JP2018028009A - Resin composition and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition that can form a thin film having excellent adhesion, resistant to degradation of solvent resistance, and having a thickness of 1 μm or less.SOLUTION: A resin composition contains (A) an oligomer modified epoxy resin component obtained by the reaction between: a polyphenylene oxide oligomer with a number average molecular weight of 800-10,000, with the content of a constitutional unit represented by general formula (1) (R-R: alkyl groups or the like) being 60 mass% or more of the total content, and having 1.2 or more phenolic hydroxyl groups in average in one molecule; and an epoxy resin, and (B) at least one resin component selected from styrene-butadiene rubber, cyanate ester, and a derivative thereof.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition and a cured product thereof.

  Resin compositions represented by epoxy resins and the like are excellent in heat resistance, adhesiveness, water resistance, mechanical strength, electrical properties, and the like, and thus are used in various fields. In particular, in the electrical and electronic fields, it is widely used in insulation casting, laminate materials, sealing materials, etc. When used in these applications, it has good physical properties such as dielectric constant, adhesion, and solvent resistance. There is a need to be.

  For example, Patent Document 1 proposes a method of using an epoxy resin in which an alicyclic structure is introduced into the skeleton. Patent Document 2 discloses an oligomer-modified epoxy resin that gives a cured product having good moisture resistance, low dielectric constant, and low dielectric loss tangent without impairing heat resistance, adhesiveness, and workability. .

Japanese Patent Laid-Open No. 08-325355 JP 2004-256717 A

  However, since the flame retardancy of the resin is reduced by the method proposed in Patent Document 1, it is necessary to add more flame retardant. For this reason, the subject that the dielectric constant of the hardened | cured material obtained increased occurred. Moreover, it is difficult for the cured product obtained by curing the oligomer-modified epoxy resin disclosed in Patent Document 2 to sufficiently exhibit the adhesion required in the recent electric / electronic field. In particular, a thin film having a thickness of 1 μm or less obtained by curing the oligomer-modified epoxy resin has a problem that adhesion to a substrate such as PET and solvent resistance are low. From the above, there has been a demand for a resin composition capable of forming a thin film having a thickness of 1 μm or less that is excellent in adhesion and solvent resistance.

  Accordingly, the present invention has been made to solve the above-mentioned problems, and the object of the present invention is to form a thin film having a thickness of 1 μm or less that has good adhesion and is resistant to deterioration of solvent resistance. It is in providing the resin composition which can be performed. Moreover, the place made into the subject of this invention is providing the hardened | cured material obtained by hardening the said resin composition.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a resin composition containing a specific resin component can solve the above-mentioned problems, and have reached the present invention.

  That is, according to the present invention, (A) the number average molecular weight is 800 to 10,000, the content of the structural unit represented by the following general formula (1) is 60% by mass or more, and one molecule Selected from an oligomer-modified epoxy resin component obtained by reacting a polyphenylene oxide oligomer having an average of 1.2 or more phenolic hydroxyl groups with an epoxy resin, and (B) styrene butadiene rubber, cyanate ester, and derivatives thereof A resin composition containing at least one resin component is provided.

（前記一般式（１）中、Ｒ¹、Ｒ²、Ｒ³及びＲ⁴は、各々独立して、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいフェニル基、置換基を有していてもよいアミノ基、カルボキシ基、ニトロ基、ハロゲン原子、又は水素原子を表し、＊は結合手を表す）

(In said general formula (1), R < ¹ >, R < ² >, R < ³ > and R < ⁴ > are each independently the alkyl group which may have a substituent, the alkoxy group which may have a substituent. A phenyl group which may have a substituent, an amino group which may have a substituent, a carboxy group, a nitro group, a halogen atom or a hydrogen atom, and * represents a bond)

  Moreover, according to this invention, the hardened | cured material which hardened said resin composition is provided.

  According to the present invention, it is possible to provide a resin composition capable of forming a thin film having a thickness of 1 μm or less, which has good adhesion and hardly deteriorates solvent resistance. Moreover, according to this invention, the hardened | cured material obtained by hardening the said resin composition can be provided.

  Hereinafter, embodiments of the present invention will be specifically described. The resin composition of the present invention is at least selected from (A) a specific oligomer-modified epoxy resin component (hereinafter also referred to as “(A) component”), (B) a styrene butadiene rubber, a cyanate ester, and derivatives thereof. 1 type of resin component (henceforth "(B) component") is contained.

