JPWO2019065246A1 - Resin composition and resin film - Google Patents

Abstract

It is a resin composition containing a carboxyl group-containing resin, a polyfunctional vinyl ether compound, and a nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms.

Description

The present invention relates to a resin composition and a resin film, and more particularly to a resin composition and a resin film containing a carboxyl group-containing resin.

Various display elements such as organic EL elements and liquid crystal display elements, integrated circuit elements, solid-state imaging elements, and electronic components such as color filters and black matrices have protective films, element surfaces, and other elements to prevent deterioration and damage. Various resin films are provided as a flattening film for flattening the surface of a substrate having wiring, an electrically insulating film for maintaining electrical insulation, and the like. Further, for example, the organic EL element is provided with a resin film as a pixel separation film in order to separate the light emitting body portion. Furthermore, for example, elements such as display elements and integrated circuit elements for thin film transistor type liquid crystals are provided with a resin film as an interlayer insulating film in order to insulate between wirings arranged in layers.

Conventionally, various resin compositions have been proposed as the resin composition for forming the above-mentioned resin film. For example, Patent Document 1 proposes a negative photosensitive resin composition containing a cyclic olefin polymer having a protic polar group, an unsaturated group-containing compound, and a radical-generating photopolymerization initiator. According to such a resin composition, it is possible to form a resin film which is excellent in pattern forming property, transparency and heat resistance by development and in which the generation of outgas is suppressed.

Japanese Unexamined Patent Publication No. 2015-25892

Here, conventionally, a material such as glass has been generally used as a substrate for a display element. When forming a resin film on a glass substrate, when the resin film is cured, the resin film is cured at a high curing temperature such as 200 ° C. or higher to promote the curing reaction and obtain a resin film having high chemical resistance. It was possible to form. However, in recent years, with the flexibility of display elements, it has been required to use a flexible plastic film or the like as a substrate instead of a glass substrate. Here, the heat resistance of the plastic substrate is lower than the heat resistance of the glass substrate. Therefore, in order to form the resin film on the plastic substrate, it is necessary to lower the curing temperature when the resin film is cured. Therefore, there is a demand for the development of a resin composition capable of forming a resin film having high chemical resistance even under low temperature curing conditions.

Further, in the step of laminating various films on a substrate at the time of manufacturing electronic components, it is common to use various chemicals and the like. Here, if the composition can enhance the chemical resistance to various chemicals, the storage stability of the resin composition deteriorates, the chemical resistance of the obtained resin film is enhanced, and the storage stability of the resin composition itself is improved. There was a problem that it was difficult to achieve both.

In view of the above circumstances, the present invention provides a resin composition capable of both ensuring the storage stability of the resin composition itself and enhancing the chemical resistance of the obtained resin film. The purpose is.
Another object of the present invention is to provide a resin film having excellent chemical resistance.

The present inventor has conducted diligent studies for the purpose of solving the above problems. Then, the present inventor preserves the resin composition itself when the resin having a predetermined functional group, the polyfunctional vinyl ether compound, and the predetermined nitrogen-containing condensed heterocyclic compound coexist in the resin composition. The present invention has been completed by newly finding that it is possible to achieve both ensuring stability and enhancing the chemical resistance of the resin film obtained by using such a resin composition.

That is, the present invention aims to advantageously solve the above problems, and the resin composition of the present invention contains a carboxyl group-containing resin, a polyfunctional vinyl ether compound, and nitrogen-containing nitrogen having 3 nitrogen atoms. It is characterized by containing a condensed heterocyclic compound. By blending the resin composition into such a specific blend, it is possible to achieve both ensuring the storage stability of the resin composition itself and enhancing the chemical resistance of the obtained resin film.

Further, in the resin composition of the present invention, it is preferable that the nitrogen-containing condensed heterocyclic compound is a benzotriazole-based compound. When the resin composition contains a benzotriazole-based compound, it is possible to more satisfactorily secure the storage stability of the resin composition itself and enhance the chemical resistance of the obtained resin film. ..

Further, it is preferable that the resin composition of the present invention further contains a polyfunctional epoxy compound. If the resin composition further contains a polyfunctional epoxy compound, the crack resistance of the obtained resin film can be further improved.

Further, in the resin composition of the present invention, it is preferable that the polyfunctional epoxy compound has an alicyclic epoxy group. If the polyfunctional epoxy compound contained in the resin composition has an alicyclic epoxy group, the crack resistance of the obtained resin film can be further improved.

Further, in the resin composition of the present invention, it is preferable that the carboxyl group-containing resin is a resin containing a cyclic olefin monomer unit. When the resin composition is a resin containing a cyclic olefin monomer unit, the amount of outgass from the obtained resin film can be suppressed and the water absorption of the obtained resin film can be reduced.

Further, it is preferable that the resin composition of the present invention contains the nitrogen-containing condensed heterocyclic compound in a proportion of 1 part by mass or more with respect to 100 parts by mass of the carboxyl group-containing resin. When the content ratio of the nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms is at least the above lower limit value, the crack resistance of the obtained resin film can be further improved.

Here, the present invention is intended to advantageously solve the above problems, and the resin film of the present invention is characterized in that it is formed by using any of the above resin compositions. Since the resin film of the present invention is formed by using the resin composition of the present invention, it has excellent chemical resistance.

According to the present invention, it is possible to provide a resin composition capable of ensuring the storage stability of the resin composition itself and enhancing the chemical resistance of the obtained resin film.
Further, according to the present invention, it is possible to provide a resin film having excellent chemical resistance.

