JP2018123103A - Diamine compound, and heat-resistant resin and resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition that makes it possible to obtain a cured film having excellent chemical resistance and film properties even with low-temperature heating at 200°C or less, and a heat-resistant resin used for the resin composition and also a diamine compound that serves raw materials therefor.SOLUTION: The present invention provides a diamine compound represented by formula (1) (Rand Rare a divalent aliphatic group; A is a divalent aliphatic group, an alicyclic group, an aromatic group, a divalent organic group in which a plurality of aromatic groups are bonded together via a single bond, or a divalent organic group in which a plurality of aromatic groups are bonded together via -O-, -S-, -CO-, -SO-, -CH-, -C(CH)-, or -C(CF)-; p, q and an integer of 0-3).SELECTED DRAWING: None

Description

  The present invention relates to a novel diamine compound, a heat resistant resin using the same, and a resin composition using the heat resistant resin. More specifically, the present invention relates to a photosensitive resin composition suitable for a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, and the like.

  Conventionally, polyimide resins, polybenzoxazole resins, and the like that are excellent in heat resistance, mechanical properties, and the like have been widely used for surface protective films and interlayer insulating films of semiconductor elements of electronic devices (Patent Document 1). When polyimide or polybenzoxazole is used as a surface protective film or an interlayer insulating film, one method for forming a through hole or the like is etching using a positive photoresist. However, this method has a problem that it requires a step of applying and removing a photoresist and is complicated. Therefore, studies have been made on heat-resistant materials imparted with photosensitivity for the purpose of rationalizing work processes (Patent Document 2).

  In general, polyimide and polybenzoxazole thermally dehydrate and cyclize their precursor coating film to obtain a thin film having excellent heat resistance and mechanical properties. In that case, high temperature firing is usually required at around 350 ° C. However, for example, MRAM (Magnetic Resistive Access Memory), which is promising as a next generation memory, and a sealing resin are vulnerable to high temperatures. Therefore, in order to use it as a surface protection film of such an element or an interlayer insulating film of a fan-out wafer level package that forms a rewiring structure on a sealing resin, it is cured by baking at a low temperature of about 200 ° C. or less. There is a demand for polyimide resins or polybenzoxazole resins that can obtain characteristics comparable to those obtained by firing conventional materials at a high temperature around 350 ° C.

  When the resin composition is used for applications such as semiconductors, the film after heat-curing remains as a permanent film in the device. Therefore, the physical properties of the cured film, particularly the elongation, is very important. In addition, when used as an insulating film between wiring layers of a wafer level package, chemical processing is repeatedly performed at the time of forming metal wiring, so that chemical resistance that can withstand the processing is required.

  For these problems, a method using a polybenzoxazole precursor having an aliphatic group (Patent Document 3) and a photosensitive resin composition containing a novolak resin having a crosslinkable group has been proposed (Patent Document). 4).

JP-A-11-199557 Japanese Patent Laid-Open No. 11-24271 JP 2008-224984 A JP 2011-197362 A

  However, the polybenzoxazole precursor having an aliphatic group has a problem of poorer chemical resistance as the curing temperature becomes lower. Moreover, the photosensitive resin composition containing the novolak resin which has a crosslinkable group had a problem inferior in elongation.

  The present invention has been made in view of the problems associated with the prior art as described above, and a resin composition capable of obtaining a cured film having excellent chemical resistance and film characteristics even at a low-temperature heat treatment of 200 ° C. or lower. And a heat resistant resin used in the resin composition, and further, a diamine compound as a raw material thereof.

  In order to solve the above problems, the present invention relates to the following.

  That is, it is related with the diamine compound represented by General formula (1).

(In the general formula (1), R ¹ and R ² are hydrogen atom, halogen atom, hydroxyl group, nitro group, cyano group, aliphatic group, aromatic group, acetyl group, carboxyl group, ester group, amide group, imide. Represents an organic group having any one of a group, a urea group, and a urethane group, p and q are integers in the range of 0 to 3. A is a divalent aliphatic group, alicyclic group, or aromatic group. The aromatic group is —O—, —CO—, —SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, or —C (CF ₃ ) ₂ — (where F is fluorine). A bonded divalent organic group, a divalent organic group in which a plurality of aromatic groups are bonded by a single bond, or a plurality of aromatic groups are —O—, —CO—, —SO ₂ —, —CH _{2. -, - C (CH 3)} 2 -, or _{-C (CF 3) 2 - :(} 2 divalent organic group where F coupled with fluorine) In some cases, it indicates a.)
Moreover, it is related with the heat resistant resin which has a structure derived from the diamine compound as described in General formula (1).

