications, and by being used in thin liquid crystal displays in electrical and electronic parts applications. There are many opportunities to do so. Therefore, the resin composition used is usually required to have heat resistance more than before.

For example, Patent Document 1 discloses that a polyester resin composition containing a polyester resin having a low glass transition temperature and a polyester resin having a high glass transition temperature is used as an adhesive for a flexible flat cable. Patent Document 2 discloses that a polyester-based hot melt resin composition is used as an adhesive for a flexible flat cable. Further, Patent Document 3 discloses that a conductive paste containing an aromatic dicarboxylic acid component and a polyester resin containing an aliphatic polycarbonate diol or the like as a main component is used for automobile parts applications and OA equipment.

International Publication No. 2010/035822 Pamphlet Japanese Unexamined Patent Publication No. 2010-159331 Japanese Unexamined Patent Publication No. 2001-319524

In recent years, when polyester resin is used as an adhesive for automobile parts and electrical and electronic parts, excellent heat-resistant adhesiveness and moisture-heat resistance are required in addition to adhesiveness and heat resistance in order to further improve performance. However, the polyester resin compositions of Patent Documents 1 and 2 have insufficient heat-resistant adhesiveness and moisture-heat resistance.
Further, in recent years, when polyester resin is used as a conductive paste or coating agent for automobile parts or electrical and electronic parts, excellent flexibility and hardness are required in addition to adhesion and heat resistance in order to further improve performance. Has been done. However, the polyester resin of Patent Document 3 has insufficient flexibility and hardness.

In the present invention, by using a specific polyarylate resin and a polyester resin in a specific ratio, when a polyester resin having a low glass transition temperature is used, heat resistance is improved as compared with when the polyester resin is used alone. When a resin composition that is remarkably excellent and also has excellent adhesiveness, heat resistance, and moisture heat resistance, and a polyester resin having a high glass transition temperature are used, the adhesiveness, heat resistance, flexibility, and hardness are all improved. Also aims to provide an excellent resin composition.

As a result of diligent studies, the present inventors have found that the above object can be achieved by using a polyarylate resin having a specific hydroxy group concentration or more in combination with a polyester resin, and have reached the present invention.
That is, the gist of the present invention is as follows.

［式（１）中、Ｒ^１およびＲ^２は、独立して、水素、炭素数が１〜１２の炭化水素基またはハロゲンを表し、ｍおよびｎは、独立して、０〜４の整数を表し、Ｘ_１およびＸ_２は、水素、炭素数が１〜２０の直鎖状の炭化水素基、枝分かれ状の炭化水素基、芳香族および脂環族を含む環状の炭化水素基、トリハロメタン基、または、炭素数が１〜２０のアルキルエステル基、または、フェニルエステル基を表す。］
＜３＞ポリアリレート樹脂（Ｂ）の二価フェノール成分として、一般式（２）で示される二価フェノールを含有することを特徴とする、＜２＞の樹脂組成物。

［式（２）中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、独立して、水素、炭素数が１〜１２の炭化水素基またはハロゲンを表し、Ｒ^５およびＲ^６は、独立して、水素または炭素数が１〜４の炭化水素基を表す。ｍは４〜１１の整数を表し、Ｘは、ヒドロキシフェニル基が結合する炭素原子とともに飽和脂肪族炭化水素環を形成する炭素を表す。］
＜４＞ポリアリレート樹脂（Ｂ）の二価フェノール成分として、２，２−ビス（４−ヒドロキシフェニル）プロパン（ＢｉｓＡ）と１，１−ビス（４−ヒドロキシフェニル）−３，３，５−トリメチルシクロヘキサン（ＢｉｓＴＭＣ）とが用いられることを特徴とする、＜１＞〜＜３＞の何れかの樹脂組成物。
＜５＞ポリアリレート樹脂（Ｂ）のＢｉｓＡとＢｉｓＴＭＣの含有比率（ＢｉｓＡ／ＢｉｓＴＭＣ）が、３０／７０〜７０／３０（モル比）であることを特徴とする、＜４＞の樹脂組成物。
＜６＞さらに硬化剤（Ｃ）を含有することを特徴とする、＜１＞〜＜５＞の何れかの樹脂組成物。
＜７＞＜１＞〜＜６＞の何れかの樹脂組成物を用いて形成された塗膜。
＜８＞＜７＞の塗膜を有する積層体。 <1> A resin composition containing a polyester resin (A) excluding a polyarylate resin and a polyarylate resin (B).
The polyester resin (A) contains terephthalic acid as a divalent carboxylic acid component and ethylene glycol as a divalent alcohol component.
The polyarylate resin (B) is composed of a dihydric phenol component, an aromatic dicarboxylic acid component, and a hydroxycarboxylic acid component.
The content ratio of the hydroxycarboxylic acid component to 100 mol% of the total monomer component of the polyarylate resin (B) is 2 to 18 mol%.
The hydroxy group concentration of the polyarylate resin (B) is 100 geq / ton or more.
A resin composition characterized in that the mass ratio (A / B) of the polyester resin (A) and the polyarylate resin (B) is 5/95 to 95/5.
<2> polyarylate resin (B), as the dihydric phenol component, characterized by containing a dihydric phenol represented by the general formula (1), the resin composition of <1>.

[In formula (1), R ¹ and R ² independently represent hydrogen, a hydrocarbon group having 1 to 12 carbon atoms or a halogen, and m and n independently represent an integer of 0 to 4. Represented, X ₁ and X ₂ are hydrogen, a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group, a cyclic hydrocarbon group containing an aromatic and alicyclic group, a trihalomethane group, and the like. Alternatively, it represents an alkyl ester group having 1 to 20 carbon atoms or a phenyl ester group. ]
<3> The resin composition of <2>, which contains the divalent phenol represented by the general formula (2) as the divalent phenol component of the polyarylate resin (B).

[In formula (2), R ¹ , R ² , R ³ and R ⁴ independently represent hydrogen, a hydrocarbon group having 1 to 12 carbon atoms or a halogen, and R ⁵ and R ⁶ are independent. Represents hydrogen or a hydrocarbon group having 1 to 4 carbon atoms. m represents an integer of 4 to 11, and X represents a carbon that forms a saturated aliphatic hydrocarbon ring with a carbon atom to which a hydroxyphenyl group is bonded. ]
<4 > As the dihydric phenol component of the polyarylate resin (B), 2,2-bis (4-hydroxyphenyl) propane (BisA) and 1,1-bis (4-hydroxyphenyl) -3,3,5- The resin composition according to any one of <1> to < 3 >, wherein trimethylcyclohexane (BisTMC) is used.
< 5 > The resin composition of < 4 >, wherein the content ratio (BisA / BisTMC) of BisA and BisTMC of the polyarylate resin (B) is 30/70 to 70/30 (molar ratio).
< 6 > The resin composition according to any one of <1> to < 5 >, which further contains a curing agent (C).
A coating film formed by using any of the resin compositions of < 7 ><1> to < 6 >.
A laminate having a coating film of < 8 > and < 7 >.

According to the present invention, when a polyester resin having a low glass transition temperature is used, by using a specific polyarylate resin and a polyester resin in a specific ratio, heat-resistant adhesion is performed as compared with the case where the polyester resin is used alone. It is possible to provide a resin composition having remarkably excellent properties and also excellent adhesiveness, heat resistance, and moisture heat resistance.
When the polyarylate resin is used alone, the glass transition temperature is higher than that of the polyester resin, so that the adhesiveness is inferior and the heat-resistant adhesiveness is low. On the other hand, when a polyester resin having a low glass transition temperature is used alone, the glass transition temperature is lower than that of a polyarylate resin, so that the adhesiveness is excellent, but the heat-resistant adhesiveness is low. On the other hand, the resin composition of the present invention remarkably improves the heat-resistant adhesiveness without significantly impairing the adhesiveness.
Further, when a polyester resin having a high glass transition temperature is used, by using a specific polyarylate resin and a polyester resin in a specific ratio, the adhesion, heat resistance, flexibility, and hardness are all excellent. A resin composition can be provided.

