TWI763926B - Resin composition and resin film - Google Patents

Abstract

A resin composition comprising a carboxyl group-containing resin, a polyfunctional vinyl ether compound and a nitrogen-containing fused heterocyclic compound with 3 nitrogen atoms.

Description

Resin composition and resin film

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

Various resin films are provided on 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 as protective films to prevent deterioration or damage. , A planarization film used to planarize the surface of an element or a substrate surface with wiring, and an electrical insulating film used to maintain electrical insulating properties. Further, for example, on the organic EL element, a resin film serving as a pixel separation film is provided in order to separate the light-emitting body portion. Furthermore, for example, on elements such as display elements for thin film transistor liquid crystals, integrated circuit elements, and the like, in order to insulate wirings arranged in layers, a resin film is provided as an interlayer insulating film.

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

"Patent Document" "Patent Document 1": Japanese Patent Laid-Open No. 2015-25892

Here, conventionally, materials such as glass are generally used as substrates of display elements. In the case of forming a resin film on a glass substrate, when the resin film is to be cured, the curing reaction can be accelerated by curing at a curing temperature as high as 200° C. or higher, and a resin film rich in chemical resistance can be formed. However, in recent years, with the flexibility of display elements, it is 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 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 when curing the resin film. Therefore, it is required to develop a resin composition capable of forming a resin film with high chemical resistance even under low temperature curing conditions.

In addition, in the process of stacking various films on a substrate when manufacturing electronic components, various chemicals and the like are generally used. Here, if a composition is made to improve chemical resistance to various chemicals, the storage stability of the resin composition will be deteriorated, and there are "improving the chemical resistance of the obtained resin film" and "maintaining the resin composition". Its own storage stability" is a problem that is difficult to achieve both.

In view of the above-mentioned situation, the present invention aims to provide a resin composition which can ensure both the storage stability of the resin composition itself and improve the chemical resistance of the obtained resin film.

Furthermore, the present invention aims to provide a resin film excellent in chemical resistance.

The inventors of the present invention have devoted themselves to research with the aim of solving the above-mentioned problems. Then, the present inventors newly discovered that, in the resin composition, when a resin having a specified functional group, a polyfunctional vinyl ether compound, and a specified nitrogen-containing fused heterocyclic compound coexist, the resin composition can be ensured at the same time. The storage stability of itself and the improvement of the chemical resistance of the resin film obtained by using the resin composition have led to the completion of the present invention.

That is, the present invention aims to solve the above-mentioned problems smoothly, and 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 making the blending of the resin composition into such a specific blending, both the storage stability of the resin composition itself can be ensured and the chemical resistance of the obtained resin film can be improved.

Furthermore, in the resin composition of the present invention, the aforementioned nitrogen-containing fused heterocyclic compound is preferably a benzotriazole-based compound. When the resin composition contains the benzotriazole-based compound, it is possible to achieve both better storage stability of the resin composition itself and improvement of the chemical resistance of the obtained resin film.

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

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

Furthermore, in the resin composition of the present invention, it is preferable that the aforementioned carboxyl group-containing resin is a resin containing a cycloolefin monomer unit. If the resin composition is a resin containing cycloolefin monomer units, the amount of outgassing from the obtained resin film can be suppressed while reducing the water absorption of the obtained resin film.

Furthermore, the resin composition of the present invention preferably contains the nitrogen-containing fused heterocyclic compound in a ratio of 1 part by mass or more relative 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 equal to or more than the above lower limit value, the crack resistance of the obtained resin film can be further improved.

Here, the present invention aims to solve the above-mentioned problems smoothly, and the resin film of the present invention is characterized by being formed using any of the above-mentioned resin compositions. Since the resin film of the present invention is formed using the resin composition of the present invention, it is excellent in 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 improving the chemical resistance of the obtained resin film.

Furthermore, according to the present invention, a resin film excellent in chemical resistance can be provided.

Embodiments of the present invention will be described in detail below. The resin composition of the present invention can be suitably used to form a resin film "applicable to various elements, parts, etc., and capable of functioning as a protective film, a planarizing film, an insulating film, and the like".

(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 blending the resin composition with a carboxyl group-containing resin, a polyfunctional vinyl ether compound, and a nitrogen-containing fused heterocyclic compound with 3 nitrogen atoms, both the storage stability of the resin composition itself can be ensured, and the use of such a resin composition can be improved. And the chemical resistance of the resin film obtained. Here, it is presumed that 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 fused heterocyclic compound having 3 nitrogen atoms is moderately basic, and the above-mentioned performance is obtained. the effect described. Especially with regard to chemical resistance, it can be considered that the carboxyl group contained in the resin and the polyfunctional vinyl ether compound can start to react at low temperatures, and the basic nitrogen-containing fused heterocyclic compound acts in a manner that promotes this reaction. bring benefits. Based on such a reason, it is presumed that the resin composition of the present invention can form a resin film having good chemical resistance. Furthermore, the resin composition of the present invention preferably further contains a polyfunctional epoxy compound.