  The present invention also relates to a resin composition containing the heat resistant resin, a photosensitive compound and a solvent.

  A step of applying the resin composition on a substrate and drying to form a resin film, or a step of laminating a resin sheet formed from the resin composition on a substrate to form a resin film; and a mask It is related with the manufacturing method of the cured film including the process of exposing via a process, the process of eluting or removing an irradiation part with an alkaline solution, and the process of heat-processing the resin film after image development.

  The present invention also relates to an interlayer insulating film or a semiconductor protective film, a semiconductor electronic component, and a semiconductor device in which the cured film is disposed.

  A resin composition capable of obtaining a cured film having excellent chemical resistance and film characteristics even at a low-temperature heat treatment of 200 ° C. or lower, a heat-resistant resin used in the resin composition, and these raw materials A diamine compound is provided.

It is the figure which showed the expanded cross section of the pad part of the semiconductor device which has a bump. It is the figure which showed the detailed manufacturing method of the semiconductor device which has a bump. It is sectional drawing of the manufacturing process of the semiconductor device which shows the Example of this invention. It is sectional drawing of the coil components of the inductor apparatus which shows the Example of this invention.

  Hereinafter, the present invention will be described in detail.

<Diamine compound represented by the general formula (1)>
The present invention is a diamine compound represented by the general formula (1). In the diamine compound represented by the general formula (1), R ¹ and R ² are hydrogen atom, halogen atom, hydroxyl group, nitro group, cyano group, aliphatic group, aromatic group, acetyl group, carboxyl group, ester group. , An organic group having any one of an amide group, an imide group, a urea group, and a urethane group. p and q are integers within a range of 0 to 3. A is a divalent aliphatic group, alicyclic group, aromatic group, aromatic group is —O—, —CO—, —SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, Or a divalent organic group bonded by —C (CF ₃ ) ₂ —: (where F is fluorine), a divalent organic group having a plurality of aromatic groups bonded by a single bond, or a plurality of aromatic groups The group was bonded with —O—, —CO—, —SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, or —C (CF ₃ ) ₂ —: where F is fluorine. In the case of a divalent organic group,

  In general formula (1), since A has an aliphatic group, the diamine compound itself can be dehydrated and ring-closed at 200 ° C. or lower to have an oxazole structure, thereby obtaining high chemical resistance even at low temperature curing. In addition, a highly stretched cured film can be obtained due to the flexibility of the aliphatic group.

  A in the general formula (1) is preferably a divalent aliphatic group represented by the general formula (2) or the general formula (3). The divalent aliphatic group represented by the general formula (2) or the general formula (3) is preferable because it has high flexibility and thus has a high effect of improving elongation.

(In General Formula (2), R ^{3 to} R ⁶ each independently represent an alkylene group having 1 to 10 carbon atoms, and a, b, and c are 1 ≦ a ≦ 20, 0 ≦ b ≦ 20, 0, respectively. Represents an integer within the range of ≦ c ≦ 20, and the arrangement of repeating units may be block or random, provided that the structures shown in parentheses are different, and * indicates a chemical bond.)

(In General Formula (3), R ⁷ and R ⁸ are each independently hydrogen, fluorine, or an alkyl group having 1 to 6 carbon atoms, n ₁ represents an integer of ₁ to 20, and * represents a chemical bond. Show.)
n ₁ is preferably 3 or more from the viewpoint of stretchability, and preferably 12 or less from the heat resistance of the resulting compound.

<The manufacturing method of the diamine compound represented by General formula (1)>
The diamine compound represented by the general formula (1) can be produced according to a known method for producing a diamine compound. Although not particularly limited, the following method can be employed.

  As the first step, a dinitro compound can be obtained by reacting an aminonitrophenol compound with a carboxylic acid dichloride compound.

  As the second step, the diamine represented by the general formula (1) can be obtained by reducing the dinitro compound obtained in the first step. This reduction method includes a method in which hydrogen gas is allowed to act in the presence of a metal catalyst such as palladium / carbon and Raney nickel, a method in which ammonium formate is allowed to act in the presence of a metal catalyst such as palladium / carbon and Raney nickel, stannous chloride And a method using hydrochloric acid, a method using iron and hydrochloric acid, a method using hydrazine, and the like.

<Heat resistant resin of the present invention>
The heat resistant resin of the present invention is preferably a heat resistant resin having a structure derived from the above-described diamine compound of the present invention.