  The component (A) used in the resin composition of the present invention has a number average molecular weight of 800 to 10,000, and the content of the structural unit represented by the following general formula (1) is 60% by mass or more of the whole. It is an oligomer-modified epoxy resin component obtained by reacting an epoxy resin with a polyphenylene oxide oligomer having an average of 1.2 or more phenolic hydroxyl groups in one molecule. In addition, the hydrolyzable chlorine concentration of the component (A) is preferably less than 1,000 ppm, and more preferably less than 500 ppm.

In general formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. It represents a phenyl group which may have a group, an amino group which may have a substituent, a carboxy group, a nitro group, a halogen atom, or a hydrogen atom.

Examples of the alkyl group include linear, branched, or cyclic alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and a cyclohexyl group. Can be mentioned. As an alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. can be mentioned, for example. These alkyl groups and alkoxy groups preferably have 1 to 4 carbon atoms. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be mentioned, for example. Examples of the substituent that can be bonded to an alkyl group, an alkoxy group, a phenyl group, and an amino group include, for example, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, and a halogen atom. Can be mentioned. Among them, in the general formula (1), R ² and R ⁴ are methyl groups, it is preferred that R ¹ and R ³ are hydrogen atoms.

  The polyphenylene oxide oligomer is preferably an oligomer having a structural unit represented by the general formula (1) as a main structural unit and a structural unit represented by the following general formula (2) in the main structural unit. When the polyphenylene oxide oligomer containing the structural unit represented by the following general formula (2) in the main structural unit is used in combination with the component (B), the adhesion to a substrate such as PET is better. In addition, a resin composition that is further excellent in solvent resistance and can form a thin film (cured product) having a thickness of 1 μm or less can be obtained.

（前記一般式（２）中、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹及びＲ¹²は、各々独立して、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいフェニル基、置換基を有していてもよいアミノ基、カルボキシ基、ニトロ基、ハロゲン原子、又は水素原子を表し、Ｘは、置換基を有していてもよいアルキレン基、カルボニル基、チオ基、スルフェニル基、スルホニル基、又は直接結合を表し、＊は結合手を表す）

(In the general formula (2), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each independently an alkyl group which may have a substituent. , An optionally substituted alkoxy group, an optionally substituted phenyl group, an optionally substituted amino group, a carboxy group, a nitro group, a halogen atom, or a hydrogen atom. X represents an alkylene group which may have a substituent, a carbonyl group, a thio group, a sulfenyl group, a sulfonyl group, or a direct bond, and * represents a bond.

Specific examples of the alkyl group, alkoxy group, and halogen atom, and specific examples of the substituent that can be bonded to the alkyl group, alkoxy group, phenyl group, and amino group include R ¹ in the general formula (1), The same thing as R < ² >, R < ³ > and R < ⁴ > can be mentioned. Among these, in general formula (2), R ⁵ , R ⁷ , R ¹⁰ and R ¹² are preferably methyl groups, and R ⁶ , R ⁸ , R ⁹ and R ¹¹ are preferably hydrogen atoms.

  In general formula (2), examples of the alkylene group represented by X include linear, branched, or cyclic groups such as a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, and a cyclohexylene group. An alkylene group can be mentioned. These alkylene groups preferably have 1 to 4 carbon atoms. Examples of the substituent that can be bonded to the alkylene group include an alkyl group and a phenyl group. X in the general formula (2) is preferably an alkylene group which may have a substituent, more preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably a methylene group, an ethylene group or a dimethylmethylene group.

  The number average molecular weight in terms of polystyrene of the component (A) is 800 to 10,000, preferably 800 to 8,000. When the number average molecular weight of the component (A) is less than 800, the effect of improving the dielectric properties of the formed cured product becomes insufficient. On the other hand, when the number average molecular weight of the component (A) is more than 10,000, the melt viscosity of the resin composition is increased and the moldability is lowered.

  As the component (A), a known oligomer-modified epoxy resin can be used. Such an oligomer-modified epoxy resin can be produced, for example, according to the method described in Patent Document 1. More specifically, the component (A) can be produced by a method using an enzyme catalyst, a method using a radical initiator, a method using a complex catalyst, or the like.