Each component contained in the resin composition will be described below.

<Carboxyl-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. As such a carboxyl group-containing resin, for example, a (co)polymer containing a carboxyl group-containing monomer unit (hereinafter also referred to as a "carboxyl group-containing monomer unit") is exemplified. In addition, in this specification, "(co)polymer" means a polymer or a copolymer.

Examples of (co)polymers containing carboxyl group-containing monomer units include (co)polymerization using ethylenically unsaturated carboxylic acid monomers and derivatives thereof, or carboxyl group-containing cycloolefin monomers and derivatives thereof. thing. Examples of the ethylenically unsaturated carboxylic acid monomers include ethylenically unsaturated monocarboxylic acids and derivatives thereof, ethylenically unsaturated dicarboxylic acids and their anhydrides, and derivatives thereof. As an example of an ethylenically unsaturated monocarboxylic acid, (meth)acrylic acid and a crotonic acid are mentioned. In addition, in this specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid. Examples of derivatives of ethylenically unsaturated monocarboxylic acids include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl acrylate, and the like Acrylate etc. As an example of an ethylenically unsaturated dicarboxylic acid, maleic acid, fumaric acid, and itaconic acid are mentioned. Examples of carboxyl-containing cycloolefin monomers include 5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene, 5-methyl-5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene, 5-methyl-5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene, -Carboxymethyl-5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-dihydroxycarbonylbicyclo[2.2.1]hept-2-ene, 4-hydroxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodec-9-ene, 9-methyl-9-hydroxycarbonyltetracyclo[ ^{6.2.1.13,6.02,7} ] ^dodec -4-ene, and 9, 10-Dihydroxycarbonyltetracyclo[ ^{6.2.1.13,6.02,7} ] ^dodec -4-ene, etc.

［上述式（A）中，X表示氫原子或碳數1～16的直鏈、環狀或支鏈烷基或者苯基等芳基，n為1或2。］Furthermore, the (co)polymer containing a carboxyl group-containing monomer unit may be a polymer composed of one of the above-mentioned monomers, or may be a "monomer like the above-mentioned monomer" or "co-polymer with these monomers". copolymers of other monomers. Examples of other monomers that can be copolymerized with the above-mentioned monomers include known amide group-containing monomers, hydroxyl group-containing monomers, isocyanate group-containing monomers, and carboxyl group-containing cycloolefin monomers. Olefin monomers, silane monomers, and cycloolefin monomers other than the aforementioned carboxyl group-containing cycloolefin monomers, etc. In particular, examples of cycloolefin monomers other than the aforementioned carboxyl group-containing cycloolefin monomers include those having an N-substituted imide group represented by the following formula (A) as disclosed in Japanese Patent Laid-Open No. 2015-25892. Cycloolefin monomers, oxygen-containing cycloolefin monomers such as ester groups or acid anhydride groups, cycloolefin monomers having nitrogen-containing groups such as cyano groups, cycloolefin monomers having sulfonyl groups, cycloolefin monomers having silicon groups Monomers, or cycloolefin monomers with halogen atoms, etc. "Change 1"

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

In addition, for the (co)polymer containing carboxyl group-containing monomer units, all monomer units constituting the (co)polymer are set to 100% by mass, and the ratio of carboxyl group-containing monomer units is preferably 10% by mass or more, and 15 mass % or more is preferable, and 100 mass % may be sufficient. In addition, 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 the acrylate monomer as described above", and an acrylic resin composed of "using Polyamide resin, polyester resin, polyurethane resin, polyolefin resin, polycycloolefin resin, polysiloxane resin, etc. .

Among them, polycycloolefin resin is preferable as the carboxyl group-containing resin because the amount of outgassing can be suppressed and water absorption is low. The polycycloolefin resin is a resin containing a cycloolefin monomer unit. The cycloolefin monomer unit includes the above-mentioned carboxyl group-containing cycloolefin monomer unit and other cycloolefin monomer units. Among them, as the polycycloolefin resin which is a carboxyl group-containing resin, a resin containing a carboxyl group-containing cycloolefin monomer unit is preferable, and a resin containing a carboxyl group-containing cycloolefin monomer unit, and having a compound represented by the above formula (A) is preferred. The resin of the cycloolefin monomer unit of N-substituted imide group is more preferable. In particular, as "4-hydroxycarbonyltetracyclo[ ^{6.2.1.13,6.02,7} ] ^dodec -9-ene (TCDC) was used as the carboxyl-containing cycloolefin monomer, and N-phenylbicyclo [2.2.1] Hept-5-ene-2,3-dimethylimide (NBPI) is preferably a polycyclic olefin resin which is a copolymer formed from a cyclic olefin monomer having an N-substituted imide group" .

