KR20220092851A - A resin composition, a resin sheet, a cured film, the manufacturing method of a cured film, a semiconductor device, an organic electroluminescent display apparatus, and a display apparatus - Google Patents

Abstract

The resin composition excellent in the pattern shape of the cured film after heat processing when it can provide resistance with respect to the stripper for removing the photoresist used at the time of wiring formation, and resistance to a constant temperature and humidity test (HAST), and has photosensitivity. provides (A) polyimide, polybenzoxazole, polyimide precursor, polybenzoxazole precursor, and at least one resin selected from the group consisting of copolymers thereof, (B) a phenol resin, (C) comprising a thermal crosslinking agent As a resin composition, the said (B) phenol resin has a structural unit represented by the specific general formula (4), and the structural unit represented by the said general formula (4) is a specific general formula (5) and a specific general formula (4) It has the structural unit of Formula (6), and when the number of all the structural units represented by General formula (4) in the said (B) phenol resin is 100, General formula (5) and General formula (6) It is a resin composition whose ratio of the number of structural units represented is General formula (5): General formula (6)=60:40-90:10.

Description

A resin composition, a resin sheet, a cured film, the manufacturing method of a cured film, a semiconductor device, an organic electroluminescent display apparatus, and a display apparatus

The present invention relates to a resin composition used for a surface protective film or an interlayer insulating film of a semiconductor element, an insulating layer of a display device such as an organic light emitting element, or a planarization film of a thin film transistor (hereinafter sometimes referred to as TFT) substrate. .

Conventionally, a surface protective film or an interlayer insulating film of a semiconductor element, an insulating layer of a display device such as an organic light emitting element, or a planarization film of a thin film transistor (hereinafter sometimes referred to as TFT) substrate has heat resistance, electrical insulation, mechanical properties, etc. This excellent polyimide-based resin and polybenzoxazole-based resin are widely used.

In recent years, in polyimide-based resins and polybenzoxazole-based resins, in addition to the above characteristics, in order to improve productivity, g-line (436 nm), h-line (405 nm), i-line (365 nm), etc. used as an exposure light source There is a demand for high sensitivity.

Until now, as a method of increasing the sensitivity, for example, 101 parts by mass or more of a novolak resin and/or a polyhydroxystyrene resin was contained with respect to 100 parts by mass of a polyimide precursor or a polybenzoxazole precursor (Patent Document 1). reference), the polyimide precursor or the polybenzoxazole precursor containing the phenol resin of a specific structure (refer patent documents 2 and 3), etc. are mentioned.

In addition, in order to satisfy the heat resistance required in the semiconductor manufacturing process with high sensitivity, polybenzoxazole, polybenzoxazole precursor, polyimide, and polyimide precursor containing a phenolic resin having a specific structure ( Refer to Patent Document 4) is proposed.

Japanese Patent Laid-Open No. 2005-352004 Japanese Patent Laid-Open No. 2018-22171 Japanese Patent Laid-Open No. 2018-55124 International Publication No. 2014/069091

However, in the composition described in the above document, although the sensitivity to the exposure wavelength is improved, the resistance to the stripper for removing the photoresist used in forming the pattern shape or wiring after curing at low temperature, constant temperature and humidity test (HAST) There was a problem in terms of tolerance.

In order to solve the said subject, this invention has the following structure.

[1] (A) at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, polybenzoxazole precursor, and copolymers thereof, (B) phenol resin, (C) A resin composition containing a thermal crosslinking agent, wherein (B) the phenol resin has a structural unit represented by the general formula (4), and the structural unit represented by the general formula (4) is a structural unit represented by the general formula (5) and the general formula ( It has the structural unit of 6), and when the number of all structural units represented by the general formula (4) in the above (B) phenol resin is 100, the structural units represented by the general formulas (5) and (6) The resin composition whose ratio of the number of structural units is General formula (5): General formula (6)=60:40-90:10.

In the general formula (4), R ²⁵ and R ²⁷ each independently represent a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. When a plurality of R ²⁵ and R ²⁷ exist, they may be the same or different. R ²⁶ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. j1 and j2 each independently represent an integer of 0 to 3.

In the general formula (5), R ²⁵ represents a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. When two or more R ²⁵ is present, each may be the same or different. R ²⁶ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. R ²⁸ represents a monovalent organic group having 1 to 10 carbon atoms. When two or more R ²⁸ are present, each may be the same or different. j1 and j4 each independently represent an integer of 0 to 3, and j3 represents an integer of 1 to 3.

In the general formula (6), R ²⁵ represents a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. When two or more R ²⁵ is present, each may be the same or different. R ²⁶ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. R ²⁸ represents a monovalent organic group having 1 to 10 carbon atoms. When two or more R ²⁸ are present, each may be the same or different. j1 and j4 each independently represent an integer of 0-3.

[2] A resin sheet formed on a substrate using the above resin composition.

[3] A cured film obtained by curing the resin composition or the resin sheet.

[4] A step of applying the resin composition to a substrate, or laminating the resin sheet on a substrate, followed by drying to form a resin film, an exposure step of exposing the dried resin film, a developing step of developing the exposed resin film and a heat treatment step of heat-treating the developed resin film.

[5] A semiconductor device having the cured film.

[6] An organic EL display device having at least a TFT substrate, a planarization layer, a first electrode, an insulating layer, a light emitting layer, and a second electrode, wherein the planarization layer or the insulating layer includes the cured film.

[7] A display device having at least metal wiring, the cured film, and a plurality of light emitting elements, wherein the light emitting element has a pair of electrode terminals on either surface, and the pair of electrode terminals includes the cured film A display device configured to be connected to a plurality of the metal wires extending in the middle, and the plurality of the metal wires to maintain electrical insulation by the cured film.

The resin composition of the present invention has resistance to a stripper for removing the photoresist used in wiring formation even when subjected to low-temperature heat treatment, resistance to a constant temperature and humidity test (HAST), and when it has photosensitivity, curing after heat treatment The film pattern shape is excellent.

BRIEF DESCRIPTION OF THE DRAWINGS It is a front sectional drawing which shows one form of the display apparatus of this invention.
Fig. 2 is a front cross-sectional view showing one embodiment of a display device of the present invention in which a barrier rib is formed.
It is front sectional drawing of the opening pattern of a cured film.
4 is a front cross-sectional view showing another embodiment of the display device of the present invention.

The resin composition of the present invention is (A) at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, polybenzoxazole precursor, and copolymers thereof, (B) phenol resin , (C) a resin composition containing a thermal crosslinking agent, wherein the (B) phenol resin has a structural unit represented by the general formula (4), and the structural unit represented by the general formula (4) is the general formula (5) And when it has the structural unit of General formula (6), and the number of all structural units represented by General formula (4) in the said (B) phenol resin is 100, General formula (5) and General formula (6) ) is a resin composition in which the ratio of the number of structural units represented by General Formula (5): General Formula (6) = 60:40 to 90:10.

In the general formula (4), R ²⁵ and R ²⁷ each independently represent a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. When a plurality of R ²⁵ and R ²⁷ exist, they may be the same or different. R ²⁶ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. j1 and j2 each independently represent an integer of 0 to 3.

In the general formula (5), R ²⁵ represents a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. When two or more R ²⁵ is present, each may be the same or different. R ²⁶ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. R ²⁸ represents a monovalent organic group having 1 to 10 carbon atoms. When two or more R ²⁸ are present, each may be the same or different. j1 and j4 each independently represent an integer of 0 to 3, and j3 represents an integer of 1 to 3.

In the general formula (6), R ²⁵ represents a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. When two or more R ²⁵ is present, each may be the same or different. R ²⁶ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. R ²⁸ represents a monovalent organic group having 1 to 10 carbon atoms. When two or more R ²⁸ are present, each may be the same or different. j1 and j4 each independently represent an integer of 0-3.

One or more types of resin selected from the group which consists of (A) polyimide, polybenzoxazole, a polyimide precursor, a polybenzoxazole precursor, and those copolymers which the resin composition of this invention contains is demonstrated.

<(A) at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, polybenzoxazole precursor, and copolymers thereof>

(A) At least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, polybenzoxazole precursor, and copolymers thereof may be hereinafter referred to as (A) component. .

A polyimide will not be specifically limited if it has an imide ring. Moreover, as long as it has a structure used as a polyimide which has an imide ring by dehydration ring closure, a polyimide precursor will not specifically limit, A polyamic acid, polyamic acid ester, etc. can be contained. Polybenzoxazole will not be specifically limited if it has an oxazole ring. A polybenzoxazole precursor will not specifically limit, if it has a structure used as polybenzoxazole which has a benzoxazole ring by dehydration ring closure, Polyhydroxyamide etc. can be contained.

The polyimide has a structural unit represented by the general formula (1), the polyimide precursor and the polybenzoxazole precursor have a structural unit represented by the following general formula (2), and the polybenzoxazole has the structural unit represented by the general formula (15) It has a structural unit represented by These may contain 2 or more types, and resin which copolymerized the structural unit represented by the structural unit represented by General formula (1), the structural unit represented by General formula (2), and General formula (15) may be contained.

In general formula (1), V represents a C4-C40 organic group of 4-10 valence, W represents a C4-C40 organic group of 2-8 valence. a and b each represent the integer of 0-6. R ¹ and R ² each represent a group selected from the group consisting of a hydroxyl group, a carboxy group, a sulfonic acid group and a thiol group, and a plurality of R ¹ and R ² may be the same or different, respectively.

In general formula (2), X and Y each independently represent a C4-C40 organic group of 2-8 valence. R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. c and d each represent an integer of 0-4, and e and f represent an integer of 0-2, respectively.

In the general formula (15), T and U each independently represent an organic group having 4 to 40 carbon atoms and having a valence of 2 to 8.

(A) Specifically, a polyimide, a polyimide precursor, a polybenzoxazole precursor, or those copolymers are mentioned preferably as a component. These resins may be contained independently and may be contained in combination of some resin. These resins have high heat resistance and a small amount of outgassing under a temperature condition of 160°C or higher after heat treatment. is used appropriately as

Moreover, (A) component is although it does not specifically limit, From a viewpoint of environmental load reduction, it is preferable that it is alkali-soluble resin. Alkali solubility in this invention is demonstrated. A solution obtained by dissolving a resin in γ-butylolactone is applied on a silicon wafer, and prebaked at 120° C. for 4 minutes to form a prebaked film having a thickness of 10 µm±0.5 µm. Next, after immersing the said prebaked film|membrane in 23±1 degreeC 2.38 mass % tetramethylammonium hydroxide aqueous solution for 1 minute, the film thickness reduction at the time of rinsing with pure water is calculated|required. A resin whose dissolution rate of the prebaked film is 50 nm/min or more is defined as alkali-soluble.

(A) In order to give alkali solubility to a component, it is preferable that General formula (1) is a+b>0. Moreover, it is preferable that general formula (2) is c+d+e+f>0. In general formula (2), in the case of a polyimide precursor, it is preferable that X and Y in general formula (2) have an aromatic group. Moreover, it is more preferable that X in General formula (2) has an aromatic group, e>0, has a carboxy group or a carboxy ester group at the ortho position of an aromatic amide group, and has a structure which forms an imide ring by dehydration ring closure.

In addition, in the general formula (2), in the case of a polybenzoxazole precursor, X in the general formula (2) has an aromatic group, d>0, has a hydroxyl group at the ortho position of the aromatic amide group, dehydration It is more preferable to have a structure which forms a benzoxazole ring by ring closure.

(A) It is preferable that it is 5-100,000, and, as for the repeating number (n) of the structural unit represented by General formula (1) or (2) in component, it is more preferable that it is 10-100,000.

Moreover, (A) component may have another structural unit in addition to the structural unit represented by General formula (1) or (2). As another structural unit, although a cardo structure, a siloxane structure, etc. are mentioned, for example, It is not limited to these. In this case, it is preferable to make the structural unit represented by General formula (1), (2), or (15) into a main structural unit. Here, the main structural unit refers to one having 50 mol% or more of the structural unit represented by the general formula (1), (2), or (15) in the total number of structural units, and more preferably 70 mol% or more.

<(A) residue of acid of component>

In the general formula (1), V-(R ¹ ) _a , in the general formula (2), (OH) _c -X-(COOR ³ ) _e , and in the general formula (15), T is an acid represents the residue. V is a C4-C40 tetravalent to 10-valent organic group, and among them, an organic group having 4 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferable. X and T are a C4-C40 divalent to octavalent organic group, and among these, an aromatic ring or a C4-C40 organic group containing an aliphatic group is preferable.

As an acidic component constituting the residue of the acid, examples of dicarboxylic acid include terephthalic acid, isophthalic acid, diphenyletherdicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyldicarboxylic acid, and benzophenonedicarboxylic acid. Leric acid, triphenyldicarboxylic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonane diacid, dodecanedioic acid, tridecanedioic acid , tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecandioic acid, octadecanedioic acid, nonadecandioic acid, eicosic acid diacid, heneiicosandioic acid, docoxanedioic acid, trichoic acid diacid, tetrachoic acid diacid, pentacoic acid diacid, As examples of tricarboxylic acids, such as hexacoic acid diacid, heptaconic acid diacid, octacoic acid diacid, nonaconic acid diacid, triacontandioic acid, trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyl tri Examples of tetracarboxylic acids such as carboxylic acid include pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-diphenyl ether tetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxyl Acid, 2,2',3,3'-benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane , 1,1-bis (3,4-dicarboxyphenyl) ethane, 1,1-bis (2,3-dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2,3 -dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)ether, 1,2,5,6-naphthalenetetracarboxylic acid, 9,9-bis(3,4-dicarboxyphenyl)fluorene, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid , 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane and aromatic tetracarboxylic acid, butanetetracarboxylic acid, cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid having the structure shown in . You may use 2 or more types of these.

In the formula, R ¹⁷ represents an oxygen atom, C(CF ₃ ) ₂ , or C(CH ₃ ) ₂ . R ¹⁸ and R ¹⁹ represent a hydrogen atom or a hydroxyl group.

These acids can be used as they are or as an acid anhydride, halide, or active ester.

