KR20200060360A - 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

Resin composition and resin film

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 a protective film for preventing deterioration and damage, and a device surface or wiring. Various resin films are formed as a planarization film for planarizing the surface of the substrate and an electrical insulating film for maintaining electrical insulation. Further, for example, in the organic EL element, a resin film as a pixel separation film is formed in order to separate the light-emitting body portion. Further, for example, elements such as a display element for a thin film transistor type liquid crystal or an integrated circuit element are formed with a resin film as an interlayer insulating film to insulate between wirings arranged in layers.

Conventionally, various resin compositions have been proposed as resin compositions for forming the resin films as described above. For example, Patent Document 1 proposes a negative photosensitive resin composition containing a cyclic olefin polymer having a protonic 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 excellent in pattern formation, transparency, and heat resistance due to development and in which generation of outgas is suppressed.

Japanese Patent Application Publication No. 2015-25892

Here, conventionally, materials such as glass have been generally used as a substrate for a display element. In the case of forming a resin film on a glass substrate, in curing the resin film, it was possible to form a resin film rich in chemical resistance by accelerating the curing reaction by curing at a high curing temperature of 200 ° C. or higher, for example. However, in recent years, in accordance with the flexibility of display elements, it has been desired 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 that of the glass substrate. Therefore, in order to form a resin film on a plastic substrate, it is necessary to lower the curing temperature at the time of curing the resin film. For this reason, development of a resin composition capable of forming a resin film having high chemical resistance even under low temperature curing conditions is required.

In addition, in the process of laminating various films on a substrate during the manufacture of electronic components, it is common to use various chemicals or the like. Here, when a composition capable of increasing chemical resistance to various chemicals is used, the storage stability of the resin composition is deteriorated, and there is a problem that it is difficult to achieve both the improvement of the chemical resistance of the obtained resin film and the storage stability of the resin composition itself. .

In view of the above situation, the present invention aims to provide a resin composition that is compatible with ensuring storage stability of the resin composition itself and improving the chemical resistance of the resulting resin film.

Moreover, this invention aims at providing the resin film excellent in chemical resistance.

The present inventor conducted a courtesy study for the purpose of solving the above problems. Then, the present inventor secures storage stability of the resin composition itself when a resin having a predetermined functional group, a polyfunctional vinyl ether compound, and a predetermined nitrogen-containing condensed heterocyclic compound are coexisting in the resin composition, It was found out that it is compatible with increasing the chemical resistance of the resin film obtained using such a resin composition, and the present invention has been completed.

That is, this invention aims at solving the said subject advantageously, The resin composition of this invention is a carboxyl group-containing resin, a polyfunctional vinyl ether compound, and the nitrogen-containing condensed heterocyclic compound which has 3 nitrogen atoms. It is characterized by including. By making the blending of the resin composition into such a specific blending, it is possible to make sure that both the storage stability of the resin composition itself and the chemical resistance of the resulting resin film are improved.

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 further ensure that the storage stability of the resin composition itself and the chemical resistance of the resulting resin film are improved.

Moreover, it is preferable that the resin composition of this invention contains a polyfunctional epoxy compound further. When the resin composition further contains a polyfunctional epoxy compound, the crack resistance of the resulting resin film can be further improved.

Moreover, it is preferable that the said polyfunctional epoxy compound has an alicyclic epoxy group in the resin composition of this invention. If the polyfunctional epoxy compound contained in the resin composition has an alicyclic epoxy group, the crack resistance of the resulting 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. If the resin composition is a resin containing a cyclic olefin monomer unit, the amount of outgas from the resulting resin film can be suppressed, and at the same time, the absorbency of the resulting resin film can be reduced.

Moreover, it is preferable that the resin composition of this invention contains the said nitrogen-containing condensed heterocyclic compound in the ratio of 1 mass part or more with respect to 100 mass parts of said carboxyl group-containing resin. When the content ratio of the nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms is greater than or equal to the above lower limit, the crack resistance of the resulting resin film can be further improved.

Here, this invention aims at solving the said subject advantageously, The resin film of this invention is characterized by being formed using any one of the said resin compositions. Since the resin film of this invention is formed and formed using the resin composition of this invention, it is excellent in chemical resistance.

ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can ensure the storage stability of the resin composition itself and which improves the chemical resistance of the obtained resin film can be provided.

Further, according to the present invention, it is possible to provide a resin film excellent in chemical resistance.