Hereinafter, the resin composition of the present invention will be described in detail. The resin composition of the present invention contains a polyester resin (A) and a polyarylate resin (B), and has a mass ratio (A / B) of 5/95 to 95/5.

[Polyester resin (A)]
The polyester resin (A) used in the present invention is a polyester resin other than the polyarylate resin, and contains a divalent carboxylic acid component and a dihydric alcohol component. As the divalent carboxylic acid component constituting the polyester resin (A), terephthalic acid and isophthalic acid are used to balance the heat resistance, adhesiveness, adhesiveness, and solvent solubility of the obtained polyester resin (A). Is preferably mixed and used.

When terephthalic acid and isophthalic acid are mixed and used, the content of terephthalic acid in the divalent carboxylic acid component is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and 30 to 80 mol%. It is more preferably 70 mol%. If the content of terephthalic acid is less than 10 mol%, the polyester resin (A) may be inferior in both heat resistance and adhesiveness to the substrate, and if it exceeds 90 mol%, the polyester resin (A) is solvent-soluble. May be inferior in sex. On the other hand, the content of isophthalic acid is preferably 5 to 90 mol%, more preferably 10 to 85 mol%, and further preferably 20 to 80 mol%. If the content of isophthalic acid is less than 5 mol%, the polyester resin (A) is inferior in solvent solubility, and if it exceeds 90 mol%, the polyester resin (A) is inferior in heat resistance and toughness. There is.

In addition to the above-mentioned terephthalic acid and isophthalic acid, the divalent carboxylic acid component constituting the polyester resin (A) includes, for example, adipic acid, pimelliic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid. , Tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecandioic acid, eikosandioic acid, docosandioic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, phthalic acid Acid, naphthalenedicarboxylic acid, 4,4'-dicarboxybiphenyl, 5-sodium sulfoisophthalic acid, 5-hydroxyisophthalic acid, fumaric acid, mesaconic acid, maleic acid, itaconic acid, glutaconic acid, citraconic acid, 1,4- Examples thereof include cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 2,5-norbornenedicarboxylic acid, dimer acid and hydrogenated dimer acid. The divalent carboxylic acid component may be a derivative thereof or an anhydride thereof. Of these, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid having 6 to 10 carbon atoms are preferable from the viewpoint of adhesiveness and adhesion.

The dihydric alcohol component constituting the polyester resin (A) is not particularly limited, but preferably contains ethylene glycol or an aliphatic glycol having a side chain. When ethylene glycol is contained, the content thereof is preferably 20 to 70 mol%, more preferably 25 to 65 mol%, and further preferably 30 to 60 mol% of the divalent alcohol component. preferable. Examples of the aliphatic glycol having a side chain include neopentyl glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, and 2,2-butylethylpropanediol. From the viewpoint of solvent solubility, neopentyl glycol and 2-methyl-1,3-propanediol are particularly preferable. When an aliphatic glycol having a side chain is contained, the content thereof is preferably 30 to 80 mol%, more preferably 35 to 75 mol%, and 40 to 70 mol% of the dihydric alcohol component. Is more preferable. If the content of the aliphatic glycol having a side chain is less than 30 mol%, the solvent solubility may be inferior, and if the content exceeds 80 mol%, the heat resistance may be inferior.

In addition to the above dihydric alcohol, the dihydric alcohol component constituting the polyester resin (A) includes, for example, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,4-cyclohexane. Dimethanol, 1,3-cyclohexanedimethanol, tricyclodecanedimethanol, spiroglycol, dimerdiol, 1,2-propanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol , 1,9-Nonandiol, 1,10-decanediol, 1,12-dodecanediol, polyethylene glycol, polytetramethylene glycol, ethylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane [BisA], BisA propylene oxide adducts can be mentioned. The divalent alcohol component may be used alone or in combination of two or more. Among them, alicyclics such as 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and tricyclodecanedimethanol, and ethylene oxide adducts of 2,2-bis (4-hydroxyphenyl) propane [BisA], An aromatic system such as a propylene oxide adduct of BisA is preferable from the viewpoint of heat resistance. In addition, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, polyethylene glycol, polytetramethylene glycol. It is preferable to use a constituent having 6 or more carbon atoms, such as, from the viewpoint of moisture resistance and heat resistance.

As long as the effect of the present invention is not impaired, the polyester resin (A) may contain a monomer component other than the divalent carboxylic acid component and the divalent alcohol component, if necessary. Examples of other monomer components include trivalent or higher carboxylic acids, monocarboxylic acids, trihydric or higher alcohols, monoalcohols, hydroxycarboxylic acids, lactones, and oxylanes. Examples of the trivalent or higher carboxylic acid include 1,3,4-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, pyromellitic acid, trimellitic acid, and tetrahydrophthalic acid. Examples of the monocarboxylic acid include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, p-tert-butylbenzoic acid, and cyclohexanoic acid. Examples of trihydric or higher alcohols include trimethylpropane and glycerin. Examples of the monoalcohol include octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, and 2-phenoxyethanol. Examples of the hydroxycarboxylic acid include lactic acid, glycolic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxyisobutyric acid, 2-hydroxy-2-methylbutyric acid, 2-hydroxyvaleric acid, 3 Examples thereof include −hydroxyvaleric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid, 10-hydroxystearic acid, 4-hydroxyphenylstearic acid and 4- (β-hydroxy) ethoxybenzoic acid. Examples of the lactone include β-propiolactone, β-butyrolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone. Examples of osikiran include ethylene oxide.

In the present invention, the number average molecular weight of the polyester resin (A) is preferably 500 to 35,000, more preferably 3000 to 35000, and even more preferably 5000 to 35000. When the number average molecular weight is out of the range of 500 to 35,000, the obtained resin composition may have low adhesiveness and moisture heat resistance, and the polyester resin (A) having a number exceeding 35,000 has low solvent solubility. There is.

The glass transition temperature of the polyester resin (A) is −50 ° C. or higher and 50 ° C. or lower, preferably −45 ° C. or higher and 45 ° C. or lower, when the resin composition of the present invention is used as an adhesive. More preferably, it is −30 ° C. or higher and 40 ° C. or lower, and most preferably −20 ° C. or higher and lower than 30 ° C. If the glass transition temperature is less than −50 ° C., the resulting resin composition may have reduced moist heat resistance. On the other hand, the glass transition temperature of the polyester resin (A) is more than 40 ° C. and 150 ° C. or lower, preferably more than 45 ° C. when the resin composition of the present invention is used for a conductive paste or a coating agent. It is 130 ° C. or lower, more preferably more than 50 ° C. and 120 ° C. or lower. The solvent solubility of the polyester resin (A) may decrease when the glass transition temperature exceeds 150 ° C.

[Manufacturing method of polyester resin (A)]
First, a combination of monomers such as divalent carboxylic acid and divalent alcohol is appropriately selected and polymerized by a known polymerization method to obtain a polyester resin (A). That is, the polyester resin (A) can be produced by putting the raw material monomer into a reaction can, performing an esterification reaction, and then polycondensing it by a known method until it reaches a desired molecular weight. The esterification reaction is carried out, for example, at a temperature of 180 ° C. or higher for 4 hours or longer.

The polycondensation reaction is generally carried out under a reduced pressure of 130 Pa or less and at a temperature of 220 to 280 ° C. using a polymerization catalyst. Examples of the polymerization catalyst include titanium compounds such as tetrabutyl titanate; acetates of metals such as zinc acetate, magnesium acetate and zinc acetate; antimony trioxide; and organic tin compounds such as hydroxybutyltin oxide and tin octylate. Can be mentioned. When the amount of the polymerization catalyst used is small, the reaction is slow, and when it is excessive, the color tone of the obtained polyester resin (A) deteriorates. Therefore, 0.1 × 10 ^{-4 to} 20 × 10 ⁻ per 1 mol of the acid component. It is preferably ⁴ mol.

[Polyarylate resin (B)]
The polyarylate resin (B) is a polyester resin composed of a divalent carboxylic acid component, a dihydric phenol component, and a hydroxycarboxylic acid component . In the present invention, the polyarylate resin does not contain a so-called liquid crystal polymer having a mesogen group.