<(A) residue of diamine of component>

W-(R ² ) _b in the general formula (1), (OH) _d -Y-(COOR ⁴ ) _f in the general formula (2), and U in the general formula (15) represent a residue of diamine indicates. W, Y, and U are a C4-C40 organic group of 2-8 valence, Especially, a C4-C40 organic group containing an aromatic ring or a cyclic aliphatic group is preferable.

Specific examples of the diamine constituting the residue of the diamine include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-dia minodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4 -Aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-dia Minobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4 '-Diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diamino At least a part of hydrogen atoms of biphenyl, 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, or an aromatic ring thereof and a compound in which is substituted with an alkyl group or a halogen atom, an aliphatic diamine, and a diamine having the structure shown below. You may use 2 or more types of these.

In the formula, R ²⁰ represents an oxygen atom, C(CF ₃ ) ₂ , or C(CH ₃ ) ₂ . R ²¹ to R ²⁴ each independently represent a hydrogen atom or a hydroxyl group.

These diamines can be used as diamine or as a diisocyanate compound obtained by making diamine react with phosgene, and trimethylsilylation diamine.

<A group selected from an alkylene group and an alkylene ether group>

Moreover, it is preferable that (A) component contains the group chosen from an alkylene group and an alkylene ether group. These groups may contain an aliphatic ring. As the group selected from an alkylene group and an alkylene ether group, a group represented by the general formula (3) is particularly preferable.

In the general formula (3), R ⁵ to R ⁸ each independently represents an alkylene group having 1 to 6 carbon atoms. R ⁹ to R ¹⁶ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms. However, the structures shown in parentheses are respectively different. g, h, and i each independently represent an integer of 0 to 35, and g+h+i>0.

As group represented by General formula (3), an ethylene oxide group, a propylene oxide group, a butylene oxide group etc. are mentioned, for example, Any of linear, branched, and cyclic|annular form may be sufficient.

(A) When component has group chosen from an alkylene group and an alkylene ether group, imide ring closure and benzoxazole ring closure reaction are accelerated|stimulated also in low-temperature heat processing, and chemical-resistance improves. Moreover, since interaction, such as a coordination bond, is acquired between an alkylene group and an alkylene ether group with a metal, high adhesiveness with a board|substrate metal can be acquired. In addition, since the polarity can be lowered by introducing an alkylene group and an alkylene ether group, resistance to a constant temperature and humidity test (HAST) can be improved.

(A) It is preferable that component contains group chosen from the said alkylene group and alkylene ether group in W in the said General formula (1), or Y in General formula (2). Thereby, the high chemical-resistance by ring closure acceleration|stimulation in the low-temperature heat processing in the cured film of a resin composition, high adhesiveness with a board|substrate metal, and tolerance with respect to a constant temperature and humidity test (HAST) can be acquired.

Specific examples of the diamine containing a group selected from an alkylene group and an alkylene ether group include ethylenediamine, 1,3-diaminopropane, 2-methyl-1,3-propanediamine, 1,4-diaminobutane, 1,5 -diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine; 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 4,4'-methylenebis(cyclohexylamine), 4 ,4'-methylenebis(2-methylcyclohexylamine), KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000 , THF-100, THF-140, THF-170, RE-600, RE-900, RE-2000, RP-405, RP-409, RP-2005, RP-2009, RT-1000, HE-1000, HT -1100, HT-1700, (above brand name, HUNTSMAN Co., Ltd. product) etc. are mentioned.

In addition, among these diamines, -S-, -SO-, -SO ₂ -, -NH-, -NCH ₃ -, -N(CH ₂ CH ₃ )-, -N(CH ₂ CH ₂ CH ₃ )-, A bond such as -N(CH(CH ₃ ) ₂ )-, -COO-, -CONH-, -OCONH-, and -NHCONH- may be included.

It is preferable that 5 mol% or more is contained in all the diamine residues, and, as for the diamine residue containing the group selected from an alkylene group and an alkylene ether group, it is more preferable that it is contained 10 mol% or more. Moreover, it is preferable to contain 40 mol% or less in all the diamine residues, and it is more preferable to contain 30 mol% or less. By including in the above range, while improving developability in an alkaline developer, high chemical resistance by accelerating ring closure in low-temperature heat treatment, high adhesion to a substrate metal, and resistance to constant temperature and humidity test (HAST) can be obtained.

Moreover, you may copolymerize the diamine residue which has an aliphatic polysiloxane structure in the range which does not reduce heat resistance. By copolymerizing the diamine residue having an aliphatic polysiloxane structure, the adhesion to the substrate can be improved. Specific examples of the diamine component include those obtained by copolymerizing 1 to 15 mol% of bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like in the total diamine residue. . It is preferable to copolymerize in this range from the point of improving adhesiveness with board|substrates, such as a silicon wafer, and the point which does not reduce solubility in alkali solution.

Moreover, resin which has an acidic group in the principal chain terminal can be obtained by sealing the terminal of (A) component with the monoamine which has an acidic group, an acid anhydride, an acid chloride, and monocarboxylic acid. As monoamine, acid anhydride, acid chloride, and monocarboxylic acid which have an acidic group, a well-known thing may be used and it may use two or more.

The content of the end-sealing agent such as monoamine, acid anhydride, acid chloride, monocarboxylic acid is preferably 2 to 25 mol% with respect to 100 mol% in total of the acid component and amine component constituting the component (A). .

(A) It is preferable that weight average molecular weights are 10,000 or more and 100,000 or less as for component. If the weight average molecular weight is 10,000 or more, the mechanical properties of the cured film after curing can be improved. More preferably, the weight average molecular weight is 20,000 or more. On the other hand, if the weight average molecular weight is 100,000 or less, developability with various developing solutions can be improved, and if the weight average molecular weight is 50,000 or less, developability with an alkaline solution can be improved, which is preferable.

The weight average molecular weight (Mw) can be confirmed using GPC (gel permeation chromatography). For example, it can measure as N-methyl-2-pyrrolidone (it may abbreviate as NMP hereafter) as a developing solvent, and can calculate|require in conversion of polystyrene.

(A) It is preferable to set it as 3-55 mass % in 100 mass % of all components containing a solvent, and, as for content of a component, it is more preferable to set it as 5-40 mass %. By setting it as the said range, it can be set as the appropriate viscosity in performing spin coating or slit coating.

<Production of (A) component>

(A) A component is producible by a well-known method.

In the case of a polyimide precursor, for example, polyamic acid or polyamic acid ester, the first method is a method in which tetracarboxylic dianhydride and a diamine compound are reacted at a low temperature. As a second method, a diester is obtained by using tetracarboxylic dianhydride and an alcohol. After that, a method of reacting with an amine in the presence of a condensing agent. As a third method, a diester is obtained with tetracarboxylic dianhydride and an alcohol. After that, the remaining dicarboxylic acid can be acidified and synthesized by a method of reacting with an amine.

In the case of a polybenzoxazole precursor, for example, polyhydroxyamide, it can obtain by making a bisaminophenol compound and dicarboxylic acid condensation-react as a manufacturing method. Specifically, a method in which a dehydration condensing agent such as dicyclohexylcarbodiimide (DCC) is reacted with an acid, and a bisaminophenol compound is added thereto, or a solution of a bisaminophenol compound to which a tertiary amine such as pyridine is added. There is a method in which a solution of dicarboxylic acid dichloride is added dropwise.

In the case of polyimide, for example, it can obtain by dehydrating and ring-closing the polyimide precursor obtained by the above-mentioned method by heating or chemical treatment, such as an acid or a base.

In the resin composition of this invention, you may contain other alkali-soluble resin other than (A) component. As other alkali-soluble resin, a siloxane polymer, a cyclic olefin polymer, cardo resin, etc. are mentioned specifically,. These resins may be used independently and may be used combining some resin. In that case, when the sum total of (A) component and other alkali-soluble resin is 100 mass parts, it is preferable that the content rate of other alkali-soluble resin shall be 1-50 mass parts.

<(B) Phenolic resin>

<Phenolic resin containing structural unit represented by general formula (4)>

The resin composition of this invention contains (B) phenol resin (Hereinafter, (B) component may be called), The said (B) phenol resin has a structural unit represented by General formula (4).

In the general formula (4), R ²⁵ and R ²⁷ each independently represent a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. When a plurality of R ²⁵ and R ²⁷ exist, they may be the same or different. R ²⁶ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. j1 and j2 each independently represent an integer of 0 to 3.

As in the general formula (4), by using a phenol resin obtained from a phenol compound, an aromatic aldehyde compound, and/or an aromatic ketone compound, it has excellent heat resistance and resistance to a stripper for removing the photoresist used in wiring formation can be given Moreover, when it has photosensitivity, the contrast difference between the exposed part / unexposed part at the time of development is large, and since the glass transition temperature of the resin film is raised appropriately, the pattern shape of the resin film after development and the cured film after heat processing is high tapered. great.

In addition, the structural unit represented by the said General formula (4) has the structural unit of General formula (5) and General formula (6), (B) All the structural units represented by General formula (4) in a phenol resin When the number is 100, the ratio of the number of structural units represented by General Formula (5) to the number of structural units represented by General Formula (6) is General Formula (5): General Formula (6) = 60:40- It's 90:10

In the general formula (5), R ²⁵ represents a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. When two or more R ²⁵ is present, each may be the same or different. R ²⁶ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. R ²⁸ represents a monovalent organic group having 1 to 10 carbon atoms. When two or more R ²⁸ are present, each may be the same or different. j1 and j4 each independently represent an integer of 0 to 3, and j3 represents an integer of 1 to 3.

In the general formula (6), R ²⁵ represents a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. When two or more R ²⁵ is present, each may be the same or different. R ²⁶ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. R ²⁸ represents a monovalent organic group having 1 to 10 carbon atoms. When two or more R ²⁸ are present, each may be the same or different. j1 and j4 each independently represent an integer of 0-3.

By setting it as the above range, adequate developability is imparted, and even if it is a low-temperature heat treatment, resistance to a stripper for removing the photoresist used in wiring formation, and photosensitivity, the resin film after development, the cured film after heat treatment The pattern shape is excellent.

<Phenolic compound>

As a phenol compound, As an example of alkylphenols, As an example, phenol; Methacresol, paracresol, orthocresol, xylenol, ethylphenol, butylphenol, octylphenol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-Dimethylphenol, 2-methyl-3-ethyl-phenol, 2-methyl-3-methoxyphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 2,3,6 - Examples of polyhydric phenols such as trimethylphenol include bisphenol A, bisphenol F, bisphenol S, resorcin, catechol and the like. Examples of other phenols include halogenated phenol, phenylphenol, and aminophenol. Among them, the phenol compound represented by the following formula (7) is more preferable. These phenolic compounds may be used independently and may be used combining several phenolic compounds.

<Aromatic Aldehyde Compound>

Examples of the aromatic aldehyde compound used in the structural unit represented by the general formula (5) include 4-methoxybenzaldehyde, salicylaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, and 3-methylsalicylaldehyde. , 4-methylsalicylaldehyde, 2-hydroxy-5-methoxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, etc. can Among them, the aromatic aldehyde compound represented by the following formula (8) is more preferable. These aromatic aldehyde compounds may be used independently and may be used combining several aromatic aldehyde compounds.

Examples of the aromatic aldehyde compound used in the structural unit represented by the general formula (6) include benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, 2,3-dimethylbenzaldehyde, and 2,4-dimethyl Benzaldehyde, 2,5-dimethylbenzaldehyde, 2,6-dimethylbenzaldehyde, 3,4-dimethylbenzaldehyde, 3,5-dimethylbenzaldehyde, 2,3,4-trimethylbenzaldehyde, 2,3,5-trimethylbenzaldehyde, 2, 3,6-trimethylbenzaldehyde, 2,4,5-trimethylbenzaldehyde, 2,4,6-trimethylbenzaldehyde, 3,4,5-trimethylbenzaldehyde, 4-ethylbenzaldehyde, 4-tert-butylbenzaldehyde, 4-isobutyl Benzaldehyde etc. are mentioned. Among them, the aromatic aldehyde compound represented by the following formula (9) is more preferable. These aromatic aldehyde compounds may be used independently and may be used combining several aromatic aldehyde compounds.

<Aromatic Ketone Compounds>

Examples of the aromatic ketone compound used in the structural unit represented by the general formula (5) include p-hydroxyacetophenone, m-hydroxyacetophenone, 3',5'-dihydroxyacetophenone, and p- Hydroxypropiophenone, m-hydroxypropiophenone, p-hydroxyvalerophenone, 1'-hydroxy-2'-acetonaphthone, 2'-hydroxy-1'-acetonaphthone, 2' -Hydroxy-5'-methylacetophenone, 4'-hydroxy-2'-methylacetophenone, 4'-hydroxy-3'-methylacetophenone, 2',4'-dihydroxy-3'- Methylacetophenone, 2'-hydroxyl-4',5'-dimethylacetophenone, 4'-benzoyloxy-2'-hydroxy-3'-methylacetophenone, 4'-benzyloxy-2'-methoxy -3'-methylacetophenone, 2'-hydroxy-4'-methoxyacetophenone, 2'-hydroxy-5'-methoxyacetophenone, 2'-hydroxy-6'-methoxyacetophenone, 2-(phenylsulfonyl)acetophenone, 2-hydroxy-2-methylpropiophenone, 2',4'-dihydroxy-3'-methylpropiophenone, 2-hydroxy-4'-(2 -Hydroxyethoxy)-2-methylpropiophenone, 2'-hydroxy-3-phenylpropiophenone, 4'-benzyloxy-2'-hydroxy-3'-methylpropiophenone, 2', 4'-dihydroxy-3'-methylbutyrophenone, o-hydroxybenzophenone, p-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 4,4'-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,2' ,4,4'-tetrahydroxybenzophenone, 4-fluoro-4'-hydroxybenzophenone, benzyl-4-hydroxyphenylketone, 2-hydroxy-5-methylbenzophenone, 2-hydroxy- 4-Methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 5-hydroxy-1-tetra Ron et al. Among them, the aromatic ketone compound represented by the following formula (10) is more preferable. These aromatic ketone compounds may be used independently and may be used combining several aromatic ketone compounds.