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

(Resin composition)

The resin composition of the present invention is characterized by comprising a carboxyl group-containing resin, a polyfunctional vinyl ether compound, and a nitrogen-containing fused heterocyclic compound having 3 nitrogen atoms. By mixing the resin composition with a carboxyl group-containing resin, a polyfunctional vinyl ether compound, and a nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms, the storage stability of the resin composition itself is secured, and the resin obtained using such a resin composition It is compatible to increase the chemical resistance of the membrane. Here, the carboxyl group contained in the carboxyl group-containing resin, the reactivity between the polyfunctional vinyl ether compound is good, and the nitrogen-containing nitrogen-containing nitrogen-containing condensed heterocyclic compound can exhibit proper basicity, as described above. It is estimated that the effect can be exerted. In particular, regarding the chemical resistance, it is advantageous that the carboxyl group and the polyfunctional vinyl ether compound contained in the resin are capable of initiating a reaction at a low temperature, and that the basic nitrogen-containing condensed heterocyclic compound acts to promote such a reaction. I think it works. For this reason, it is estimated that according to the resin composition of the present invention, a resin film having good chemical resistance can be formed. Moreover, it is preferable that the resin composition of this invention further contains a polyfunctional epoxy compound.

Hereinafter, each component contained in the resin composition will be described.

<Carboxyl 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 carboxyl group-containing resins include (co) polymers containing monomer units containing carboxyl groups (hereinafter also referred to as "carboxyl group-containing monomer units"). In addition, in this specification, "(co) polymer" means a polymer or a copolymer.

Examples of the (co) polymer containing a carboxyl group-containing monomer unit include, for example, an (ethyl) unsaturated carboxylic acid monomer and its derivatives, or a (co) polymer formed using a carboxyl group-containing cyclic olefin monomer and its derivatives. You can. Examples of the ethylenically unsaturated carboxylic acid monomer include ethylenically unsaturated monocarboxylic acid and its derivatives, ethylenically unsaturated dicarboxylic acid and its acid anhydride, and derivatives thereof. Examples of the ethylenically unsaturated monocarboxylic acid include (meth) acrylic acid and crotonic acid. In addition, in this specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid. Examples of the derivative of the 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] hepto-2-ene, 5-methyl-5-hydroxycarbonylbicyclo [2.2.1] hepto -2-ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hepto-2-ene, 5,6-dihydroxycarbonylbicyclo [2.2.1] hepto-2-ene , 4-hydroxycarbonyltetracyclo [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 2,7} ] dodeca-4-ene and the like.

The (co) polymer containing a carboxyl group-containing monomer unit may be a polymer composed of one of the monomers described above, or a copolymer of the monomers described above and other monomers copolymerizable therewith. For example, other monomers copolymerizable with the above-mentioned monomers include olefin monomers other than known amide group-containing monomers, hydroxyl group-containing monomers, isocyanate group-containing monomers, carboxyl group-containing cyclic olefin monomers, silane monomers, and And cyclic olefin monomers other than the carboxyl group-containing cyclic olefin monomers. In particular, as the cyclic olefin monomers other than the carboxyl group-containing cyclic olefin monomers, as disclosed in Japanese Unexamined Patent Publication No. 2015-25892, a cyclic cyclic group having an N-substituted imide group which can be represented by the following formula (A) Olefin monomers, cyclic olefin monomers having oxygen-containing groups such as ester groups or acid anhydride groups, cyclic olefin monomers having nitrogen-containing groups such as cyano groups, cyclic olefin monomers having sulfonyl groups, cyclic olefin monomers having silyl groups, or And cyclic olefin monomers having a halogen atom.

[Formula 1]

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

On the other hand, in the (co) polymer containing the carboxyl group-containing monomer unit, the total monomer unit constituting the (co) polymer is 100 mass%, and the proportion of the carboxyl group-containing monomer units is preferably 10 mass% or more, and 15 mass. % Or more is more preferable, and may be 100% by mass. On the other hand, the ratio of the carboxyl group-containing monomer units 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 includes, for example, an acrylic resin composed of a polymer obtained using the acrylic acid ester monomer as described above; And, a polyamide resin, a polyester resin, a polyurethane resin, a polyolefin resin, a polycycloolefin resin, composed of a (co) polymer that can be obtained using the above carboxyl group-containing monomer and any other monomers, And polysiloxane resins.

