Resin composition

Abstract

To provide a compound that can be blended in a resin composition to improve the adhesion of the resin composition to a substrate.SOLUTION: The present invention discloses a compound represented by general formula (I), where R1 is a hydrogen atom or a methyl group; R2 is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1-20 alkyl group, a substituted or unsubstituted C3-15 cycloalkyl group, or a substituted or unsubstituted C6-20 aromatic hydrocarbon group; X is -S- or -NH-; Y is -N= or -CH=; A is -O-(CH2)m- or a single bond, where m is a positive integer of 1-10; n is a positive integer of 1-10.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a compound, an adhesive, and a resin composition.

Background Art

[0002] When forming a cured film in an electronic device using a resin composition, first, the resin composition is applied onto a substrate to form a film, and then the film is heat-treated to form a cured film. In the formation of the cured film as described above, it is preferable that the adhesion between the resin composition and the substrate is high. In particular, in recent years, since it has been required to form a flat cured film on a substrate having a step, further improvement in the adhesion between the resin composition and the substrate is demanded.

[0003] Patent Document 1 describes an invention related to a copper foil surface treatment agent for improving the adhesion between a copper foil and a prepreg. This document mentions a trialkoxysilane having an imidazole ring as a component of the surface treatment agent.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] When forming a cured film in an electronic device using a resin composition, it is preferable that the adhesion between the resin composition and the substrate is high. The present invention has been made in view of such circumstances. An object of the present invention is to provide a compound that can improve the adhesion between a resin composition and a substrate by being blended into the resin composition.

Means for Solving the Problems

[0006] The inventors of the present invention have completed the invention provided below and solved the above problems.

[0007] According to the present invention, there is provided a compound represented by the following general formula (I). [Chemical formula] In the above general formula (I), R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 15 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms, X is -S- or -NH-, Y is -N= or -CH=, A is -O-(CH2) m - or a single bond, m is a positive integer of 1 to 10, n is a positive integer of 1 to 10.

[0008] Further, according to the present invention, there is provided an adhesive containing the above compound.

[0009] Further, according to the present invention, there is provided a resin composition containing the above compound. [Advantages of the Invention]

[0010] According to the present invention, there is provided a compound that can improve the adhesion between a resin composition and a substrate when blended into the resin composition. [Modes for Carrying Out the Invention]

[0011] In this specification, the notation "X to Y" in the description of a numerical range represents X or more and Y or less, unless otherwise specified. For example, "1 to 5 mass%" means "1 mass% or more and 5 mass% or less". The notation "(meth)acryl" in this specification represents a concept encompassing both acrylic and methacrylic. The same applies to similar notations such as "(meth)acrylate". In this specification, the term "organic group" means, unless otherwise specified, a group obtained by removing one or more hydrogen atoms from an organic compound. For example, a "monovalent organic group" represents a group obtained by removing one hydrogen atom from an arbitrary organic compound. In this specification, the term "electronic device" is used to mean elements, devices, end products, etc. to which the technology of electronics is applied, including semiconductor chips, semiconductor elements, printed wiring boards, electric circuit display devices, information communication terminals, light-emitting diodes, physical batteries, chemical batteries, etc.

[0012] [Compound] The compound of this embodiment is a compound represented by the following general formula (I). [Chemical formula] In the above general formula (I), R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 15 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms, X is -S- or -NH-, Y is -N= or -CH=, A is -O-(CH2) m - or a single bond, m is a positive integer from 1 to 10, n is a positive integer from 1 to 10.

[0013] Adhesion to the substrate is required for the cured film in the electronic device. However, the compound of this embodiment can improve the adhesion between the cured film formed from the resin composition and the substrate by being blended into the resin composition. Although the details are unknown, it is considered that the interaction between the nitrogen-containing heterocyclic ring of the compound of the present embodiment and the substrate surface contributes to the improvement of the adhesion between the cured film and the substrate. Furthermore, since the compound of the present embodiment has a reactive group selected from (meth)acryloyl groups, the compound of the present embodiment reacts with other components contained in the resin composition or polymerizes with other compounds of the present embodiment, and the compound of the present embodiment becomes closely intertwined with the resin composition. This is considered to further improve the adhesion between the cured film and the substrate.

[0014] The 5-membered nitrogen-containing heterocyclic group of the compound of the present embodiment has a particularly high affinity for copper among metals. Therefore, the resin composition containing the compound of the present embodiment has particularly excellent adhesion to a substrate having copper on its surface, such as a copper-plated substrate.

[0015] When the compound of the present embodiment is blended in a photosensitive resin composition, its effect is further exerted. When a photosensitive resin composition is used in the manufacture of an electronic device, the photosensitive resin composition applied on a substrate is finely patterned by exposure and development. Therefore, in order to prevent the occurrence of peeling in the formed fine pattern, a higher degree of adhesion is required.

[0016] As described above, in the general formula (I), X is -S- or -NH-.