The content ratio of the cycloolefin monomer unit in the resin containing the cycloolefin monomer unit (the ratio of the carboxyl group-containing cycloolefin monomer unit and the total ratio of the cycloolefin monomer unit other than the cycloolefin monomer unit) is the ratio of all the monomer units constituting the resin It is set to 100 mass %, preferably more than 50 mass %, more preferably more than 70 mass %, more preferably more than 90 mass %, and all 100 mass % may be cycloolefin monomer units.

In particular, when the "resin containing a cycloolefin monomer unit" contains a carboxyl group-containing cycloolefin monomer unit, the content ratio of the carboxyl group-containing cycloolefin monomer unit shall be 100% by mass of all the monomer units constituting the resin, and shall be more than 100% by mass. 40 mass % is preferable, more than 55 mass % is preferable, and less than 100 mass % is preferable.

In addition, the ratio of each monomer unit in the resin containing the cycloolefin 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 in accordance with a known production method can be used. The production method is not particularly limited, and for example, any method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method can be used. In addition, as the polymerization method, addition polymerization such as ionic polymerization, radical polymerization, and living radical polymerization, and ring-opening polymerization can be employed. Also, as the polymerization initiator, a known polymerization initiator can be used. In particular, in the production of polycycloolefin resins, various cycloolefin monomers can be obtained by polymerizing various cycloolefin monomers according to the method described in Japanese Patent Laid-Open No. 2015-25892 using known ring-opening polymerization catalysts and additives. After the co)polymer, the (co)polymer is hydrogenated in the presence of known hydrogenation catalysts.

<Polyfunctional vinyl ether compound>

As the polyfunctional vinyl ether compound, a vinyl ether compound having two or more functional groups can be used. As a vinyl ether compound whose functional group number is 2 or more, the compound which has a vinyl ether structure represented by "-C=C-O-" which has 2 or more in 1 molecule is mentioned. 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 vinyl ether compounds having 2 functional groups include 1,4-butanediol divinyl ether, neopentyl glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, and diethylene glycol divinyl ether. Vinyl ether, triethylene glycol divinyl ether, dipropylene glycol divinyl ether and cyclohexane glycol divinyl ether. Among them, 1,4-butanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether and cyclohexanediol divinyl ether are preferable. In addition, as the vinyl ether compound having 3 functional groups, trimethylolpropane trivinyl ether and ethoxylated trimethylolpropane trivinyl ether are preferable.

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

The nitrogen-containing condensed heterocyclic compound having three nitrogen atoms refers to a compound in which the constituent atoms of the condensed heterocyclic ring contain three nitrogen atoms. In other words, the "nitrogen-containing fused heterocyclic compound having 3 nitrogen atoms" is not particularly limited as long as one of the constituent atoms of the fused heterocycle contains 3 nitrogen atoms, and any compound may be included. More specifically, the "nitrogen-containing fused heterocyclic compound having 3 nitrogen atoms" may contain two or more "condensed heterocycles having 3 nitrogen atoms in the constituent atoms" in one compound, or Structures other than the nitrogen-containing fused heterocyclic structure constituting the compound contain nitrogen atoms.

［上述式（1）中，G¹ ～G⁹ 之中的任3者為氮原子，其他為碳原子，R¹ 為氫原子或有機基，R² 為氫原子、鹵素基、羧基或碳數1～5的烷基。］Examples of the nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms include a compound represented by the following general formula (1), and a compound having a structure represented by the following general formula (1). "Hua 2"

[In the above formula (1), any 3 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, a halogen group, a carboxyl group or a carbon number 1-5 alkyl groups. ]

Furthermore, it may be an organic group of R ¹ contained in the formula (1), a phenol group which may have one or more substituents, or a C1-10 group which may have one or more substituents. Straight or branched chain alkyl. Here, examples of the substituent of the "phenol group which may have one or more substituents" include alkyl groups having 1 to 10 carbon atoms, 3,4,5,6-tetrahydro-N-methylphthalein imino and 1-methyl-1-phenylethyl and the like. Here, when the phenol group which may have one or more substituents has a plurality of substituents, these may be the same or different. Moreover, as a substituent of "the C1-C10 linear or branched alkyl group which may have one or more substituents", a hydroxyl group etc. are mentioned.

In addition, the compound may be a nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms, or may be a compound having the structures [1] and [1]' represented by the above formula (1). Specifically, such a compound may have two structures [1] by combining an alkylene group having 1 to 10 carbon atoms (-C _m H _2m -; here, m is an integer of 1 to 10) as a linking group. and [1]' (here, the structures [1] and [1]' are not particularly limited as long as they can be represented by the above formula (1), and they may be the same or different.) A compound represented by the general formula (2): [1]-C _m H _2m -[1]'. Here, the above-mentioned alkylene group having 1 to 10 carbon atoms, which is a linking group, is bonded to each R ¹ included in the structures [1] and [1]'.