  The content of the component (A) in the resin composition of the present invention is preferably 10 to 90% by mass, and more preferably 40 to 80% by mass. By setting the content of the component (A) within the above range, a thin film (cured product) having a thickness of 1 μm or less, which has better adhesion to a substrate such as PET and further excellent solvent resistance ) Can be formed.

  The component (B) used in the resin composition of the present invention is at least one resin component selected from styrene butadiene rubber, cyanate ester, and derivatives thereof.

  Examples of the styrene butadiene rubber and derivatives thereof include styrene butadiene, hydrogenated styrene butadiene, acid-modified hydrogenated styrene butadiene, and the like. More specific examples of styrene butadiene rubber and derivatives thereof are as follows: Kraton (registered trademark) G series (manufactured by Kraton Polymer Japan); Tuftec (registered trademark) H series (manufactured by Asahi Kasei); Tuftec ( (Registered trademark) P series (manufactured by Asahi Kasei Co., Ltd.); Tuftec (registered trademark) M series (manufactured by Asahi Kasei Co., Ltd.). Furthermore, those obtained by acid-modifying these styrene butadiene rubbers and derivatives thereof with an acid such as maleic acid can also be used.

  As cyanate ester and its derivative (s), the compound represented by following General formula (3), the compound represented by following General formula (4), etc. can be mentioned, for example. Moreover, the prepolymer in which some cyanate groups in the following general formulas (3) and (4) formed a triazine ring may be used. Examples of such a prepolymer include those in which a part or all of the compound represented by the following general formula (3) is trimerized.

（前記一般式（３）中、Ｒ²¹は非置換又はフッ素置換の２価の炭化水素基を表し、Ｒ²²は、各々独立して、非置換又は１〜４個のアルキル基で置換されたフェニレン基を表す）

(In the general formula (3), R ²¹ represents an unsubstituted or fluorine-substituted divalent hydrocarbon group, and each R ²² is independently unsubstituted or substituted with 1 to 4 alkyl groups. Represents a phenylene group)

（前記一般式（４）中、ｎは１以上の整数を表し、Ｒ²⁴は水素原子又は炭素数１〜４のアルキル基を表す）

(In the general formula (4), n represents an integer of 1 or more, and R ²⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

  Among the cyanate esters, compounds represented by the following general formula (5) and prepolymers thereof are preferable, and 4,4′-ethylidenebisphenylene cyanate, 2,2′-bis (4-cyanatophenyl) propane and bis (4-Cyanato-3,5-dimethylphenyl) methane is more preferred.

（前記一般式（５）中、Ｒ²⁵は、下記いずれかの式で表される２価の基を表し、Ｒ²⁶、Ｒ²⁷、Ｒ²⁸及びＲ²⁹は、各々独立して、水素原子、又は非置換若しくはフッ素置換のメチル基を表す）

(In the general formula (5), R ²⁵ represents a divalent group represented by any one of the following formulas, and R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ are each independently a hydrogen atom, Or represents an unsubstituted or fluorine-substituted methyl group)

（前記式中、ｎは４〜１２の整数を表し、Ｒ³⁰及びＲ³¹は、各々独立して、水素原子、又は非置換若しくはフッ素置換のメチル基を表し、＊は結合手を表す）

(In the above formula, n represents an integer of 4 to 12, R ³⁰ and R ³¹ each independently represents a hydrogen atom or an unsubstituted or fluorine-substituted methyl group, and * represents a bond)

  Cyanate ester may be used independently and may be used in combination of 2 or more type. Use of a cyanate ester as the component (B) is preferable because the processability of the formed cured product is improved, and it is more preferable to use only the cyanate ester as the component (B).

  The content of the component (B) in the resin composition of the present invention is preferably 10 to 90% by mass, and more preferably 40 to 60% by mass. (B) By making content of a component in said range, while being more adhesive to base materials, such as PET, the thin film (hardened | cured material) of thickness 1 micrometer or less which was further excellent in solvent resistance ) Can be formed.

  The mass ratio of the component (A) and the component (B) contained in the resin composition of the present invention is preferably in the range of (A) component: (B) component = 90: 10 to 10:90, : More preferably within the range of 20-40: 60. By making the mass ratio of the component (A) and the component (B) within the above range, the adhesiveness to a substrate such as PET is better, and the solvent resistance is further improved, and the thickness is 1 μm or less. It can be set as the resin composition which can form a thin film (hardened | cured material).