[0017] In the general formula (I), X is preferably -S-. When X is -S-, an increase in the basicity of the compound of the present embodiment is suppressed. By suppressing the increase in basicity, the storage stability of the resin composition containing the compound of the present embodiment can be improved.

[0018] In the general formula (I), X is preferably -NH-. When X is -NH-, the compound of the present embodiment interacts with the substrate surface not only through the heterocyclic ring but also through X. Therefore, the adhesion between the cured film and the substrate can be further improved.

[0019] As described above, in the general formula (I), Y is -N= or -CH=.

[0020] In the general formula (I), Y is preferably -N=. When Y is -N= in the general formula (I), the compound of this embodiment will have a tetrazole group as a nitrogen-containing heterocyclic group. Since the tetrazole group has low basicity, it is advantageous from the viewpoint of improving the storage stability of the resin composition containing the compound of this embodiment.

[0021] In the general formula (I), Y is preferably -CH=. When Y is -CH= in the general formula (I), the compound of this embodiment will have a triazole group as a nitrogen-containing heterocyclic group. Since the triazole group has low basicity, it is advantageous from the viewpoint of improving the storage stability of the resin composition containing the compound of this embodiment.

[0022] As described above, in the general formula (I), R1 is a hydrogen atom or a methyl group.

[0023] In the general formula (I), R1 is preferably a methyl group. When R1 is a methyl group in the general formula (I), the strength of the resin composition containing the compound of this embodiment tends to be improved.

[0024] In the general formula (I), R1 is preferably a hydrogen atom. When R1 is a hydrogen atom in the general formula (I), the flexibility of the resin composition containing the compound of this embodiment tends to be improved.

[0025] In the general formula (I), as described above, R2 is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 15 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms. Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group and the like. Examples of the substituted or unsubstituted cycloalkyl group having 3 to 15 carbon atoms specifically include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like. Examples of the substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a fluorenyl group, an indenyl group, a pyrenyl group, a perylenyl group, a fluoranthenyl group, a triphenylenyl group and the like.

[0026] As described above, in General Formula (I), A is -O-(CH2) m - or a single bond, and m is a positive integer of 1 to 10.

[0027] In General Formula (I), A is -O-(CH2) m - and it is preferable that m is a positive integer of 1 to 2, or a single bond.

[0028] As described above, in General Formula (I), n is a positive integer of 1 to 10.

[0029] In General Formula (I), it is preferable that n is a positive integer of 1 to 6, more preferably a positive integer of 1 to 4, and even more preferably a positive integer of 1 to 2.

[0030] Specific examples of the compound of this embodiment can be listed as follows. Of course, the compound of this embodiment is not limited only to these.

[0031]

Chemical formula

[0032] The compound of this embodiment can be synthesized by reacting an azole compound represented by chemical formula (II) (hereinafter referred to as azole compound (II)) with a (meth)acrylic compound represented by chemical formula (III) (hereinafter referred to as (meth)acrylic compound (III)) in an appropriate amount of reaction solvent at an appropriate reaction temperature and reaction time. The reaction formula of azole compound (II) and (meth)acrylic compound (III) is shown below. In the reaction formula, X, Y, n, A, R1 and R2 are as described above.

[0033] [Chemical formula]

[0034] The solvent for reacting azole compound (II) and (meth)acrylic compound (III) is not particularly limited as long as it is inert to both, but from the viewpoints of high solubility and high boiling point, etc., γ-butyrolactone, dimethyl sulfoxide, dimethylformamide, hexamethylphosphoramide, etc. can be mentioned.

[0035] The reaction between azole compound (II) and (meth)acrylic compound (III) proceeds stoichiometrically, but the charged amount of (meth)acrylic compound (III) relative to the charged amount of azole compound (II) is preferably an appropriate ratio in the range of 0.8 to 1.2 times the molar amount, considering factors such as the reaction temperature, reaction time, types of raw materials used, type of reaction solvent, reaction scale, etc.

[0036] The reaction temperature between azole compound (II) and (meth)acrylic compound (III) is not particularly limited as long as it is within the temperature range where both react, but the range of 0 to 200 °C is preferred, and the range of 20 to 100 °C is more preferred. The reaction time is appropriately determined according to the set reaction temperature, but the range of 10 minutes to 24 hours is preferred, and the range of 1 to 8 hours is more preferred.

[0037] Adhesive The adhesive of this embodiment contains the above-mentioned compound. By blending the above-mentioned compound into the resin composition, the adhesion between the resin composition and the substrate can be improved. Therefore, it can be used as an adhesive.

[0038] The adhesive of this embodiment may contain components other than the above-mentioned compound as necessary. For example, it may contain an antioxidant, a pH adjuster, etc.

[0039] [Resin Composition The resin composition of this embodiment contains the above-mentioned compound.