Examples of the aromatic ketone compound used in the structural unit represented by the general formula (6) include acetophenone, propiophenone, butyrophenone, isobutyrophenone, valerophenone, hexanophenone, 2,2- Dimethylpropiophenone, 2-phenylbutyrophenone, phenylvinylketone, cyclohexylphenylketone, p-methylacetophenone, m-methylacetophenone, o-methylacetophenone, p-ethyl acetophenone, p-propylacetophenone , p-isobutylacetophenone, p-butylacetophenone, p-t-butylacetophenone, 2',4'-dimethylacetophenone, 3',4'-dimethylacetophenone, 2',4',6'-trimethyl Acetophenone, p-methylpropiophenone, m-methylpropiophenone, o-methylpropiophenone, p-ethylpropiophenone, m-ethylpropiophenone, o-ethylpropiophenone, p-t-butylpropiophenone Non, 1'-acetonaphthone, 2'-acetonaphthone, 6'-methyl-2'-acetonaphthone, 4-acetylbiphenyl, t-butyl-4-phenoxyphenylketone, 1- (2- Naphthyl)-3-phenyl-2-propen-1-one, 2-fluoroacetophenone, p-fluoroacetophenone, m-fluoroacetophenone, o-fluoroacetophenone, m-trifluoro Methylacetophenone, 2-fluoropropiophenone, 3-fluoropropiophenone, p-fluoropropiophenone, m-fluoropropiophenone, o-fluoropropiophenone, p-methoxyacetophenone , m-methoxyacetophenone, o-methoxyacetophenone, 2-methoxyacetophenone, p-ethoxyacetophenone, p-phenoxyacetophenone, 2',2'-diethoxyacetophenone, 2', 4'-dimethoxyacetophenone, 2',5'-dimethoxyacetophenone, 2',6'-dimethoxyacetophenone, 3',4'-dimethoxyacetophenone, 3',5'-dimethoxyaceto Phenone, 3',4'-(methylenedioxy)acetophenone, 3',4'-(methylenedioxy)propiophenone, 6'-methoxy-2'-acetonaphthone, 6'-methoxy- 2'-propiononaphthone, 2',4'-dimethoxy-3'-methylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 5'-fluoro-2'-hydroxyacetophenone , 3',5'-dimethoxy-4'-hydroxyacetophenone, 2-fluoro-p-methoxyacetophenone, 2-fluoro-m-methoxyacetophenone, 2-fluoro-o-me toxia tax Tophenone, 2'-fluoro-4'-methoxyacetophenone, 3'-fluoro-4'-methoxyacetophenone, 2',4'-dimethoxy-3'-methylpropiophenone, benzophenone , anthraquinone, p-methylbenzophenone, m-methylbenzophenone, o-methylbenzophenone, p-ethylbenzophenone, m-ethylbenzophenone, o-ethylbenzophenone, 2,5-dimethylbenzophenone, 2, 4-dimethylbenzophenone, 3,4-dimethylbenzophenone, p-morpholinobenzophenone, p-phenylbenzophenone, o-fluorobenzophenone, p-fluorobenzophenone, 2,4'-difluoroben Zophenone, p-methoxybenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-( p-triylthio)benzophenone, 1-indanone, 2-methyl-1-indanone, 3-methyl-1-indanone, 4-methoxy-1-indanone, 5-methoxy-1-indone Non, 6-methoxy-1-indanone, 4-hydroxy-1-indanone, α-tetrarone, 1-benzosuberone, and the like. Among them, the aromatic ketone compound represented by the following formula (11) is more preferable. These aromatic ketone compounds may be used independently and may be used combining several aromatic ketone compounds.

In the present invention, the aromatic aldehyde compound and the aromatic ketone compound may be used alone or in combination. In addition, as the usage ratio of the said phenol compound and an aromatic aldehyde compound and/or an aromatic ketone compound, [aromatic aldehyde compound and/or aromatic ketone compound]/[phenol compound] is made into the range which becomes 0.5-2.0 by molar ratio, It is preferable from the point where there are few reactive phenols and the novolak-type phenol resin which made the sufficiently high molecular weight was obtained, and the range used as 0.7-1.8 is more preferable.

In this invention, it is preferable to use an acid catalyst for the polycondensation reaction of (B) component. Examples of the acid catalyst to be used include hydrochloric acid, sulfuric acid, phosphoric acid and boric acid as the inorganic acid, and oxalic acid, acetic acid, and para-toluenesulfonic acid as the organic acid.

(B) It is preferable that weight average molecular weights are 500 or more and 10,000 or less, and, as for (B) component, it is more preferable that weight average molecular weights are 500 or more and 5,000 or less. When the weight average molecular weight is within the above range, compatibility with component (A), heat resistance, moderate developability, and photosensitivity, the resin film after development and the cured film after heat treatment have excellent pattern shape, and a photo used for wiring formation Resistance to a stripper for removing resist, etc. can be imparted.

The weight average molecular weight (Mw) can be confirmed using GPC (gel permeation chromatography). For example, it can measure as N-methyl-2-pyrrolidone (it may abbreviate as NMP hereafter) as a developing solvent, and can calculate|require in conversion of polystyrene.

<Production of (B) component>

Although said (B) component can be created by a well-known method, Usually, it produces using polycondensation reaction. The polycondensation reaction proceeds by stirring for several hours under heating in the presence of the acid catalyst. As reaction temperature, 50 degreeC - 140 degreeC are preferable. Moreover, it is also possible to react in a solvent by adding a solvent at the time of the reaction. Examples of the reaction solvent include methanol, ethanol, propanol and the like as an alcoholic solvent, and ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1, 5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin, etc., glycol ethers As the solvent, 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, As a cyclic ether solvent such as ethylene glycol monophenyl ether, 1,3-dioxane, 1,4-dioxane tetrahydrofuran, dioxane, etc., as a glycol ester solvent, ethylene glycol acetate, diethylene glycol monomethyl ether As ketone solvents such as acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., aromatic hydrocarbons, such as toluene, xylene, etc. Other solvents include γ-butylolactone and pure water, but limited to these I never do that. These solvents may be used alone or in combination of two or more.

As for the addition amount of a solvent, 10 mass parts or more and 300 mass parts or less are preferable with respect to 100 mass parts of phenolic compounds.

After completion of the reaction, the acid catalyst is neutralized using a base such as pyridine, triethylamine or sodium hydroxide, and if necessary, the neutralized salt is removed by extraction with an aqueous layer, followed by dehydration and monomer removal steps to recover.

After synthesis of the said phenol resin (B), the removal process of a monomer is performed normally. As the method of monomer removal, the solvent fractionation method of adding a solvent and water to remove an aqueous layer, the method of volatilizing a monomer by heating under reduced pressure, etc. can be selected.

Moreover, you may use the method of passing through the following three processes as a manufacturing method of another (B) component.

<Process 1>

A phenolic trinuclear compound is obtained by heating the phenol compound and the aromatic aldehyde compound or the aromatic ketone compound in the presence of the acid catalyst and optionally using a solvent in a range of 60 to 140° C. and polycondensing them.

<Process 2>

The phenolic trinuclear compound obtained in step 1 is isolated from the reaction solution.

<Process 3>

The phenolic trinuclear compound and the aromatic aldehyde compound and/or the aromatic ketone compound isolated in step 2 are heated in the presence of the acid catalyst and optionally using a solvent in the range of 60 to 140 ° C. get the resin

Since the molecular weight distribution is narrowed by using the phenolic trinuclear compound, resistance to the stripper for removing the photoresist used in wiring formation even when subjected to low-temperature heat treatment, and photosensitivity, the resin film after development, heat treatment Since it is excellent in the pattern shape of a later cured film, it is preferable.

After completion of the reaction in steps 1 and 3, the acid catalyst is neutralized using a base such as pyridine, triethylamine, sodium hydroxide, and if necessary, the neutralized salt is removed by extracting the aqueous layer, followed by dehydration, monomer removal step or It is recovered by isolation, etc.

The input ratio of the phenol compound and the aromatic aldehyde compound or the aromatic ketone compound [phenol compound/(aromatic aldehyde compound or aromatic ketone compound)] in step 1 is the removability of the unreacted phenol compound and the yield of the product. And from the viewpoint of excellent purity of the reaction product, the molar ratio is preferably in the range of 1/0.2 to 1/0.5, and more preferably in the range of 1/0.25 to 1/3.45.

As a method for isolating the phenolic trinuclear compound from the reaction solution in step 2, for example, the reaction solution is poured into a poor solvent in which the reaction product is insoluble or sparingly soluble, and the resulting precipitate is filtered out, and then the reaction product is The method of melt|dissolving in the solvent which melt|dissolves and mixes also with a poor solvent, and the method of filtering and sorting out the deposit which inject|throws-in to a poor solvent again and generate|occur|produces is mentioned. Examples of the poor solvent used at this time include water, methanol, ethanol, propanol, etc. as monoalcohols, n-hexane, n-heptane, n-octane, cyclohexane, etc. as aliphatic hydrocarbons, and toluene, xylene, etc. as aromatic hydrocarbons. can be heard Among these poor solvents, water and methanol are preferable from the viewpoint that the acid catalyst can also be efficiently removed at the same time. On the other hand, examples of the solvent include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol as the polyol solvent. , 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin, etc., as glycol ether solvents such as 2-ethoxyethanol, ethylene glycol mono As a cyclic ether solvent such as methyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol monophenyl ether, etc. , 1,3-dioxane, 1,4-dioxane tetrahydrofuran, dioxane, etc., as glycol ester solvents such as ethylene glycol acetate and diethylene glycol monomethyl ether acetate, ketone solvents such as acetone, methyl ethyl ketone, As other solvents, such as methyl isobutyl ketone, (gamma)-butylolactone etc. are mentioned. It may be used only by 1 type, respectively, or may use 2 or more types together. A phenolic trinuclear compound can be obtained by the isolation method of step 2 above.

As the ratio of use of the phenolic trinuclear compound to the aromatic aldehyde compound and/or the aromatic ketone compound in step 3, [phenolic trinuclear compound]/[aromatic aldehyde compound and/or aromatic ketone compound] is excessive Since high molecular weight formation (gelation) can be suppressed and the thing of an appropriate molecular weight is obtained, the range of 1/0.5 - 1/1.2 is preferable in molar ratio, and the range of 1/0.6 - 1/0.9 is more preferable.

As a solvent used as needed in the said process 1 and process 3, for example, methanol, ethanol, propanol etc. as an alcohol solvent, ethylene glycol, 1,2-propanediol, 1, 3- propane as a polyol solvent. Diol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol , polyethylene glycol, glycerin, etc., as glycol ether solvents such as 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol Dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol monophenyl ether, etc., as a cyclic ether solvent, such as 1,3-dioxane, 1,4-dioxane tetrahydrofuran, dioxane, etc., as a glycol ester solvent, ethylene glycol acetate , diethylene glycol monomethyl ether acetate, etc. ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, aromatic hydrocarbons such as toluene and xylene, other solvents such as γ-butylollactone, pure water, etc. , but not limited to these. These solvents may be used alone or in combination of two or more.

(B) Content of component is excellent in the pattern shape of the cured film after heat processing, from viewpoints, such as tolerance with respect to the stripper for removing the photoresist used at the time of wiring formation, 5 mass with respect to 100 mass parts of (A) component A part or more is preferable, and 10 mass parts or more are still more preferable. Moreover, 200 mass parts or less are preferable with respect to 100 mass parts of (A) component from viewpoints, such as compatibility with (A) component, and 150 mass parts or less are more preferable.

<(C) Thermal crosslinking agent>

The resin composition of the present invention contains (C) a thermal crosslinking agent. A thermal crosslinking agent refers to the resin or compound which has at least two thermally reactive functional groups which are thermal crosslinking groups in a molecule|numerator.

Specific examples of the thermal crosslinking group include a cyclic ether group, an alkoxymethyl group, and a methylol group.

(C) It is preferable that the thermal crosslinking agent contains the thermal crosslinking agent which has a biphenyl structure which may have a substituent, and/or the thermal crosslinking agent which has a structural unit represented by general formula (14) demonstrated later.

<Thermal crosslinking agent having a biphenyl structure which may have a substituent>

It is preferable that the resin composition of this invention contains the thermal crosslinking agent which has a biphenyl structure which may have a substituent as (C) a thermal crosslinking agent.

By having a biphenyl structure that may have a substituent, chemical resistance to strippers of the cured film can be improved, and low water absorption can be imparted, so resistance to constant temperature and humidity test (HAST), etc. can be improved. . Moreover, it is excellent in control of the pattern shape of the resin film after image development and the cured film after heat processing from the point which can reduce the glass transition temperature of a resin film or a cured film suitably, and can provide fluidity|liquidity.

(C) It is preferable that the thermal crosslinking agent which has a biphenyl structure which may have a substituent contains the structure of general formula (12) or general formula (13) among thermal crosslinking agents.

As a biphenyl structure which may have a substituent, the structure represented by General formula (12) and General formula (13) is preferable from the point of improving chemical-resistance, and also improving the resistance with respect to a constant temperature and humidity test (HAST) etc.

In the general formula (12), R ²⁹ and R ³⁰ each independently represent a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. When a plurality of R ²⁹ and R ³⁰ are present, they may be the same or different. R ³¹ and R ³² represent a thermal crosslinking group. m1 and m2 each independently represent an integer of 0 to 4, m3 and m4 each independently represent an integer of 1 to 3, satisfying 1≤m1+m3≤5 and 1≤m2+m4≤5.

In the general formula (13), R ³³ , R ³⁴ , R ³⁵ and R ³⁶ each independently represent a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. When a plurality of R ³³ , R ³⁴ , R ³⁵ and R ³⁶ exist, each may be the same or different. R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ represent a thermal crosslinking group. R ⁴¹ represents a monovalent organic group having 1 to 10 carbon atoms. n1, n4, n5, n8 are each independently an integer of 1 to 3, n2, n3, n6, and n7 are each independently an integer of 0 to 4, n9 represents a repeating unit, an integer of 1 to 10, n10 is 0 or an integer of 1.

Specific examples of the structures represented by the general formulas (12) and (13) include the following cyclic ether compound, methylol compound, or an alkoxymethyl compound in which the hydrogen atom of the methylol group is substituted with a methyl group or an alkyl group having 2 to 10 carbon atoms. , but it is not limited to these. Moreover, a copolymer may be sufficient.

n9 represents a repeating unit and represents the integer of 1-10.