  The hydrolyzable chlorine concentration of the resin composition of the present invention is preferably 0 to 1,000 ppm, more preferably 1 to 500 ppm, and particularly preferably 10 to 300 ppm. When the hydrolyzable chlorine concentration is within the above range, the resin composition has better adhesion to a substrate such as PET and can form a cured product having further excellent solvent resistance. Can do.

  In the resin composition of the present invention, a normal curing agent used for epoxy resins can be used. Examples of the curing agent include a latent curing agent, an acid anhydride, a polyamine compound, a polyphenol compound, and a cationic photoinitiator.

  Examples of the latent curing agent include dicyandiamide, hydrazide, imidazole compound, amine adduct, sulfonium salt, onium salt, ketimine, acid anhydride, and tertiary amine. Use of these latent curing agents is preferable because it can be made into a one-component curable composition and is easy to handle.

  Examples of the imidazole compound include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, and 1-benzyl. 2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methylimidazole (1 ′ )) Ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl, 4-methylimidazole) (1 ′)) Ethyl-s-triazine, 2,4-diamino- (2'-methylimidazole (1 ')) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3, Various imidazoles such as 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole; these various imidazoles and phthalates Examples thereof include salts with polyvalent carboxylic acids such as acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, and succinic acid.

  Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, succinic anhydride, 2, Examples thereof include 2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride.

  Examples of the polyamine compound include aliphatic polyamines such as ethylenediamine, diethylenetriamine, and triethylenetetramine; mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9 -Alicyclic polyamines such as bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro [5,5] undecane; aliphatic amines having an aromatic ring such as m-xylenediamine; m-phenylenediamine 2,2-bis (4-aminophenyl) propane, diaminodiphenylmethane, diaminodiphenylsulfone, α, α-bis (4-aminophenyl) -p-diisopropylbenzene, 2,2-bis (4-aminophenyl)- 1,1,1,3,3,3-hexafluoro Aromatic polyamines such as propane can be mentioned.

  Examples of the polyphenol compound include phenol novolak, o-cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol, terpene diphenol, terpene dicatechol, 1,1,3-tris (3-tert-butyl-4-hydroxy -6-methylphenyl) butane, butylidenebis (3-tert-butyl-4-hydroxy-6-methylphenyl), 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3- Examples include hexafluoropropane.

  The resin composition of the present invention can also be used in combination with a filler. When used in combination with a filler, the resulting cured product has a small thermal expansion, and the cured product has good hardness and can prevent scratches. Examples of the filler include silicas such as fused silica, fused spherical silica, crystalline silica, colloidal silica, fumed silica, and silica gel; metal oxides such as alumina, iron oxide, titanium oxide, zirconium oxide, and antimony trioxide. Ceramics such as silicon nitride, aluminum nitride, boron nitride and silicon carbide; minerals such as mica and montmorillonite; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; and those modified by organic modification treatment; Metal carbonates such as calcium carbonate, calcium silicate, magnesium carbonate and barium carbonate, and those modified by organic modification treatment; pigments such as metal borate and carbon black; carbon fiber, graphite, whisker, kaolin , Talc, glass fiber, glass beads, glass my Rosufia, silica glass, may be mentioned layered clay mineral, clay, silicon carbide, quartz, aluminum, zinc and the like.

  Additives can be added to the resin composition of the present invention as long as the effects thereof are not impaired. Examples of additives include plasticizers such as natural waxes, synthetic waxes, and metal salts of long-chain aliphatic acids; release agents such as acid amides, esters, and paraffins; nitrile rubber, butadiene rubber, and the like Inorganic flame retardants such as antimony trioxide, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide, magnesium hydroxide, calcium aluminate; Brominated flame retardants such as tetrabromobisphenol A, tetrabromophthalic anhydride, hexabromobenzene, brominated phenol novolak; couplings such as phosphorus compounds, silane coupling agents, titanate coupling agents, aluminum coupling agents Agents; coloring agents such as dyes and pigments; oxidation stabilizers, light stabilizers, moisture resistance improvers, Tiki Toropi imparting agents, diluents can include defoamers, other various resins, tackifiers, antistatic agents, lubricants, UV absorbers.