Hereinafter, embodiments of the present invention will be described in detail. The resin composition of the present invention can be suitably used for applying to various elements, parts and the like to form a resin film that can function as a protective film, a flattening film, an insulating film and the like.

(Resin composition)
The resin composition of the present invention is characterized by containing a carboxyl group-containing resin, a polyfunctional vinyl ether compound, and a nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms. By blending the carboxyl group-containing resin, the polyfunctional vinyl ether compound, and the nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms in the resin composition, the storage stability of the resin composition itself can be ensured. It is possible to improve the chemical resistance of the resin film obtained by using such a resin composition. Here, the reactivity between the carboxyl group contained in the carboxyl group-containing resin and the polyfunctional vinyl ether compound is good, and the nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms exhibits appropriate basicity. It is presumed that the above effects can be achieved due to the acquisition. In particular, regarding chemical resistance, the carboxyl group contained in the resin and the polyfunctional vinyl ether compound can initiate the reaction at a low temperature, and the basic nitrogen-containing condensed heterocyclic compound promotes the reaction. It is considered that it works in an advantageous manner. For this reason, it is presumed that the resin composition of the present invention can form a resin film having good chemical resistance. Further, the resin composition of the present invention preferably further contains a polyfunctional epoxy compound.
Hereinafter, each component contained in the resin composition will be described.

<Carboxylic group-containing resin>
The carboxyl group-containing resin is not particularly limited as long as it is composed of a polymer having a carboxyl group, and any resin can be used. Examples of such a carboxyl group-containing resin include (co) polymers containing a carboxyl group-containing monomer unit (hereinafter, also referred to as “carboxyl group-containing monomer unit”). In addition, in this specification, "(co) polymer" means a polymer or a copolymer.

As the (co) polymer containing a carboxyl group-containing monomer unit, for example, an ethylenically unsaturated carboxylic acid monomer and its derivative, and a carboxyl group-containing cyclic olefin monomer and its derivative were used (form). Co) Polymers can be mentioned. Examples of the ethylenically unsaturated carboxylic acid monomer include ethylenically unsaturated monocarboxylic acid and its derivative, ethylenically unsaturated dicarboxylic acid and its acid anhydride, and their derivatives. Examples of ethylenically unsaturated monocarboxylic acids include (meth) acrylic acid and crotonic acid. In addition, in this specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid. Examples of derivatives of ethylenically unsaturated monocarboxylic acid include acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and 2-ethylhexyl acrylate. Examples of ethylenically unsaturated dicarboxylic acids include maleic acid, fumaric acid and itaconic acid. Examples of the carboxyl group-containing cyclic olefin monomer include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2. -En, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-dihydroxycarbonylbicyclo [2.2.1] hept-2-ene, 4-hydroxycarbonyl Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-9-ene, 9-methyl-9-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-4-ene, and 9,10-dihydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-4-en and the like can be mentioned.

［上記式（Ａ）中、Ｘは水素原子もしくは炭素数１〜１６の直鎖、環状、若しくは分岐状アルキル基又はベンジル基等のアリール基を表し、ｎは１又は２である。］The (co) polymer containing a carboxyl group-containing monomer unit may be a polymer composed of one of the above-mentioned monomers, or the above-mentioned monomers and these. It may be a copolymer with another monomer copolymerizable with. For example, as other monomers copolymerizable with the above-mentioned monomers, known amide group-containing monomers, hydroxyl group-containing monomers, isocyanate group-containing monomers, and carboxyl group-containing cyclic olefins alone. Examples thereof include olefin monomers other than the body, silane monomers, and cyclic olefin monomers other than the above-mentioned carboxyl group-containing cyclic olefin monomers. In particular, as the cyclic olefin monomer other than the carboxyl group-containing cyclic olefin monomer, an N-substituted imide group that can be represented by the following formula (A) as disclosed in JP-A-2015-25892 is used. Cyclic olefin monomer having, cyclic olefin monomer having oxygen-containing group such as ester group and acid anhydride group, cyclic olefin monomer having nitrogen-containing group such as cyano group, cyclic olefin single amount having sulfonyl group Examples thereof include a body, a cyclic olefin monomer having a silyl group, a cyclic olefin monomer having a halogen atom, and the like.

[In the above formula (A), X represents a hydrogen atom or an aryl group such as a linear, cyclic or branched alkyl group having 1 to 16 carbon atoms or a benzyl group, and n is 1 or 2. ]

In the (co) polymer containing a carboxyl group-containing monomer unit, the ratio of the carboxyl group-containing monomer unit is 10% by mass, with 100% by mass of all the monomer units constituting the (co) polymer. It is preferably% or more, more preferably 15% by mass or more, and may be 100% by mass. The ratio of the carboxyl group-containing monomer unit in the (co) polymer can be measured by ¹ H-NMR or the like.

More specifically, the (co) polymer containing a carboxyl group-containing monomer unit is, for example, an acrylic resin composed of a polymer obtained by using an acrylic acid ester monomer as described above; , Polyamide resin, polyester resin, polyurethane resin, polyolefin resin, poly, which is composed of a (co) polymer that can be obtained by using a carboxyl group-containing monomer as described above and any other monomer. It may be a cycloolefin resin, a polysiloxane resin, or the like.