In this invention, you may contain a well-known cyclic ether group compound, an alkoxymethyl compound, and a methylol compound as another thermal crosslinking agent.

<Thermal crosslinking agent which has a structural unit represented by General formula (14)>

It is preferable that the resin composition of this invention contains the thermal crosslinking agent which has a structural unit represented by general formula (14).

In the general formula (14), R ⁴² is a divalent organic group having an alkylene group or an alkylene ether group having 1 to 15 carbon atoms, and R ⁴³ and R ⁴⁴ each independently represent a hydrogen atom or a methyl group.

Since the thermal crosslinking agent having a structural unit represented by the general formula (14) has a flexible alkylene group and a rigid aromatic group, chemical resistance to strippers of the cured film can be improved, and low water absorption can be imparted. It is possible to improve the resistance to the test (HAST) and the like. Moreover, it is excellent in control of the pattern shape of the resin film after image development and the cured film after heat processing from the point which can reduce the glass transition temperature of a resin film or a cured film suitably, and can provide fluidity|liquidity.

Examples of the crosslinking group contained in the thermal crosslinking agent having a structural unit represented by the general formula (14) include, but are not limited to, an acryl group, a methylol group, an alkoxymethyl group, and a cyclic ether group. Among these, a cyclic ether group is preferable from the point which reacts with the hydroxyl group of (A) component, and can improve the heat resistance of a cured film, and the point which can react without dehydration.

Although the following are mentioned as a specific example of the compound containing the structural unit represented by General formula (14), It is not limited to the following structure.

In the formula, o ² is an integer of 1 to 5, o ¹ is 1 to 20, and from the viewpoint of chemical resistance, low water absorption, and control of pattern shape, o ² is preferably 1 to 2, and o ¹ is preferably 3 to 7 .

(C) As the thermal crosslinking agent, a thermal crosslinking agent having a biphenyl structure which may have a substituent and/or a thermal crosslinking agent having a structural unit represented by the general formula (14), and other thermal crosslinking agents may be contained in combination of two or more types. good night.

(C) When the whole thermal crosslinking agent is 100 mass %, the content rate of the thermal crosslinking agent which has a thermal crosslinking agent which has a biphenyl structure which may have a substituent, and a thermal crosslinking agent which has a structural unit represented by General formula (14) is 15 mass % It is preferable that it is 80 mass % or more and 80 mass % or less. Since this can improve the chemical-resistance with respect to the stripper etc. of a cured film, and can provide low water absorption, tolerance with respect to a constant temperature and humidity test (HAST) etc. can be improved. Moreover, when it has photosensitivity from the point which reduces the glass transition temperature of a resin film or a cured film suitably, it is excellent in control of the pattern shape of a cured film.

In the resin composition of the present invention, the (C) thermal crosslinking agent contains a thermal crosslinking agent having a biphenyl structure which may have a substituent, and the content of the thermal crosslinking agent having a biphenyl structure which may have a substituent is the above (B) ) 30 parts by mass or more and 150 parts by mass or less are preferable with respect to 100 parts by mass of the phenol resin.

The content of (C) thermal crosslinking agent having a biphenyl structure which may have a substituent is determined from the viewpoint of improving resistance to strippers for removing photoresist used in wiring formation, resistance to constant temperature and humidity testing (HAST), etc. , (B) 30 parts by mass or more is preferable with respect to 100 parts by mass of the phenol resin, more preferably 40 parts by mass or more, and still more preferably 50 parts by mass or more. In addition, from the viewpoint of improving resistance to a stripper for removing the photoresist used in wiring formation while maintaining the pattern shape, resistance to constant temperature and humidity testing (HAST), etc., (B) 150 parts by mass per 100 parts by mass of phenol resin A part or less is preferable, 120 mass parts or less are more preferable, and 100 mass parts or less are still more preferable.

<(D) photosensitive compound>

It is preferable that the resin composition of this invention contains (D) photosensitive compound (Hereinafter, it may call (D)component).

(D) Photosensitivity can be provided to a resin composition by containing a component. (D) A component is a compound by which a chemical structure changes in response to an ultraviolet-ray, For example, a photo-acid generator, a photobase generator, a photoinitiator, etc. are mentioned. (D) When a photo-acid generator is used as a component, acid is generated in the light-irradiated portion of the photosensitive resin composition, and the solubility of the light-irradiated portion in an alkali developer increases, so a positive pattern in which the light-irradiated portion dissolves can be obtained. have.

(D) When a photobase generator is used as a component, a base is generated in the light-irradiated portion of the resin composition, and the solubility of the light-irradiated portion in an alkali developer is lowered, so a negative pattern in which the light-irradiated portion is insolubilized can be obtained

(D) When a photoinitiator is used as a component, a radical generate|occur|produces in the light irradiation part of a resin composition, radical polymerization advances, and a negative pattern can be formed by insolubilizing with respect to an alkali developing solution. In addition, UV curing at the time of exposure is accelerated, so that the sensitivity can be improved.

A photo-acid generator is preferable at the point from which a high-resolution pattern is obtained with high sensitivity in said (D)component. Examples of the photoacid generator include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. In addition, a sensitizer or the like may be included as needed.

As a quinonediazide compound, the compound which the sulfonic acid of naphthoquinonediazide couple|bonded with ester to the compound which has a phenolic hydroxyl group is preferable. Examples of the compound having a phenolic hydroxyl group used herein include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP- PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methyleneless-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML -PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade name, Asahiyukizai High School, Ltd.) ) agent), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzo 4-naphthoquinonediazidesulfonic acid or 5-naphthoquinonedia to compounds such as phenone, methyl gallic acid ester, bisphenol A, bisphenol E, methylenebisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) Examples of preferable ones in which zidsulfonic acid is introduced through an ester bond can be exemplified, but compounds other than this can also be used.

Moreover, it is preferable that 50 mol% or more of the whole functional group of the compound which has a phenolic hydroxyl group is substituted by the quinonediazide. By using the quinonediazide compound substituted by 50 mol% or more, the affinity with respect to the aqueous alkali solution of a quinonediazide compound falls. As a result, the solubility with respect to the aqueous alkali solution of the resin composition of an unexposed part falls largely. Moreover, the quinonediazide sulfonyl group changes to indenecarboxylic acid by exposure, and the large dissolution rate with respect to the aqueous alkali solution of the photosensitive resin composition of an exposure part can be acquired. That is, as a result, the dissolution rate ratio of the exposed portion and the unexposed portion of the composition is increased, and a pattern can be obtained with high resolution.

By containing such a quinonediazide compound, the resin composition which has positive photosensitivity which is sensitive to i-line (365 nm), h-line (405 nm), g-line (436 nm) of general mercury lamp, and broadband containing them. can get Moreover, (D)component may contain only 1 type, or may contain it in combination of 2 or more types, and a highly sensitive resin composition can be obtained.

Examples of the quinonediazide include a 5-naphthoquinonediazidesulfonyl group, a 4-naphthoquinonediazidesulfonyl group, a 4-naphthoquinonediazidesulfonyl group and a 5-naphthoquinonediazidesulfonyl group in the same molecule. things and the like.

It is preferable that 5-naphthoquinone diazide sulfonyl ester compound (D-1) is included as a naphthoquinone diazide sulfonyl ester compound. (D-1) As for the component, absorption is extended to the g-line|region of a mercury lamp, and it is suitable for g-line|wire exposure and full-wave-wavelength exposure. Moreover, by reacting with (A) component or (B) component at the time of hardening, a crosslinked structure is formed and chemical-resistance improves.

Examples of the naphthoquinone diazide sulfonyl ester compound include a 5-naphthoquinone diazide sulfonyl ester compound (D-1) and a 4-naphthoquinone diazide sulfonyl ester compound (D-2), and the content ratio is It is preferable that (D-2)/(D-1)=0.3-3. (D-2) A component has absorption in i-line|wire area|region of a mercury vapor lamp, and is suitable for i-line|wire exposure. Further, since the acid generated by exposure is a strong sulfonic acid, alkali dissolution of the entire exposed portion increases during development, so that the pattern shape after development and heat treatment can be improved. Therefore, chemical-resistance and the pattern shape after heat processing can be compatible by making the content rate into (D-2)/(D-1)=0.3-3.

A quinonediazide compound can be synthesize|combined by a well-known method by the esterification reaction of the compound which has a phenolic hydroxyl group, and a quinonediazide sulfonic acid compound. By using a quinonediazide compound, a resolution, a sensitivity, and a remaining-film rate improve more.

(D) The molecular weight of the component is preferably 300 or more, more preferably 350 or more, and preferably 3,000 or less, more preferably 1,500 or less from the viewpoint of heat resistance, mechanical properties, and adhesiveness of the film obtained by heat treatment. .

(D) Among components, a sulfonium salt, a phosphonium salt, and a diazonium salt are preferable in order to stabilize the acidic component which generate|occur|produced by exposure suitably. Among them, a sulfonium salt is preferable.

(D) As for content of component, 0.1 mass part or more and 100 mass parts or less are preferable with respect to 100 mass parts of (A) component. (D) Photosensitivity can be provided, maintaining the heat resistance of the film|membrane after heat processing, chemical-resistance, and mechanical property that content of (D)component is 0.1 mass part or more and 100 mass parts or less.

When (D)component contains a quinonediazide compound, 1 mass part or more is more preferable with respect to 100 mass parts of (A) component, and, as for content of (D)component, 3 mass parts or more are still more preferable. Moreover, 100 mass parts or less are more preferable, and 80 mass parts or less are still more preferable. If it is 1 mass part or more and 100 mass parts or less, photosensitivity can be provided, maintaining the heat resistance of the film|membrane after heat processing, chemical-resistance, and mechanical characteristics.

When (D)component contains a sulfonium salt, a phosphonium salt, or a diazonium salt, as for content of (D)component, 0.1 mass part or more is more preferable with respect to 100 mass parts of (A) component, 1 mass part More preferably, 3 parts by mass or more is particularly preferable. Moreover, 100 mass parts or less are more preferable, 80 mass parts or less are still more preferable, and 50 mass parts or less are especially preferable. If it is 0.1 mass part or more and 100 mass parts or less, photosensitivity can be provided, maintaining the heat resistance of the film|membrane after heat processing, chemical-resistance, and mechanical characteristic.

(D) When a photobase generator is contained as a component, an amide compound, an ammonium salt, etc. are specifically mentioned as a photobase generator.

Examples of the amide compound include 2-nitrophenylmethyl-4-methacryloyloxypiperidine-1-carboxylate, 9-anthrylmethyl-N,N-dimethylcarbamate, 1-(anthraquinone- 2-yl) ethylimidazole carboxylate, (E)-1-[3-(2-hydroxyphenyl)-2-propenoyl]piperidine, etc. are mentioned.

As the ammonium salt, for example, 1,2-diisopropyl-3-(bisdimethylamino)methylene)guanidium 2-(3-benzoylphenyl)propionate, (Z)-{[bis(dimethylamino) Methylidene]amino}-N-cyclohexylamino)methaniminiumtetrakis(3-fluorophenyl)borate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyl Triphenyl borate etc. are mentioned.

When it contains a photobase generator as (D)component, as for content of (D)component in a resin composition, 0.1 mass part or more is preferable with respect to 100 mass parts of (A) component, and 0.5 mass part or more More preferably, 0.7 mass part or more is still more preferable, and 1 mass part or more is especially preferable. When content is in the said range, the sensitivity at the time of exposure can be improved. On the other hand, as for content, 25 mass parts or less are preferable, 20 mass parts or less are more preferable, 17 mass parts or less are still more preferable, and 15 mass parts or less are especially preferable. When content is in the said range, the resolution after image development can be improved.

(D) When a photoinitiator is contained as a component, as a photoinitiator, as a photoinitiator, for example, a benzyl ketal system photoinitiator, an alpha-hydroxy ketone type photoinitiator, an alpha -amino ketone type photoinitiator, an acylphosphine oxide type photoinitiator. An initiator, an oxime ester-based photopolymerization initiator, an acridine-based photopolymerization initiator, a benzophenone-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, an aromatic ketoester-based photopolymerization initiator or a benzoic acid ester-based photopolymerization initiator, and a titanocene-based photopolymerization initiator are preferable. From the viewpoint of improving sensitivity during exposure, α-hydroxyketone-based photoinitiator, α-aminoketone-based photoinitiator, acylphosphine oxide-based photopolymerization initiator, oxime ester-based photoinitiator, acridine-based photoinitiator or benzophenone-based photopolymerization An initiator is more preferable, and an alpha -amino ketone type photoinitiator, an acylphosphine oxide type photoinitiator, and an oxime ester type photoinitiator are still more preferable.

Examples of the α-aminoketone-based photopolymerization initiator include 2-dimethylamino-2-methyl-1-phenylpropan-1-one, 2-diethylamino-2-methyl-1-phenylpropan-1-one; 2-Methyl-2-morpholino-1-phenylpropan-1-one, 2-dimethylamino-2-methyl-1-(4-methylphenyl)propan-1-one, 2-dimethylamino-1-(4 -Ethylphenyl)-2-methylpropan-1-one, 2-dimethylamino-1-(4-isopropylphenyl)-2-methylpropan-1-one, 1-(4-butylphenyl)-2-dimethyl Amino-2-methylpropan-1-one, 2-dimethylamino-1-(4-methoxyphenyl)-2-methylpropan-1-one, 2-dimethylamino-2-methyl-1-(4-methyl Thiophenyl)propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morphol Nophenyl)-butan-1-one, 2-benzyl-2-dimethylamino-1-(4-dimethylaminophenyl)-butan-1-one, 2-dimethylamino-2-[(4-methylphenyl)methyl] -1-[4-(4-morphonyl)phenyl]-1-butanone.

Examples of the acylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide or bis(2,6). -dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide is mentioned.

Examples of the oxime ester photoinitiator include 1-phenylpropane-1,2-dione-2-(O-ethoxycarbonyl)oxime, 1-phenylbutane-1,2-dione-2-(O- Methoxycarbonyl)oxime, 1,3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]octane-1 ,2-dione-2-(O-benzoyl)oxime, 1-[4-[4-(carboxyphenyl)thio]phenyl]propane-1,2-dione-2-(O-acetyl)oxime, 1-[ 9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, 1-[9-ethyl-6-[2-methyl-4- [1-(2,2-dimethyl-1,3-dioxolan-4-yl)methyloxy]benzoyl]-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime or “ah Deca Arcles" (trademark) NCI-831 is mentioned.