Among them, as the nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms, in the above formula (1) (2), G ¹ to G ³ are nitrogen atoms, and G ⁴ to G ⁹ are benzos of carbon atoms. Triazole-based compounds are preferred. If the resin composition contains the benzotriazole-based compound, it is possible to more effectively ensure both the storage stability of the resin composition itself and the improvement of the chemical resistance of the obtained resin film.

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'-tertidine yl-5'-methylphenyl)-5-chlorobenzotriazole (manufactured by Johoku Chemical Co., Ltd., "JF-79"), 2-[2'-hydroxy-3',5'-bis(tertiary pentane) base)phenyl]benzotriazole (manufactured by Johoku Chemical Co., Ltd., "JF-80"), 2-[2'-hydroxy-5'-(tertiary octyl)phenyl]benzotriazole (manufactured by Johoku Chemical Co., Ltd. manufactured by “JF-83”), 2-[2-hydroxy-3-(3,4,5,6,7-tetrahydro-1,3-dioxy-1H-isoindol-2-ylmethyl) base)-5-methylphenyl]-2H-benzotriazole (manufactured by Sumika Chemtex, "Sumisorb 250"), and 2-(2H-benzotriazol-2-yl)-4,6-bis (1-methyl-1-phenylethyl)phenol ("ADK STAB LA-24" manufactured by ADEKA) and the like. In addition, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1, 1,3,3-Tetramethylbutyl)phenol] (manufactured by ADEKA, "ADK STAB LA-31").

Among them, from the viewpoint of improving the compatibility with the carboxyl group-containing resin and the solubility to the solvent described below, and from the viewpoint of better securing the storage stability of the resin composition, 1H-benzotriazole is used as the benzotriazole-based compound. Azole-1-methanol is preferred.

[Content of nitrogen-containing fused heterocyclic compound having 3 nitrogen atoms]

The content of the nitrogen-containing fused heterocyclic compound in the resin composition is preferably 1 part by mass or more, preferably 2 parts by mass or more, and preferably less than 20 parts by mass relative to 100 parts by mass of the carboxyl group-containing resin , preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 7 parts by mass or less. When the content ratio of the nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms is equal to or more than the above lower limit value, the crack resistance of the obtained resin film can be further improved. Furthermore, when the content ratio of the nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms is equal to or less than the above upper limit value, an excessive increase in the viscosity of the resin composition can be suppressed and a resin film can be formed favorably.

<Polyfunctional epoxy compound>

Although it does not specifically limit as a polyfunctional epoxy compound, The compound which has two or more epoxy groups in 1 molecule is mentioned. By including 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 moderately suppresses the increase of the internal stress due to the carboxylic acid and the polyfunctional vinyl ether in the resin film.

Examples of compounds having two or more epoxy groups in one molecule include epoxidized butanetetracarboxylic acid tetra(3-cyclohexenylmethyl)-modified ε-caprolactone, trimeric isocyanurate (2,3-glycidyl ester), 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol tricyclic Oxypropyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenylglycidyl ether, 1,1,3-para[p-(2,3-epoxypropyl ether Oxy)phenyl]propane, Diglycidyl 1,2-cyclohexanedicarboxylate, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4- Epoxycyclohexanecarboxylic acid-3,4-epoxycyclohexylmethyl ester, trimethylolethane triglycidyl ether and bisphenol A diglycidyl ether, and neotaerythritol polyepoxide propyl ether. Commercially available products include, for example: EPOLEAD GT-401, Same GT-403, Same GT-301, Same GT-302, Celloxide 2021, Celloxide 3000 (the above are manufactured by DAICEL); jER1001, jER1002, jER1003, jER1004 , jER1007, jER1009, jER1010, jER828, jER871, jER872, jER180S75, jER807, jER152, jER154 (the above are manufactured by Mitsubishi Chemical Corporation); EPPN201, EPPN202, EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN -1025, EOCN-1027 (the above are manufactured by Nippon Kayaku Co., Ltd.), EPICLON 200, EPICLON 400 (the above are manufactured by DIC Corporation), Denacol EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, EX-321 (the above are manufactured by Nagase ChemteX Corporation), etc. Among them, it is preferable that the polyfunctional epoxy compound has an alicyclic epoxy group from the viewpoint of further improving the crack resistance of the obtained resin film. Furthermore, the number of alicyclic epoxy groups contained in the polyfunctional epoxy compound is preferably 2 or more, more preferably 3 or more, more preferably 4 or more, and usually 6 or less. In particular, ε-caprolactone (the number of alicyclic epoxy groups: 4) modified with epoxidized butanetetracarboxylic acid 4 (3-cyclohexene methyl ester) is preferable. In addition, "the number of alicyclic epoxy groups contained in the polyfunctional epoxy compound" means that when the polyfunctional epoxy compound is a polymer composed of repeating structural units containing alicyclic epoxy groups, the number of units per unit structure The number of alicyclic epoxy groups in (1 molecule).