Among them, a polycycloolefin resin is preferable as the carboxyl group-containing resin because the amount of outgas can be suppressed and the water absorption is low. The polycycloolefin resin is a resin containing a cyclic olefin monomer unit. The cyclic olefin monomer unit includes the above-mentioned carboxyl group-containing cyclic olefin monomer unit and other cyclic olefin monomer units. Among them, as the polycycloolefin resin which is a carboxyl group-containing resin, a resin containing a carboxyl group-containing cyclic olefin monomer unit is more preferable, and the carboxyl group-containing cyclic olefin monomer unit and the above-mentioned formula (A) are used. A resin containing a cyclic olefin monomer unit having the represented N-substituted imide group is more preferable. In particular, as a carboxyl group-containing cyclic olefin monomer, 4-hydroxycarbonyltetracyclo [6.2.1.1 ^{3, 6, 6} . 0 ^{2, 7} ] Dodeca-9-ene (TCDC) as a cyclic olefin monomer having an N-substituted imide group, N-phenylbicyclo [2.2.1] hept-5-ene-2,3-di A polycycloolefin resin, which is a copolymer formed using carboxyimide (NBPI), is preferable.

The content ratio of the cyclic olefin monomer unit in the resin containing the cyclic olefin monomer unit (the ratio of the carboxyl group-containing cyclic olefin monomer unit and the total ratio of the other cyclic olefin monomer units) constitutes the resin. It is preferably more than 50% by mass, more preferably more than 70% by mass, further preferably more than 90% by mass, and 100% by mass is a cyclic olefin, with 100% by mass of all the monomer units. It may be a monomer unit.
In particular, when the "resin containing a cyclic olefin monomer unit" contains a carboxyl group-containing cyclic olefin monomer unit, the content ratio of the carboxyl group-containing cyclic olefin monomer unit is the total unit amount constituting the resin. Assuming that the body unit is 100% by mass, it is preferably more than 40% by mass, more preferably more than 55% by mass, and preferably less than 100% by mass.
The ratio of each monomer unit in the resin containing the cyclic olefin monomer unit can be measured by ¹ H-NMR.

As the (co) polymer containing a carboxyl group-containing monomer unit, a commercially available product or a (co) polymer produced according to a known production method can be used. The production method is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, a massive polymerization method, and an emulsion polymerization method can be used. Further, as the polymerization mode, addition polymerization such as ionic polymerization, radical polymerization and living radical polymerization and ring-opening polymerization can be adopted. Further, as the polymerization initiator, a known polymerization initiator can be used. In particular, in the production of the polycycloolefin resin, various cyclic olefin monomers are polymerized according to a method using, for example, a known ring-opening polymerization catalyst and additive as described in JP-A-2015-25892 (co-polymerization). ) After obtaining the polymer, the (co) polymer may be hydrogenated in the presence of a known hydrogenation catalyst.

<Polyfunctional vinyl ether compound>
As the polyfunctional vinyl ether compound, a vinyl ether compound having two or more functional groups can be used. Examples of the vinyl ether compound having two or more functional groups include compounds having two or more vinyl ether structures in one molecule, which can be represented by (-C = CO-). The number of functional groups of the polyfunctional vinyl ether compound, that is, the number of vinyl ether structures contained in one molecule is preferably 2 or more, and more preferably 2 or more and 5 or less. By setting the number of functional groups of the polyfunctional vinyl ether within the above range, the crack resistance of the obtained resin film can be further improved.

Examples of the vinyl ether compound having 2 functional groups include 1,4-butanediol divinyl ether, neopentyl glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, and dipropylene glycol. Examples thereof include divinyl ether and cyclohexanediol divinyl ether. Of these, 1,4-butanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, and cyclohexanediol divinyl ether are preferable. Further, as the vinyl ether compound having 3 functional groups, trimethylolpropane trivinyl ether and trimethylolpropane ethoxylate trivinyl ether are preferable.

［上記式（１）中、Ｇ^１〜Ｇ^９のうちの何れか３つが窒素原子であり、その他は炭素原子であり、Ｒ^１は水素原子又は有機基であり、Ｒ^２は水素原子、ハロゲン基、カルボキシル基、又は炭素数１〜５のアルキル基である。］<Nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms>
The nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms is a compound containing 3 nitrogen atoms as constituent atoms of the condensed heterocycle. In other words, the "nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms" is not particularly limited as long as the constituent atoms of one condensed heterocycle contain three nitrogen atoms, and may include any compound. More specifically, the "nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms" may contain two or more condensed heterocycles containing three nitrogen atoms as constituent atoms in one compound. , A nitrogen atom may be contained in a structure other than the nitrogen-containing condensed heterocyclic structure constituting the compound.
Examples of the nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms include a compound that can be represented by the following general formula (1) and a compound having a structure that can be represented by the following general formula (1).

[In the above formula (1), any three of G ^{1 to} G ⁹ are nitrogen atoms, the others are carbon atoms, R ¹ is a hydrogen atom or an organic group, and R ² is a hydrogen atom or halogen. It is a group, a carboxyl group, or an alkyl group having 1 to 5 carbon atoms. ]

Further, the organic group which can be R ¹ contained in the formula (1) is a phenol group which may have one or more substituents and a carbon which may have one or more substituents. It can be a linear or branched alkyl group of number 1-10. Here, examples of the substituent of the phenol group which may have one or more substituents include an alkyl group having 1 to 10 carbon atoms, a 3,4,5,6-tetrahydro-N-methylphthalimide group, and the like. And 1-methyl-1-phenylethyl group and the like. Here, when the phenol group which may have one or more substituents has a plurality of substituents, they may be the same or different. Further, examples of the substituent of the linear or branched alkyl group having 1 to 10 carbon atoms which may have one or a plurality of substituents include a hydroxyl group and the like.