  Moreover, it is preferable that the heat resistant resin of this invention is a heat resistant resin which has 1 or more types of structural units selected from General formula (4), General formula (5), and General formula (6).

(In the general formulas (4) to (6), B is an organic group represented by the general formula (7). X ¹ represents a divalent to hexavalent organic group, and X ² and X ³ are each independently 4 to 10-valent organic group, R represents hydrogen or an organic group having 1 to 20 carbon atoms, and p, q, and r are each independently an integer of 0 to 4.)

(In General Formula (7), R ⁹ and R ¹⁰ represent a divalent aliphatic group. C represents a divalent aliphatic group, an alicyclic group, an aromatic group, or a plurality of aromatic groups in a single bond. A bonded divalent organic group or a plurality of aromatic groups are —O—, —S—, —CO—, —SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, or —C. In the case of a divalent organic group bonded by (CF ₃ ) ₂ —: (where F is fluorine), s and t are integers in the range of 0 to 3. * is chemical Indicates binding.)
The organic group represented by the general formula (7) represents a structure derived from the diamine compound of the present invention.

  The heat resistant resin of the present invention preferably contains one or more kinds of resins selected from polyimide, polyamide, polybenzoxazole, precursors thereof, and copolymers thereof.

  In addition, one or more kinds of resins selected from polyimide, polyamide, polybenzoxazole, precursors thereof, and copolymers thereof may include general formula (4), general formula (5), and general formula (6). It is preferable to have one or more types of structural units selected from

  Although not limited, the polyamide is a structure represented by the general formula (8), and the polyimide precursor is a structure represented by the general formula (9), and the polyimide is represented by the general formula (10). It is preferable that the polybenzoxazole is a structure represented by the general formula (11).

(In General Formulas (8) to (11), Y ^{1 to} Y ³ each independently represent a ⁴ to 6 valent organic group, Y ⁴ represents a 6 to 8 valent organic group, and X ⁴ represents 2 to 6 X ⁵ and X ⁶ each independently represent a 4 to 10 valent organic group, X ⁷ represents a 2 to 6 valent organic group, and R represents hydrogen or an organic group having 1 to 20 carbon atoms. And v, x, z, and m are each independently an integer of 2 to 4, and u, w, y, and k are each independently an integer of 0 to 4.)
In the general formulas (8) and (11), X ⁴ and X ⁷ represent a divalent to hexavalent organic group having 2 or more carbon atoms and represent an acid structural component. X ⁴ and X ⁷ are terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid, aromatic dicarboxylic acid such as bis (carboxyphenyl) propane, cyclobutanedicarboxylic acid, cyclohexanedicarboxylic acid, malonic acid, dimethylmalonic acid, ethyl Malonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid Glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, Octafluoroadipic acid, 3-methylazi Acid, octafluoroadipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic 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, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid , Tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosandioic acid, triacontanedioic acid, hentriacontandioic acid, dotriacontanedioic acid, diglycolic acid and other aliphatic dicarboxylic acids Acids and tricarric acids such as trimellitic acid and trimesic acid Acid, those in which a part of hydrogen atoms of these aromatic rings and hydrocarbons are substituted with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, and the like, and —S—, —SO— , —SO ₂ —, —NH—, —NCH ₃ —, —N (CH ₂ CH ₃ ) —, —N (CH ₂ CH ₂ CH ₃ ) —, —N (CH (CH ₃ ) ₂ ) —, — It is a structure derived from one containing a bond such as COO-, -CONH-, -OCONH-, or -NHCONH-.

Among these, a structure in which X ⁴ and X ⁷ are derived from an aromatic dicarboxylic acid is preferable because ring closure hardly occurs at the time of thermosetting, thereby suppressing an increase in stress due to film shrinkage and improving adhesion.

In producing the heat resistant resin of the present invention, when polycondensation is carried out, for example, a compound in which the carboxylic acid groups of X ¹ and X ⁴ are substituted with active carboxylic acid groups as shown in the following general formula (12) is used. It is done.

  In general formula (12), D and E are each independently a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, trifluoromethyl group, halogen group, phenoxy group, nitro group, etc. However, it is not limited to these.