  Furthermore, the resin composition of the present invention includes alcohols, ethers, acetals, ketones, esters, alcohol esters, ketone alcohols, ether alcohols, ketone ethers, ketone esters and ester ethers, An organic solvent such as an aromatic solvent can also be blended.

  The cured product of the present invention can be formed by curing the above resin composition. The cured product of the present invention can be suitably used for applications such as interlayer insulating materials for flexible substrates, interlayer insulating materials for multilayer substrates, thin film adhesive sheets, solvent-resistant coatings, and sheets for optical materials.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited by these.

<(A) component>
(Production Example 1) Synthesis of oligomer-modified epoxy resin α 1 L of acetone, 1 L of distilled water, 80 g of dihydric phenol (3,3 ′, 5,5′-tetramethylbisphenol A), and catalyst (Pycnoporus cocineus-derived laccase (high 200 mg) was charged into a reaction vessel, and a polymerization reaction was performed at 30 ° C. for 24 hours. After completion of the reaction, 5 L of methanol was added and the precipitated polymer was filtered, washed with distilled water and methanol, and then vacuum-dried to obtain 35.8 g of a polyphenylene oxide oligomer α. The number average molecular weight of the polyphenylene oxide oligomer α measured by gel permeation chromatography was 1,900. Further, the hydroxyl equivalent of the polyphenylene oxide oligomer α measured by a titration method is 1,290 g / eq. It was confirmed that 1 molecule had an average of 1.47 phenolic hydroxyl groups. Furthermore, by analyzing by ¹ H-NMR, ¹³ C-NMR, and two-dimensional NMR, a structural unit represented by the following general formula (6) and a structural unit represented by the following general formula (7) are obtained. Having an average molar ratio of 7.5: 1. 120 g of the obtained polyphenylene oxide oligomer α, 40 g of bisphenol A novolak type epoxy resin (trade name “Epicoat 157S70”, manufactured by Japan Epoxy Resin, epoxy equivalent = 210 g / equivalent), 50 g of cyclohexanone, and 50% tetramethylammonium chloride aqueous solution 0 0.02 g was charged into the reaction vessel. The temperature was raised to 135 ° C. and stirred for 3 hours to carry out a polymerization reaction to obtain an oligomer-modified epoxy resin α. The epoxy equivalent of the oligomer-modified epoxy resin α measured by the perchloric acid titration method was 920 g / equivalent. Further, the hydrolyzable chlorine concentration of the oligomer-modified epoxy resin α was 250 ppm, the number average molecular weight measured by gel permeation chromatography was 2,850, and the softening temperature was 165 ° C. The obtained oligomer-modified epoxy resin α is hereinafter also referred to as “A-1”.

(Production Example 2) Synthesis of oligomer-modified epoxy resin β A polyphenylene oxide oligomer was prepared in the same manner as in Production Example 1 except that 3,3 ′, 5,5′-tetramethylbisphenol F was used as the divalent phenol. β 34.6 g was obtained. The obtained oligomer-modified epoxy resin was soluble in chloroform and tetrahydrofuran, and the number average molecular weight measured by gel permeation chromatography was 1,200. Further, the hydroxyl equivalent of polyphenylene oxide oligomer β measured by titration was 780 g / eq. It was confirmed that each molecule had an average of 1.54 phenolic hydroxyl groups. Furthermore, by analyzing by ¹ H-NMR, ¹³ C-NMR, and two-dimensional NMR, a structural unit represented by the general formula (6) and a structural unit represented by the following general formula (8) are obtained. And having an average molar ratio of 21: 1. 120 g of the obtained polyphenylene oxide oligomer β, 40 g of bisphenol A novolak type epoxy resin (trade name “Epicoat 157S70”, manufactured by Japan Epoxy Resin, epoxy equivalent = 210 g / equivalent), 50 g of cyclohexanone, and 50% tetramethylammonium chloride aqueous solution 0 0.02 g was charged into the reaction vessel. The temperature was raised to 135 ° C. and stirred for 3 hours to conduct a polymerization reaction, to obtain an oligomer-modified epoxy resin β. The epoxy equivalent of the oligomer-modified epoxy resin β measured by the perchloric acid titration method was 900 g / equivalent. Further, the hydrolyzable chlorine concentration of the oligomer-modified epoxy resin β was 280 ppm, the number average molecular weight measured by gel permeation chromatography was 1,620, and the softening temperature was 155 ° C. The obtained oligomer-modified epoxy resin β is hereinafter also referred to as “A-2”.