Further, the compound that can be a nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms may be a compound having structures [1] and [1]'that can be represented by the above formula (1). Specifically, such compounds are particularly limited as long as the two structures [1] and [1]'(where both the structures [1] and [1]' can be represented by the above formula (1)). The alkylene group having 1 to 10 carbon atoms as a linking group (-C _m H _{2 m-} ; where m is an integer of 1 to 10) is the same or different from each other. formed by interconnected by), the general formula _{(2): [1] -C} m H 2m - may be a compound that may be represented by [1] '. Here, the alkylene group having 1 to 10 carbon atoms, which is a linking group, is bonded to each R ¹ contained in the structures [1] and [1]'.

Among them, as the nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms, in the above formulas (1) and (2), G ^{1 to} G ³ are nitrogen atoms and G ^{4 to} G ⁹ are carbon atoms benzotriazole. Based compounds are preferred. If the resin composition contains a benzotriazole-based compound, it is possible to more effectively secure the storage stability of the resin composition itself and enhance the chemical resistance of the obtained resin film. it can.

Examples of the benzotriazole-based compound satisfying the above formula (1) include 1H-benzotriazole-1-methanol, 1,2,3-benzotriazole (manufactured by Johoku Chemical Co., Ltd., "BT-120"), 2- (2). '-Hydroxy-5'-Methylphenyl) Benzotriazole (manufactured by Johoku Chemical Co., Ltd., "JF-77"), 2- (2'-Hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chloro Benzotriazole (manufactured by Johoku Chemical Co., Ltd., "JF-79"), 2- (2'-hydroxy-3', 5'-di-tert-amylphenyl) Benzotriazole (manufactured by Johoku Chemical Co., Ltd., "JF-80") , 2- (2'-Hydroxy-5'-tert-octylphenyl) benzotriazole (manufactured by Johoku Chemical Co., Ltd., "JF-83"), 2- [2-Hydroxy-3- (3,4,5,6) 7-Tetrahydro-1,3-dioxo-1H-isoindole-2-ylmethyl) -5-methylphenyl] -2H-benzotriazole (manufactured by Sumika Chemtex, "Sumisorb 250"), and 2- (2H-benzo Examples thereof include triazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (“Adecastab LA-24” manufactured by Adeca). Examples of the benzotriazole-based compound satisfying the above formula (2) include 2,2'-methylenebis [6- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl). ) Phenol] (manufactured by ADEKA, "ADEKASTAB LA-31").
Among them, 1H-benzo is a benzotriazole-based compound from the viewpoint of improving compatibility with a carboxyl group-containing resin and solubility in a solvent described later to further secure storage stability of the resin composition. Triazole-1-methanol is preferred.

[Content of nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms]
The content of the nitrogen-containing condensed heterocyclic compound in the resin composition is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and preferably 2 parts by mass or more with respect to 100 parts by mass of the carboxyl group-containing resin. It is less than 20 parts by mass, more preferably 15 parts by mass or less, further preferably 10 parts by mass or less, and particularly preferably 7 parts by mass or less. When the content ratio of the nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms is at least the above lower limit value, the crack resistance of the obtained resin film can be further improved. Further, when the content ratio of the nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms is not more than the above upper limit value, it is possible to suppress the excessive increase in the viscosity of the resin composition and to form the resin film satisfactorily. it can.

<Polyfunctional epoxy compound>
The polyfunctional epoxy compound is not particularly limited, and examples thereof include compounds having two or more epoxy groups in one molecule. By containing the polyfunctional epoxy compound in the resin composition, the crack resistance of the obtained resin film can be further improved. It is presumed that this is because the polyfunctional epoxy compound present in the resin composition can appropriately suppress the increase in internal stress due to the carboxylic acid and the polyfunctional vinyl ether in the resin film.

Compounds having two or more epoxy groups in one molecule include epoxidized butane tetracarboxylic acid tetrakis (3-cyclohexenylmethyl) -modified ε-caprolactone, tris (2,3-epoxypropyl) isocyanurate, 1,4-. Butanediol diglycidyl ether, 1,2-epoxide-4- (epoxide ethyl) cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenylglycidyl ether, 1,1,3-tris [p- (2,3-Epoxide propoxy) phenyl] Propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis (N, N-diglycidylaniline), 3,4-epoxide cyclohexylmethyl-3,4 -Epoxide cyclohexane carboxylate, trimethylol ethane triglycidyl ether and bisphenol-A-diglycidyl ether, and pentaerythritol polyglycidyl ether. Commercially available products include, for example, Epolide GT-401, GT-403, GT-301, GT-302, seroxide 2021, seroxide 3000 (all manufactured by Daicel Corporation); jER1001, jER1002, jER1003, jER1004, jER1007, jER1009. , JER1010, jER828, jER871, jER872, jER180S75, jER807, jER152, jER154 (all manufactured by Mitsubishi Chemical Corporation); EPPN201, EPPN202, EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN -1027 (above, manufactured by Nippon Kayaku Corporation), Epicron 200, Epicron 400 (above, manufactured by DIC), Denacol EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, Examples thereof include EX-522, EX-421, EX-313, EX-314, and EX-321 (all manufactured by Nagase ChemteX Corporation). Above all, from the viewpoint of further improving the crack resistance of the obtained resin film, the polyfunctional epoxy compound preferably has an alicyclic epoxy group. Further, the number of alicyclic epoxy groups contained in the polyfunctional epoxy compound is preferably 2 or more, more preferably 3 or more, further preferably 4 or more, and usually 6 or less. Is. In particular, epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) -modified ε-caprolactone (alicyclic epoxy group number: 4) is preferable. The "number of alicyclic epoxy groups contained in the polyfunctional epoxy compound" is per unit structure (1 molecule) when the polyfunctional epoxy compound is a polymer composed of repeating structural units containing alicyclic epoxy groups. Means the number of alicyclic epoxy groups.