[0040] The resin composition of this embodiment preferably contains a photosensitizer in addition to the above-mentioned compound, that is, it is preferably a photosensitive resin composition. This is because when the above-mentioned compound is blended into the photosensitive resin composition, the effect of adhesion is further exerted. When the photosensitive resin composition is used in the manufacture of electronic devices, in order to finely pattern the photosensitive resin composition coated on the substrate by exposure and development, a higher degree of adhesion is required to prevent the occurrence of peeling in the formed fine pattern.

[0041] The resin composition of this embodiment preferably contains one or more resins selected from the group consisting of polyimide resin and its precursor, polybenzoxazole resin and its precursor, polyamide resin, novolak resin, and cycloolefin resin. From the viewpoint of suppressing shrinkage due to heating, it is more preferable to contain polyimide resin.

[0042] The content of the resin in the resin composition of this embodiment is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more in the total solid content of the above resin composition. By using a certain amount of resin, it becomes easier to form a cured film with an appropriate thickness. Also, the upper limit value of the resin is not particularly limited, but is usually 90% by mass or less, preferably 80% by mass or less. In the resin composition of this embodiment, the content of the above-mentioned compound with respect to the resin is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 5% by mass or more, and still more preferably 10% by mass from the viewpoint of improving the adhesion between the resin composition and the substrate. Further, the content of the above-mentioned compound with respect to the resin in the resin composition of this embodiment is usually 100% by mass or less, preferably 50% by mass or less from the viewpoint of maintaining the strength of the cured film.

[0043] The resin composition of this embodiment preferably contains a polyfunctional (meth)acrylic compound. The polyfunctional (meth)acrylic compound refers to a resin having two or more (meth)acryloyl groups. It is considered that the polyfunctional (meth)acrylic compound forms a network structure that "wraps" the imide ring of the polyimide resin by polymerization. It is presumed that the performance of the cured film is improved by the formation of such a complex intertwined structure.

[0044] There is no particular upper limit to the number of (meth)acryloyl groups, but it is, for example, about 11 from the viewpoint of easy availability of raw materials.

[0045] As a general tendency, when the number of (meth)acryloyl groups is large, the chemical resistance of the cured film tends to increase. On the other hand, when the number of (meth)acryloyl groups is small, the mechanical properties such as tensile elongation of the cured film tend to be good.

[0046] As an example of the polyfunctional (meth)acrylic compound, a polyfunctional (meth)acrylic compound represented by the following general formula can be used. In the following general formula, R´ is a hydrogen atom or a methyl group, n is 0 to 3, and R is a hydrogen atom or a (meth)acryloyl group.

[0047]

Chemical formula

[0048] When using a polyfunctional (meth)acrylic compound, the amount of the polyfunctional (meth)acrylic compound relative to 100 parts by mass of the resin is preferably 50 to 150 parts by mass, more preferably 60 to 100 parts by mass.

[0049] The resin composition of this embodiment preferably contains a photosensitizer. The photosensitizer is not particularly limited as long as it can generate active species by light and cure the photosensitive resin composition. The photosensitizer preferably contains a photo radical generator. The photo radical generator is particularly effective for polymerizing a polyfunctional (meth)acrylate compound.

[0050] The photo radical generator that can be used is not particularly limited, and known ones can be appropriately used. For example, alkylphenone compounds such as 2,2 - diethoxyacetophenone, 2,2 - dimethoxy - 2 - phenylacetophenone, 1 - hydroxycyclohexyl phenyl ketone, 2 - hydroxy - 2 - methyl - 1 - phenylpropan - 1 - one, 1 - [4 - (2 - hydroxyethoxy)phenyl] - 2 - hydroxy - 2 - methyl - 1 - propan - 1 - one, 2 - hydroxy - 1 - {4 - [4 - (2 - hydroxy - 2 - methylpropionyl)benzyl]phenyl} - 2 - methylpropan - 1 - one, 2 - methyl - 1 - (4 - methylthiophenyl) - 2 - morpholinopropan - 1 - one, 2 - benzyl - 2 - dimethylamino - 1 - (4 - morpholinophenyl) - butanone - 1, 2 - (dimethylamino) - 2 - [(4 - methylphenyl)methyl] - 1 - [4 - (4 - morpholinyl)phenyl] - 1 - butanone; benzophenone compounds such as benzophenone, 4,4′ - bis(dimethylamino)benzophenone, 2 - carboxybenzophenone; benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; thioxanthone compounds such as thioxanthone, 2 - ethylthioxanthone, 2 - isopropylthioxanthone, 2 - chlorothioxanthone, 2,4 - dimethylthioxanthone, 2,4 - diethylthioxanthone; halomethylated triazine compounds such as 2 - (4 - methoxyphenyl) - 4,6 - bis(trichloromethyl) - s - triazine, 2 - (4 - methoxynaphthyl) - 4,6 - bis(trichloromethyl) - s - triazine, 2 - (4 - ethoxynaphthyl) - 4,6 - bis(trichloromethyl) - s - triazine, 2 - (4 - ethoxycarbonylnaphthyl) - 4,6 - bis(trichloromethyl) - s - triazine; halomethylated oxadiazole compounds such as 2 - trichloromethyl - 5 - (2′ - benzofuryl) - 1,3,4 - oxadiazole, 2 - trichloromethyl - 5 - [β - (2′ - benzofuryl)vinyl] - 1,3,4 - oxadiazole, 4 - oxadiazole, 2 - trichloromethyl - 5 - furyl - 1,3,4 - oxadiazole;Imidazole compounds such as 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis(2,4-dichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis(2,4,6-trichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole; Oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetoxime); Titanocene compounds such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium; Benzoic acid ester compounds such as p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid; Acridine compounds such as 9-phenylacridine; etc. Among these, oxime ester compounds can be particularly preferably used.;