The divalent phenol component may be any organic compound containing two phenolic hydroxy groups in one molecule. The phenolic hydroxy group is a hydroxy group directly bonded to the aromatic ring. The divalent phenol component preferably contains the divalent phenol represented by the general formula (1) from the viewpoint of solvent solubility of the polyarylate resin (B).

In formula (1), R ¹ and R ² independently represent hydrogen, a hydrocarbon group having 1 to 12 carbon atoms or a halogen, and m and n independently represent an integer of 0 to 4. , X ₁ and X ₂ are hydrogen, linear hydrocarbon groups having 1 to 20 carbon atoms, branched hydrocarbon groups, cyclic hydrocarbon groups containing aromatics and alicyclic groups, trihalomethane groups, or , Represents an alkyl ester group or a phenyl ester group having 1 to 20 carbon atoms.

The divalent phenol component more preferably contains an alicyclic divalent phenol represented by the general formula (2) from the viewpoint of further improving the solvent solubility of the polyarylate resin (B).

In formula (2), R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a hydrocarbon group or a halogen atom, respectively. The hydrocarbon group may be a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, an unsaturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, and 6 to 10 carbon atoms. It may be an aromatic hydrocarbon group. The saturated aliphatic hydrocarbon group is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. Examples of the saturated aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group and an n-hexyl group. .. The unsaturated aliphatic hydrocarbon group is preferably an alkenyl group having 1 to 3 carbon atoms. Examples of the unsaturated aliphatic hydrocarbon group include a vinyl group and an allyl group. The aromatic hydrocarbon group is preferably an aryl group having 6 carbon atoms. Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom and a bromine atom are preferable.

In formula (2), R ¹ , R ² , R ³ and R ⁴ are preferably the same group. Further, it preferred ^{R 1,} R 2, ^{R 3} and ^{R 4} are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, aryl group having 6 to 10 carbon atoms or a halogen atom.

In formula (2), R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group. The hydrocarbon group may be a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, or an unsaturated aliphatic hydrocarbon group having 1 to 4 carbon atoms. The saturated aliphatic hydrocarbon group is preferably an alkyl group having 1 to 3 carbon atoms. Examples of the saturated aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a t-butyl group. The unsaturated aliphatic hydrocarbon group is preferably an alkenyl group having 1 to 3 carbon atoms. Examples of the unsaturated aliphatic hydrocarbon group include a vinyl group and an allyl group. R ⁵ and R ⁶ are present in plurality in accordance with the value of m will be described later, the plurality of R ⁵ and the plurality of R ⁶ are each independently, only to be selected from within the above range, a hydrogen atom or Alkyl groups having 1 to 4 carbon atoms are preferable. In formula (2), m is an integer of 4 to 11, preferably 4 or 5.

In the formula (2), X represents a carbon atom that forms a saturated aliphatic hydrocarbon ring (monocycle) together with a carbon atom to which a hydroxyphenyl group is bonded. The saturated aliphatic hydrocarbon ring shows a cycloalkane ring according to the number of m. Examples of the saturated aliphatic hydrocarbon ring include a cyclopentane ring (m = 4), a cyclohexane ring (m = 5), a cycloheptane ring (m = 6), a cyclooctane ring (m = 7), and a cyclododecane ring (m = 7). m = 11) can be mentioned.

Among the alicyclic divalent phenols represented by the general formula (2), the alicyclic divalent phenol represented by the general formula (3) is preferable.

In the formula ^(3), respectively R ^1, R 2, ^{R 3} and ^{R 4} are the same as ^{R 1,} R 2, ^{R 3} and ^{R 4} in the formula (2), preferred ^{R 1, R} 2, R ³ and R ⁴ and more preferably R ¹ , R ² , R ³ and R ⁴ are also the same as in the above formula (2). In the formula (3), n is an integer of 0 to 10, preferably an integer of 0 to 5, and more preferably an integer of 2 to 4.

In formula (3), R ¹⁰ is a hydrocarbon group having 1 to 4 carbon atoms. The hydrocarbon group having 1 to 4 carbon atoms may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The saturated aliphatic hydrocarbon group is preferably an alkyl group having 1 to 3 carbon atoms. Examples of the saturated aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a t-butyl group. The unsaturated aliphatic hydrocarbon group is preferably 1 to 3 alkenyl groups. Examples of the unsaturated aliphatic hydrocarbon group include a vinyl group and an allyl group. When the above n is an integer of 2 or more, the plurality of R ^10s may be independently selected from the above range. Although not bound position particularly limited in R ¹⁰ in the cyclohexane ring, when the hydroxyphenyl group is the first place carbon atoms cyclohexane rings linked in the formula (3), a three-position, selected from carbon atoms of the four-position and ranked fifth It is preferable that each R ¹⁰ is bonded to the carbon atom to be formed. Preferred R ^10s each independently represent an alkyl group having 1 to 4 carbon atoms.

Examples of the alicyclic divalent phenol represented by the general formula (3) include 1,1-bis (4-hydroxyphenyl) cyclohexane and 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane. , 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane [BisTMC], 1,1-bis- (4-hydroxyphenyl) -3,3,5,5-tetramethyl-cyclohexane , 1,1-bis- (4-hydroxyphenyl) -3,3,4-trimethyl-cyclohexane, 1,1-bis- (4-hydroxyphenyl) -3,3-dimethyl-5-ethyl-cyclohexane, 1 , 1-bis- (3,5-dimethyl-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis- (3,5-diphenyl-4-hydroxyphenyl) -3,3 , 5-trimethyl-Cyclohexane, 1,1-bis- (3-methyl-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis- (3-phenyl-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis- (3,5-dichloro-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis- (3,5) −Dibromo-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane. Among them, BisTMC is more preferable because of its high versatility.

Examples of the alicyclic divalent phenol contained in the general formula (2) but not in the general formula (3) include 1,1-bis- (4-hydroxyphenyl) -3,3,5-. Examples include trimethyl-cyclopentane.

The content ratio of the alicyclic divalent phenol represented by the general formula (2), particularly the alicyclic divalent phenol represented by the general formula (3) is not particularly limited, and is usually a total divalent phenol component. On the other hand, it is 15 mol% or more (15 to 100 mol%). From the viewpoint of further improving the solvent solubility of the polyarylate resin (B), the content ratio is preferably 15 to 90 mol% with respect to the total divalent phenol component, and is 25 to 75 mol%. Is more preferable. From the viewpoint of further improving the heat resistance of the polyarylate resin (B), the content ratio is preferably 40 to 100 mol% with respect to the total divalent phenol component, and more preferably 55 to 100 mol%. It is preferably 90 to 100 mol%, and more preferably 90 to 100 mol%. From the viewpoint of the balance between the solvent solubility and heat resistance of the polyarylate resin (B), the content ratio is preferably 40 to 90 mol%, preferably 50 to 90 mol%, based on the total divalent phenol component. It is more preferable to do so. The alicyclic divalent phenol represented by the general formula (2), particularly the alicyclic divalent phenol represented by the general formula (3) may be used alone or in combination of two or more. , In that case, the total amount thereof may be within the above range.

Examples of divalent phenols included in the general formula (1) but not included in the general formula (2) include 2,2-bis (4-hydroxyphenyl) propane [BisA] and 2,2-bis. (3,5-Dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane [BisAP] , 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) ethane, 1,1-bis (3-methyl-4-hydroxyphenyl) ethane, Examples thereof include bis (4-hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) methane and bis (3-methyl-4-hydroxyphenyl) methane. Among them, BisA and / or BisAP are preferable because of their high versatility and solvent solubility.

As the divalent phenol component, the above divalent phenol may be used alone or in combination of two or more, but it is preferable to use a plurality of types in order to improve solvent solubility. Among them, the divalent phenol component is preferably contained in combination with BisA and / or BisAP and BisTMC. When BisA and / or BisAP and BisTMC are used, the content ratio ((BisA + BisAP) / BisTMC) between the total content of BisA and BisAP and the content of BisTMC shall be 10/90 to 90/10 (molar ratio). Is preferable, and in particular, since the solubility in methyl ethyl ketone is high, it is more preferably 15/85 to 85/15 (molar ratio), and further preferably 30/70 to 70/30 (molar ratio). .. From the viewpoint of solvent solubility, it is most preferable that BisA / BisTMC is 30/70 to 70/30 (molar ratio).