Among them, 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 a carboxyl group-containing cyclic olefin monomer unit as described above, and other cyclic olefin monomer units. Especially, as a polycycloolefin resin which is a carboxyl group-containing resin, the resin containing a carboxyl group-containing cyclic olefin monomer unit is more preferable, and the carboxyl group-containing cyclic olefin monomer unit and N- represented by the formula (A) described above A resin containing a cyclic olefin monomer unit having a substituted imide group is more preferable. In particular, 4-hydroxycarbonyltetracyclo [6.2.1.1 ^{3,6 2,7} ] dodeca-9-ene (TCDC) as a cyclic olefin monomer containing a carboxyl group, has a cyclic form having an N-substituted imide group As the olefin monomer, a polycycloolefin resin that is a copolymer formed using N-phenylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide (NBPI) is preferred.

The content ratio of the cyclic olefin monomer units in the resin containing the cyclic olefin monomer units (the ratio of the total proportion of the cyclic olefin monomer units containing the carboxyl group to the cyclic olefin monomer units) is the total amount constituting the resin. The monomer unit is 100% by mass, preferably more than 50% by mass, more preferably more than 70% by mass, even more preferably more than 90% by mass, and 100% by mass may be a cyclic olefin monomer unit.

In particular, when the "resin containing a cyclic olefin monomer unit" includes a carboxyl group-containing cyclic olefin monomer unit, the content ratio of the carboxyl group-containing cyclic olefin monomer unit is 100% by mass of the total monomer units constituting the resin. Therefore, it is preferably more than 40% by mass, more preferably more than 55% by mass, and preferably less than 100% by mass.

On the other hand, 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 commercial product or a (co) polymer produced according to a known production method can be used. The manufacturing method is not particularly limited, and, for example, any method such as solution polymerization, suspension polymerization, bulk polymerization, or emulsion polymerization can be used. Moreover, addition polymerization and ring-opening polymerization, such as ion polymerization, radical polymerization, living radical polymerization, can be employ | adopted as a polymerization mode. Moreover, a known polymerization initiator can be used as a polymerization initiator. Particularly, in the production of polycycloolefin resins, various cyclic olefin monomers are polymerized according to a method using known ring-opening polymerization catalysts and additives as described in JP 2015-25892 A (Co) After the polymer is obtained, 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 a functional group number of 2 or more can be used. Examples of the vinyl ether compound having a functional group number of 2 or more include a compound having two or more vinyl ether structures in one molecule that can be represented by (-C = C-O-). 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 making the number of functional groups of the polyfunctional vinyl ether within the above range, the crack resistance of the resulting resin film can be further improved.

Examples of the vinyl ether compound having a functional group number of 2 include, for example, 1,4-butanediol divinyl ether, neopentyl glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, and tri And ethylene glycol divinyl ether, dipropylene glycol divinyl ether, and cyclohexanediol divinyl ether. Especially, 1,4-butanediol divinyl ether, 1,4-cyclohexane dimethanol divinyl ether, diethylene glycol divinyl ether, and cyclohexanediol divinyl ether are preferable. Further, as the vinyl ether compound having a functional group number of 3, trimethylolpropane trivinyl ether and trimethylolpropane ethoxylate trivinyl ether are preferable.

<Nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms>

A nitrogen-containing fused heterocyclic compound having 3 nitrogen atoms is a compound containing three nitrogen atoms in the constituent atoms of the fused heterocycle. In other words, "a nitrogen-containing fused heterocyclic compound having 3 nitrogen atoms" is not particularly limited as long as it contains three nitrogen atoms in a constituent atom of one fused heterocyclic ring, and may include all compounds. More specifically, "a nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms" may contain two or more condensed heterocyclic rings containing three nitrogen atoms in a constituent atom in one compound, and constitute a compound The nitrogen atom may be contained in structures other than the nitrogen-containing condensed heterocyclic structure.

Examples of the nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms include, for example, compounds represented by the following general formula (1) and compounds having a structure represented by the following general formula (1). have.

[Formula 2]

[In the formula (1), any three of G ¹ to G ⁹ are nitrogen atoms, other carbon atoms, R ¹ is a hydrogen atom or an organic group, R ² is a hydrogen atom, a halogen group, a carboxyl group, or carbon number It is an alkyl group of 1 to 5.]

Moreover, the organic group which may be R ¹ in Formula (1) may be a phenol group which may have one or more substituents, or a straight or branched alkyl group having 1 to 10 carbon atoms which may have one or more substituents. You can. Here, as a substituent of the phenol group which may have one or more substituents, a C1-C10 alkyl group, 3,4,5,6-tetrahydro-N-methylphthalimide group, and 1-methyl- And 1-phenylethyl groups. Here, when a phenol group which may have one or more substituents has a plurality of substituents, these may be the same or different. Moreover, a hydroxyl group etc. are mentioned as a substituent of the C1-C10 linear or branched alkyl group which may have one or more substituents.