<optional ingredient>

In addition to the above-mentioned 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 optional components, known ones can be used (see, for example, International Patent Publication No. 2015/033901 and Japanese Patent Publication No. 2015-25892). Furthermore, the content of these additives can be appropriately adjusted within a general range as long as the effects of the present invention are not impaired.

<Solvent>

As the solvent to be contained in the resin composition of the present invention, a known organic solvent used in the preparation of the resin composition can be used (for example, refer to International Patent Publication No. 2015/033901). Among them, diethylene glycol containing diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether can be appropriately used. class of solvents.

<Preparation method of resin composition>

The preparation method of the resin composition of the present invention is not particularly limited, as long as each component constituting the resin composition is mixed by a well-known method. The method of mixing 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.

As a specific mixing method, the mixing method using, for example, stirring using a stirring bar, a high-speed homogenizer, a disperser, a planetary mixer, a twin-shaft mixer, a ball mill, a three-roll mill, and the like can be mentioned. Moreover, the solution or dispersion liquid obtained by mixing can also be filtered using, for example, a filter having a pore diameter of about 0.45 μm.

(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 the present invention is formed using the resin composition of the present 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 to a desired substrate. That is, the resin film of the present invention is formed from the dried product of the resin composition of the present invention, 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. Furthermore, the resin film of the present invention preferably contains a polyfunctional epoxy compound. In addition, each component contained in the resin film is contained in the above-mentioned resin composition, so the appropriate content ratio of these components is the same as the appropriate content ratio of each component in the resin composition. Moreover, for example, the polyfunctional vinyl ether compound contained in the resin film, the polyfunctional epoxy compound contained arbitrarily, etc., can also be crosslinked by the time of the crosslinking treatment that can be performed arbitrarily. In other words, the resin film may contain a cross-linked product of the above-mentioned polyfunctional vinyl ether compound and polyfunctional epoxy compound.

As the substrate, for example, a printed wiring substrate, a silicon wafer substrate, a glass substrate, a plastic substrate, and the like can be used. In addition, substrates used in the field of displays that "form a thin transistor type liquid crystal display element, color filter, black matrix, etc. on a glass substrate or a plastic substrate" can also be suitably used. Among them, the resin composition of the present invention can be cured at low temperature, so the resin film of the present invention formed by using the resin composition can be suitably arranged on the plastic substrate.

The method of applying the resin film to the substrate is not particularly limited, and methods such as a coating method and a thin film stacking method can be used, for example.

The coating method is, for example, a method of removing a solvent after coating a resin composition on a substrate such as a plastic substrate. As a method of applying the resin composition, various methods such as spray coating, spin coating, roll coating, die coating, blade coating, bar coating, and screen printing can be employed. Solvents, for example, can be removed by drying. The drying conditions vary depending on the type of each component, the mixing ratio, and the heat-resistant temperature of substrates such as plastic substrates, etc., but usually it can be set at a temperature of 30°C or higher and 150°C or lower, preferably 60°C or higher and 120°C or lower. Under the conditions, 0.5 minutes or more and 90 minutes or less, preferably 1 minute or more and 60 minutes or less, and preferably 1 minute or more and 30 minutes or less. According to the resin composition of this invention, even if the temperature at the time of drying is below the said upper limit, the resin film excellent in chemical resistance can be obtained. Moreover, when the temperature at the time of drying is made into the said lower limit or more, the chemical resistance of a resin film can fully be improved.

The film stacking method is a method of coating a resin composition on a substrate for forming a resin film, removing a solvent to obtain a resin film, and stacking the obtained resin film on a substrate to form a substrate with a resin film. The solvent can be removed, for example, by drying. The drying conditions can be appropriately selected depending on the type and blending ratio of each component. The drying conditions can usually be set to be 0.5 minutes or more and 90 minutes or less under the temperature conditions of 30°C or more and 150°C or less. Moreover, when stacking a resin film on a board|substrate, a pressing machine, such as a pressure bonding machine, a press, a vacuum bonding machine, a vacuum press, and a roll bonding machine, 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 can be set to be preferably 0.1 μm or more and 100 μm or less, preferably 0.5 μm or more and 50 μm or less, more preferably 0.5 μm or more and 30 μm or less, and preferably 0.5 μm or more And 10 μm or less is particularly preferred. According to the resin composition of the present invention, even when the thickness of the resin film is made relatively thin, the chemical resistance can be sufficiently improved.