The aromatic dicarboxylic acid component may be any organic compound containing two carboxy groups directly bonded to the aromatic ring in one molecule. As the aromatic dicarboxylic acid component, for example, terephthalic acid [TPA], isophthalic acid [IPA], orthophthalic acid, 4,4'-diphenyldicarboxylic acid, diphenylether-2,2'-dicarboxylic acid, diphenylether-2,3'- Dicarboxylic acid, diphenyl ether-2,4'-dicarboxylic acid, diphenyl ether-3,3'-dicarboxylic acid, diphenyl ether-3,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid Can be mentioned.

As the aromatic dicarboxylic acid component, one of the above compounds may be used alone, or a plurality of types of compounds may be used in combination. Above all, from the viewpoint of solvent solubility of the polyarylate resin (B), it is preferable that IPA is used alone or TPA and IPA are used in combination. The content ratio of IPA is preferably 20 mol% or more, more preferably 40 mol% or more, further preferably 50 mol% or more, and 60 mol, based on the total aromatic dicarboxylic acid component. Most preferably, it is% or more. When the aromatic dicarboxylic acid component contains TPA and IPA, the content ratio of TPA / IPA may be 0/100 to 80/20 in terms of the solvent solubility of the polyarylate resin (B). It is preferably 0/100 to 60/40, more preferably 0/100 to 50/50, still more preferably 0/100 to 40/60, and 10/90 to 40/40. Most preferably, it is 60.

The polyarylate resin (B) further contains a hydroxycarboxylic acid component as a monomer component. The hydroxycarboxylic acid may be any organic compound (particularly an aromatic compound) containing one hydroxy group and one carboxy group in one molecule. Examples of the hydroxycarboxylic acid include p-hydroxybenzoic acid [PHBA], m-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 2-hydroxy-3-naphthoic acid, and 1-hydroxy-4-naphthoic acid. Can be mentioned. Among them, PHBA is preferable because of its high versatility.

The content ratio of the hydroxycarboxylic acid component is 2 to 18 mol% with respect to 100 mol% of the total monomer component of the polyarylate resin (B) . When the content ratio of the hydroxycarboxylic acid component is less than 2 mol%, it is difficult to obtain a polyarylate resin (B) having a predetermined hydroxy group concentration. When the content of the hydroxycarboxylic acid component exceeds 50 mol%, the solubility in a general-purpose solvent (particularly a non-halogenated solvent) and the solution stability become low. Note that the total monomer component, polyarylate resin (B) means der that all of the monomer components constituting the is, is a dihydric phenol component and an aromatic dicarboxylic acid component and all of the hydroxy acid component (total amount) ..

Polyarylate resin (B), the dihydric phenol component noted above, the aromatic dicarboxylic acid component and other content ratio of the monomer Ingredients other than hydroxycarboxylic acid component, the total monomer components 100 mole%, 0 mol it is%.

The hydroxy group concentration of the polyarylate resin (B) needs to be 100 geq / ton or more, and is preferably 200 geq / ton or more from the viewpoint of further improving the solvent solubility and the heat resistance of the cured product. It is more preferably 300 geq / ton or more, and further preferably 500 geq / ton or more. When the hydroxy group concentration is less than 100 geq / ton, the solvent solubility is lowered. In addition, it may be inferior in adhesiveness and heat-resistant adhesiveness in the use of adhesives, and may be inferior in adhesion, flexibility and hardness in the use of conductive pastes and coating agents. The upper limit of the hydroxy group concentration is not particularly limited, but does not exceed the hydroxy group concentration of the divalent phenol component, and the hydroxy group concentration is usually 2500 geq / ton or less and 1500 geq / ton or less. Is more preferable, and 1000 eq / ton or less is even more preferable.

The method for determining the hydroxy group concentration is not particularly limited as long as the hydroxy group can be quantified, and may be determined by a known method such as a neutralization titration method, but in ¹ H-NMR analysis described in detail later, It can be obtained by calculating the peak area of the proton located at the ortho-position or the meta-position with respect to the phenolic hydroxy group and quantifying the group.

The monomer concentration in the polyarylate resin (B) is preferably 2% by mass or less, and more preferably 1.5% by mass or less from the viewpoint of further improving solvent solubility and heat resistance, 1.0. It is more preferably mass% or less, and particularly preferably 0.5 mass% or less. When the monomer concentration exceeds 2% by mass, when the polyallylate resin (B) is dissolved in a solvent, insoluble matter precipitates in the solution and / or the solution becomes turbid, so that the polyallylate resin (B) becomes turbid. Solubility is reduced. The lower limit of the monomer concentration is not particularly limited, and the monomer concentration is usually 0.01% by mass or more, preferably 0.1% by mass or more.

The monomer concentration is the total concentration of all the monomer components used in the production of the polyarylate resin (B). Specifically, the monomer concentration consisted of a monomer component that was used in the production of the polyarylate resin (B) but remained unreacted, and a polymer chain of the polyarylate resin (B), which was released (decomposed) from the polymer chain. ) And the total concentration of the produced monomer components. The monomer component contained in the polyarylate resin is difficult to separate, and is precipitated as an insoluble matter when the polyarylate resin is dissolved in a solvent. It is considered that the solubility of the polyarylate resin in a general-purpose solvent depends not only on the structure and monomer composition of the polymer itself of the polyarylate resin but also on the presence of the monomer component contained in the polyarylate resin.

The monomer concentration is a ratio of the mixture containing the residual monomer component and the free monomer component to the total amount of the polyarylate resin (B), and can be measured from the solution of the polyarylate resin (B) by high-speed liquid chromatography. Specifically, the measurement by high performance liquid chromatography is performed by the method described later.

The number average molecular weight of the polyarylate resin (B) is not particularly limited, but is preferably less than 20,000, more preferably less than 10,000, further preferably less than 6000, and particularly preferably less than 3,000. preferable. When the number average molecular weight is 20000 or more, the hydroxy group concentration may be low and the solvent solubility may be lowered. The number average molecular weight of the polyarylate resin (B) is usually 500 or more, preferably 1000 or more.

[Manufacturing method of polyarylate resin (B)]
The method for producing the polyarylate resin (B) is not particularly limited as long as the hydroxy group concentration can be kept within a predetermined range, but since the hydroxy group concentration can be easily controlled, a hydroxycarboxylic acid component is used at the time of melt polymerization. The method of control is preferable.

The method of controlling the hydroxy group concentration using a hydroxycarboxylic acid component during melt polymerization is a method of performing an acetylation reaction and a deacetic acid polymerization reaction, in which the hydroxycarboxylic acid is used after the acetylation reaction and before the deacetic acid polymerization reaction. It is a method of adding an ingredient. That is, the hydroxycarboxylic acid component is added after the acetylation reaction and before the deacetic acid polymerization reaction. As long as the effect of the present invention is not impaired, the remaining hydroxy is added after a part of the hydroxycarboxylic acid component is added to carry out the acetylation reaction, and after the acetylation reaction and before the deacetic acid polymerization reaction. A carboxylic acid component may be added.

The acetylation reaction is a reaction for acetylating a divalent phenol component, or a divalent phenol component and a hydroxycarboxylic acid component. In the acetylation reaction, an aromatic dicarboxylic acid component, a divalent phenol component and acetic anhydride are charged into the reaction can, or an aromatic dicarboxylic acid component, a divalent phenol component, a hydroxycarboxylic acid and acetic anhydride are charged. Then, nitrogen substitution is carried out, and the mixture is stirred under an inert atmosphere at a temperature of 100 to 240 ° C., preferably 120 to 180 ° C. for 5 minutes to 8 hours, preferably 30 minutes to 5 hours under normal pressure or pressure. The molar ratio of acetic anhydride to the hydroxy group of the divalent phenol component is preferably 1.00 to 1.20.