Moreover, the compound which may be a nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms may be a compound having structures [1] and [1] 'which can be represented by the formula (1). Specifically, these compounds have two structures [1] and [1] '(where structures [1] and [1]' are both specifically limited as long as they can be represented by the formula (1)). . not, and may be the same or different) has, as a connecting group of 1 to 10 carbon atoms in the alkylene group (-C _m H _2m -; where, m is formed are connected to each other by a whole number of 1 to 10), formula ( 2): [1] -C _m H _2m- [1] 'may be a compound. Here, the alkylene group having 1 to 10 carbon atoms, which is a linking group, is bonded to each of R ¹ included in structures [1] and [1] '.

Among them, as the nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms, in the formula (1) (2), G ¹ to G ³ are nitrogen atoms, and G ⁴ to G ⁹ are carbon atom benzotriazole-based compounds. This is preferred. When the resin composition contains a benzotriazole-based compound, it is possible to more effectively and effectively secure the storage stability of the resin composition itself and improve the chemical resistance of the resulting resin film.

Examples of the benzotriazole-based compound satisfying the formula (1) include, for example, 1H-benzotriazole-1-methanol and 1,2,3-benzotriazole (manufactured by Johoku Chemical Co., Ltd., "BT-120"). , 2- (2'-hydroxy-5'-methylphenyl) benzotriazole (manufactured by Johoku Chemical Company, "JF-77"), 2- (2'-hydroxy-3'-tert-butyl-5'- Methylphenyl) -5-chlorobenzotriazole (manufactured by Johoku Chemical Corporation, `` JF-79 ''), 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole (Johoku `` JF-80 '' manufactured by a chemical company, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole (made by Johoku Chemical Company, `` JF-83 ''), 2- [2-hydroxy -3- (3,4,5,6,7-tetrahydro-1,3-dioxo-1H-isoindol-2-ylmethyl) -5-methylphenyl] -2H-benzotriazole (Sumika Chemtex) Preparation, `` Sumisorb 250 ''), and 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (made by Adeka Corporation `` adekastab LA-24 」) And the like. Further, as the benzotriazole-based compound satisfying the formula (2), 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3- Tetramethylbutyl) phenol] (manufactured by Adeka, "Adekastab LA-31").

Among them, 1H-benzotriazole- is a benzotriazole-based compound from the viewpoint of improving compatibility with a carboxyl group-containing resin and solubility in a solvent to be described later, and further ensuring storage stability of the resin composition even better. 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 less than 20 parts by mass, with respect to 100 parts by mass of the carboxyl group-containing resin. It is more preferably 15 parts by mass or less, still more 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 greater than or equal to the above lower limit, the crack resistance of the resulting resin film can be further improved. Moreover, when the content ratio of the nitrogen-containing fused heterocyclic compound having 3 nitrogen atoms is equal to or less than the above upper limit, the excessively high viscosity of the resin composition can be suppressed, and the resin film can be formed satisfactorily.

<Polyfunctional epoxy compound>

It does not specifically limit as a polyfunctional epoxy compound, The compound which has 2 or more epoxy groups in 1 molecule is mentioned. By containing a polyfunctional epoxy compound in the resin composition, the crack resistance of the resulting resin film can be further improved. It is presumed that this is due to the fact that the polyfunctional epoxy compound present in the resin composition can appropriately suppress the increase in internal stress caused by the carboxylic acid in the resin film and the polyfunctional vinyl ether.

As a compound having two or more epoxy groups in one molecule, epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) formula ε-caprolactone, tris (2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl Glycidyl ether, 1,1,3-tris [p- (2,3-epoxypropoxy) phenyl] propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis (N, N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether and bisphenol-A-diglycidyl ether, And pentaerythritol polyglycidyl ether. As a commercial item, for example, EPORID GT-401, Copper GT-403, Copper GT-301, Copper GT-302, Celoxide 2021, Celoxide 3000 (above, Daicel company make); jER1001, jER1002, jER1003, jER1004, jER1007, jER1009, jER1010, jER828, jER871, jER872, jER180S75, jER807, jER152, jER154 (above, manufactured by Mitsubishi Chemical Corporation); EPPN201, EPPN202, EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above, manufactured by Nippon Kayaku Co., Ltd.), Epiclon 200, Epiclon 400 (above, manufactured by DIC Corporation) , Denacall EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, EX-321 (above, Nagase Chemtex). Especially, it is preferable that a polyfunctional epoxy compound has an alicyclic epoxy group from a viewpoint of further improving the crack resistance of the obtained resin film. Moreover, the number of alicyclic epoxy groups contained in the polyfunctional epoxy compound is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and usually 6 or less. In particular, the epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) formula ε-caprolactone (alicyclic epoxy group number: 4) is preferred. On the other hand, "the number of alicyclic epoxy groups contained in the polyfunctional epoxy compound" refers to the number of alicyclic epoxy groups per unit structure (one molecule) when the polyfunctional epoxy compound is a polymer composed of repeating structural units containing an alicyclic epoxy group. it means.