[0051] When using a photosensitizer, only one photosensitizer may be used, or two or more photosensitizers may be used. The content of the photosensitizer is, for example, 1 to 30 parts by mass, preferably 5 to 20 parts by mass, based on 100 parts by mass of the polyfunctional (meth)acrylic compound.

[0052] In addition to the above components, the resin composition of the present embodiment may contain components other than the above-mentioned components as necessary. Such components include, for example, thermal radical initiators, epoxy resins, curing catalysts, silane coupling agents, surfactants, water, solvents, antioxidants, fillers such as silica, sensitizers, film-forming agents, etc.

[0053] The resin composition of the present embodiment is suitably used in the manufacture of electronic devices.

[0054] For example, the resin composition of the present embodiment A film-forming step of forming a resin film on a substrate using the above resin composition, and An exposure step of exposing a resin film, A development step of developing the exposed resin film, It is suitably used for the manufacture of an electronic device obtained by a manufacturing process including

[0055] The film formation step is usually performed by applying a resin composition onto a substrate. The film formation step can be carried out using a spin coater, a bar coater, a spray device, an inkjet device, etc. Before the next exposure step, it is preferable to perform appropriate heating for the purpose of drying the solvent in the applied resin composition. The heating at this time is performed, for example, by heating at a temperature of 80 to 150 °C for 1 to 60 minutes. The thickness of the dried resin film appropriately varies depending on the structure of the electronic device to be finally obtained, but is, for example, about 1 to 100 μm, specifically about 1 to 50 μm.

[0056] The exposure amount in the exposure step is not particularly limited. 100 to 2000 mJ / cm 2 is preferable, and 200 to 1000 mJ / cm 2 is more preferable. The light source used for exposure is not particularly limited, and any light source that emits light of a wavelength at which the photosensitizer in the photosensitive resin composition reacts (for example, g-line or i-line) may be used. Typically, a high-pressure mercury lamp is used. If necessary, post-exposure baking may be performed. The temperature of the post-exposure baking is not particularly limited. Preferably it is 50 to 150 °C, more preferably 50 to 130 °C, still more preferably 55 to 120 °C, and particularly preferably 60 to 110 °C. Also, the time of the post-exposure baking is preferably 1 to 30 minutes, more preferably 1 to 20 minutes, still more preferably 1 to 15 minutes. In the exposure step, a photomask can be used. Thereby, a desired "pattern" can be formed using the resin composition.

[0057] Examples of the developer include organic developers, water-soluble developers, etc. The developer preferably contains an organic solvent. More specifically, the developer is preferably a developer mainly composed of an organic solvent (a developer in which 95% by mass or more of the components are organic solvents). By developing with a developer containing an organic solvent, it is possible to suppress the swelling of the pattern by the developer, etc., compared to the case of developing with an alkaline developer (aqueous system). That is, it is easier to obtain a finer pattern. The method of bringing the developer into contact with the resin film is not particularly limited. Generally known methods such as the dipping method, paddle method, spray method, etc. can be appropriately applied. The time of the developing step is usually about 5 to 300 seconds, preferably about 10 to 120 seconds, and is appropriately adjusted based on the film thickness of the resin film, the shape of the pattern to be formed, etc.

[0058] In the manufacturing process of the electronic device using the resin composition of this embodiment, a heat curing step may be provided as necessary. The conditions of the heat curing step are not particularly limited, but for example, the heating temperature can be about 160 to 250 °C and the time can be about 30 to 240 minutes.

[0059] As described above, the embodiments of the present invention have been described, but these are examples of the present invention, and various configurations other than the above can be adopted. Also, the present invention is not limited to the above-described embodiments, and modifications, improvements, etc. within the range that can achieve the object of the present invention are included in the present invention.

Examples

[0060] The embodiments of the present invention will be described in detail based on examples and comparative examples. Just to be on the safe side, the present invention is not limited only to the examples.