The deacetic acid polymerization reaction is a reaction in which an acetylated divalent phenol is reacted with an aromatic dicarboxylic acid to carry out polycondensation. In the deacetic acid polymerization reaction, the temperature was maintained at 240 ° C. or higher, preferably 260 ° C. or higher, more preferably 280 ° C. or higher, 500 Pa or lower, preferably 260 Pa or lower, more preferably 130 Pa or lower, for 30 minutes or longer. Stir. If the temperature is less than 240 ° C., the degree of decompression exceeds 500 Pa, or the holding time is less than 30 minutes, the deacetic acid reaction becomes insufficient and the amount of acetic acid in the resulting polyarylate resin (B) becomes high. , The overall polymerization time may become longer, or the polymer color tone may deteriorate.

After the acetylation reaction and before the deacetic acid polymerization reaction, there is usually a preliminary step of adjusting the temperature and pressure of the reaction system to the temperature and pressure for the deacetic acid polymerization reaction. In the production method of the present invention, the hydroxycarboxylic acid component may be added in this preliminary step. Specifically, in the preliminary step, when the reaction system is heated and the pressure is reduced, the hydroxycarboxylic acid component may be added before the temperature is raised, or hydroxy after the temperature is raised and before the pressure is reduced. A carboxylic acid component may be added. The hydroxycarboxylic acid component may be added both before the temperature rise and after the temperature rise and before the pressure reduction.

The hydroxycarboxylic acid component is added after reacting acetic anhydride with the dihydric phenol component or with the dihydric phenol component and the hydroxycarboxylic acid component. Therefore, the hydroxy group of the hydroxycarboxylic acid component added after the acetylation reaction is not acetylated. As a result, among the terminal groups of the hydroxycarboxylic acid component, the carboxy group having excellent reactivity proceeds to react with the polyarylate resin (B) at the deacetic acid polymerization reaction stage, but is not acetylated. Does not proceed with the reaction with the polyarylate resin (B). Therefore, it is presumed that the hydroxy group concentration of the obtained polyarylate resin (B) can be within a predetermined range.

In the acetylation reaction and the deacetic acid polymerization reaction, it is preferable to use a catalyst, if necessary. Examples of the catalyst include organic titanic acid compounds such as tetrabutyl titanate; zinc acetate; alkali metal salts such as potassium acetate; alkaline earth metal salts such as magnesium acetate; antimony trioxide; hydroxybutyltin oxide, tin octylate and the like. Organic tin compounds; examples include heterocyclic compounds such as N-methylimidazole. The amount of the catalyst added is usually 1.0 mol% or less, preferably 0.5 mol% or less, and 0.2 mol% or less, based on all the monomer components of the obtained polyarylate resin (B). Is more preferable.
Examples of the device for producing the polyarylate resin (B) include known reaction devices, and examples thereof include a batch type reaction device and a continuous type reaction device.

As a method for increasing the hydroxy group concentration of polyester, a method of adding a polyhydric alcohol component and carrying out a depolymerization reaction after the polycondensation reaction is completed is widely known. However, in the case of the polyarylate resin (B), the progress of the depolymerization reaction by the polyhydric alcohol component or the hydroxycarboxylic acid component is slow, and the reaction time of the entire reaction becomes long. Moreover, a part of the monomer components added during the depolymerization reaction remains unreacted, and a part of the monomer components constituting the polyarylate resin (B) is produced as a monomer by the depolymerization reaction. Therefore, the method of carrying out the depolymerization reaction is not preferable.

[Resin composition of the present invention]
The resin composition of the present invention has a glass transition temperature of the polyester resin (A) of −50 to 50 ° C. and can be used as an adhesive, and the resin composition of the polyester resin (A) has a glass transition temperature of 40 to 40 to 50. It is roughly classified into those that can be used for conductive pastes and adhesives at 150 ° C.

The resin composition of the present invention needs to have a mass ratio (A / B) of the polyester resin (A) and the polyarylate resin (B) of 5/95 to 95/5, and is 30/70 to 80. It is more preferably 20/20, and even more preferably 50/50 to 80/20. When the content of the polyester resin (A) with respect to the total of the polyester resin (A) and the polyarylate resin (B) is less than 5% by mass, the obtained resin composition is adhesive or heat-resistant in the use of an adhesive. It may be inferior in properties, and in the use of conductive pastes and coating agents, it may be inferior in adhesion, flexibility and hardness. When the content exceeds 95% by mass, the obtained resin composition is an adhesive. It may be inferior in heat resistance and heat-resistant adhesiveness in the above applications, and may be inferior in hardness and heat resistance in the applications of conductive pastes and coating agents.

The resin composition of the present invention can be produced by polymerizing the above-mentioned polyester resin (A) and polyarylate resin (B), and then melt-kneading them in a polymerization pot or using an extruder. .. Further, it can be produced by dissolving each of the polyester resin (A) and the polyarylate resin (B) in an organic solvent and then mixing these solutions. As the organic solvent, the same solvent as the organic solvent constituting the coating liquid can be used. Since the coating liquid for forming the coating film of the present invention contains a resin composition and an organic solvent, it is preferable to adopt the latter production method.

Further, the coating liquid for forming the coating film of the present invention is a method of simultaneously adding the polyester resin (A) and the polyarylate resin (B) to an organic solvent to dissolve them, or the polyester resin (A) and the polyarylate resin. It can be produced by a method of dissolving the resin composition of the present invention obtained by melt-kneading with (B) in an organic solvent.

The resin composition of the present invention is dissolved in a solvent, coated on a base material such as a polyethylene terephthalate film (PET base material) or a copper foil, and dried to form a coating film. This coating film constitutes a laminate with the base material.

Examples of the solvent used in the present invention include amide compounds such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran and the like. Ether compounds; Ketone compounds such as methyl ethyl ketone, cyclopentanone, cyclohexanone; Aromatic hydrocarbons such as toluene and xylene; Acetate esters such as ethyl acetate and propylene glycol monoethyl ether acetate; Chlorine-based solvents such as methylene chloride Can be mentioned. Among them, methyl ethyl ketone and toluene are useful as more general-purpose solvents. The solvent may be used alone or in combination of two or more.

Examples of the base material include PET film, polyimide film, copper foil, copper plate, glass plate, and stainless steel plate. Examples of the coating method include wire bar coater coating method, film applicator coating method, brush coating method, spray coating method, gravure roll coating method, screen printing method, reverse roll coating method, lip coating method, air knife coating method, and curtain. Examples include a flow coating method and a dip coating method.

The resin composition of the present invention preferably further contains a curing agent (C). By containing the curing agent (C), the resin composition can further enhance adhesiveness, heat-resistant adhesiveness, moisture-heat resistance and heat resistance in the use of adhesives, and adheres in the use of conductive pastes and coating agents. It can improve the property, flexibility, hardness and heat resistance. Examples of the curing agent (C) include known ones, in which the functional groups of the polyester resin (A) and the polyarylate resin (B), or the reaction of the polyester resin (A) and the polyarylate resin (B). The compound is not particularly limited as long as it is a compound having reactivity with the functional group to be formed (for example, a carboxyl group or its anhydride, a hydroxyl group, an epoxy group, an isocyanate group, etc.).

Examples of the curing agent (C) include formaldehyde adducts such as phenol resin, urea, melamine, benzoguanamine and acetguanamine; glyoxal adducts such as urea and acrylamide; alkyl compounds of these adducts using alcohols having 1 to 6 carbon atoms. Such as amino resin; epoxy resin; acid anhydride; isocyanate compound and various blocked isocyanate compounds thereof; aziridine compound; carbodiimide group-containing compound; oxazoline group-containing compound. Of these, isocyanate compounds, various blocked isocyanate compounds thereof, epoxy resins, and oxazoline group-containing compounds are preferable because they are excellent in curing reactivity. Further, an isocyanate compound and various blocked isocyanate compounds thereof are preferable from the viewpoint that the curing reactivity at a relatively low temperature of 150 ° C. or lower is excellent and the thermal effect on the substrate can be minimized.