<Optional ingredients>

In addition to the above various components, the resin composition of the present invention may contain optional components such as a silane coupling agent, an antioxidant, and a surfactant. As such an optional component, a known one can be used (for example, see International Publication No. 2015/033901 and Japanese Patent Publication No. 2015-25892). And the content of these additives can also be appropriately adjusted within the 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 (for example, see International Publication No. 2015/033901). Among them, solvents 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 are suitably used. Can be.

<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 method of mixing is not particularly limited, and by adding and mixing each component constituting the resin composition with respect to the solvent, a solution or dispersion in which each component is dissolved or dispersed in a solvent can be obtained.

As a specific mixing method, for example, a stirring method using a stirrer or the like, a mixing method using a high-speed homogenizer, a disper, a planetary stirrer, a biaxial stirrer, a ball mill, and a three roll can be used. 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 or the like.

(Resin film)

The resin film of the present invention is characterized by being formed using the resin composition of the present invention. Since the resin film of this invention is formed using the resin composition of this invention, it is excellent in 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 is made of a dried product of the resin composition of the present invention described above, and usually contains at least a carboxyl group-containing resin, a polyfunctional vinyl ether compound, and a nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms. . Moreover, it is preferable that the resin film of this invention contains a polyfunctional epoxy compound. On the other hand, since each component contained in the resin film is contained in the resin composition, the suitable abundance ratio of each component is the same as the suitable abundance ratio of each component in the resin composition. Moreover, for example, the polyfunctional vinyl ether compound contained in the resin film, and the polyfunctional epoxy compound that may be optionally contained, may be crosslinked by a crosslinking treatment or the like that can be optionally performed. In other words, the resin film may contain the crosslinked product of the above-mentioned polyfunctional vinyl ether compound and 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 formed of a thin transistor type liquid crystal display element, a color filter, or a black matrix, etc. is preferably used on a glass substrate or a plastic substrate used in the display field. Especially, since the resin composition of this invention is curable at low temperature, the resin film of this invention formed using such a resin composition can be suitably formed on a plastic substrate.

It does not specifically limit as a method of applying a resin film on a board | substrate, For example, methods, such as a coating method and a film lamination method, can be used.

The coating method is, for example, a method of removing a solvent after applying a resin composition on a substrate such as a plastic substrate. As a method of applying the resin composition, various methods such as a spray method, a spin coat method, a roll coat method, a die coat method, a doctor blade method, a rotation coating method, a bar coating method, and a screen printing method are adopted, for example. can do. The solvent can be removed, for example, by drying. Drying conditions are different depending on the type of each component, the mixing ratio, and the heat resistance temperature of the substrate such as a plastic substrate, but are usually 30 ° C or more and 150 ° C or less, preferably 60 ° C or more and 120 ° C or less, for 0.5 minutes. More than 90 minutes, preferably 1 minute or more and 60 minutes or less, more preferably 1 minute or more and 30 minutes or less. According to the resin composition of the present invention, even when the temperature during drying is less than or equal to the above upper limit, a resin film excellent in chemical resistance can be obtained. Moreover, when the temperature at the time of drying is equal to or more than the above lower limit, the chemical resistance of the resin film can be sufficiently improved.

The film lamination method is a method of forming a substrate having a resin film by applying a resin composition on a substrate for forming a resin film, removing a solvent to obtain a resin film, and laminating the obtained resin film on a substrate. The solvent can be removed, for example, by drying. Drying conditions can be appropriately selected according to the kind and blending ratio of each component. The drying conditions can be usually 0.5 minutes or more and 90 minutes or less under a temperature condition of 30 ° C or more and 150 ° C or less. Moreover, when laminating a resin film on a board | substrate, a press machine, such as a press laminator, a press, a vacuum laminator, a vacuum press, a roll laminator, can be used.