In addition, the resin film formed by the above-mentioned coating method or thin film stacking method may be subjected to a cross-linking treatment as required. The cross-linking treatment is not particularly limited, and can be performed by, for example, a general method as disclosed in Japanese Patent 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 the bleaching exposure process. Here, the light transmittance, for example, can be measured according to the method described in the embodiment.

Moreover, the resin film of the present invention can achieve the high light transmittance as described above, and does not need to perform a so-called bleaching exposure process. In addition, the bleach exposure step means an operation for exposing the resin film to overexposure conditions to discolor the colored resin film after drying the resin composition to form a resin film. For example, this bleaching exposure process means that the resin film formed under the given conditions is exposed to g-line (wavelength 436 nm), h-line (wavelength 405 nm) or i-line (wavelength 365 nm) ), the process of converting the light amount of light in the range of 100 J/m ² to 20,000 J/m ² .

"Example"

The present invention is specifically described below based on the embodiments, but the present invention is not limited to these embodiments. In addition, in the following description, unless otherwise noted, "%" and "part" representing the amount are based on mass.

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 in the following manner. In addition, the light transmittance of the resin film obtained in the Example was evaluated by the following method.

<Storage stability of resin composition>

For the resin compositions prepared in the Examples and Comparative Examples, the viscosity was measured with an E-type viscometer in accordance with "10 Viscosity measurement method according to a cone-plate type rotational viscometer" described in JIS Z 8803:2011. The viscosity of the resin composition just prepared is defined as V0. Then, 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 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: The viscosity change rate is within 5% B: The viscosity change rate exceeds 5%

<Chemical resistance of resin film>

The resin compositions prepared in the examples and comparative examples were coated on a silicon wafer substrate by spin coating, and heated and dried (pre-baked) at 90°C using a hot plate for 2 minutes to form a film with a thickness of 2.0 μm. Pre-baked resin film. Then, the resin film was post-baked by heating at 130° C. for 20 minutes in an atmospheric environment using an oven, thereby obtaining a stack of silicon wafer substrates having a post-baked resin film on the surface. .

The stack obtained as described above was used as a sample, and was immersed in 200 mL of chemicals for 5 minutes, and the ratio (%) of the film thickness after immersion was calculated when the film thickness before immersion was 100%. As chemicals, the following three types were prepared: (i) Acetone solution maintained at 25°C in a thermostatic bath; (ii) Photoresist stripping solution maintained at 25°C in a thermostatic bath (manufactured by Tokyo Oka Industry Co., Ltd., "ST-106", composition : monoethanolamine (MEA)/dimethylsulfoxide (DMSO) = volume ratio 7/3); and (iii) photoresist stripping solution maintained at 60°C in a thermostatic bath (manufactured by Tokyo Oka Industry Co., Ltd., "ST-106" ); and immerse the sample in each solution respectively.

In addition, the film thickness was measured using an optical interference type film thickness measuring device (manufactured by SCREEN, "Lambda Ace").

<Crack resistance of resin film>

[Crack resistance of prebaked resin film]

The resin compositions prepared in the examples and comparative examples were coated on a silicon wafer substrate by spin coating, and heated and dried (pre-baked) at 90°C using a hot plate for 2 minutes to form a film with a thickness of 2.0 μm. A pre-baked resin film is obtained to obtain a stack of silicon wafer substrates having a pre-baked resin film on the surface. The surface of the stacked body was visually observed, and the crack resistance was evaluated according to the following criteria. A: The surface of the stack has no cracks. B: Cracks were confirmed on the surface of the stacked body.

[Resistance to acetone cracking of resin film]

For the sample "immersed in an acetone solution following the procedure described in the item "Chemical Resistance of Resin Film" above, the same criteria as the above [Crack resistance of pre-baked resin film] were followed. Crack resistance.

<Insulation reliability of resin film>

On a glass substrate (Corning Corporation, product name: Corning 1737), a Cu thin film with a thickness of 100 nm was formed using a sputtering apparatus. Then, using a photoresist, the Cu thin film was patterned to produce a comb-shaped electrode substrate with a Cu wiring width of 7 μm and a wiring pitch of 7 μm. The resin compositions prepared in the examples and comparative examples were coated on such comb-shaped electrode substrates by spin coating, and heated and dried (pre-baking) at 90°C using a hot plate for 2 minutes to form a film thickness of 2.0. μm resin film. This resin film was then subjected to post-baking by heating at 130° C. for 20 minutes in an atmospheric environment using an oven, thereby obtaining a stack of samples, which were stacked in the order of resin film, Cu wiring, and glass substrate. body. Then, the obtained sample was placed in a high temperature and humidity tank with a temperature of 85°C and a humidity of 85% under the state of applying a voltage of 15V. Then, after 500 hours, the sample was taken out from the high temperature and humidity chamber, and the Cu wiring provided in the sample was observed with a digital microscope (manufactured by HIROX Corporation, KH-1300), 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 observed in the Cu wiring after 500 hours.