[0061] <Synthesis of Compound (A-1)> Into a separable flask equipped with a stirrer, 142.15 g (1.00 mol) of glycidyl methacrylate, gamma-butyrolactone <gbl>589 g was charged and stirred for dissolution at room temperature. While further stirring, 110.3 g (0.95 mol) of 5-mercapto-1-methyltetrazole was added. Subsequently, the solution was heated to 60 °C in an oil bath, and the reaction was further carried out at 60 °C for 6 hours to obtain a 30% GBL solution of the compound (A-1) of the present embodiment. The reaction formula for the synthesis of the compound (A-1) is shown below.

[0062]

Chemical formula

[0063] <Structural analysis of compound (A-1)> Regarding the obtained compound (A-1), 13 qualitative analysis was performed by 13C-NMR and GPC. From the GPC chart, the disappearance of the peaks of each raw material (retention times of 22.3 minutes and 22.5 minutes) and the detection of the peak corresponding to the compound (A-1) (retention time of 21.4 minutes) were confirmed, indicating that the reaction was 100% complete. Furthermore, 13 from 13C-NMR, the disappearance of the peaks (peak (a) at 44.6 ppm and peak (b) at 49.4 ppm) derived from the epoxy group of glycidyl methacrylate and the detection of the peak (peak (c) at 28 ppm) derived from the compound (A-1) were confirmed.

[0064]

Chemical formula

[0065] <Synthesis of compound (A-2)> Into a separable flask equipped with a stirring device, 200.23 g (1.00 mol) of glycidyl ether of 4-hydroxybutyl acrylate and 691 g of GBL were charged and stirred for dissolution at room temperature. While further stirring, 96.07 g (0.95 mol) of 3-mercapto-1,2,4-triazole was added. Subsequently, the solution was heated to 60 °C in an oil bath, and the reaction was further carried out at 60 °C for 6 hours to obtain a 30% GBL solution of the compound (A-2) of the present embodiment. The reaction formula for the synthesis of the compound (A-2) is shown below.

[0066] [Chemical formula]

[0067] <Structural Analysis of Compound (A-2)> Regarding the obtained compound (A-2), 13 Qualitative analysis was performed by 13C-NMR and GPC. From the GPC chart, the disappearance of the peaks of each raw material (retention times of 22.1 minutes and 22.6 minutes) and the detection of the peak corresponding to compound (A-2) (retention time of 21.0 minutes) were confirmed, thus confirming that the reaction was 100% complete. Furthermore, 13 From 13C-NMR, the disappearance of the peaks (e) at 44.6 ppm and (f) at 49.4 ppm derived from the epoxy group of 4-hydroxybutyl acrylate glycidyl ether and the detection of the peak (d) at 28 ppm derived from compound (A-2) were confirmed.

[0068] [Chemical formula]

[0069] <Synthesis of Compound (A-3)> 200.23 g (1.00 mol) of 4-hydroxybutyl acrylate glycidyl ether and 589 g of GBL were charged into a separable flask equipped with a stirrer and dissolved by stirring at room temperature. While stirring further, 80.82 g (0.95 mol) of 5-amino-1H-tetrazole was added. Then the solution was heated to 60 °C in an oil bath and reacted at 60 °C for 6 hours to obtain a 30% GBL solution of compound (A-3) of the present embodiment. The reaction formula for the synthesis of compound (A-3) is shown below.

[0070] [Chemical formula]

[0071] <Structural Analysis of Compound (A-3)> Regarding the obtained compound (A-3), 13 Qualitative analysis was performed by ¹³C-NMR and GPC. From the GPC chart, the disappearance of the peaks of each raw material (retention times of 22.1 minutes and 22.5 minutes) and the detection of the peak corresponding to compound (A-3) (retention time of 21.1 minutes) were confirmed, indicating that the reaction was 100% complete. Furthermore, 13 From ¹³C-NMR, the disappearance of the peaks (e) at 44.6 ppm and (f) at 49.4 ppm derived from the epoxy group of 4-hydroxybutyl acrylate glycidyl ether and the detection of the peak (g) at 58 ppm derived from compound (A-3) were confirmed.

[0072]

Chemical Structure

[0073] The measurement conditions for GPC are as follows. · Measuring device: HPLC-8320GPC manufactured by Tosoh Corporation · Column: TSKgel SuperMultipore XZ-M manufactured by Tosoh Corporation · Elution solvent: Tetrahydrofuran · Flow rate: 0.35 ml / min · Column temperature: 40 °C · Detector: Differential refractive index (RI) detector (manufactured by Tosoh Corporation)

[0074] 13 The measurement conditions for ¹³C-NMR are as follows. · Measurement sample: Prepared by adding a measurement solvent to the weighed sample to adjust the concentration and then pouring a specified amount into an NMR measurement sample tube. · Measuring device: JEOL JNM-ECA400 superconducting FT-NMR device · Resonance frequency: 100.53 MHz · Nucleus measured: 13 ¹³C · Measurement method: NNE measurement (inverse gated decoupling method) · Pulse width: 3.83 μsec · Pulse repetition waiting time: 30 s · Number of integrations: 4096 times · Measurement temperature: Room temperature · Measurement solvent: DMSO-d6 (deuterated dimethyl sulfoxide)