  Among these, it is preferable to use an active carboxylic acid group other than the chloride compound. By using an active carboxylic acid group other than the chloride compound, chlorine ions in the resulting resin can be reduced, and peeling from the metal substrate due to the presence of chlorine ions can be prevented. Further, as the active carboxylic acid group, it is more preferable to use a diimidazolide compound. Since the leaving group of the diimidazolide compound becomes water-soluble imidazole, reprecipitation and washing of the obtained resin can be performed with water. Furthermore, since the detached imidazole is basic, it acts as a ring closure accelerator for the polyimide precursor structure during polymerization, and at the stage of producing the polyamide resin, it is possible to increase the ring closure rate of imidization. . As a result, the ring closure rate when a cured film is produced by heat treatment can be lowered.

In general formulas (8) to (10), Y ¹ to Y ³ represent tetravalent to hexavalent organic groups, Y ⁴ represents a 6 to 8 valent organic group, and represents an organic group derived from diamine. .

Since the heat resistant resin has a structure derived from the diamine compound represented by the general formula (1), Y ¹ to Y ⁴ in the general formulas (8) to (11) contain a phenolic hydroxyl group. By including a diamine residue having a phenolic hydroxyl group, moderate solubility of the resin in an alkaline developer can be obtained, so that a high contrast between the exposed area and the unexposed area can be obtained, and a desired pattern can be formed.

  The heat resistant resin used in the present invention may have a structure derived from a diamine compound having a phenolic hydroxyl group other than the diamine compound represented by the general formula (1).

  Specific examples include, for example, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, Bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, 2,2′-ditrifluoromethyl-5,5 Aromatic diamines such as' -dihydroxyl-4,4'-diaminobiphenyl, bis (3-amino-4-hydroxyphenyl) fluorene, 2,2'-bis (trifluoromethyl) -5,5'-dihydroxybenzidine Or some of these aromatic rings and hydrocarbon hydrogen atoms may be substituted with alkyl groups having 1 to 10 carbon atoms or fluoroalkyls. Group, compounds substituted with a halogen atom, and the like can be given. Diamine having a structure shown below, but are not limited to. Other diamine to be copolymerized can be used as it is or as a corresponding diisocyanate compound or trimethylsilylated diamine. Moreover, you may use combining these 2 or more types of diamine components.

  The heat resistant resin of the present invention may contain a diamine residue other than a diamine having a phenolic hydroxyl group. By copolymerizing these, heat resistance can be improved.

  Specific examples of the diamine residue having an aromatic group include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4 '-Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, m- Phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl Bis {4- (4-amino Enoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 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, Aromatic diamines such as 3,3 ′, 4,4′-tetramethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, and fragrances thereof Examples include compounds in which a part of hydrogen atoms of a group ring or hydrocarbon are substituted with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, etc., but are not limited thereto. There. Other diamine to be copolymerized can be used as it is or as a corresponding diisocyanate compound or trimethylsilylated diamine. Moreover, you may use combining these 2 or more types of diamine components.

  Moreover, it is preferable that the heat resistant resin of this invention contains the diamine residue which has an aliphatic group other than the diamine compound represented by General formula (1). Since the diamine residue having an aliphatic group has high affinity with a metal, it can be a resin having high metal adhesion. In addition, since aliphatic diamine has high basicity, it acts as a ring closure accelerator during polymerization, so that the ring closure rate of the imide skeleton can be increased at the stage of producing the polyamide resin. As a result, it is possible to reduce the ring closure rate during thermosetting, and to suppress the shrinkage of the cured film and the resulting increase in the stress of the cured film. As a result, it is possible to suppress a decrease in adhesion due to stress. Furthermore, since a flexible aliphatic diamine residue contributes to high elongation of polyamide, it is possible to obtain a cured film having improved adhesion to metal and having low stress and high elongation.

The diamine having an aliphatic group used in the heat resistant resin of the present invention preferably has an organic group of at least one of an alkylene group and an alkyl ether group. Specifically, it is a diamine selected from at least one of an alkylene group, a cycloalkyl group, an alkyl ether group, and a cycloalkyl ether group, and a part of hydrogen atoms of these hydrocarbons is substituted with an alkyl having 1 to 10 carbon atoms. May be substituted with a group, a fluoroalkyl group, a halogen atom, or the like, and —S—, —SO—, —SO ₂ —, —NH—, —NCH ₃ —, —N (CH ₂ CH ₃ ) —, — N (CH ₂ CH ₂ CH ₃ ) —, —N (CH (CH ₃ ) ₂ ) —, —COO—, —CONH—, —OCONH—, or —NHCONH— may be included. These organic groups may have an unsaturated bond or an alicyclic structure.