The thickness of the resin film is not particularly limited, and can be appropriately set depending on the application. 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, more preferably 0.5 μm or more and 30 μm or less, particularly preferably 0.5 μm or more and 10 μm It can be done as follows. 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 increased.

In addition, a crosslinking process can be performed with respect to the resin film formed by the above-mentioned coating method or film lamination method as needed. The crosslinking treatment is not particularly limited, and can be carried out by a general method, for example, as disclosed in JP 2015-25892 A.

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 a bleaching exposure process. Here, the light transmittance can be measured, for example, according to the method described in Examples.

And the resin film of this invention can achieve the above high light transmittance without performing a so-called bleaching exposure process. On the other hand, the bleaching exposure process means an operation for fading the colored resin film by exposing the resin film under over-exposure conditions, such as after drying the resin composition to form a resin film. For example, in this bleaching exposure process, a resin film formed under a given condition is 100 J / in terms of the exposure amount of g-line (wavelength 436 nm), h-line (wavelength 405 nm), or i-line (365 nm wavelength). Refers to a process of exposing to light of a light amount in the range of m ² to 20,000 J / m ² .

[Example]

Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited to these Examples. On the other hand, in the following description, "%" and "part" indicating amounts are based on mass unless otherwise specified.

In Examples and Comparative Examples, storage stability of the resin composition, and chemical resistance, crack resistance, and insulation reliability of the resin film were evaluated as follows. In addition, the light transmittance of the resin film obtained in the Example was evaluated as follows.

<Storage stability of the resin composition>

The viscosity of the resin composition prepared in Examples and Comparative Examples was measured by an E-type viscometer according to the "Method for Measuring Viscosity Using a 10-Cone-Plate Rotational Viscometer" described in JIS Z 8803: 2011. The viscosity of the resin composition immediately after preparation was set to V0. In addition, the resin composition was sealed in a light-shielding bottle, and the viscosity V1 of the resin composition after being stored in a clean room (temperature 23 ° C., humidity 45%) for one week was measured in the same manner. And, the expression: | (V1-V0) / V0 | Viscosity change rate (%) was calculated according to × 100. The calculated rate of viscosity change was evaluated according to the following criteria.

A: Viscosity change rate is within 5%

B: Viscosity change rate exceeds 5%

<Resin chemical resistance>

The resin composition prepared in Examples and Comparative Examples was coated on a silicon wafer substrate by a spin coat method, followed by heating and drying (pre-baking) at 90 ° C. for 2 minutes using a hot plate to complete pre-baking with a thickness of 2.0 μm. A resin film was formed. Subsequently, a laminated body made of a silicon wafer substrate having a post-baked resin film on its surface was obtained by post-baking the resin film for 20 minutes at 130 ° C in an air atmosphere using an oven.

The laminate obtained as described above was used as a test body, immersed in 200 ml of the drug for 5 minutes, and the ratio (%) of the film thickness after immersion was calculated when the film thickness before immersion was 100%. As a medicine,

(i) acetone solution maintained at 25 ° C in a thermostat;

(ii) resist stripping solution maintained at 25 ° C in a constant temperature bath (manufactured by Tokyo Okako Co., Ltd., "ST-106", composition: monoethanolamine (MEA) / dimethylsulfoxide (DMSO) = volume ratio 7/3); And

(iii) Resist stripping liquid maintained at 60 ° C in a constant temperature bath (manufactured by Tokyo Okako Kogyo, `` ST-106 '')

Three types were prepared, and the test body was immersed in each solution.

On the other hand, the film thickness was measured using an optical interference-type film thickness measuring device ("Lamda Ace" manufactured by SCREEN).

<Crack resistance of resin film>

[Crack resistance of prebaked resin film]

The resin composition prepared in Examples and Comparative Examples was coated on a silicon wafer substrate by a spin coat method, followed by heating and drying (pre-baking) at 90 ° C. for 2 minutes using a hot plate to complete pre-baking with a thickness of 2.0 μm. A resin film was formed, and a laminate composed of a silicon wafer substrate having a prebaked resin film on the surface was obtained. The surface of the laminate was visually observed to evaluate crack resistance according to the following criteria.

A: There are no cracks on the surface of the laminate.

B: Cracks were observed on the surface of the laminate.

[Acetone crack resistance of resin film]

Crack resistance was evaluated in accordance with the same criteria as [Crack resistance of pre-baked resin film] with respect to the test body immersed in the acetone solution according to the procedure described in the section of <Resin film chemical resistance>.