Examples of the isocyanate compound include aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), and xylylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and dicyclohexylmethane diisocyanate. Examples thereof include aliphatic diisocyanate monomers and trimerics thereof. Among them, HDI, MDI, and TDI are preferable in terms of improving performance such as adhesiveness, HDI is more preferable, and MDI is preferable in that the curing reaction rate is fast. Further, since a coating film having excellent solvent resistance and processability can be formed, an amino resin can also be preferably used as a curing agent.

In the present invention, when the curing agent (C) is used, the content thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass in total of the polyester resin (A) and the polyarylate resin (B). , 0.5 to 20 parts by mass, more preferably 1.0 to 10 parts by mass. If the content of the curing agent (C) is less than 0.1 parts by mass, the above effect may not be exhibited. On the other hand, if the content of the curing agent (C) exceeds 30 parts by mass, the adhesiveness may be insufficient.

The resin composition of the present invention may contain additives as long as the effects of the present invention are not impaired. Additives include, for example, cross-linking agents, antioxidants, viscosity modifiers, bulking agents, dyes, pigments, UV absorbers, void-forming agents, lubricants, radical scavengers, heat stabilizers, flame retardants, inhibitors, etc. Examples thereof include anti-blocking agents, surface activators, slip aids, gloss improvers, decomposition accelerators, viscosity modifiers, and dispersion stabilizers.

Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to these examples.

1. Measurement method (1) Composition of polyester resin (A) and polyarylate resin (B) Using an NMR measuring device (JNM-LA400 type manufactured by JEOL Ltd.), ¹ H-NMR measurement was performed to determine the respective compositions. .. As the measurement solvent, deuterated trifluoroacetic acid was used.

(2) Number average molecular weight of polyester resin (A) and polyarylate resin (B) Using gel permeation chromatography (GPC), the polystyrene-equivalent number average molecular weight was measured under the following conditions.
Liquid transfer unit: LC-10ADvp manufactured by Shimadzu Corporation
Ultraviolet-visible spectrophotometer: SPD-6AV manufactured by Shimadzu Corporation, detection wavelength: 254 nm
Column: One KF-803 manufactured by Shodex and two KF-804 manufactured by Shodex are connected in series and used. Solvent: tetrahydrofuran Measurement temperature: 40 ° C.

(3) Glass transition temperature (Tg) of polyester resin (A) and polyarylate resin (B)
Obtained by measuring from -60 ° C to 200 ° C at a temperature rise rate of 10 ° C / min using an input compensation type differential scanning calorimetry device (Diamond DSC type manufactured by Perkin Elmer) in accordance with JIS-K 7121. Find the temperature at the intersection of the straight line extending the low temperature side baseline to the high temperature side and the tangent line drawn at the point where the slope of the curve of the stepwise change part of the glass transition is maximized. The glass transition temperature was used.

(4) Hydroxy Group Concentration of Polyarylate Resin (B) Peak area of each copolymer component by ¹ H-NMR analysis using a high-resolution nuclear magnetic resonance apparatus (LA-400 NMR manufactured by JEOL Ltd.) The resin composition was determined from. In addition, the peak area of the protons located at the ortho or meta position with respect to the phenolic hydroxy group was calculated by ¹ H-NMR analysis, and the hydroxy group concentration was determined by quantifying the hydroxy group.

(5) Monomer concentration in polyarylate resin (preparation of sample solution A)
0.2 g of the freeze-milled polyarylate resin (B) was immersed in 3 mL of acetonitrile and statically extracted for 3 days at room temperature. Then, the extract was filtered through a filter having a pore size of 0.45 μm and diluted with acetonitrile to prepare a sample solution A for measurement.
(Preparation of sample solution B)
0.2 g of the freeze-milled polyarylate resin (B) was immersed in 3 mL of methanol and statically extracted for 3 days at room temperature. Then, the extract was filtered through a filter having a pore size of 0.45 μm to prepare a sample solution B for measurement.
(Calculation of monomer concentration)
The HPLC measurement of the sample solution A and the sample solution B was performed using an HPLC apparatus (HP1100 manufactured by Hewlett-Packard). From the measurement results of the sample solution A, the monomer concentrations of the dihydric phenol component and the hydroxycarboxylic acid component were determined. In addition, the monomer concentration of the aromatic dicarboxylic acid component was determined from the measurement results of the sample solution B. The monomer concentration in the polyarylate resin (B) was determined from the total of the monomer concentrations of the divalent phenol component, the hydroxycarboxylic acid component and the aromatic dicarboxylic acid component. (Column: Waters Atlantis T3 5 μm φ4.6 × 15 mm, temperature: 40 ° C., detector: UV275 nm, eluent A: 0.1% formic acid aqueous solution, eluent B: acrylonitrile / formic acid = 100/2, flow rate: 0.5 mL / min)
⊚: The monomer concentration in the polyarylate resin was 0.5% by mass or less.
◯: The monomer concentration in the polyarylate resin was more than 0.5% by mass and 2.0% by mass or less.
Δ: The monomer concentration in the polyarylate resin exceeded 2.0% by mass.

(6) Solvent solubility of polyester resin (A) and polyarylate resin (B) It was visually confirmed whether or not the obtained polyester resin (A) and polyarylate resin (B) were each dissolved in methyl ethyl ketone. Those that dissolve at a solid content concentration of 10% by mass or more were judged to be "⊚".
For those that did not dissolve, visually check whether or not they dissolve in a mixed solvent of 80% by mass of toluene and 20% by mass of methyl ethyl ketone, and those that dissolve at a solid content concentration of 10% by mass or more are marked with "○". It was judged.
Furthermore, for those that did not dissolve, it was visually confirmed whether or not they were dissolved in methylene chloride, and those that dissolved at a solid content concentration of 10% by mass or more were judged as "Δ", and those that dissolved at a solid content concentration of less than 10% by mass Those that did not dissolve were judged as "x".

(7) Adhesiveness to PET Substrate The resin composition was dissolved in the solvent soluble in (6) above to obtain a solution. The solution was applied to a polyethylene terephthalate film (PET substrate) having a thickness of 75 μm, and a desktop coating device (manufactured by Yasuda Seiki Co., Ltd., film applicator No. 542-AB type) so that the thickness after drying became 10 μm. It was coated with a bar coater device) and dried at 120 ° C. for 1 minute to prepare a laminate in which the coating film was laminated on a PET substrate. Two of the prepared laminates were used, the coating film forming surfaces were overlapped with each other, and using an air press machine (manufactured by Hayashi Kikai Seisakusho Co., Ltd.), the temperature was 180 ° C. and the pressure was 0.2 MPa / cm ² for 60 seconds. Thermocompression bonding was performed to obtain a thermocompression bonding film. The obtained thermocompression bonding film was cut into strips (length 100 mm × width 25 mm) to prepare test pieces.
The peel strength of the obtained test piece was measured at room temperature under the conditions of a tensile speed of 50 mm / min and a tensile angle of 180 degrees using a tensile tester (precision universal material tester 2020 manufactured by Intesco). The measurement was performed 5 times, and the initial adhesiveness was evaluated according to the following criteria, using the average value as the adhesive strength.
⊚: Adhesive strength is 7 N / 25 mm width or more.
◯: The adhesive strength is 4N / 25mm width or more and less than 7N / 25mm width.
Δ: Adhesive strength is 2N / 25mm width or more and less than 4N / 25mm width.
X: The adhesive strength is less than 2N / 25 mm width.

(8) Adhesion to Copper Foil The test piece prepared by the same method as (7) above except that a copper foil having a thickness of 0.03 mm was used as the base material was the same as the method described in (7) above. The adhesive strength was measured by the method, and the initial adhesiveness was evaluated according to the following criteria.
⊚: Adhesive strength is 7 N / 25 mm width or more.
◯: The adhesive strength is 4N / 25mm width or more and less than 7N / 25mm width.
Δ: Adhesive strength is 2N / 25mm width or more and less than 4N / 25mm width.
X: The adhesive strength is less than 2N / 25 mm width.