Specific examples of the diamine having an aliphatic 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 (cyclohex Silamine), 4,4′-methylenebis (2-methylcyclohexylamine), 1,2-bis (2-aminoethoxy) ethane, 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, trade name, manufactured by HUNTSMAN Co., Ltd.), and the following compounds, and these aromatic rings and carbonized A part of hydrogen atoms of hydrogen may be substituted with an alkylene group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, or the like, —S—, —SO—, —SO ₂ —, —NH—, —NCH ₃ —, —N (CH ₂ CH ₃ ) —, —N (CH ₂ CH ₂ CH ₃ ) —, —N (CH (CH ₃ ) ₂ )-, —COO—, —CONH—, —OCONH—, or —NHCONH— may be included.

In the present invention, the diamine having an aliphatic group is an organic group having at least one selected from an alkylene group and an alkyl ether group, and these are acyclic structures in which the main chain is a straight chain. Among these alkyl ethers, the tetramethylene ether group is superior in heat resistance and has been evaluated for reliability, because it provides flexibility and stretchability, and can achieve low stress and high elongation when used as a cured film. It is preferable because the metal adhesion can be imparted. Examples include, but are not limited to, RT-1000, HE-1000, HT-1100, HT-1700 (trade name, manufactured by HUNTSMAN Co., Ltd.) and the like.

  By using such a diamine having an aliphatic group, it is possible to impart low stress, high extensibility, and high metal adhesion to the resulting cured film while maintaining solubility in an alkaline solution. it can.

  In this invention, it is preferable that content of the diamine residue which has an aliphatic group is 5-40 mol% in all the diamine residues. By containing 5 mol% or more, the effect of high metal adhesion due to the diamine residue having an aliphatic group is obtained, and by containing 40 mol% or less, the hygroscopicity of the resin becomes low. Peeling can be prevented and a cured film having high reliability can be obtained, which is preferable.

  The arrangement of the repeating unit of the diamine residue having an aliphatic group may be block-like or random, but in addition to being able to impart high metal adhesion and low stress to the polyamide structure, the elongation is improved. It is preferably included in the structure.

  Furthermore, in order to improve the adhesion to the silicon substrate, the heat resistant resin of the present invention may copolymerize an aliphatic group having a siloxane structure. Specific examples of the diamine component include those obtained by copolymerizing 0.1 to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, and the like. .

Similarly, the general formula is a polyimide precursor structure (9) or the general formula a polyimide structure (10), X ^5, X ⁶ represents a residue of a dianhydride, a tetravalent to 10-valent Organic group.

  Specific examples of the acid dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 2,3,3 ′, 4′-biphenyltetracarboxylic acid. Dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′- Benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1- Bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxy Phenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid Anhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorenic dianhydride, 9,9-bis {4- (3,4-dicarboxyphenoxy) phenyl} fluorenic dianhydride, 2, 3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2- Aromatic tetracarboxylic dianhydrides such as bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, , 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3, 4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Acid dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic acid dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 3,5,6-tricarboxy-2-norbornane acetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (Tet Hydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione and acid dianhydrides having the structure shown in the following formula, aromatic rings and hydrocarbons thereof. Although the compound etc. which substituted a part of hydrogen atom by the C1-C10 alkyl group, a fluoroalkyl group, a halogen atom, etc. can be mentioned, It is not limited to these.

R ¹¹ represents an oxygen atom, a sulfur atom, —C (CF ₃ ) ₂ —, —C (CH ₃ ) ₂ — or —SO ₂ —, and R ¹² and R ¹³ represent a hydrogen atom, a hydroxyl group or a thiol group.

Of these, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′- Biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 2,2-bis ( 3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, Bis (3,4-dicarboxyfe Nyl) sulfone dianhydride, bis (3,4-
Dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 9 , 9-bis (3,4-dicarboxyphenyl) fluorenic dianhydride, 9,9-bis {4- (3,4-dicarboxyphenoxy) phenyl} fluorenic dianhydride, butanetetracarboxylic dianhydride 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (Tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione is preferred. These are used alone or in combination of two or more.

  R in the general formula (9) represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms. From the viewpoint of solubility in an alkaline developer and the solution stability of the resulting photosensitive resin composition, it is preferable that 10 mol% to 90 mol% of R is hydrogen. Furthermore, it is more preferable that R contains at least one monovalent hydrocarbon group having 1 to 16 carbon atoms, and the others are hydrogen atoms.