<Insulation reliability of resin film>

On a glass substrate (Corning, product name: Corning 1737), a Cu thin film having a film thickness of 100 nm was formed using a sputtering device. Subsequently, a Cu thin film was patterned using a photoresist, and a comb electrode substrate having a Cu wiring width of 7 μm and an inter-wiring distance of 7 μm was produced. On this comb-shaped electrode substrate, the resin composition prepared in Examples and Comparative Examples was applied by a spin coat method, followed by heating and drying (pre-baking) at 90 ° C. for 2 minutes using a hot plate to obtain a resin film having a thickness of 2.0 μm. Formed. Subsequently, this resin film was subjected to post-bake heating at 130 ° C. for 20 minutes in an air atmosphere using an oven to obtain a laminate obtained by laminating in the order of a test chain and a resin film-Cu wiring-glass substrate. Then, the obtained test body was placed in a high temperature and humidity tank at a temperature of 85 ° C and a humidity of 85% while a voltage of 15 V was applied. Then, after 500 hours, the test body was taken out from the high temperature and humidity chamber, and the Cu wiring formed on the test body was observed by a digital microscope (KH-1300 manufactured by Hyrox Corporation), and the insulation reliability of the resin film was evaluated according to the following criteria. .

A: No corrosion was observed in the Cu wiring after 500 hours.

B: Corrosion was confirmed in the Cu wiring after 500 hours.

<Light transmittance of resin film>

On the glass substrate (Corning, product name Corning 1737), the resin composition obtained in the example was applied by a spin coat method, and then heated and dried (pre-baked) at 90 ° C for 2 minutes using a hot plate to obtain a resin having a film thickness of 2.0 μm. A film was formed. Subsequently, a post-baking was performed by heating at 130 ° C. for 20 minutes in an atmospheric atmosphere using an oven 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 Nippon Spectroscopy). From the measurement results, light transmittance (%) at 400 nm was calculated. On the other hand, the light transmittance (%) of the resin film was calculated as a conversion value when the thickness of the resin film was 2.0 μm using a glass substrate without a 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), a cyclic olefin monomer having an N-substituted imide group, 31.5 mol%, and a carboxyl group-containing cyclic olefin monomer 100 parts of monomer mixture consisting of 4-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-9-ene (TCDC) 68.5 mol%, 6.9 parts of 1,5-hexadiene, ring opening Polymerization catalyst (1,3-dimesitylimidazoline-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride (Org. Lett., Vol. 1, p. 953, 1999) ), 0.01 parts, and 200 parts of diethylene glycol ethyl methyl ether were charged into a nitrogen-resistant glass pressure reactor, and reacted at 80 ° C for 4 hours while stirring to obtain a polymerization reaction solution.

The obtained polymerization reaction solution was placed in an autoclave, and stirred under a condition of 150 ° C and hydrogen pressure of 4 MPa for 5 hours to carry out a hydrogenation reaction to obtain a solution containing a carboxyl group-containing polyolefin resin composed of an alicyclic olefin copolymer. Got. The alicyclic olefin copolymer had 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%. Moreover, the solid content concentration of the solution containing a carboxyl group-containing polyolefin resin was 32.0 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, epoxidized butanetetra as a polyfunctional epoxy compound 40 parts of carboxylic acid tetrakis (3-cyclohexenylmethyl) -modified ε-caprolactone (Daicel Chemical Industry: Eporide GT401), 1H as benzotriazole-based compound, a nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms -Benzotriazole-1-methanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 5 parts, glycidoxypropyl trimethoxysilane (silane produced by XIAMETER: OFS6040) as a silane coupling agent, pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (manufactured by BASF: Irganox1010) 2 parts, organosiloxane polymer (Shin-Etsu Chemical Co .: KP341) 300 ppm as surfactant, and solvent 100 parts of diethylene glycol ethyl methyl ether (manufactured by Toho Chemical Co., Ltd .: EDM) were mixed, 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 in accordance with the above, and a resin film was formed using the obtained resin composition, and various evaluations were performed according to the above. Table 1 shows the results.

(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. Table 1 shows the results.

(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 a polyfunctional vinyl ether compound.

In Example 5, trimethylolpropaneethoxylate trivinyl ether was used as a 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.

A resin composition was prepared respectively in the same manner as in Example 2 except for these points, and various evaluations were performed. Table 1 shows the results.

(Example 8)

A resin composition was prepared in the same manner as in Example 2, except that the polyfunctional epoxy compound was not blended, and various evaluations were performed. Table 1 shows the results.