[0075] <Synthesis of resin (B-1)> To a 3 L separable flask equipped with a stirrer and a condenser, 304.2 g (0.95 mol) of 2,2'-bis(trifluoromethyl)benzidine, 310.22 g (1.00 mol) of 4,4'-oxydiphthalic dianhydride, and 1434 g of GBL were added, and a polymerization reaction was carried out at room temperature for 16 hours under a nitrogen atmosphere with stirring. Subsequently, the temperature of the reaction solution was raised to 180 °C in an oil bath and reacted for 3 hours, and then cooled to room temperature to prepare a polyimide resin solution. Subsequently, the reaction solution was added dropwise to a mixed solution of isopropanol / water = 4 / 7 with stirring to precipitate resin solids. The obtained solids were roughly filtered and then washed with isopropanol / water = 4 / 7 to obtain white solids of polyimide. The obtained white solids were vacuum dried at 200 °C to obtain resin (B-1). The weight average molecular weight (Mw) of resin (B-1) by GPC measurement was 50,000. Also, resin (B-1) was 1 measured by 1H-NMR, and the imidization rate (definition as described above) was calculated from the quantitative value of the amide peak relative to the peak of the aromatic ring of the polyimide. The imidization rate was 99% or more.

[0076] <Synthesis of resin (B-2)> To a 2 L separable flask, 428 g of γ-butyrolactone, 155.11 g of 4,4'-oxydiphthalic dianhydride, and 130.14 g of 2-hydroxyethyl methacrylate were added, and the components in the flask were stirred at room temperature to be completely dissolved. Subsequently, 79.1 g of pyridine was added while stirring at room temperature, and further stirred at room temperature for 16 hours. While cooling and stirring the solution obtained as described above under ice-cooling, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide in 206 g of γ-butyrolactone was added to the solution over 30 minutes. Subsequently, 120.1 g of 4,4'-diaminodiphenyl ether and 240 g of γ-butyrolactone were added, and stirring was continued at room temperature for 2 hours. After completion of the reaction, 30 g of ethanol was added and stirred for 1 hour. Then, 400 g of γ-butyrolactone was added and further stirred, and the resulting precipitate was removed by filtration. Thus, a reaction solution of polyamic acid ester was obtained. The obtained reaction solution was added dropwise to a large amount of 30% by mass aqueous methanol solution with stirring at room temperature to precipitate the polymer. The obtained precipitate was collected by filtration and dried under vacuum to obtain resin (B-2).

[0077] <Synthesis of curing catalyst (G-1)> Into a separable flask equipped with a stirrer, 37.5 g (0.15 mol) of 4,4'-bisphenol S and 100 mL of methanol were charged, stirred and dissolved at room temperature, and while further stirring, a solution prepared by dissolving 4.0 g (0.1 mol) of sodium hydroxide in 50 mL of methanol in advance was added. Subsequently, a solution prepared by dissolving 41.9 g (0.1 mol) of tetraphenylphosphonium bromide in 150 mL of methanol in advance was added. Stirring was continued for a while, and after adding 300 mL of methanol, the solution in the flask was added dropwise to a large amount of water with stirring to obtain a white precipitate. The precipitate was filtered and dried to obtain a white crystalline curing catalyst (G-1).

[0078] <Preparation of photosensitive resin composition> Each raw material formulated according to Table 1 shown below was stirred at room temperature until the raw materials were completely dissolved to obtain a solution. Then, the solution was filtered through a nylon filter with a pore size of 0.2 μm. Thus, a varnish-like photosensitive resin composition was obtained.

[0079] Table 1 shows the compounding amounts (parts by mass) of each component. The details of each component are as follows.

[0080] <Compound (A)> (A-1) The compound having a tetrazole ring and a methacryl group synthesized above (A-2) The compound having a triazole ring and an acrylic group synthesized above (A-3) The compound having a tetrazole ring and an acrylic group synthesized above

[0081] <(B) Resin> (B-1) The polymer (polyimide resin) synthesized above (B-2) The polymer (polyamic acid ester resin) synthesized above

[0082] <(C) Polyfunctional (meth)acrylic compound> (C-1) Biscoat #802 (manufactured by Osaka Organic Chemical Industry Co., Ltd., polyfunctional acrylic compound) (C-2) A-9550 (manufactured by Shin-Nakamura Chemical Co., Ltd., polyfunctional acrylic compound) (C-3) Biscoat #300 (manufactured by Osaka Organic Chemical Industry Co., Ltd., polyfunctional acrylic compound) (C-4) Biscoat #230 (manufactured by Osaka Organic Chemical Industry Co., Ltd., polyfunctional acrylic compound)

[0083] <(D) Photosensitizer> (D-1) Irgacure OXE02 (manufactured by BASF, oxime ester type photo radical generator)

[0084] <(E) Epoxy resin> (E-1) EXA-830CRP (manufactured by DIC Corporation, epoxy resin)

[0085] <(F) Thermal radical generator> (F-1) Percadox BC (manufactured by Kayaku Nouryon Co., Ltd.)