<Arbitrary ingredient>
In addition to the above various components, the resin composition of the present invention may contain arbitrary components such as a silane coupling agent, an antioxidant, and a surfactant. As such an optional component, a known one can be used (see, for example, International Publication No. 2015/033901 and JP-A-2015-25892). The content of these additives can also be appropriately adjusted within a general range as long as the effects of the present invention are not impaired.

<Solvent>
As the solvent that can be contained in the resin composition of the present invention, a known organic solvent used for preparing the resin composition can be used (see, for example, International Publication No. 2015/033901). Among them, a solvent containing diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether can be preferably used.

<Preparation method of resin composition>
The method for preparing the resin composition of the present invention is not particularly limited, and each component constituting the resin composition may be mixed by a known method. The mixing method is not particularly limited, and each component constituting the resin composition can be added to a solvent and mixed to obtain a solution or dispersion in which each component is dissolved or dispersed in the solvent. it can.

Specific examples of the mixing method include stirring using a stirrer or the like, a high-speed homogenizer, a dispar, a planetary stirrer, a twin-screw stirrer, a ball mill, a three-roll or the like. Further, the solution or dispersion obtained by mixing may be filtered using, for example, a filter having a pore size of about 0.45 μm.

(Resin film)
The resin film of the present invention is characterized in that it is formed by using the resin composition of the present invention. Since the resin film of the present invention is formed by using the resin composition of the present invention, it has excellent chemical resistance. The resin film of the present invention can be formed by applying the resin composition of the present invention on a desired substrate. That is, the resin film of the present invention comprises a dried product of the above-mentioned resin composition of the present invention, and is usually at least a carboxyl group-containing resin, a polyfunctional vinyl ether compound, and a nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms. Contains. Further, the resin film of the present invention preferably contains a polyfunctional epoxy compound. Since each component contained in the resin film was contained in the above resin composition, the suitable abundance ratio of each component is the same as the suitable abundance ratio of each component in the resin composition. It is the same. Further, for example, the polyfunctional vinyl ether compound contained in the resin film, the polyfunctional epoxy compound which can be optionally contained, and the like may be crosslinked by an optional crosslinking treatment or the like. In other words, the resin film may contain a crosslinked product of the above-mentioned polyfunctional vinyl ether compound and the polyfunctional epoxy compound.

As the substrate, for example, a printed wiring board, a silicon wafer substrate, a glass substrate, a plastic substrate, or the like can be used. Further, a substrate in which a thin transistor type liquid crystal display element, a color filter, a black matrix or the like is formed on a glass base material or a plastic base material used in the display field is also preferably used. Above all, since the resin composition of the present invention can be cured at a low temperature, the resin film of the present invention formed by using such a resin composition can be suitably provided on a plastic substrate.

The method of applying the resin film on the substrate is not particularly limited, and for example, a coating method, a film lamination method, or the like can be used.

The coating method is, for example, a method of coating a resin composition on a substrate such as a plastic substrate and then removing the solvent. As a method for applying the resin composition, for example, various methods such as a spray method, a spin coating method, a roll coating method, a die coating method, a doctor blade method, a rotary coating method, a bar coating method, and a screen printing method are adopted. be able to. The solvent can be removed, for example, by drying. The drying conditions vary depending on the type of each component, the mixing ratio, the heat resistant temperature of the substrate such as a plastic substrate, etc., but are usually 30 ° C. or higher and 150 ° C. or lower, preferably 60 ° C. or higher and 120 ° C. or lower. It can be 0.5 minutes or more and 90 minutes or less, preferably 1 minute or more and 60 minutes or less, and more preferably 1 minute or more and 30 minutes or less. According to the resin composition of the present invention, a resin film having excellent chemical resistance can be obtained even if the drying temperature is not more than the above upper limit value. Further, if the temperature at the time of drying is set to the above lower limit value or more, the chemical resistance of the resin film can be sufficiently improved.

In the film laminating method, a resin composition is applied onto a base material for forming a resin film, the solvent is removed to obtain a resin film, and the obtained resin film is laminated on the substrate to obtain a substrate having a resin film. It is a method of forming. The solvent can be removed, for example, by drying. The drying conditions can be appropriately selected according to the type and blending ratio of each component. The drying conditions can usually be 0.5 minutes or more and 90 minutes or less under temperature conditions of 30 ° C. or higher and 150 ° C. or lower. Further, when laminating the resin film on the substrate, a crimping machine such as a pressure laminator, a press, a vacuum laminator, a vacuum press, or a roll laminator can be used.