(Comparative Examples 1-4)

Resin compositions were prepared in the same manner as in Examples 2 to 5, respectively, except that the nitrogen-containing nitrogen-containing fused heterocyclic compound was not blended, and various evaluations were performed. Table 1 shows the results. On the other hand, in these examples, since the chemical resistance of the obtained resin film was low, evaluation of insulation reliability was not performed.

(Comparative Examples 5-7)

The nitrogen-containing nitrogen-containing fused heterocyclic compound is not compounded, and instead, a heterophthalic compound is not a heterophthalic acid (Comparative Example 5), a nitrogen atom is a heterocyclic compound of 3, 3-mercapto-1H-tetrazole (Comparative Example 6) was prepared in the same manner as in Example 3, except that 5 parts of benzoimidazole (Comparative Example 7), which was a nitrogen-containing condensed heterocyclic compound having 2 nitrogen atoms, were each mixed, to prepare a resin composition. And various evaluations were performed. Table 1 shows the results.

(Comparative Examples 8-10)

A resin composition was prepared in the same manner as in Example 2, except that each of the monofunctional monovinyl ether compounds shown in Table 1 was substituted for the polyfunctional vinyl ether compounds, and various evaluations were performed. Table 1 shows the results. On the other hand, in these examples, since the chemical resistance of the obtained resin film was low and cracks were also generated by immersion in acetone, evaluation of insulation reliability was not performed.

(Comparative Example 11)

4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] as a photosensitizer without mixing a polyfunctional vinyl ether compound and a nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms ] Phenyl] ethylidene] ester of bisphenol and 6-diazo-5,6-dihydro-5-oxo-naphthalene-1-sulfonic acid (1,2-naphthoquinone diazide-5-sulfonic acid chloride) (2.0 Molecular body) A resin composition was prepared in the same manner as in Example 1, except for mixing (MiTP Co., Ltd., "TPA-520"), and various evaluations were performed. Table 1 shows the results. On the other hand, the resin film obtained according to this example was reddish brown. In addition, in this example, evaluation other than chemical resistance and acetone crack resistance was not performed.

In Table 1,

"GT401" is an epoxidized butane tetracarboxylic acid tetrakis (3-cyclohexenyl methyl) modified ε-caprolactone (Daicel Chemical Industries, Inc .: eporide GT401),

"TPA520" is 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 6-diazo-5,6-dihydro Ester body (2.0 mol) of -5-oxo-naphthalene-1-sulfonic acid (1,2-naphthoquinone diazide-5-sulfonic acid chloride),

"OFS6040" is glycidoxypropyl trimethoxysilane (XIAMETER Corporation make: OFS6040),

"Irg1010" is pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (manufactured by BASF: Irganox1010),

"KP341" is an organosiloxane polymer (Shin-Etsu Chemical Co., Ltd .: KP341),

"EDM" is diethylene glycol ethyl methyl ether,

Respectively.

From Table 1, in Examples 1 to 8 using a resin composition containing a carboxyl group-containing resin, a polyfunctional vinyl ether compound, and a nitrogen-containing fused heterocyclic compound having 3 nitrogen atoms, the storage stability of the resin composition itself was secured. It was also found that the chemical resistance of the obtained resin film was high. On the other hand, in Comparative Examples 1 to 7 in which the nitrogen-containing nitrogen-containing fused heterocyclic compound, benzotriazole-based compound, was not blended, it was compatible with securing storage stability of the resin composition itself and increasing the chemical resistance of the resulting resin film. You can see that it could not. Among them, in Comparative Example 5 in which homophthalic acid was blended in place of the nitrogen-containing condensed heterocyclic compound, storage stability of the resin composition was lowered, and insulation reliability of the resin film was not obtained. This acts to cause crosslinking reaction between the polyfunctional vinyl ether compound and the polyfunctional epoxy compound contained in the resin composition to increase the viscosity, thereby lowering the storage stability, and further, the homophthalic acid contained in the obtained resin film to corrode the Cu wiring. It is estimated that it is because. In addition, it can be seen that in Comparative Examples 8 to 10 in which no polyfunctional vinyl ether compound was blended, the chemical resistance of the resulting resin film could not be increased. In addition, in Comparative Example 11 in which neither the polyfunctional vinyl ether compound nor the nitrogen-containing fused heterocyclic compound having 3 nitrogen atoms was blended, it was found that the chemical resistance of the resulting resin film could not be increased.

[Industrial availability]

ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can ensure the storage stability of the resin composition itself and which improves the chemical resistance of the obtained resin film can be provided.

Further, according to the present invention, it is possible to provide a resin film excellent in chemical resistance.

Claims (7)

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