<(B) component>
As components (B), B-1 to B-5 shown below were prepared.
B-1: Bisphenol A dicyanate B-2: Liquid cyanate ester, trade name “LECy”, manufactured by Lonza Japan B-3: Cyanate ester, product name “LVT-50”, manufactured by Lonza Japan B-4: Multifunctional Cyanate ester, trade name “PT-30”, manufactured by Lonza Japan B-5: Hydrogenated styrene butadiene rubber, trade name “Tuftec M1913”, manufactured by Asahi Kasei Chemicals

<Resin composition>
(Examples 1-8)
(A) component and (B) component are mixed so that it may become the mixing | blending shown in Table 1, Example composition No. 1-8 were produced.

(Comparative Examples 1-5)
Comparative compositions 1 to 5 having the formulations shown in Table 2 were prepared.

<Formation of thin film (cured product)>
(Examples 9 to 16)
Example Composition No. 1-No. 8 was diluted with a mixed solvent of xylene and MEK, respectively, and 5% by mass of 4,4′-biphenol was added as a curing agent to the total of component (A) and component (B) to obtain a liquid composition. . The obtained liquid composition was applied onto a PET film, and then dried at 180 ° C., and an Example thin film No. 1-8 were produced.

(Comparative Examples 6 to 10)
The comparative compositions 1 to 5 were diluted with xylene and MEK mixed solvents, respectively, and 5% by mass of 4,4′-biphenol was added as a curing agent to the total of the components (A) and (B) to form a liquid. A composition was obtained. After apply | coating the obtained liquid composition on PET film, it dried at 180 degreeC and manufactured the comparative example thin films 1-5 of thickness about 0.5 micrometer.

<Evaluation>
(Evaluation example 1) Adhesion evaluation Example thin film No. The surfaces of 1 to 8 and comparative example thin films 1 to 5 were cross-cut with a knife, and the tape was peeled to evaluate the adhesion. The case where it did not peel was evaluated as “+”, and the case where even a part was peeled was evaluated as “−”. The evaluation results are shown in Table 3.

(Evaluation example 2) Solvent resistance evaluation Example thin film No. About 1-8 and the comparative example thin films 1-5, each was rubbed 100 times using isopropanol, and solvent resistance was evaluated. The case where no appearance abnormality occurred was evaluated as “+”, and the case where appearance abnormality occurred was evaluated as “−”. The evaluation results are shown in Table 3.

  From the results shown in Table 3, it can be seen that Comparative Examples Thin Films 1 to 5 have insufficient adhesion. In contrast, Example Composition No. It can be seen that the thin film formed using 1 to 8 has good adhesion to the PET film and excellent solvent resistance even when the film thickness is 1 μm or less.

Claims (3)

(A) The number average molecular weight is 800 to 10,000, the content of the structural unit represented by the following general formula (1) is 60% by mass or more of the whole, and an average of 1.2 or more in one molecule An oligomer-modified epoxy resin component obtained by reacting a polyphenylene oxide oligomer having a phenolic hydroxyl group with an epoxy resin, and (B) at least one resin component selected from styrene butadiene rubber, cyanate ester, and derivatives thereof A resin composition to contain.

(In said general formula (1), R < ¹ >, R < ² >, R < ³ > and R < ⁴ > are each independently the alkyl group which may have a substituent, the alkoxy group which may have a substituent. A phenyl group which may have a substituent, an amino group which may have a substituent, a carboxy group, a nitro group, a halogen atom or a hydrogen atom, and * represents a bond) The polyphenylene oxide oligomer is an oligomer having a structural unit represented by the general formula (1) as a main structural unit and a structural unit represented by the following general formula (2) in the main structural unit. The resin composition described in 1.

(In the general formula (2), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each independently an alkyl group which may have a substituent. , An optionally substituted alkoxy group, an optionally substituted phenyl group, an optionally substituted amino group, a carboxy group, a nitro group, a halogen atom, or a hydrogen atom. X represents an alkylene group which may have a substituent, a carbonyl group, a thio group, a sulfenyl group, a sulfonyl group, or a direct bond, and * represents a bond.   A cured product obtained by curing the resin composition according to claim 1.