(9) Heat-resistant adhesive strength With respect to the test piece prepared by the same method as the above (7), the adhesive strength is the same as the method described in (7) above except that it was carried out in a furnace at 80 ° C. Was measured, and the heat-resistant adhesiveness was evaluated according to the following criteria.
⊚: Adhesive strength is 7 N / 25 mm width or more.
◯: The adhesive strength is 4N / 25mm width or more and less than 7N / 25mm width.
Δ: Adhesive strength is 2N / 25mm width or more and less than 4N / 25mm width.
X: The adhesive strength is less than 2N / 25 mm width.

(10) Moisture and Heat Resistance The thermocompression bonding film produced by the method described in (7) above is subjected to a wet heat treatment under the conditions of 85 ° C., 85% RH, and 500 hours, and then strip-shaped (length 100 mm × width 15 mm). ), And used as a test piece.
The peel strength of the obtained test piece was measured at room temperature under the conditions of a tensile speed of 50 mm / min and a tensile angle of 180 degrees using a tensile tester (precision universal material tester 2020 manufactured by Intesco). The measurement was performed 5 times, and the average value was taken as the adhesive strength after the treatment.
The adhesive strength retention rate was determined from the adhesive strength before and after the wet heat treatment, and evaluated according to the following criteria.
⊚: Adhesive strength retention rate is 80% or more.
◯: The adhesive strength retention rate is 65% or more and less than 80%.
Δ: Adhesive strength retention rate is 40% or more and less than 65%.
X: The adhesive strength retention rate is less than 40%.

(11) Adhesion to PET Substrate The resin composition was dissolved in the solvent soluble in (6) above to obtain a solution. The solution is applied to a PET substrate having a thickness of 75 μm with a desktop coating device (film applicator No. 542-AB type, bar coater device manufactured by Yasuda Seiki Co., Ltd.) so that the thickness after drying is 10 μm. It was processed and dried at 120 ° C. for 1 minute to form a coating film on the PET substrate. After a cellophane tape (CT-18 manufactured by Nichiban Co., Ltd.) was attached to this coating film, the cellophane tape was peeled off to evaluate the adhesion of the coating film to the PET substrate.
◯: The coating film did not peel off from the PET substrate.
Δ: Less than 30% of the coating film area was peeled off from the PET substrate.
X: 30% or more of the coating film area was peeled off from the PET substrate.

(12) Adhesion to Copper Plate The resin composition was dissolved in the solvent soluble in (6) above to obtain a solution. The solution is applied to a copper plate having a thickness of 0.3 mm with a desktop coating device (film applicator No. 542-AB type, bar coater device manufactured by Yasuda Seiki Co., Ltd.) so that the thickness after drying is 10 μm. It was processed and dried at 120 ° C. for 1 minute to form a coating film on a copper plate. After a cellophane tape (CT-18 manufactured by Nichiban Co., Ltd.) was attached to this coating film, the cellophane tape was peeled off to evaluate the adhesion of the coating film to the copper plate.
◯: The coating film did not peel off from the copper plate.
Δ: Less than 30% of the coating film area was peeled off from the copper plate.
X: 30% or more of the coating film area was peeled off from the copper plate.

(13) Flexibility when a coating film is formed (bending test)
The resin composition was dissolved in the solvent soluble in (6) above to obtain a solution. The solution was applied to a PET substrate having a thickness of 75 μm using a tabletop coating device (film applicator No. 542-AB type, bar coater device manufactured by Yasuda Seiki Co., Ltd.). Then, it was heat-treated at 180 ° C. for 30 seconds to form a coating film having a thickness of 25 μm when dried. The laminate in which the coating film was formed on the PET substrate was visually observed in a state of being bent in the 180 ° direction, and evaluated according to the following criteria.
⊚: The coating film was not cracked and no bending mark was left.
◯: The coating film was not cracked, but a bending mark remained.
Δ: The coating film was cracked, but the crack was less than 30% of the bent portion.
X: The coating film was cracked by 30% or more of the bent portion.

(14) Hardness when coated (test using pencils with different hardness)
The resin composition was dissolved in the solvent soluble in (6) above to obtain a solution. The solution was applied to a copper plate having a thickness of 0.3 mm using a tabletop coating device (film applicator No. 542-AB type, bar coater device manufactured by Yasuda Seiki Co., Ltd.). Then, it was heat-treated at 180 ° C. for 30 seconds to form a coating film having a thickness of 30 μm when dried. This coating film is scratched with a pencil having various hardnesses (Mitsubishi Pencil Co., Ltd., "UNI" series), and the hardness of the pencil when the coating film is damaged and the tip of the pencil reaches the substrate is measured. , Evaluated according to the following criteria.
⊚: The hardness of the pencil was H or more.
◯: The hardness of the pencil was B or more and less than H.
Δ: The hardness of the pencil was 6B or more and less than B.
X: The hardness of the pencil was less than 6B.

(15) Heat resistance when a coating film is formed (thermal pressure test)
The resin composition was dissolved in the solvent soluble in (6) above to obtain a solution. The solution was applied to a copper plate having a thickness of 0.3 mm using a tabletop coating device (film applicator No. 542-AB type, bar coater device manufactured by Yasuda Seiki Co., Ltd.). Then, it was heat-treated at 100 ° C. for 30 seconds to form a coating film having a thickness of 25 μm when dried. After aging this coating film at 50 ° C. for 96 hours, a copper plate was further placed on the coating film, and heat pressure was applied at a temperature of 120 ° C. and a pressure of 0.1 MPa with a heat press machine. The amount of the coating film flowing out at the time of heat pressure (that is, the amount of protrusion from the copper plate) was visually observed and evaluated according to the following criteria.
⊚: There was almost no outflow of the coating film.
◯: The coating film slightly flowed out.
Δ: Many coating films flowed out.
X: Almost all of the coating film flowed out.

2. Raw material (1) Hardener (C)
Hardener (S-1): TPA-100 (manufactured by Asahi Kasei Chemicals, HDI)
Hardener (S-2): L75 (manufactured by Sumika Covestro Urethane, TDI)
Hardener (S-3): MT (manufactured by Tosoh Corporation, MDI)

(2) Preparation of polyester resin (A) Preparation example 1
83 parts by mass (50 mol%) of terephthalic acid, 83 parts by mass (50 mol%) of isophthalic acid, 42 parts by mass (67 mol%) of ethylene glycol, 71 parts by mass (63 mol%) of neopentyl glycol, 50 polytetramethylene glycol A part by mass (5 mol%) and 0.1 part by mass of tetrabutyl titanate as a polymerization catalyst were charged into the reactor, and the inside of the system was replaced with nitrogen. Then, while stirring these raw materials at 1000 rpm, the reactor was heated at 245 ° C. to melt them. After the temperature in the reactor reached 245 ° C., the esterification reaction was allowed to proceed for 3 hours. After 3 hours, the temperature in the system was adjusted to 240 ° C. and the pressure in the system was reduced. After the inside of the system reached a high vacuum (pressure: 0.1 to ^10-5 Pa), a polymerization reaction was further carried out for 3 hours to obtain a polyester resin (P-1).

Preparation Examples 2 to 15
Polyester resins (P-2) to (P-15) were obtained in the same manner as in Preparation Example 1 except that the type of monomer used, its composition and the polymerization reaction time were changed as shown in Table 1.

Table 1 shows the charged composition, final resin composition, and characteristic values of the polyester resins (P-1) to (P-15) at the time of preparation.

The abbreviations in Table 1 indicate the following.
TPA: terephthalic acid IPA: isophthalic acid ADA: adipate SEA: sebacate EG: ethylene glycol PG: 1,2-propanediol NPG: neopentyl glycol BAEO: ethylene oxide adduct of bisphenol A CHDM: 1,4-cyclohexanedimethanol TCD: Tricyclodecanedimethanol PTMG: Polytetramethylene glycol (molecular weight: 1000, carbon number is about 54)

(3) Preparation of polyarylate resin (B) Preparation example 1
83 parts by mass (50 mol%) of terephthalic acid, 83 parts by mass (50 mol%) of isophthalic acid, 114 parts by mass (50 mol%) of 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4) −Hydroxyphenyl) -3,3,5-trimethylcyclohexane 230 parts by mass (75 mol%) and anhydrous acetic acid 255 parts by mass (250 mol%) were placed in a reaction vessel equipped with a stirrer and kept under a nitrogen atmosphere. The reaction was carried out by stirring and mixing at a pressure of 140 ° C. for 2 hours (acetylation reaction).
Subsequently, 69 parts by mass (50 mol%) of p-hydroxybenzoic acid was added at 140 ° C., the temperature was raised to 280 ° C. over 3 hours, and the temperature was maintained at 280 ° C. for 1 hour. Then, the pressure was reduced to 130 Pa at 280 ° C. over 90 minutes, and the mixture was stirred for 2 hours to obtain a polyarylate resin (Q-1) (deacetic acid polymerization reaction). When the resin composition of the obtained polyarylate resin was analyzed, the resin composition was the same as the charged composition at the time of preparation.