<Light transmittance of resin film>

The resin composition obtained in the examples was coated on a glass substrate (Corning Corporation, product name Corning 1737) by spin coating, and was heated and dried (pre-baked) at 90° C. for 2 minutes using a hot plate to form a film. 2.0 μm thick resin film. Then, by performing post-baking by heating at 130° C. for 20 minutes in an atmosphere using an oven, a stacked body of a resin film and a glass substrate was obtained.

The obtained stack was measured at a wavelength of 400 nm to 800 nm using a spectrophotometer V-560 (manufactured by JASCO Corporation). The light transmittance (%) at 400 nm was calculated from the measurement results. In addition, the light transmittance (%) of the resin film was calculated from the conversion value when the thickness of the resin film was 2.0 μm with the glass substrate to which the resin film was not adhered as a control.

(Example 1)

<Preparation of carboxyl-containing resin>

N-phenylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimide (NBPI) 31.5 mol% and 100 parts of a monomer mixture containing 68.5 mol% of 4-hydroxycarbonyltetracyclo[ ^{6.2.1.13,6.02,7} ] ^dodec -9-ene (TCDC) as a carboxyl-containing cycloolefin monomer, 6.9 parts of 1,5-hexadiene, which is dichloro[1,3-bis(1,3,5-trimethylphenyl)imidazoline-2-ylidene](tricyclic) as a ring-opening polymerization catalyst Hexylphosphine) benzylidene ruthenium (synthesized by the method described in Org. Lett., Vol. 1, p. 953, 1999) 0.01 part and 200 parts of diethylene glycol ethyl methyl ether were filled into a glass substituted with nitrogen A pressure-resistant reactor was prepared, and a polymerization reaction liquid was obtained by making it react at 80° C. for 4 hours while stirring.

The obtained polymerization reaction solution was put into an autoclave, stirred for 5 hours at 150° C. and a hydrogen pressure of 4 MPa, and hydrogenated to obtain a carboxyl-containing polyolefin composed of an alicyclic olefin copolymer. resin solution. 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 the 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 Co., Ltd., "CHDVE") as a polyfunctional vinyl ether compound, and a polyfunctional epoxy resin were mixed 40 parts of epoxidized butane tetracarboxylic acid (3-cyclohexenyl methyl ester) modified ε-caprolactone (produced by DAICEL: EPOLEAD GT 401), as a nitrogen-containing fluorocarbon having 3 nitrogen atoms 2 parts of 1H-benzotriazole-1-methanol (manufactured by Tokyo Chemical Industry Co., Ltd.) as a benzotriazole-based compound of heterocyclic compounds, and glycidoxypropyltrimethoxysilane (manufactured by XIAMETER: OFS 6040) as a silane coupling agent ) 2 parts, 4 {3-[3,5-di(tert-butyl)-4-hydroxyphenyl]propionic acid} neopentaerythritol ester (BASF: Irganox 1010) as an antioxidant, 2 parts, 300 ppm of organosiloxane polymer (Shin-Etsu Chemical Co., Ltd.: KP 341) as a surfactant, and 100 parts of diethylene glycol ethyl methyl ether (Toho Chemical Co., Ltd.: EDM) as a solvent, and dissolved , filtered with a polytetrafluoroethylene filter with a pore size of 0.45 μm to complete the preparation of the resin composition.

Regarding the obtained resin composition, the above was followed to evaluate the storage stability, and the obtained resin composition was used to form a resin film, followed by the above to perform various evaluations. The results are disclosed 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 and the like were performed. The results are disclosed 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, ethoxylated trimethylolpropane 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, the same procedure as in Example 2 was carried out, resin compositions were prepared, and various evaluations and the like were performed. The results are disclosed in Table 1.

(Example 8)

Except that the polyfunctional epoxy compound was not blended, the resin compositions were prepared in the same manner as in Example 2, and various evaluations and the like were performed. The results are disclosed in Table 1.

(Comparative Examples 1 to 4)

Except that the nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms was not incorporated, resin compositions were prepared by the same procedures as in Examples 2 to 5, and various evaluations were performed. The results are disclosed in Table 1. In addition, in these examples, since the chemical resistance of the obtained resin film was low, the evaluation of insulation reliability was not performed.

(Comparative Examples 5 to 7)

Except that 5 parts of phthalic acid (Comparative Example 5), which is a non-heterocyclic compound, and 5-mercapto-1H-tetrazole (Comparative Example 6), which is a heterocyclic compound with 3 nitrogen atoms, are added. Benzimidazole (Comparative Example 7), a nitrogen-containing fused heterocyclic compound with 2 atoms, except that the nitrogen-containing fused heterocyclic compound with 3 nitrogen atoms was not incorporated, were operated according to Example 3 to prepare resin compositions respectively. , and carry out various evaluations, etc. The results are disclosed in Table 1.