The thickness of the resin film is not particularly limited and can be appropriately set according to the intended use. For example, the thickness of the resin film is preferably 0.1 μm or more and 100 μm or less, more preferably 0.5 μm or more and 50 μm or less, further preferably 0.5 μm or more and 30 μm or less, and particularly preferably 0.5 μm or more and 10 μm or less. Can be done. According to the resin composition of the present invention, even when the thickness of the resin film is relatively thin, the chemical resistance can be sufficiently enhanced.

Further, if necessary, the resin film formed by the above-mentioned coating method or film lamination method can be crosslinked. The cross-linking treatment is not particularly limited, and can be carried out by a general method, for example, as disclosed in Japanese Patent Application Laid-Open No. 2015-25892.

The resin film of the present invention preferably has a light transmittance of 95% or more at a wavelength of 400 nm when measured without going through the bleaching exposure step. Here, the light transmittance can be measured, for example, according to the method described in the examples.

The resin film of the present invention can achieve the above-mentioned high light transmittance without performing a so-called bleaching exposure step. The bleaching exposure step means an operation for exposing the resin film under overexposure conditions to fade the colored resin film after the resin composition is dried to form the resin film. For example, in such a bleaching exposure step, a resin film formed under a given condition is exposed to 100 J in terms of exposure amount of g-line (wavelength 436 nm), h-line (wavelength 405 nm), or i-line (wavelength 365 nm). It means a step of exposing to a light amount in the range of / m ^{2 to} 20,000 J / m ² .

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. In the following description, "%" and "part" representing the amount are based on mass unless otherwise specified.
In Examples and Comparative Examples, the storage stability of the resin composition and the chemical resistance, crack resistance, and insulation reliability of the resin film were evaluated as follows. The light transmittance of the resin film obtained in the examples was evaluated as follows.

<Storage stability of resin composition>
The viscosity of the resin compositions prepared in Examples and Comparative Examples was measured with an E-type viscometer according to the "10-cone-viscosity measurement method using a flat plate type rotational viscometer" described in JIS Z 8803: 2011. The viscosity of the resin composition immediately after preparation was set to V0. Further, the viscosity V1 of the resin composition after enclosing the resin composition in a light-shielding bottle and storing it in a clean room (temperature 23 ° C., humidity 45%) for 1 week was measured in the same manner. Then, the viscosity change rate (%) was calculated according to the formula: | (V1-V0) / V0 | × 100. The calculated viscosity change rate was evaluated according to the following criteria.
A: Viscosity change rate within 5% B: Viscosity change rate exceeds 5%

<Chemical resistance of resin film>
The resin compositions prepared in Examples and Comparative Examples were applied onto a silicon wafer substrate by a spin coating method, heated and dried (prebaked) at 90 ° C. for 2 minutes using a hot plate, and prebaked with a film thickness of 2.0 μm. A finished resin film was formed. Next, the resin film was post-baked by heating it at 130 ° C. for 20 minutes in an air atmosphere using an oven to obtain a laminate made of a silicon wafer substrate having the post-baked resin film on the surface.
This is the ratio of the film thickness after immersion when the laminate obtained as described above is used as a test body and immersed in 200 ml of chemicals for 5 minutes and the film thickness before immersion is 100% (%). Was calculated. As a chemical,
(I) Acetone solution kept at 25 ° C in a constant temperature bath;
(Ii) A resist stripping solution maintained at 25 ° C. in a constant temperature bath (manufactured by Tokyo Ohka Kogyo Co., Ltd., "ST-106", composition: monoethanolamine (MEA) / dimethyl sulfoxide (DMSO) = volume ratio 7/3); And (iii) resist stripping solution kept at 60 ° C in a constant temperature bath (manufactured by Tokyo Ohka Kogyo Co., Ltd., "ST-106")
3 types were prepared, and the test piece was immersed in each solution.
The film thickness was measured using an optical interference type film thickness measuring device (“Lambda Ace” manufactured by SCREEN).

<Crack resistance of resin film>
[Crack resistance of prebaked resin film]
The resin compositions prepared in Examples and Comparative Examples were applied onto a silicon wafer substrate by a spin coating method, heated and dried (prebaked) at 90 ° C. for 2 minutes using a hot plate, and prebaked with a film thickness of 2.0 μm. A laminated body made of a silicon wafer substrate having a prebaked resin film on the surface was obtained by forming a finished resin film. The surface of the laminate was visually observed and the crack resistance was evaluated according to the following criteria.
A: There are no cracks on the surface of the laminate.
B: Cracks were confirmed on the surface of the laminate.
[Acetone crack resistance of resin film]
The crack resistance of the test piece immersed in the acetone solution according to the procedure described in the above <Chemical resistance of the resin film> was evaluated according to the same criteria as the above [Crack resistance of the prebaked resin film]. ..

<Insulation reliability of resin film>
A Cu thin film having a film thickness of 100 nm was formed on a glass substrate (Corning Inc., product name: Corning 1737) using a sputtering device. Next, a Cu thin film was patterned using a photoresist to prepare a comb-shaped electrode substrate having a Cu wiring width of 7 μm and a distance between wirings of 7 μm. The resin compositions prepared in Examples and Comparative Examples were applied onto such a comb-shaped electrode substrate by a spin coating method, and heat-dried (prebaked) at 90 ° C. for 2 minutes using a hot plate to obtain a film thickness of 2.0 μm. A resin film was formed. Next, the resin film is post-baked by heating it at 130 ° C. for 20 minutes in an air atmosphere using an oven, so that the resin film-Cu wiring-glass substrate, which is a test piece, is laminated in this order. Got Then, the obtained test piece was placed in a high temperature and humidity chamber having a temperature of 85 ° C. and a humidity of 85% in a state where a voltage of 15 V was applied. Then, after 500 hours, the test piece was taken out from the high temperature and humidity chamber, and the Cu wiring provided in the test piece was observed with a digital microscope (KH-1300 manufactured by Hirox), and the insulation reliability of the resin film was determined as follows. Evaluated according to the criteria.
A: No corrosion is confirmed in the Cu wiring after 500 hours.
B: Corrosion was confirmed in the Cu wiring after 500 hours.