When it contains a photoinitiator as (D)component, 0.1 mass part or more is preferable with respect to 100 mass parts of (A) component, and, as for content of (D)component in a resin composition, 0.5 mass part or more is more preferable And 0.7 mass part or more is more preferable, and 1 mass part or more is especially preferable. When content is in the said range, the sensitivity at the time of exposure can be improved. On the other hand, as for content, 25 mass parts or less are preferable, 20 mass parts or less are more preferable, 17 mass parts or less are still more preferable, and 15 mass parts or less are especially preferable. When content is in the said range, the resolution after image development can be improved.

<Others>

The resin composition of the present invention may contain a radically polymerizable compound, an antioxidant, a solvent, a compound having a phenolic hydroxyl group, an adhesion improving agent, an adhesion improving agent, and a surfactant as other components as needed.

<Method for producing a resin composition>

Next, the manufacturing method of the resin composition of this invention is demonstrated. For example, each component of the above (A), (B) and (C) and, if necessary, (D) component, a radically polymerizable compound, an antioxidant, a solvent, a compound having a phenolic hydroxyl group, an adhesion improving agent, A resin composition can be obtained by mixing and dissolving an adhesion improving agent, a surfactant, etc.

As a dissolution method, well-known methods, such as heating and stirring, are mentioned.

As for the viscosity of a resin composition, 2-5,000 mPa*s is preferable. It becomes easy to obtain a desired film thickness by adjusting solid content concentration so that a viscosity may become 2 mPa*s or more. On the other hand, if the viscosity is 5,000 mPa·s or less, it becomes easy to obtain a coating film with high uniformity. The resin composition which has such a viscosity can be obtained easily by making solid content concentration into 5-60 mass %, for example. Here, solid content concentration means components other than a solvent.

It is preferable to filter the obtained resin composition using a filtration filter, and to remove refuse and particle|grains. Although there exist polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc. as a material of a filtration filter, polyethylene and nylon are preferable.

<Resin sheet>

The resin sheet of this invention is the resin sheet formed in the base material using the said resin composition. Specifically, it refers to a sheet obtained by applying a resin composition to a substrate and drying it.

Films, such as polyethylene terephthalate (PET), can be used for the base material to which the resin composition is apply|coated. When the resin sheet is bonded to a substrate such as a silicon wafer, and it is necessary to peel and remove the substrate, using a substrate coated with a release agent such as a silicone resin on the surface, the resin sheet and the substrate can be easily peeled off. It is preferable because it can

<Method for producing a cured film>

Next, the cured film of this invention which hardened|cured the resin composition of this invention or the resin sheet of this invention, and its manufacturing method are demonstrated.

Hereinafter, the resin film means the film|membrane obtained by apply|coating the resin composition of this invention to a board|substrate, and drying. In addition, a cured film means the film|membrane obtained by hardening|curing a resin film or a resin sheet.

The manufacturing method of the cured film of this invention apply|coats the said resin composition to a board|substrate, or laminates a resin sheet to a board|substrate, after that, it dries and forms a resin film, the exposure process of exposing the dried resin film, the exposed resin The manufacturing method of the cured film including the developing process of developing a film|membrane, and the heat processing process of heat-processing the developed resin film is preferable.

First, the resin composition of this invention is apply|coated to a board|substrate, and the coating film of a resin composition is obtained. As the substrate, a silicon wafer, ceramics, gallium arsenide, an organic circuit substrate, an inorganic circuit substrate, and a substrate in which a constituent material of a circuit is disposed on these substrates are used, but the substrate is not limited thereto. As a coating method, there exist methods, such as a spin-coating method, the slit-coating method, the dip-coating method, the spray-coating method, and the printing method. In addition, although a coating film thickness changes with an application|coating method, solid content concentration of a composition, a viscosity, etc., it apply|coats so that the film thickness after drying may be normally set to 0.1-150 micrometers.

Prior to application, the substrate to which the resin composition is applied may be pre-treated with the adhesion improving agent previously described above. For example, 0.5 to 20% by mass of the adhesion improving agent is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate. A method of treating the surface of the substrate by a method such as spin coating, slit die coating, bar coating, dip coating, spray coating, or steam treatment using the prepared solution is exemplified. After treating the substrate surface, you may perform a reduced pressure drying process as needed. Moreover, you may advance reaction of a board|substrate and an adhesion|adherence improving agent by 50 degreeC - 280 degreeC heat processing after that.

Next, the coating film of the resin composition is dried to obtain a resin film. It is preferable to perform drying in an oven, a hot plate, infrared rays, etc. in the range of 50 degreeC - 140 degreeC for 1 minute - several hours.

On the other hand, when using the resin sheet formed from the resin composition of the present invention, if the resin sheet has a protective film, it is peeled off, the resin sheet and the substrate are opposed, and the resin sheet and the substrate are bonded by thermocompression bonding (the resin sheet and the substrate are opposed to each other). and bonding by thermocompression bonding is sometimes described as laminating a resin sheet to a substrate). Next, the resin sheet laminated on the board|substrate is dried similarly to the time of obtaining the said resin film, and a resin film is formed. A resin sheet can be obtained by apply|coating and drying the resin composition of this invention on the support film comprised with the polyethylene terephthalate etc. which are a peelable board|substrate.

Thermocompression bonding can be performed by a hot press process, a hot lamination process, a hot vacuum lamination process, etc. As for bonding temperature, 40 degreeC or more is preferable from the point of adhesiveness to a board|substrate, and embedding property. In addition, when the resin sheet has photosensitivity, the bonding temperature is preferably 140° C. or less in order to prevent the resin sheet from hardening at the time of bonding and the resolution of pattern formation in the exposure and development step from lowering.

In an exposure process, actinic ray is irradiated through the mask which has a desired pattern on the resin film which has photosensitivity. Actinic rays used for exposure include ultraviolet rays, visible rays, electron rays, and X-rays, but in the present invention, general exposure wavelengths such as g-ray (436 nm), h-ray (405 nm) or i-ray (365 nm) are used. it is preferable In a resin film which does not have photosensitivity, after forming a photoresist after resin film formation, the said actinic ray is irradiated.

Then, the exposed resin film having photosensitivity is developed. As a developer, tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol An aqueous solution of a compound showing alkalinity such as , dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine or hexamethylenediamine is preferable. In addition, in some cases, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butylolactone, dimethylacrylamide, etc. polar solvents, alcohols such as methanol, ethanol and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone, etc. Or you may add 2 or more types. After development, it is common to rinse with water. Here too, alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.

Thus, the obtained resin film is heated, thermal crosslinking reaction is advanced, and the cured film of this invention is obtained. A cured film improves heat resistance and chemical-resistance by crosslinking. This heat treatment may be performed by raising the temperature stepwise, or may be performed while continuously increasing the temperature. It is preferable to perform heat processing for 5 minutes - 5 hours. As an example, after heat-processing at 100 degreeC for 30 minutes, the example which heat-processes at 230 degreeC for 60 minutes is given. As heat processing conditions, 140 degreeC or more and 400 degrees C or less are preferable. In order to advance a thermal crosslinking reaction, 140 degreeC or more is preferable and, as for heat processing conditions, 160 degreeC or more is more preferable. Moreover, in order to provide the outstanding cured film, in order to improve the reliability of a semiconductor device or a display device, 300 degrees C or less is preferable and, as for heat processing conditions, 250 degrees C or less is more preferable.

Thus, it is preferable that the cured film of this invention obtained has an opening pattern, and that the angles of the inclined side in the said opening pattern cross section are 40 degrees or more and 80 degrees or less.

The front sectional drawing of the opening pattern of a cured film in FIG. 3 is shown. The angle of the inclined side 14 is 15 with respect to the opening pattern formed in the cured film 3 in FIG. In addition, the inclined side was made to connect the upper opening pattern and the lower opening pattern by a straight line.

By making the angle of the inclination side in the cross section of the opening pattern of a cured film into this range, it is hard to produce defects, such as wiring defect, such as a short circuit of wiring, for the semiconductor device and display apparatus mentioned later to which this cured film is applied, and it is excellent in reliability.

<Semiconductor device>

The cured film of this invention which hardened|cured the resin composition of this invention or the resin sheet of this invention can be used for electronic components, such as a well-known semiconductor device. That is, the semiconductor device of this invention has the cured film of this invention. The semiconductor device of this invention has metal wiring and an insulating film, and has the cured film of this invention as an insulating film. A semiconductor device generally refers to a device including a semiconductor element or an integrated circuit integrating the same as a component. The semiconductor device of the present invention includes not only devices including semiconductor elements, but also components for semiconductor devices such as wiring boards. The semiconductor device of the present invention also includes a semiconductor package in which a semiconductor element or the like is protected by a sealing resin and has a function of being electrically connected to the outside. Specifically, the cured film of this invention is used suitably for uses, such as a passivation film of a semiconductor, a protective film of a semiconductor element, and the interlayer insulating film of the multilayer wiring for high-density mounting.

In particular, in recent semiconductor devices, with the further miniaturization of electrodes of semiconductor elements and metal wirings of substrates, semiconductor devices having electrodes, metal wirings, and vamps using gold, silver, copper, nickel, aluminum, etc., have become mainstream. And in the etching process of metal wiring or barrier metal at the time of these formation, or the pattern formation process of a resist, it comes into contact with many chemical|medical solutions, such as a stripper for flux and photoresist removal. When the cured film which consists of the resin composition or resin sheet of this invention is used as such a protective film of an electrode or metal wiring, since it has high tolerance with respect to those chemical|medical solutions, it is used especially preferably. In addition, the copper wiring may be oxidized in the manufacturing process. Also in such a case, the cured film of this invention can be used suitably.

As a preferable example of the semiconductor device which has the resin composition of this invention, or the cured film of this invention which hardened|cured the resin sheet of this invention (Hereinafter, it may call the cured film which consists of the resin composition or resin sheet of this invention.) , for example, a polymer memory (Polymer Ferroelectric RAM: PFRAM) or Phase Change RAM (PCRAM, or Ovonic) promising as a logic device such as a CPU or GPU described in International Publication No. 2018/066395, MRAM, or next-generation memory Memory such as Unified Memory: OUM), semiconductor devices with vamps, fan-out wafer-level packages (fan-out WLP) or fan-out panel-level packages (fan-out PLP), coil components for inductor devices, chip sizes of 100 to 700 μm In-mini LEDs, micro LEDs whose chip size is 100 micrometers or less, etc. are mentioned.

In a semiconductor device having a vamp, a fan-out wafer level package (fan-out WLP) or a fan-out panel level package (fan-out PLP), and a coil component of an inductor device, a cured film made of the resin composition or resin sheet of the present invention is formed as an insulating film After that, a metal wiring (so-called rewiring) may be further formed thereon. By repeatedly performing the above steps, it is possible to form a multilayer wiring structure in which two or more layers of rewiring are separated by an insulating film made of a cured product of the resin composition or resin sheet of the present invention. The insulating film separating this rewiring is called an interlayer insulating film. At this time, the formed insulating film comes into contact with various chemical liquids several times, but the insulating film made of the resin composition or cured product of the resin sheet of the present invention has excellent adhesion and chemical resistance, so that a good multilayer wiring structure can be formed. have. In addition, when the resin composition or resin sheet of the present invention has photosensitivity, since the tapered shape after curing is excellent, the degree of freedom in the layout design of the copper wiring when forming the multilayer metal wiring is improved. It can be used preferably. Although there is no upper limit to the number of layers of a multilayer wiring structure, 10 or less layers are often used.

In the fan-out WLP or the fan-out PLP, the miniaturization of rewiring is progressing. Since the cured film of this invention has high metal adhesiveness also to the metal wiring whose width|variety of metal wiring and the space|interval of adjacent metal wiring are 5 micrometers or less, it is used suitably also for fine rewiring. Here, when the width of the metal wiring and the interval between adjacent metal wirings are 5 μm or less, it means that the width of the metal wiring is 5 μm or less, and the interval between adjacent metal wirings is also 5 μm or less.

In the fan-out WLP or fan-out PLP having such a fine structure, it has a multi-layered stack structure in which a plurality of redistribution layers are stacked, and among the adjacent redistribution layers, the width of the metal wiring in the redistribution layer closer to the semiconductor chip; It is preferable that the spacing between adjacent metal wires is the same or narrower than the width of the metal wires in the redistribution layer on the far side from the semiconductor chip and the spacing between adjacent metal wires. Here, the redistribution layer refers to a layer comprising a set of redistribution wires and an interlayer insulating film formed thereon in a multilayer wiring structure in which a plurality of redistribution wires are separated by a plurality of interlayer insulating films. Moreover, there exists a case where a redistribution layer consists of only one layer. In addition, when the width of the metal wiring of the redistribution layer and the spacing between adjacent metal wirings are the same or narrow, the width of the metal wiring in the redistribution layer closer to the semiconductor chip is the width of the metal wiring in the redistribution layer farther from the semiconductor chip. The same or narrower than the width, and the distance between adjacent metal wires in the redistribution layer closer to the semiconductor chip is the spacing between adjacent metal wires in the redistribution layer farther from the semiconductor chip. Compared to , it means the same or narrower.

In these structures, the thickness of the interlayer insulating film of the redistribution layer closer to the semiconductor chip among the adjacent redistribution layers is equal to or narrower than the thickness of the interlayer insulating film of the redistribution layer farther from the semiconductor chip. It is preferable to lose

<Display device>

A cured film obtained by curing the resin composition or resin sheet of the present invention is a display device including a first electrode formed on a substrate and a second electrode formed to face the first electrode, specifically, for example, LCD, ECD, ELD , a display device using organic EL, and the like.

The organic electroluminescent display of this invention is an organic electroluminescent display which has at least a TFT substrate, a flattening layer, a 1st electrode, an insulating layer, a light emitting layer, and a 2nd electrode, The said planarizing layer or the said insulating layer is the cured film of this invention. It is preferable to include

Moreover, it is a display apparatus which has at least metal wiring, the cured film of this invention, and a some light emitting element, The said light emitting element is equipped with a pair of electrode terminals on either surface, The said pair of electrode terminals is the said cured film. It is preferable that it is connected with the several said metal wiring extending in the middle, and it is the structure which maintains electrical insulation by the said cured film of several said metal wiring.