(Comparative Examples 8 to 10)

The resin compositions were prepared in the same manner as in Example 2, except that the monofunctional monoalcohol ether compounds shown in Table 1 were blended in place of the polyfunctional vinyl ether compounds, and various evaluations were performed. The results are disclosed in Table 1. In addition, in these examples, since the chemical resistance of the obtained resin film was low, and a crack was also generated by immersion in acetone, the evaluation of insulation reliability was not performed.

(Comparative Example 11)

Except that the polyfunctional vinyl ether compound and the nitrogen-containing fused heterocyclic compound with 3 nitrogen atoms are not blended, 4,4'-(1-{4-[1-(4-hydroxyl which is a photosensitizer is blended instead. Phenyl)-1-methylethyl]phenyl}ethylene)bisphenol and 6-diazo-5,6-dihydro-5-oxynaphthalene-1-sulfonic acid (1,2- Except for the ester compound (2.0 molar) of naphthoquinonediazide-5-sulfonyl chloride) (manufactured by Migen Shoji Co., Ltd., "TPA-520"), the same procedures as in Example 1 were carried out to prepare resin compositions respectively, and Various evaluations, etc. are performed. The results are disclosed in Table 1. In addition, the resin film obtained following this example was reddish-brown. In addition, in this example, evaluations other than those concerning chemical resistance and acetone cracking resistance were not performed.

In Table 1, "GT 401" represents epoxidized butanetetracarboxylic acid tetra(3-cyclohexenylmethyl) modified ε-caprolactone (manufactured by DAICEL: EPOLEAD GT 401); "TPA 520" represents 4, 4'-(1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}ethylene)bisphenol and 6-diazo-5,6-dihydro- Esterate of 5-oxynaphthalene-1-sulfonic acid (1,2-naphthoquinonediazide-5-sulfonyl chloride) (2.0 moles); "OFS 6040" means glycidoxypropyl Trimethoxysilane (manufactured by XIAMETER: OFS 6040); "Irg 1010" means tetra{methylene-3-[3,5-di(tertiarybutyl)-4-hydroxyphenyl]propionic acid}pivaltetracycline Alcohol ester (manufactured by BASF: Irganox 1010); "KP 341" means organosiloxane polymer (manufactured by Shin-Etsu Chemical: KP 341); "EDM" means diethylene glycol ethyl methyl ether.

"Table 1"

As can be seen from Table 1, in Examples 1 to 8 in which resin compositions containing a carboxyl group-containing resin, a polyfunctional vinyl ether compound, and a nitrogen-containing fused heterocyclic compound having 3 nitrogen atoms were used, the storage of the resin composition itself was ensured. stability, and the chemical resistance of the obtained resin film increases. On the other hand, it was found that in Comparative Examples 1 to 7 in which the benzotriazole-based compound, which is a nitrogen-containing fused heterocyclic compound having 3 nitrogen atoms, was not blended, both the storage stability of the resin composition itself and the storage stability of the resin composition itself could not be achieved. The chemical resistance of the obtained resin film is improved. Among them, in Comparative Example 5 in which phthalic acid was blended in place of the nitrogen-containing fused heterocyclic compound, the storage stability of the resin composition decreased, and the insulation reliability of the resin film could not be obtained. It is presumed that this is due to the increase in viscosity and the decrease in storage stability due to the cross-linking reaction between the polyfunctional vinyl ether compound and the polyfunctional epoxy compound contained in the resin composition. The phthalic acid contained therein acts to corrode the Cu wiring. In addition, in Comparative Examples 8 to 10 in which the polyfunctional vinyl ether compound was not blended, it was found that the chemical resistance of the obtained resin film could not be improved. Even in Comparative Example 11 in which neither the polyfunctional vinyl ether compound nor the nitrogen-containing condensed heterocyclic compound having 3 nitrogen atoms was incorporated, it was found that 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 improving the chemical resistance of the obtained resin film.

Furthermore, according to the present invention, a resin film excellent in chemical resistance can be provided.

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Claims (6)

A resin composition comprising a carboxyl group-containing resin, a polyfunctional vinyl ether compound, a nitrogen-containing fused heterocyclic compound with 3 nitrogen atoms, and a polyfunctional epoxy compound. The resin composition according to claim 1, wherein the nitrogen-containing fused heterocyclic compound is a benzotriazole-based compound. The resin composition according to claim 1, wherein the polyfunctional epoxy compound has an alicyclic epoxy group. The resin composition according to claim 1 or 2, wherein the carboxyl group-containing resin is a resin containing a cycloolefin monomer unit. The resin composition according to claim 1 or 2, which contains the nitrogen-containing fused heterocyclic compound in a ratio of 1 part by mass or more relative 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 5.