<Light transmittance of resin film>
The resin composition obtained in the example was applied onto a glass substrate (Corning Inc., product name Corning 1737) by a spin coating method, and heated and dried (prebaked) at 90 ° C. for 2 minutes using a hot plate to obtain a film thickness. A 2.0 μm resin film was formed. Then, using an oven, post-baking was performed by heating at 130 ° C. for 20 minutes in an air atmosphere to obtain a laminate composed of a resin film and a glass substrate.
The obtained laminate was measured at a wavelength of 400 nm to 800 nm using a spectrophotometer V-560 (manufactured by JASCO Corporation). From the measurement result, the light transmittance (%) at 400 nm was calculated. The light transmittance (%) of the resin film was calculated as a converted value when the thickness of the resin film was 2.0 μm with the glass substrate without the resin film as a blank.

(Example 1)
<Preparation of carboxyl group-containing resin>
N-Phenylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide (NBPI), which is a cyclic olefin monomer having an N-substituted imide group, 31.5 mol%, and carboxyl 4-Hydroxycarbonyltetracyclo, which is a group-containing cyclic olefin monomer [6.2.1.1 ^3,6 . 0 ^2,7 ] 100 parts of a monomer mixture consisting of 68.5 mol% of dodeca-9-ene (TCDC), 6.9 parts of 1,5-hexadiene, a ring-opening polymerization catalyst (1,3-dimesh). Thiruimidazolin-2-iriden) (tricyclohexylphosphine) benzylidene ruthenium dichloride (Org. Lett., Vol. 1, p. 953, synthesized by the method described in 1999), 0.01 part, and diethylene glycol ethylmethyl ether. 200 parts were filled in a nitrogen-substituted glass pressure-resistant reactor and reacted at 80 ° C. for 4 hours with stirring to obtain a polymerization reaction solution.
The obtained polymerization reaction solution was placed in an autoclave and subjected to a hydrogenation reaction under the conditions of 150 ° C. and a hydrogen pressure of 4 MPa for 5 hours to carry out a hydrogenation reaction, and containing a carboxyl group composed of an alicyclic olefin copolymer. A solution containing a polyolefin resin was obtained. The alicyclic olefin copolymer has a polymerization conversion rate of 99.9%, a polystyrene-equivalent weight average molecular weight of 5,280, a number average molecular weight of 3,490, a molecular weight distribution of 1.51, and a hydrogenation rate of 99.9. %Met. The solid content concentration of the solution containing the carboxyl group-containing polyolefin resin was 32.0% by mass.

<Preparation of resin composition>
100 parts of the carboxyl group-containing polyolefin resin obtained above, 40 parts of 1,4-cyclohexanedimethanol divinyl ether (manufactured by Nippon Carbide, "CHDVE") as a polyfunctional vinyl ether compound, epoxidation as a polyfunctional epoxy compound. 40 parts of butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) -modified ε-caprolactone (manufactured by Daicel Chemical Industries: Epolide GT401), 1H- as a benzotriazole-based compound which is a nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms. Benzotriazole-1-methanol (manufactured by Tokyo Kasei) 5 parts, glycidoxypropyltrimethoxysilane (manufactured by XIAMETER: OFS6040) 2 parts as a silane coupling agent, pentaerythritol-tetrakis [3- (3, 3,) as an antioxidant 2-part 5-di-tert-butyl-4-hydroxyphenyl) propionate (BASF: Irganox1010), organosiloxane polymer (Shinetsu Chemicals: KP341) 300 ppm as a surfactant, and diethylene glycol ethylmethyl ether (Toho Chemicals) as a solvent. Manufacture: EDM) 100 parts were mixed and dissolved, and then filtered through a filter made of polytetrafluoroethylene having a pore size of 0.45 μm to prepare a resin composition.
The storage stability of the obtained resin composition was evaluated according to the above, and a resin film was formed using the obtained resin composition and various evaluations were carried out according to the above. The results are shown in Table 1.

(Example 2)
A resin composition was prepared in the same manner as in Example 1 except that the blending amount of the benzotriazole-based compound was changed to 5 parts, and various evaluations were performed. The results are shown in Table 1.

(Examples 3 to 7)
In Example 3, 1,4-butanediol divinyl ether (BDVE) was used as the polyfunctional vinyl ether compound.
In Example 4, diethylene glycol divinyl ether (DEGDVE) was used as the polyfunctional vinyl ether compound.
In Example 5, trimethylolpropane ethoxylate trivinyl ether was used as the polyfunctional vinyl ether compound.
In Example 6, trimethylolpropane trivinyl ether was used as the polyfunctional vinyl ether compound.
In Example 7, cyclohexanediol divinyl ether (CHODVE) was used as the polyfunctional vinyl ether compound.
Except for these points, resin compositions were prepared in the same manner as in Example 2, and various evaluations were performed. The results are shown in Table 1.