The display device will be described with reference to FIG. 1 as an example of one embodiment.

In FIG. 1 , in the display device 1 , a plurality of light-emitting elements 2 are disposed on a counter substrate 5 , and a cured film 3 is disposed on the light-emitting elements 2 . The light emitting element top may be not only on the surface of the light emitting element but above the support substrate or the light emitting element. In the form shown in FIG. 1, the some cured film 3 is further laminated|stacked on the cured film 3 mix|blended so that it may contact with at least one part of the light emitting element 2, and the structure which laminates|stacks three layers in total is illustrated, It is not limited to this, Furthermore, the cured film 3 may be a single layer. The light emitting element 2 is provided with a pair of electrode terminals 6 on the surface opposite to the surface in contact with the counter substrate 5, and each electrode terminal 6 extends into the cured film 3, a metal wiring ( 4) is connected. Moreover, since the some metal wiring 4 extended in the cured film 3 is covered with the cured film 3, and since the cured film 3 functions also as an insulating film, it is a structure which maintains electrical insulation. . Further, the light emitting element 2 is electrically connected to the driving element 8 attached to the light emitting element driving substrate 7 formed at a position opposite to the counter substrate 5 through the metal wiring 4 or 4c, , the light emission of the light emitting element 2 can be controlled. In addition, the light emitting element driving board 7 is electrically connected to the metal wiring 4 via, for example, a solder vamp 10 . Moreover, in order to prevent diffusion of metals, such as the metal wiring 4, you may arrange|position the barrier metal 9. As shown in FIG. Further, in the following figures, the metal wiring 4c may pass through the light emitting element driving substrate 7 and be connected to the driving element 8 .

The said cured film 3 is the cured film which hardened|cured the resin composition or resin sheet of this invention.

It does not specifically limit as a material of the metal wiring 4, A well-known thing can be used. For example, gold, silver, copper, aluminum, nickel, etc. are mentioned, Copper is preferable.

As another embodiment of the display device, as shown in FIG. 4 , a configuration in which a cured film 16 blended so as to be in contact with at least a part of the light emitting element 2 is formed with respect to the display device of FIG. 1 is exemplified, have. The cured film 16 arrange|positioned so that it may contact with at least one part of the light emitting element 2 may be comprised from the cured film which hardened|cured the resin composition or resin sheet of this invention, and also hardened the resin composition or resin sheet of this invention. It may be comprised from materials other than one cured film, and well-known things, such as an epoxy resin, a silicone resin, and a fluororesin, may be used.

Moreover, in this invention, it is preferable that the thickness of the whole cured film is 5 micrometers - 100 micrometers.

When the overall thickness of the cured film is 5 µm to 100 µm, it is possible to reduce the height of the display device having a light emitting element itself, to suppress wiring defects such as short circuit due to wiring short distance, to suppress the reduction in loss, and to improve the high-speed responsiveness. becomes

The whole thickness of a cured film means the thickness of the whole layer of the continuous cured film in which at least one part of one cured film contact|connects another cured film. For example, when two or more cured films 3 are laminated|stacked like above-mentioned FIG. 1, the area|region shown by 12 of FIG. 1 is the thickness of the whole layer of a cured film. The whole thickness becomes like this. Preferably it is 7-70 micrometers, More preferably, it is 8-60 micrometers. If it is less than 5 μm, since protection of metal wiring is insufficient, there is a risk of wiring defects such as short circuit. Defects may occur in terms of suppression of loss reduction and improvement of high-speed responsiveness.

Moreover, when laminating|stacking two or more cured films, it is preferable that the number of layers of a cured film is 2 or more and 10 or less layers.

From the viewpoint of arranging a plurality of light-emitting elements, the cured film is preferably one or more layers, and since the number of metal wirings connectable to the light-emitting elements can be increased by using two or more layers, a plurality of light-emitting elements can be arranged, , 10 layers or less is preferable from the viewpoint of suppression of wiring defects such as short circuiting of wiring due to reduction in package height or shortening of wiring, reduction in loss, and improvement of high-speed responsiveness.

According to this structure, a micro light emitting element can be applied, and high-density mounting of a plurality of light emitting elements is attained, and the display device which has a high resolution light emitting element in a wide size can be obtained. In addition, it becomes possible to form fine metal wiring, and since the number of wirings that can be formed in a unit area increases, the overall thickness of the cured film can be reduced, and the display device itself having a light emitting element can be reduced in height and wiring distance. It is possible to suppress wiring defects such as short circuit of the wiring due to this, suppression of loss reduction, and improvement of high-speed responsiveness.

From the viewpoint of applying a minute light-emitting element or high-density mounting of the light-emitting element, the longest length of the bottom surface portion of the metal wiring is preferably 2 to 15 µm, more preferably 2 to 10 µm, still more preferably, It is 2-5 μm. If it is less than 2 µm, poor connection with the light-emitting element 2 may occur, and if it exceeds 20 µm, it may be detrimental to application of a minute light-emitting element or high-density mounting.

In addition, it is preferable that the light emitting element is an LED having a side length of 5 µm or more and 700 µm or less, and more preferably, the light emitting element is an LED having a side length of 5 µm or more and 100 µm or less.

Moreover, in this invention, it has a thickness more than the thickness of the said light emitting element between several said light emitting elements, and you may form the partition comprised from the cured film which hardened|cured the resin composition containing the said (A) resin.

As another embodiment, as shown in FIG. 2 , a repeating pattern corresponding to the number of pixels of the display device 1 having the light emitting elements 2 , that is, between or around each light emitting element 2 , the barrier rib 11 is formed. It is desirable to have This configuration is preferable because bonding to the counter substrate 5 is facilitated.

It is preferable that the thickness of a partition is larger than the thickness of each light emitting element, and, specifically, 5 micrometers - 120 micrometers are preferable.

The partition wall may be a cured film obtained by curing the resin composition or resin sheet of the present invention, or may be composed of other materials, such as epoxy resin, (meth)acrylic polymer, polyurethane, polyester, polyolefin, polysiloxane, etc. You may use a well-known thing.

Moreover, it is preferable to arrange|position the partition which has a thickness more than the thickness of the said light emitting element in the said cured film which covers a light emitting element between some said light emitting element.

(Example)

Hereinafter, although an Example etc. are given and this invention is demonstrated, this invention is not limited by these examples. In addition, evaluation of the resin composition or resin sheet in an Example was performed with the following method. In addition, the resin composition (henceforth a varnish) filtered with a 1 micrometer polytetrafluoroethylene filter (made by Sumitomo Denki Kogyo Co., Ltd.) was used for evaluation.

<Evaluation of the resin composition which does not have photosensitivity>

(1) Evaluation of the opening pattern shape of a cured film made of a resin composition having no photosensitivity

A varnish was prepared and applied onto an 8-inch silicon wafer by a spin coating method using a coating/developing apparatus ACT-8 (manufactured by Tokyo Electron Co., Ltd.) so that the film thickness after heat treatment was 7 µm, followed by prebaking. It performed and produced the prebaking film|membrane. Prebaking was performed at 110 degreeC for 3 minutes. Then, the positive photoresist OFPR-800 (made in Tokyo) was apply|coated on the prebaking film|membrane, and it prebaked at 100 degreeC for 10 minute(s). Next, exposure was carried out at an exposure dose of 100 to 800 mJ/cm 2 , respectively, using an i-line stepper (manufactured by Nikon Corporation, NSR-2205i14). The size of the circular pattern used for exposure is 30 micrometers. After exposure, using a 2.38 mass % aqueous solution of tetramethylammonium (TMAH) (manufactured by Tama Chemical Co., Ltd.), development was carried out under conditions such that the film thickness change of the unexposed part before and after development was 1.5 µm, followed by rinsing with pure water; It swung and dried, and the pattern formation film was obtained. In addition, the film thickness after prebaking and image development was measured using Dainippon Screen Seijo Co., Ltd. product optical interference type film thickness measuring apparatus Lambda Ace STM-602, the refractive index was 1.629.

Subsequently, the temperature was raised from 50°C to 100°C at 3.5°C/min, and then heat treatment was performed at 100°C for 30 minutes. After that, the temperature was raised to 160°C at 3.5°C/min, followed by baking at 160°C for 10 minutes, immersed in stripper 106 (Oka, Tokyo) for 3 minutes, and rinsing with pure water to remove the photoresist film.

Thereafter, using an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.), the temperature was raised from 50° C. to 3.5° C./min to 100° C. at an oxygen concentration of 20 ppm or less under a nitrogen stream, and then It heat-processed at 100 degreeC for 30 minutes. After that, at 3.5 ° C./min, the temperature is raised to 200 ° C., 230 ° C. or 250 ° C., which is the curing temperature shown in Table 3, and then heat treatment is performed at the curing temperature after the temperature increase shown in Table 3 for 1 hour, and the pattern forming film is cured and a cured film was obtained.

After the wafer was taken out at a temperature of 50 DEG C or lower, the wafer was cut, and a circular pattern cross-sectional shape of 5 mu m was observed and measured using a scanning electron microscope S-4800 (manufactured by Hitachi Hi-Tech). In addition, the angle of the inclination side was calculated|required as the inclined side of what connected the upper opening pattern and the lower opening pattern by a straight line.

As a result, when the angle of the inclination side was 40 degrees or more and 80 degrees or less, it evaluated as 2 as favorable, and when it was 2, 40 degrees or less, or 80 degrees or more, it evaluated as 1 as bad.

(2) Evaluation of chemical resistance of a resin composition that does not have photosensitivity

A varnish was prepared and applied on an 8-inch silicon wafer by a spin coating method using a coating/developing device ACT-8 (manufactured by Tokyo Electron Co., Ltd.) so that the film thickness after heat treatment was 7 µm, and pre-baked. It performed and produced the prebaking film|membrane. All prebaking was performed at 110 degreeC for 3 minutes. Thereafter, using a 2.38 mass % aqueous solution of tetramethylammonium (TMAH) (manufactured by Tama Chemical Co., Ltd.), development was performed under the condition that the change in the film thickness of the unexposed part before and after development was 1.5 µm, followed by rinsing with pure water, It swung to dryness, and the developed resin film was obtained.

Then, using an inert oven (Kyoyo Thermo System Co., Ltd., CLH-21CD-S), the coating film was heated from 50 ° C. to 3.5 ° C./min at an oxygen concentration of 20 ppm or less under a nitrogen stream, from 50 ° C. to 100 ° C. Then, it heat-processed at 100 degreeC for 30 minutes. After that, at 3.5 ° C. / min, the temperature is raised to 200 ° C., 230 ° C. or 250 ° C., which is the curing temperature shown in Table 3, and then, heat treatment is performed at the curing temperature after the temperature increase shown in Table 3 for 1 hour to cure the coating film, A cured film was obtained. In addition, the film thickness of the coating film after prebaking and image development is measured using Dainippon Screen Seijo Co., Ltd. product optical interference type film thickness measuring apparatus lambda ace STM-602, the refractive index is 1.629, The film|membrane of a cured film The thickness was measured with a refractive index of 1.629.

The cured film obtained by taking out a silicon wafer when temperature became 50 degrees C or less was immersed in the stripper which consists of NMP/DMSO/ethanolamine =70/20/10, and it processed at 70 degreeC for 30 minutes. After that, the presence or absence of peeling and elution was observed, and the rate of change of the film thickness was measured.

As a result, when the rate of change in film thickness before and after immersion is 5% or less, 3 is very good, 2 is good when the rate of change in film thickness exceeds 5% and is 10% or less, and the rate of change in film thickness exceeds 10% or peeling or dissolution When this was observed, it was evaluated as 1 as defective. When the numerical value of a film thickness change rate is small, it shows that chemical-resistance is better.

(3) HAST tolerance evaluation of the resin composition which does not have photosensitivity on a copper wiring board In performing peeling evaluation in copper wiring, the following evaluation board|substrates were prepared. Copper wirings having a thickness of 3 µm, a width of 50 µm and a wiring spacing of 100 µm were formed on an 8-inch silicon wafer. This was used as an evaluation board|substrate.

The varnish was applied and prebaked by spin coating using a coating/developing apparatus ACT-8 (manufactured by Tokyo Electron Co., Ltd.) on the evaluation substrate to have a film thickness of 7 µm after heat treatment, and prebaking. curtain was made All prebaking was performed at 110 degreeC for 3 minutes. Thereafter, using an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.), the temperature was raised from 50° C. to 3.5° C./min to 100° C. at an oxygen concentration of 20 ppm or less under a nitrogen stream, and then It heat-processed at 100 degreeC for 30 minutes. After that, at 3.5 ° C./min, the temperature is raised to 200 ° C., 230 ° C. or 250 ° C., which is the curing temperature shown in Table 3, and then heat treatment is performed at the curing temperature after the temperature increase shown in Table 3 for 1 hour, and the prebaked film is cured. and a cured film was obtained. The evaluation board|substrate (hereafter referred to as a sample) was taken out when the temperature had become 50 degrees C or less.

Next, the sample was put into a HAST apparatus, and the process was performed at the temperature of 130 degreeC, and 85% of humidity for 168 hours. After that, in order to take out the sample and observe peeling between the resin composition and copper wiring, the sample was cut using a scanning electron microscope Versa 3D Dual Beam (manufactured by FEI Co., Ltd.) with a converged ion beam processing device. , and cross-sectional observation was performed at a magnification of 50,000 times.

As a result, no peeling between the resin composition and copper wiring was confirmed as 2 as very good, 1 as slightly defective when some defects such as peeling or voids were confirmed, and 0 as bad when defects such as peeling or voids were confirmed as a whole. evaluated. It shows that HAST resistance is so good that there are few peelings, a void, etc.