[0086] <(G) Curing catalyst> (G-1) The curing catalyst (phosphonium salt) synthesized above

[0087] <(H) Silane coupling agent> (H-1) X-12-967C (manufactured by Shin-Etsu Chemical Co., Ltd.) (H-2)KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0088] <(J) Surfactant> (J-1) FC4432 (manufactured by 3M, fluorine-based)

[0089] <(K) (Solvent)> (K-1) Ethyl lactate (EL) (K-2) Gamma-butyrolactone (GBL)

[0090] <Adhesion: Tape Test Evaluation> (Preparation of Substrate for Tape Test Evaluation) The photosensitive resin composition was spin-coated onto a 12-inch silicon wafer having a 3000 Å copper plating layer on the surface so that the film thickness after drying was 10 μm, and then heated at 120 °C for 3 minutes to obtain a photosensitive resin film. The obtained photosensitive resin film was exposed to 300 mJ / cm 2 without using a photomask with an i-line stepper. Thereafter, the exposed resin film was developed with cyclopentanone and propylene glycol monomethyl ether acetate using a spray developer for the entire silicon wafer, and then air-dried by spin-drying and dried on a hot plate at 120 °C for 2 minutes. Further, thereafter, heat treatment was performed at 200 °C for 90 minutes under a nitrogen atmosphere. Thus, a substrate for tape test evaluation was obtained.

[0091] (Tape Test Evaluation) Using a cutter, 100 patterns of 1 mm × 1 mm were created on the film on the substrate obtained in the preparation of the substrate for tape test evaluation. Next, a cellophane tape (registered trademark) with a peel strength of 3.0 mN / 10 mm was carefully attached to the surface of such a pattern, and then the cellophane tape (registered trademark) was peeled off vertically. Next, the number of peeled patterns was counted. In this evaluation, it was evaluated that the better the adhesion to the substrate, the fewer the number of peeled patterns. The results are shown in Table 1.

[0092] <Adhesion: 90-degree Peel Strength Evaluation> (Preparation of Substrate for 90-degree Peel Strength Evaluation) A photosensitive resin composition was spin-coated onto a 12-inch silicon wafer having a 3000 Å copper plating layer on its surface so that the film thickness after drying would be 10 μm, and then heated at 120 °C for 3 minutes to obtain a photosensitive resin film. The obtained photosensitive resin film was exposed through a photomask so that an area with a width of 6.5 mm and a length of 50 mm was exposed by an i-line stepper at 300 mJ / cm 2 ². After that, the exposed resin film on the silicon wafer was developed with cyclopentanone and propylene glycol monomethyl ether acetate in a spray developer, and then air-dried by spin-drying and dried on a hot plate at 120 °C for 2 minutes. Furthermore, after that, heat treatment was performed at 200 °C for 90 minutes in a nitrogen atmosphere to obtain a cured film. Subsequently, the silicon wafer was cut so that a cured film with a width of 6.5 mm and a length of 50 mm remained. The end portion (5 mm) of the cured film was immersed in a Cu etching solution at 23 °C for 24 hours, washed with water and dried to obtain a substrate for evaluating the 90-degree peel strength from which the end film was peeled off.

[0093] (90-degree peel strength evaluation) Regarding the substrate obtained in the preparation of the substrate for 90-degree peel strength evaluation, it was set on a 90-degree peel strength measuring device (AUTOGRAPH AG-Xplus, manufactured by Shimadzu Corporation), and 1 cm peeling was performed at a peeling speed of 20 mm / min, and the average value of the peeling strength was evaluated. The unit of the 90-degree peel strength is N / cm. A higher 90-degree peel strength is preferable in terms of reliability. The results are shown in Table 1.

[0094] <Patternability> A photosensitive resin composition was spin-coated onto a 12-inch silicon wafer having a 3000 Å copper plating layer on its surface so that the film thickness after drying would be 5 μm, and dried on a hot plate at 100 °C for 3 minutes to obtain a photosensitive resin film. This photosensitive resin film was irradiated with i-line while changing the exposure amount using an i-line stepper (manufactured by Nikon Corporation, NSR-4425i) through a mask manufactured by Toppan Printing Co., Ltd. (Test Chart No. 1: a remaining pattern and a punched pattern with a width of 0.5 to 50 μm are drawn). Using a spray developer, the substrate was developed at 2500 rpm for 30 seconds using cyclopentanone, followed by development at 2500 rpm for 10 seconds using propylene glycol monomethyl ether acetate, and then air-dried by spin-drying at 2500 rpm for 10 seconds. After that, it was dried on a hot plate at 120 °C for 2 minutes. Subsequently, it was heat-treated at 200 °C for 90 minutes in a nitrogen atmosphere to obtain a cured film with a pattern. The obtained patterns were observed, and those with 7-μm Φ via holes opened were rated as ◎ (very good), those with 10-μm Φ via holes opened were rated as ○ (good), and those with no 10-μm via holes opened were rated as × (bad). The results are shown in Table 1.