(Example 8)
Resin compositions were prepared in the same manner as in Example 2 except that the polyfunctional epoxy compound was not blended, and various evaluations were performed. The results are shown in Table 1.

(Comparative Examples 1 to 4)
Resin compositions were prepared in the same manner as in Examples 2 to 5 except that the nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms was not blended, and various evaluations were performed. The results are shown in Table 1. In these examples, the chemical resistance of the obtained resin film was low, so the insulation reliability was not evaluated.

(Comparative Examples 5 to 7)
A nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms is not blended, and instead, homophthalic acid (Comparative Example 5), which is not a heterocyclic compound, and 5-mercapto-1H, which is a heterocyclic compound having 3 nitrogen atoms, are not blended. -A resin in the same manner as in Example 3 except that 5 parts each of benzimidazole (Comparative Example 7), which is a nitrogen-containing condensed heterocyclic compound having 2 nitrogen atoms, was blended with tetrazole (Comparative Example 6). The composition was prepared and various evaluations were performed. The results are shown in Table 1.

(Comparative Examples 8 to 10)
Resin compositions were prepared in the same manner as in Example 2 except that the monofunctional monovinyl ether compounds shown in Table 1 were blended in place of the polyfunctional vinyl ether compounds, and various evaluations were performed. The results are shown in Table 1. In these examples, the chemical resistance of the obtained resin film was low, and cracks were generated by immersion in acetone. Therefore, the insulation reliability was not evaluated.

(Comparative Example 11)
It does not contain a polyfunctional vinyl ether compound or a nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms, and is a photosensitizer 4,4'-[1- [4- [1- [4-hydroxyphenyl] -1-methyl). Ethyl] phenyl] ethylidene] bisphenol and 6-diazo-5,6-dihydro-5-oxo-naphthalene-1-sulfonic acid (1,2-naphthoquinonediazide-5-sulfonic acid chloride) ester compound (2.0) A resin composition was prepared in the same manner as in Example 1 except that the molar compound) (manufactured by Bigen Shoji Co., Ltd., “TPA-520”) was blended, and various evaluations were performed. The results are shown in Table 1. The resin film obtained according to this example was reddish brown. Moreover, in this example, the evaluation other than the chemical resistance and the acetone crack resistance was not performed.

In Table 1,
"GT401" is an epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-caprolactone (manufactured by Daicel Chemical Industries: Epolide GT401).
"TPA520" is 4,4'-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 6-diazo-5,6-dihydro-5-oxo. An ester form (2.0 mol form) with −naphthalene-1-sulfonic acid (1,2-naphthoquinonediazide-5-sulfonic acid chloride),
"OFS6040" is a glycidoxypropyltrimethoxysilane (manufactured by XIAMETER: OFS6040).
"Irg1010" is a pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (BASF: Irganox1010),
"KP341" is an organosiloxane polymer (manufactured by Shin-Etsu Chemical Co., Ltd .: KP341).
"EDM" is a diethylene glycol ethyl methyl ether,
Each is shown.

From Table 1, in Examples 1 to 8 using the resin composition containing the carboxyl group-containing resin, the polyfunctional vinyl ether compound, and the nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms, the resin composition itself was preserved. It can be seen that the stability could be ensured and the chemical resistance of the obtained resin film was high. On the other hand, in Comparative Examples 1 to 7 in which the benzotriazole-based compound, which is a nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms, was not blended, the storage stability of the resin composition itself was ensured and the obtained resin film was obtained. It can be seen that it was not possible to achieve both the enhancement of the chemical resistance of Among them, in Comparative Example 5 in which homophthalic acid was blended instead of the nitrogen-containing condensed heterocyclic compound, the storage stability of the resin composition was lowered and the insulation reliability of the resin film could not be obtained. This is contained in the obtained resin film after a cross-linking reaction occurs between the polyfunctional vinyl ether compound and the polyfunctional epoxy compound contained in the resin composition to increase the viscosity and decrease the storage stability. It is presumed that this is because homophthalic acid acts to corrode Cu wiring. Further, it can be seen that in Comparative Examples 8 to 10 in which the polyfunctional vinyl ether compound was not blended, the chemical resistance of the obtained resin film could not be improved. Furthermore, it can be seen that in Comparative Example 11 in which neither the polyfunctional vinyl ether compound nor the nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms was blended, the chemical resistance of the obtained resin film could not be improved.

According to the present invention, it is possible to provide a resin composition capable of ensuring the storage stability of the resin composition itself and enhancing the chemical resistance of the obtained resin film.
Further, according to the present invention, it is possible to provide a resin film having excellent chemical resistance.

Claims (7)

A resin composition containing a carboxyl group-containing resin, a polyfunctional vinyl ether compound, and a nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms. The resin composition according to claim 1, wherein the nitrogen-containing condensed heterocyclic compound is a benzotriazole-based compound. The resin composition according to claim 1 or 2, further comprising a polyfunctional epoxy compound. The resin composition according to claim 3, wherein the polyfunctional epoxy compound has an alicyclic epoxy group. The resin composition according to any one of claims 1 to 4, wherein the carboxyl group-containing resin is a resin containing a cyclic olefin monomer unit. The resin composition according to any one of claims 1 to 5, wherein the nitrogen-containing condensed heterocyclic compound is contained in an amount of 1 part by mass or more with respect to 100 parts by mass of the carboxyl group-containing resin. A resin film formed by using the resin composition according to any one of claims 1 to 6.