<Evaluation of the resin composition which has photosensitivity>

(4) Evaluation of the opening pattern shape of a cured film comprising a resin composition having photosensitivity

A varnish was prepared and applied onto an 8-inch silicon wafer by a spin coating method using a coating/developing apparatus ACT-8 (manufactured by Tokyo Electron Co., Ltd.) so that the film thickness after heat treatment was 7 µm, followed by prebaking. It performed and produced the prebaking film|membrane. Prebaking was performed at 110 degreeC for 3 minutes. Then, it exposed with the exposure amount of 100-800 mJ/cm<2>, respectively using an i-line|wire stepper (Nikon Co., Ltd. product, NSR-2205i14). The size of the circular pattern used for exposure is 5 mu m. After exposure, using a 2.38 mass % aqueous solution of tetramethylammonium (TMAH) (manufactured by Tama Chemical Co., Ltd.), development was performed under the condition that the film thickness change of the unexposed part before and after development was 1.5 µm, followed by rinsing with pure water, Diffusion drying was carried out to obtain a pattern-forming film. In addition, the film thickness after prebaking and image development was measured using Dainippon Screen Seijo Co., Ltd. product optical interference type film thickness measuring apparatus lambda ace STM-602, and made refractive index 1.629.

After development, using an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.), the temperature was raised from 50° C. to 3.5° C./min to 100° C. at an oxygen concentration of 20 ppm or less under a nitrogen stream, and then It heat-processed at 100 degreeC for 30 minutes. After that, at 3.5 ° C./min, the temperature is raised to 200 ° C., 230 ° C. or 250 ° C., which is the curing temperature shown in Table 4, and then heat treatment is performed at the curing temperature after the temperature increase shown in Table 4 for 1 hour, and the pattern forming film is cured and a cured film was obtained.

After the wafer was taken out at a temperature of 50 DEG C or lower, the wafer was cut, and a circular pattern cross-sectional shape of 5 mu m was observed and measured using a scanning electron microscope S-4800 (manufactured by Hitachi Hi-Tech). In addition, the angle of the inclination side was calculated|required as the inclined side of what connected the upper opening pattern and the lower opening pattern by a straight line.

As a result, when the angle of the inclination side was 40 degrees or more and 80 degrees or less, it evaluated as 2 as favorable, and when it was 40 degrees or less, or 80 degrees or more, it evaluated as 1 as bad.

(5) Evaluation of chemical resistance of a resin composition having photosensitivity

Except for those shown in Table 4, it is the same as in (2) above.

(6) HAST tolerance evaluation of the resin composition which has photosensitivity on a copper wiring board

Except for those shown in Table 4, it is the same as (3) above.

<Synthesis Example 1 Synthesis of hydroxyl group-containing diamine compound>

18.3 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (manufactured by Central Glass Co., Ltd., hereinafter referred to as BAHF) in 100 mL of acetone and propylene oxide (Tokyo Kasei) It was dissolved in 17.4 g (0.3 mol) of Co., Ltd. product, and cooled to -15 degreeC. A solution obtained by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Kasei Co., Ltd.) in 100 mL of acetone was added dropwise thereto. After completion of dripping, it stirred at -15 degreeC for 4 hours, and returned to room temperature after that. The precipitated white solid was filtered out and vacuum-dried at 50 degreeC.

30 g of the obtained white solid was put in a 300 mL stainless steel autoclave, it was disperse|distributed to 250 mL of methyl cellusolve, and 2 g of 5% palladium-carbon (made by Wako Pure Chemical Industries, Ltd.) was added. Hydrogen was introduced here by balloon, and the reduction reaction was performed at room temperature. After about 2 hours, it was confirmed that the balloon did not retract more than this, and the reaction was terminated. After completion of the reaction, it was filtered to remove the palladium compound as a catalyst, and concentrated with a rotary evaporator to obtain a hydroxyl group-containing diamine compound represented by the following formula.

<Synthesis Example 2 Synthesis of phenol trinuclear>

In a 100 mL two-necked flask equipped with a cooling tube and a thermometer, 3.2 g (30 mmol) of m-cresol and 1.2 g (10 mmol) of p-hydroxybenzaldehyde were charged, and dissolved in 10 mL of 2-ethoxyethanol. After adding 1 mL of sulfuric acid while cooling in an ice bath, it was made to react by heating and stirring at 100 degreeC for 2 hours. After the reaction, the obtained solution was subjected to a reprecipitation operation with water to obtain a crude product. After re-dissolving the crude product in acetone and performing a reprecipitation operation with water, the obtained product was filtered and dried in a vacuum to obtain a phenol trinuclear compound represented by the following formula.

<Synthesis Example 3 Synthesis of phenol trinuclear>

In a 100 mL two-necked flask equipped with a cooling tube and a thermometer, 3.2 g (30 mmol) of m-cresol and 1.4 g (10 mmol) of p-hydroxyacetophenone were charged and dissolved in 10 mL of 2-ethoxyethanol. After adding 1 mL of sulfuric acid while cooling in an ice bath, it was made to react by heating and stirring at 100 degreeC for 2 hours. After the reaction, the obtained solution was subjected to a reprecipitation operation with water to obtain a crude product. After re-dissolving the crude product in acetone and performing reprecipitation with water, the obtained product was subjected to filtration and vacuum drying to obtain a phenol trinuclear compound represented by the following formula.

<Synthesis Example 4 Synthesis of polybenzoxazole precursor (A-1)>

Under dry nitrogen stream, 4,4'-diaminodiphenyl ether (hereinafter referred to as 4,4'-DAE) 1.5 g (0.0075 mol), BAHF 12.8 g (0.035 mol), RT-1000 (HUNTSMAN Co., Ltd.) First) 5.0 g (0.0050 mol) was dissolved in 100 g of NMP. Here, diimidazole dodecanoic acid (7.4 g, 0.023 mol) and PBOM (8.1 g, 0.023 mol) were added together with 25 g of NMP, and reacted at 85°C for 3 hours. Next, SiDA 0.6g (0.0025 mol), ODPA 0.8g (0.0025 mol), NA 0.8g (0.0050 mol) were added together with NMP 25g, and it was made to react at 85 degreeC for 1 hour. After completion of the reaction, the mixture was cooled to room temperature, 13.2 g (0.25 mol) of acetic acid was added together with 25 g of NMP, and the mixture was stirred at room temperature for 1 hour. After completion of stirring, the solution was poured into 1.5 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water 3 times, and then dried in a ventilation dryer at 50°C for 3 days to obtain a powder of a polybenzoxazole precursor (A-1).

<Synthesis Example 5 Synthesis of polybenzoxazole precursor (A-2)>

Under a stream of dry nitrogen, 27.5 g of BAHF, (0.075 mol) was dissolved in 257 g of NMP. Here, 17.2 g (0.048 mol) of PBOM was added together with 20 g of NMP, and reacted at 85° C. for 3 hours. Then, 20.0 g (0.02 mol) of RT-1000 (manufactured by HUNTSMAN Co., Ltd.), 1.2 g (0.005 mol) of SiDA, and 14.3 g (0.04 mol) of PBOM were added together with 50 g of NMP, and reacted at 85°C for 1 hour. . Further, as an end-sealing agent, 3.9 g (0.024 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride was added together with 10 g of NMP, followed by reaction at 85°C for 30 minutes. After completion of the reaction, the mixture was cooled to room temperature, 52.8 g (0.50 mol) of acetic acid was added together with 87 g of NMP, and the mixture was stirred at room temperature for 1 hour. After completion of stirring, the solution was added to 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water 3 times, and then dried in a ventilation dryer at 50°C for 3 days to obtain a powder of a polybenzoxazole precursor (A-2).

<Synthesis Example 6 Synthesis of polyimide precursor (A-3)>

In a dry nitrogen stream, 51.9 g (0.086 mol) of the hydroxyl group-containing diamine obtained in Synthesis Example 1 and 1.0 g (0.004 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (hereinafter referred to as SiDA) was dissolved in 200 g of NMP. 31.0 g (0.10 mol) of 4,4'- oxydiphthalic anhydride (henceforth ODPA) was added here, and it stirred at 40 degreeC for 2 hours. Then, 1.1 g (0.01 mol) of 3-aminophenol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as an end-sealing agent was added together with 10 g of NMP, followed by reaction at 40°C for 1 hour. Then, the solution which diluted 7.1 g (0.06 mol) of dimethylformamide dimethyl acetal (Mitsubishi Rayon Co., Ltd. product, hereafter called DFA) with 5g of NMP was dripped. After dripping, stirring was continued at 40 degreeC for 2 hours. After the stirring was completed, the solution was poured into 2 L of water, and the precipitate of the polymer solid was collected by filtration. Furthermore, 2L of water wash|cleaned 3 times, the collected polymer solid was dried with 50 degreeC vacuum dryer for 72 hours, and the polyimide precursor (A-3) was obtained.

<Synthesis Example 7 Synthesis of polyimide precursor (A-4)>

Under a stream of dry nitrogen, 41.1 g (0.068 mol) of the hydroxyl group-containing diamine obtained in Synthesis Example 1, a diamine containing propylene oxide and a tetramethylene ether glycol structure (RT-1000, manufactured by HUNTSMAN Co., Ltd.)) 18.0 g ( 0.018 mol) and 1.0 g (0.004 mol) of SiDA were dissolved in 200 g of NMP. 31.0 g (0.10 mol) of ODPA was added here, and it stirred at 40 degreeC for 2 hours. Then, 1.1 g (0.01 mol) of 3-aminophenol as an end-sealing agent was added together with 10 g of NMP and reacted at 40° C. for 1 hour. Then, the solution which diluted DFA (Mitsubishi Rayon Co., Ltd. product) 6.0 g (0.05 mol) with NMP 5g was dripped. After dripping, stirring was continued at 40 degreeC for 2 hours. After the stirring was completed, the solution was poured into 2 L of water, and the precipitate of the polymer solid was collected by filtration. Furthermore, it wash|cleaned 3 times with 2 L of water, and the polymer solid collected was dried with 50 degreeC vacuum dryer for 72 hours, and the polyimide precursor (A-4) was obtained.

<Synthesis Example 8 Synthesis of polyimide (A-5)>

Under a stream of dry nitrogen, 29.3 g (0.08 mol) of BAHF, 1.2 g (0.005 mol) of SiDA, and 3.3 g (0.03 mol) of 3-aminophenol as an end-sealing agent were dissolved in 80 g of NMP. 31.2 g (0.1 mol) of ODPA was added here with NMP 20g, it was made to react at 60 degreeC for 1 hour, and then it stirred at 180 degreeC for 4 hours. After completion of stirring, the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water 3 times, and then dried with a vacuum dryer at 80°C for 20 hours to obtain a powder of polyimide (A-5).

<Synthesis Example 9 Synthesis of phenol resin (B-1)>

In a dry nitrogen stream, 108.1 g (1.0 mol) of m-cresol, 34.0 g (0.32 mol) of benzaldehyde, 90.4 g (0.74 mol) of salicylaldehyde, 200 g of ethanol and 8.6 g (0.05 mol) of paratoluenesulfonic acid were put into the reaction vessel. and reacted under reflux at 65°C for 18 hours. After neutralizing the reaction system with caustic soda, methyl isobutyl ketone and water were added, and liquid washing was performed 5 times. The methyl isobutyl ketone was distilled off under reduced pressure at 100 degreeC with the evaporator, and the phenol resin (B-1) was obtained. The ratio of the number of structural units represented by general formula (5) and general formula (6) is general formula (5): general formula (6) = 70:30.

<Synthesis Example 10 Synthesis of phenol resin (B-2)>

In a dry nitrogen stream, 108.1 g (1.0 mol) of m-cresol, 11.7 g (0.11 mol) of benzaldehyde, 116.0 g (0.95 mol) of salicylaldehyde, 200 g of ethanol and 8.6 g (0.05 mol) of para-toluenesulfonic acid were put into the reaction vessel. and reacted under reflux at 65°C for 18 hours. After neutralizing the reaction system with caustic soda, methyl isobutyl ketone and water were added, and liquid washing was performed 5 times. Methyl isobutyl ketone was distilled off under reduced pressure at 100°C with an evaporator to obtain a phenol resin (B-2). The ratio of the number of structural units represented by general formula (5) and general formula (6) is general formula (5): general formula (6) = 90:10.

<Synthesis Example 11 Synthesis of phenol resin (B-3)>

Under a stream of dry nitrogen, 108.1 g (1.0 mol) of m-cresol, 44.6 g (0.42 mol) of benzaldehyde, 76.9 g (0.63 mol) of salicylaldehyde, 200 g of ethanol and 8.6 g (0.05 mol) of paratoluenesulfonic acid were put into the reaction vessel. and reacted under reflux at 65°C for 18 hours. After neutralizing the reaction system with caustic soda, methyl isobutyl ketone and water were added, and liquid washing was performed 5 times. Methyl isobutyl ketone was distilled off under reduced pressure at 100°C with an evaporator to obtain a phenol resin (B-3). The ratio of the number of structural units represented by General Formula (5) and General Formula (6) is General Formula (5): General Formula (6)=60:40.

<Synthesis Example 12 Synthesis of phenol resin (B-4)>

In a dry nitrogen stream, 108.1 g (1.0 mol) of m-cresol, 128.2 g (1.05 mol) of salicylaldehyde, 200 g of ethanol and 8.6 g (0.05 mol) of para-toluenesulfonic acid were put into a reaction vessel, and refluxed at 65° C. for 18 hours. reacted. After neutralizing the reaction system with caustic soda, methyl isobutyl ketone and water were added, and liquid washing was performed 5 times. Methyl isobutyl ketone was distilled off under reduced pressure at 100°C with an evaporator to obtain a phenol resin (B-4). The ratio of the number of structural units represented by general formula (5) and general formula (6) is general formula (5): general formula (6) = 100: 0.

<Synthesis Example 13 Synthesis of phenol resin (B-5)>

In a dry nitrogen stream, 108.1 g (1.0 mol) of m-cresol, 56.2 g (0.53 mol) of benzaldehyde, 64.7 g (0.53 mol) of salicylaldehyde, 200 g of ethanol and 8.6 g (0.05 mol) of para-toluenesulfonic acid were put into the reaction vessel. and reacted under reflux at 65°C for 18 hours. After neutralizing the reaction system with caustic soda, methyl isobutyl ketone and water were added, and liquid washing was performed 5 times. Methyl isobutyl ketone was distilled off under reduced pressure at 100°C with an evaporator to obtain a phenol resin (B-5). The ratio of the number of structural units represented by General Formula (5) and General Formula (6) is General Formula (5): General Formula (6)=50:50.