[0095] <Normal temperature viscosity change rate> The viscosity of the photosensitive resin composition immediately after mixing was measured using an E-type viscometer (TVE-25L). The viscosity at this time was designated as A. Subsequently, the varnish of the photosensitive resin composition was stored at 23 °C for 7 days, and the viscosity was measured again. The viscosity at this time was designated as B. Viscosity A and viscosity B were substituted into the following formula to calculate the viscosity change rate. Those with a viscosity change rate of 5% or less were rated as ◎ (very good), those with more than 5% and 10% or less were rated as ○ (good), and those with more than 10% were rated as × (bad). The viscosity change rate is preferably lower in order to obtain a stable film thickness. The results are shown in Table 1. Viscosity change rate [%] = {(viscosity B - viscosity A) / viscosity A} × 100

[0096] <Thermal cycle test> (Preparation of samples for thermal cycle test) A Cu wiring substrate with a comb-shaped Cu wiring having a width of 5 μm / pitch of 5 μm and a height of 5 μm was fabricated on a 12-inch silicon wafer with an oxide film. The photosensitive resin composition was spin-coated on the above Cu wiring substrate so that the film thickness after drying (the thickness of the part without wiring) was 10 μm, and dried at 120 °C for 3 minutes to form a photosensitive resin film. On the obtained photosensitive resin film, using an i-line stepper, without passing through a photomask, 300 mJ / cm 2 Exposure was performed. Subsequently, development was carried out using cyclopentanone at 2500 revolutions for 30 seconds with a spray developer, followed by development using propylene glycol monomethyl ether acetate at 2500 revolutions for 10 seconds, and then air drying by spin drying at 2500 revolutions for 10 seconds. After that, drying was performed on a hot plate at 120 °C for 2 minutes. Furthermore, after that, heat treatment was carried out at 200 °C for 90 minutes under a nitrogen atmosphere to obtain a sample for the thermal cycle test.

[0097] (Thermal Cycle Test Evaluation) The test samples obtained in the preparation of the samples for the thermal cycle test were set in a temperature cycle test apparatus (TCT apparatus) (manufactured by Espec, TSA-72EH-W), and the temperature increase from -60 °C to 200 °C and subsequent temperature decrease to -60 °C were taken as one cycle, and 200 cycles of treatment were performed. Subsequently, a cross-section of the Cu wiring portion was taken by FIB (focused ion beam) treatment and observed by SEM. In each example and comparative example, a total of 10 interfaces between the wiring and the resin film were observed. When peeling was not observed at all 10 locations, it was evaluated as ◎ (good), and when peeling was observed at even one location, it was evaluated as × (bad). The results are shown in Table 1.

[0098]

Table 1

[0099] As shown in Table 1, the photosensitive resin compositions of Examples 1 to 6 containing the compounds (A-1) to (A-3) of the present embodiment were all excellent in the results of the tape test, 90 °C peel test, patterning property, normal temperature viscosity change rate, and thermal cycle evaluation compared with Comparative Example 1. From these evaluation results, it is understood that by blending the compound of the present embodiment into the resin composition, the adhesion between the resin composition and the substrate is improved.< / gbl>

Claims

1. A resin composition comprising an adhesive containing a compound represented by the following general formula (I) and a polyfunctional (meth)acrylic compound. 【Chemical 1】 In the general formula (I), R １ is a hydrogen atom or a methyl group, R ２ is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 15 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms, X is -S- or -NH-, Y is -N= or -CH=, A is -O-(CH ２ ) ｍ - or a single bond, m is a positive integer from 1 to 10, n is a positive integer from 1 to 10.

2. The resin composition according to claim 1, wherein in the general formula (I), X is -S-.

3. The resin composition according to claim 1, wherein in the general formula (I), X is -NH-.

4. The resin composition according to any one of claims 1 to 3, wherein in the general formula (I), Y is -N=.

5. The resin composition according to any one of claims 1 to 3, wherein in the general formula (I), Y is -CH=.

6. In the general formula (I), R １ The resin composition according to any one of claims 1 to 5, wherein is a methyl group.

7. In the general formula (I), R １ is a hydrogen atom, and the resin composition according to any one of claims 1 to 5.

8. The resin composition according to any one of claims 1 to 7, wherein in the general formula (I), n is a positive integer from 1 to 4.

9. The resin composition according to any one of claims 1 to 8, further comprising a photosensitizer.

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