Preparation Examples 2-9 and 11-13
Polyester resins (Q-2) to (Q-9) and (Q-11) to (Q-11) to the same as in Preparation Example 1 except that the type of monomer used, its composition and the polymerization reaction time were changed as shown in Table 2. (Q-13) was obtained.

Adjustment example 10
50 parts by mass (30 mol%) of terephthalic acid, 116 parts by mass (70 mol%) of isophthalic acid, 143 parts by mass (62.5 mol%) of 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis 194 parts by mass (62.5 mol%) of (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 255 parts by mass (250 mol%) of anhydrous acetic acid were placed in a reaction vessel equipped with a stirrer to create a nitrogen atmosphere. Under normal pressure, the mixture was stirred and mixed at 140 ° C. for 2 hours to react (acetylation reaction).
Subsequently, the temperature was raised to 280 ° C. over 3 hours, held at 280 ° C. for 1 hour, reduced pressure to 130 Pa over 90 minutes, and stirred for 2 hours (deacetic acid polymerization reaction). Then, the pressure was adjusted to normal pressure under a nitrogen atmosphere, 69 parts by mass (50 mol%) of p-hydroxybenzoic acid was added at 280 ° C., and the mixture was stirred at 280 ° C. for 2 hours to obtain a polyarylate resin (Q-10). (Depolymerization reaction).

Table 2 shows the final resin composition and characteristic values of the polyarylate resins (Q-1) to (Q-13).

The abbreviations in Table 2 are as follows.
TPA: Telephthalic acid IPA: Isophthalic acid BisA: 2,2-bis (4-hydroxyphenyl) Propane BisAP: 1,1-bis (4-hydroxyphenyl) -1-phenylethane BisTMC: 1,1-bis (4-hydroxyphenyl) Hydroxyphenyl) -3,3,5-trimethylcyclohexane PHBA: p-hydroxybenzoic acid Ac ₂ O: anhydrous PTBP acetate: p-tert-butylphenol

Example 1
The polyester resin (P-1) and the polyarylate resin (Q-1) are dissolved and mixed in a solvent so that the mass ratio is (P-1) / (Q-1) = 80/20, and the resin composition is obtained. I got something. The results of various evaluations are shown in Tables 3 and 4.

Examples 2-57, Comparative Examples 1-17
A resin composition was obtained in the same manner as in Example 1 except that the types and parts by mass of the polyester resin and the polyarylate resin were changed as shown in Tables 3 and 4. Table 3 shows the resins of Examples 1 to 31 and Comparative Examples 1 to 10 having a glass transition temperature of -50 to 50 ° C. and containing polyester resins (P-1 to P-11) that can be used as adhesives. This is the result of evaluating the adhesiveness to the PET base material, the adhesiveness to the copper foil, the heat-resistant adhesiveness, the moisture-heat resistance, and the heat resistance of the composition. Table 4 shows Examples 32 to 57 and Comparative Example 11 having a glass transition temperature of 40 to 150 ° C. and containing polyester resins (P-9) to (P-15) that can be used for conductive pastes and coating agents. It is the result of having evaluated the adhesiveness, flexibility, hardness and heat resistance of the resin compositions of ~ 17.

In Table 3, since the resin compositions of Examples 1 to 31 have the constitutions specified in the present invention, the formed coating film is excellent in adhesiveness and heat resistance, and also in heat adhesiveness and moisture heat resistance. It was excellent. On the other hand, the resin compositions of Comparative Examples 1 to 5 were inferior in heat resistance and moisture heat resistance because the content of the polyarylate resin (B) was less than the lower limit specified in the present invention. The resin compositions of Comparative Examples 6 and 7 were inferior in adhesiveness and heat-resistant adhesiveness because the content of the polyester resin (A) was less than the lower limit specified in the present invention. Since the resin compositions of Comparative Examples 8 to 10 contain polyarylate resins (Q-11) to (Q-13) having a hydroxy group concentration of not less than the lower limit specified in the present invention, they have adhesiveness and heat resistance. It was inferior in adhesiveness.

In Table 4, since the resin compositions of Examples 32 to 57 have the constitutions specified in the present invention, the formed coating film is excellent in adhesion and heat resistance, and also excellent in flexibility and hardness. Was there. On the other hand, the resin compositions of Comparative Examples 11 and 12 were inferior in heat resistance and hardness because the content of the polyarylate resin (B) was less than the lower limit specified in the present invention. The resin compositions of Comparative Examples 13 and 14 were inferior in adhesion, flexibility, and hardness because the content of the polyester resin (A) was less than the lower limit specified in the present invention. Since the resin compositions of Comparative Examples 15 to 17 contain polyarylate resins (Q-11) to (Q-13) having a hydroxy group concentration equal to or lower than the lower limit specified in the present invention, they have good adhesion and are acceptable. It was inferior in flexibility.

Claims (8)

A resin composition containing a polyester resin (A) excluding a polyarylate resin and a polyarylate resin (B).
The polyester resin (A) contains terephthalic acid as a divalent carboxylic acid component and ethylene glycol as a divalent alcohol component.
The polyarylate resin (B) is composed of a dihydric phenol component, an aromatic dicarboxylic acid component, and a hydroxycarboxylic acid component.
The content ratio of the hydroxycarboxylic acid component to 100 mol% of the total monomer component of the polyarylate resin (B) is 2 to 18 mol%.
The hydroxy group concentration of the polyarylate resin (B) is 100 geq / ton or more.
A resin composition characterized in that the mass ratio (A / B) of the polyester resin (A) and the polyarylate resin (B) is 5/95 to 95/5. Polyarylate resin (B), as the dihydric phenol component, the resin composition according to claim 1, characterized by containing a divalent phenol represented by the general formula (1).

[In formula (1), R ¹ and R ² independently represent hydrogen, a hydrocarbon group having 1 to 12 carbon atoms or a halogen, and m and n independently represent an integer of 0 to 4. Represented, X ₁ and X ₂ are hydrogen, a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group, a cyclic hydrocarbon group containing an aromatic and alicyclic group, a trihalomethane group, and the like. Alternatively, it represents an alkyl ester group having 1 to 20 carbon atoms or a phenyl ester group. ] The resin composition according to claim 2, wherein the polyarylate resin (B) contains a divalent phenol represented by the general formula (2) as a divalent phenol component.

[In formula (2), R ¹ , R ² , R ³ and R ⁴ independently represent hydrogen, a hydrocarbon group having 1 to 12 carbon atoms or a halogen, and R ⁵ and R ⁶ are independent. Represents hydrogen or a hydrocarbon group having 1 to 4 carbon atoms. m represents an integer of 4 to 11, and X represents a carbon that forms a saturated aliphatic hydrocarbon ring with a carbon atom to which a hydroxyphenyl group is bonded. ] As the dihydric phenol component of the polyarylate resin (B), 2,2-bis (4-hydroxyphenyl) propane (BizA) and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane ( The resin composition according to any one of claims 1 to 3 , wherein BisTMC) is used. The resin composition according to claim 4 , wherein the content ratio (BisA / BisTMC) of BisA and BisTMC of the polyarylate resin (B) is 30/70 to 70/30 (molar ratio). The resin composition according to any one of claims 1 to 5 , further containing a curing agent (C). A coating film formed by using the resin composition according to any one of claims 1 to 6 . A laminate having the coating film according to claim 7 .