<Synthesis Example 14 Synthesis of phenol resin (B-6)>

Under a dry nitrogen stream, 108.1 g (1.0 mol) of m-cresol, 38.4 g (0.32 mol) of acetophenone, 100.8 g (0.74 mol) of 4-hydroxyacetophenone, 200 g of 2-ethoxyethanol and 8.6 g of paratoluenesulfonic acid ( 0.05 mol) was put into a reaction vessel and reacted at 120°C for 18 hours. After neutralizing the reaction system with caustic soda, methyl isobutyl ketone and water were added, and liquid washing was performed 5 times. Methyl isobutyl ketone was distilled off under reduced pressure at 100°C with an evaporator to obtain a phenol resin (B-6). The ratio of the number of structural units represented by general formula (5) and general formula (6) is general formula (5): general formula (6) = 70:30.

<Synthesis Example 15 Synthesis of phenol resin (B-7)>

Under a dry nitrogen stream, 320.4 g (1.0 mol) of the trinuclear phenol compound obtained in Synthesis Example 2, 34.0 g (0.32 mol) of benzaldehyde, 90.4 g (0.74 mol) of salicylaldehyde, 200 g of ethanol, and 8.6 g (0.05 mol) of para-toluenesulfonic acid ) was put into a reaction vessel and reacted under reflux at 65°C for 18 hours. After neutralizing the reaction system with caustic soda, methyl isobutyl ketone and water were added, and liquid washing was performed 5 times. The methyl isobutyl ketone was distilled off under reduced pressure at 100 degreeC with the evaporator, and the phenol resin (B-7) was obtained. The ratio of the number of structural units represented by general formula (5) and general formula (6) is general formula (5): general formula (6) = 70:30.

<Synthesis Example 16 Synthesis of Phenolic Resin (B-8)>

Under a dry nitrogen stream, 320.4 g (1.0 mol) of the trinuclear phenol compound obtained in Synthesis Example 2, 11.7 g (0.11 mol) of benzaldehyde, 116.0 g (0.95 mol) of salicylaldehyde, 200 g of ethanol, and 8.6 g (0.05 mol) of para-toluenesulfonic acid ) was put into a reaction vessel and reacted under reflux at 65°C for 18 hours. After neutralizing the reaction system with caustic soda, methyl isobutyl ketone and water were added, and liquid washing was performed 5 times. Methyl isobutyl ketone was distilled off under reduced pressure at 100°C with an evaporator to obtain a phenol resin (B-8). The ratio of the number of structural units represented by general formula (5) and general formula (6) is general formula (5): general formula (6) = 90:10.

<Synthesis Example 17 Synthesis of phenol resin (B-9)>

Under a stream of dry nitrogen, 320.4 g (1.0 mol) of the trinuclear phenol compound obtained in Synthesis Example 2, 44.6 g (0.42 mol) of benzaldehyde, 76.9 g (0.63 mol) of salicylaldehyde, 200 g of ethanol, and 8.6 g (0.05 mol) of para-toluenesulfonic acid ) was put into a reaction vessel and reacted under reflux at 65°C for 18 hours. After neutralizing the reaction system with caustic soda, methyl isobutyl ketone and water were added, and liquid washing was performed 5 times. Methyl isobutyl ketone was distilled off under reduced pressure at 100°C with an evaporator to obtain a phenol resin (B-9). The ratio of the number of structural units represented by General Formula (5) and General Formula (6) is General Formula (5): General Formula (6)=60:40.

<Synthesis Example 18 Synthesis of phenol resin (B-10)>

Under a dry nitrogen stream, 320.4 g (1.0 mol) of the trinuclear phenol compound obtained in Synthesis Example 2, 38.4 g (0.32 mol) of acetophenone, 100.8 g (0.74 mol) of 4-hydroxyacetophenone, 200 g of 2-ethoxyethanol and 8.6 g (0.05 mol) of para-toluenesulfonic acid was put into the reaction vessel, and it was made to react at 120 degreeC for 18 hours. After neutralizing the reaction system with caustic soda, methyl isobutyl ketone and water were added, and liquid washing was performed 5 times. Methyl isobutyl ketone was distilled off under reduced pressure at 100°C with an evaporator to obtain a phenol resin (B-10). The ratio of the number of structural units represented by general formula (5) and general formula (6) is general formula (5): general formula (6) = 70:30.

<Synthesis Example 19 Synthesis of phenol resin (B-11)>

Under dry nitrogen stream, 70.2 g (0.65 mol) of m-cresol, 37.8 g (0.35 mol) of p-cresol, 37% by weight, 75.5 g (0.93 mol) of formaldehyde aqueous solution, 0.63 g (0.005 mol) of oxalic acid dihydrate , After putting 264 g of methyl isobutyl ketone into the flask, it was immersed in an oil bath, and polycondensation reaction was performed for 4 hours while refluxing the reaction solution. Thereafter, the temperature of the oil bath was raised over 3 hours, and then the pressure in the flask was reduced to 40 to 67 hPa to remove volatiles, and then cooled to room temperature to obtain a polymer solid of a phenol resin (B-11). The weight average molecular weight calculated|required by GPC was 3500.

<Synthesis Example 20 Synthesis of photosensitizer (quinonediazide compound) (D-1)>

Under dry nitrogen stream, 4,4'-[1-[4-[1-(4-hydroxyphenyl-1)-1-methylethyl]phenyl]ethylidene]bisphenol (manufactured by Honshu Chemical Industry Co., Ltd.; (hereinafter referred to as TrisP-PA), 21.2 g (0.05 mol) and 5-naphthoquinonediazidesulfonic acid chloride (Toyogosei Co., Ltd., NAC-5) 37.5 g (0.14 mol) to 450 g of γ-butylolactone It was dissolved in room temperature. 12.7 g of triethylamine mixed with 50 g of (gamma)-butylollactone was dripped here so that the inside of a system might not become 35 degreeC or more. After dripping, it stirred at 40 degreeC for 2 hours. The triethylamine salt was filtered, and the filtrate was thrown into water. Thereafter, the precipitated precipitate was collected by filtration and further washed with 1 L of 1% hydrochloric acid. Then, it wash|cleaned 2 more times with 2L of water. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (D-1) represented by the following formula.

<Synthesis Example 21 Synthesis of photosensitizer (quinonediazide compound) (D-2)>

Under dry nitrogen stream, 4,4'-[1-[4-[1-(4-hydroxyphenyl-1)-1-methylethyl]phenyl]ethylidene]bisphenol (manufactured by Honshu Chemical Industry Co., Ltd.; (hereinafter referred to as TrisP-PA), 21.2 g (0.05 mol) and 4-naphthoquinonediazide sulfonic acid chloride (Toyogosei Co., Ltd., NAC-5) 37.5 g (0.14 mol) to 450 g of γ-butylolactone It was dissolved in room temperature. 12.7 g of triethylamine mixed with 50 g of (gamma)-butylollactone was dripped here so that the inside of a system might not become 35 degreeC or more. After dripping, it stirred at 40 degreeC for 2 hours. The triethylamine salt was filtered, and the filtrate was thrown into water. Thereafter, the precipitated precipitate was collected by filtration and further washed with 1 L of 1% hydrochloric acid. Then, it wash|cleaned 2 more times with 2L of water. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (D-2) represented by the following formula.

The structure and solvent of (C-1) component, (C-2) component, (C-3) component, (C-4) component, (C-5) component used for the Example and the comparative example are shown below.

(C-1): YX-4000HK [biphenyl type cyclic ether type thermal crosslinking agent] (manufactured by Mitsubishi Chemical Co., Ltd.)

(C-3): TMOM-BP [biphenyl type alkoxymethyl type thermal crosslinking agent] (manufactured by Honshu Chemical Industry Co., Ltd.)

(C-4): HMOM-TPHAP [triphenylmethane type alkoxymethyl type thermal crosslinking agent] (manufactured by Honshu Kagaku Kogyo Co., Ltd.)

Solvent: Gamma Butylolactone (GBL)

[Examples 1-23, 25-43, Comparative Examples 1-16]

To (A) resins (A-1) to (A-5) obtained in Synthesis Examples 4 to 8, (B) Phenolic resins (B-1) to (B-11), (C) obtained in Synthesis Examples 9 to 19 ) Thermal crosslinking agents (C-1) to (C-5), the photosensitive compounds (D-1) and (D-2) obtained in Synthesis Examples 20 to 21 were added in parts by mass shown in Tables 1 and 2 to obtain GBL as a solvent. was used to make varnish. These characteristics were measured by the said evaluation method. A component and a measurement result are shown to Tables 3-4.

[Table 1]

[Table 2-1]

[Table 2-2]

[Table 3]

[Table 4-1]

[Table 4-2]

1: display device
2: light emitting element
3: cured film
4, 4c: metal wiring
5: counter substrate
6: electrode terminal
7: light emitting element driving board
8: drive element
9: barrier metal
10 : Solder Vamp
11: bulkhead
12: the overall thickness of the cured film
13: substrate
14: slope
15: the angle of the inclined side
16: cured film

Claims (13)

(A) at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, polybenzoxazole precursor, and copolymers thereof;
(B) a phenolic resin;
(C) thermal crosslinking agent
As a resin composition comprising a,
(B) the phenol resin has a structural unit represented by the general formula (4), the structural unit represented by the general formula (4) has the structural units of the general formulas (5) and (6),
When the number of all structural units represented by general formula (4) in the said (B) phenol resin is 100, the ratio of the number of structural units represented by general formula (5) and general formula (6) is general formula (5): The resin composition of general formula (6) = 60:40-90:10.

(In general formula (4), R ²⁵ and R ²⁷ each independently represent a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. When a plurality of R ²⁵ and R ²⁷ exist, each may be the same or different. R ²⁶ is hydrogen Represents an atom or a monovalent organic group having 1 to 20 carbon atoms, j1 and j2 each independently represent an integer of 0 to 3)

(In the general formula (5), R ²⁵ represents a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. When a plurality of R ²⁵ is present, each may be the same or different. R ²⁶ is a hydrogen atom or 1 having 1 to 20 carbon atoms. represents a valent organic ^group.R28 represents a monovalent organic group having 1 to 10 carbon ^atoms.When there are a plurality of R28s, each may be the same or different.j1 and j4 are each independently an integer of 0 to 3, j3 is an integer of 1 to 3 represents an integer.)

(In general formula (6), R ²⁵ represents a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. When a plurality of R ²⁵ is present, each may be the same or different. R ²⁶ is a hydrogen atom or 1 having 1 to 20 carbon atoms. Represents a valent organic group. R ²⁸ represents a monovalent organic group having 1 to 10 carbon atoms. When there are a plurality of R ²⁸ , each may be the same or different. j1 and j4 each independently represent an integer of 0 to 3.) The method of claim 1,
(C) A resin composition containing the thermal crosslinking agent having a structural unit represented by the general formula (14) and/or the thermal crosslinking agent having a biphenyl structure which may have a substituent.

(In the general formula (14), R ⁴² is an alkylene group having 1 to 15 carbon atoms or a divalent organic group having an alkylene ether group, and R ⁴³ and R ⁴⁴ each independently represent a hydrogen atom or a methyl group.) 3. The method of claim 2,
(C) When the total amount of the thermal crosslinking agent is 100% by mass, the content ratio of the thermal crosslinking agent having a biphenyl structure which may have a substituent and the thermal crosslinking agent having a structural unit represented by the general formula (14) is 15% by mass or more The resin composition which is 80 mass % or less. 4. The method of claim 2 or 3,
A resin composition in which a thermal crosslinking agent having a biphenyl structure which may have a substituent contains the structure of the general formula (12) or (13).

(In formula (12), R ²⁹ and R ³⁰ each independently represent a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. When a plurality of R ²⁹ and R ³⁰ are present, they may be the same or different. R ³¹ , R ³² represents a thermal crosslinking group, m1 and m2 each independently represent an integer of 0 to 4, m3 and m4 each independently represent an integer of 1 to 3, 1≤m1+m3≤5, 1≤m2+m4≤5 satisfies.)

(In the general formula (13), R ³³ , R ³⁴ , R ³⁵ and R ³⁶ each independently represent a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. R ³³ , R ³⁴ , R ³⁵ and R ³⁶ are When there is a plurality, each may be the same or different.R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ represent a thermal crosslinking group R ⁴¹ represents a monovalent organic group having 1 to 10 carbon atoms n1 , n4 , n5 and n8 are each independently as an integer from 1 to 3, n2, n3, n6, and n7 are each independently an integer from 0 to 4, n9 represents a repeating unit, an integer from 1 to 10, and n10 represents an integer of 0 or 1.) 5. The method according to any one of claims 2 to 4,
The (C) thermal crosslinking agent contains the thermal crosslinking agent having a biphenyl structure which may have a substituent, and the content of the thermal crosslinking agent having a biphenyl structure which may have a substituent is (B) 100 parts by mass of the phenol resin The resin composition which is 30 mass parts or more and 150 mass parts or less with respect to it. 6. The method according to any one of claims 1 to 5,
Moreover, (D) The resin composition containing a photosensitive compound. The resin sheet formed in the base material using the resin composition in any one of Claims 1-6. The cured film which hardened|cured the resin composition in any one of Claims 1-6, or the resin sheet of Claim 7. 9. The method of claim 8,
The said cured film has an opening pattern, The cured film whose angles of the inclined side in the said opening pattern cross section are 40 degrees or more and 80 degrees or less. The resin composition of any one of Claims 1-6 is apply|coated to a board|substrate, or the resin sheet of Claim 7 is laminated on a board|substrate, After that,
The manufacturing method of a cured film including the process of drying and forming a resin film, the exposure process of exposing the dried resin film, the developing process of developing the exposed resin film, and the heat processing process of heat-processing the developed resin film. The semiconductor device which has the cured film of Claim 8. An organic EL display device having at least a TFT substrate, a planarization layer, a first electrode, an insulating layer, a light emitting layer, and a second electrode, wherein the planarization layer or the insulating layer contains the cured film according to claim 8 . A display device having at least metal wiring, the cured film according to claim 8, and a plurality of light emitting elements, wherein the light emitting element has a pair of electrode terminals on either surface, and the pair of electrode terminals is the cured film A display device configured to be connected to a plurality of the metal wires extending in the middle, and the plurality of the metal wires to maintain electrical insulation by the cured film.

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