  The molar ratio of the structures represented by the general formulas (8) to (11) in the present invention can be obtained using a method of calculating from the molar ratio of monomers used for polymerization or a nuclear magnetic resonance apparatus (NMR). It can be confirmed by a method for detecting a peak of a polyamide structure, an imide precursor structure, or an imide structure in a cured resin, a photosensitive resin composition, or a cured film.

  The heat resistant resin of the present invention preferably has a weight average molecular weight in the range of 3,000 to 200,000. In this range, moderate solubility in an alkali developer can be obtained, so that a high contrast between the exposed area and the unexposed area can be obtained, and a desired pattern can be formed. In terms of solubility in an alkali developer, 100,000 or less is more preferable, and 50,000 or less is more preferable. Moreover, 10,000 or more are preferable from the surface of an elongation improvement.

  Here, the molecular weight can be measured by gel permeation chromatography (GPC) and converted from a standard polystyrene calibration curve.

  In order to improve the storage stability of the resin composition of the present invention, the heat-resistant resin is sealed with other end-capping agents such as monoamine, monocarboxylic acid, acid anhydride, monoactive ester compound at the main chain end. May be.

  The introduction ratio of the end-capping agent is preferably 0.1 mol% with respect to the total amine component in order to suppress the increase in the weight average molecular weight of the heat-resistant resin of the present invention and the decrease in solubility in an alkaline solution. As mentioned above, More preferably, it is 5 mol% or more. Moreover, in order to suppress that the mechanical characteristic of the cured film obtained when the weight average molecular weight of a polyamide resin becomes low is suppressed, Preferably it is 60 mol% or less, More preferably, it is 50 mol% or less. Further, a plurality of terminal blocking agents may be reacted to introduce a plurality of different terminal groups.

  Specific examples of monoamines used as end-capping agents include M-600, M-1000, M-2005, and M-2070 (above trade names, manufactured by HUNTSMAN Co., Ltd.), aniline, 2-ethynylaniline, and 3-ethynyl. Aniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-amino Naphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy -5-aminonaphthalene, 2-carboxy-7-aminonaphthalene 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-amino Salicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2 -Aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like can be used. Two or more of these may be used.

  Monocarboxylic acid and monoactive ester compound as end-capping agents are 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy -6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4 -Monocarboxylic acids such as carboxybenzenesulfonic acid and active ester compounds in which these carboxyl groups are esterified, phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydride Acid anhydrides such as xylphthalic anhydride, dicarboxylic acid phthalic acid, maleic acid, nadic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, and tricarboxylic acid, Trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2, Active ester compounds obtained by reacting one carboxyl group of dicarboxylic acids such as 6-dicarboxynaphthalene with N-hydroxybenzotriazole, imidazole, N-hydroxy-5-norbornene-2,3-dicarboximide, these Aromatic And a part of hydrogen atoms of a hydrocarbon, an alkyl group or a fluoroalkyl group having 1 to 10 carbon atoms, or the like can be used compounds substituted with a halogen atom. Two or more of these may be used.

  Moreover, the resin terminal and resin side chain of the heat resistant resin in the present invention preferably have a structure sealed with an imide precursor or imide such as amide acid or amide acid ester. Since the resin terminal has more parts that are in contact with other components and the substrate than the main chain of the resin, it is possible to enhance the adhesion and improve the storage stability of the resin composition. For this reason, it is preferable to have an imide precursor structure or an imide precursor structure, and the general formula (9), which is a polyimide precursor structure, or a general formula (10), which is a polyimide structure, is present near the end of the heat resistant resin. More preferably. Thereby, adhesiveness can be improved and the storage stability of alkali-soluble resin can further be improved. For this purpose, it is preferable to copolymerize the polyamide structure with at least one of a polyimide precursor structure and a polyimide structure after polymerization.

  The structure in which the resin terminal and the resin side chain of the heat resistant resin of the present invention are sealed with an imide precursor or imide such as amide acid or amide acid ester are phthalic anhydride, maleic anhydride, nadic acid anhydride, cyclohexanedicarboxylic acid. Acid anhydrides, acid anhydrides such as 3-hydroxyphthalic anhydride, dicarboxylic acid phthalic acid, maleic acid, nadic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid Or trimellitic acid, trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7 -Dicarboxynaphthalene, 2,6-dicarboxynaphthalene Active ester compounds obtained by reacting one carboxyl group of dicarboxylic acids with N-hydroxybenzotriazole, imidazole, N-hydroxy-5-norbornene-2,3-dicarboximide, aromatic rings and hydrocarbons thereof Is obtained from a compound in which a part of the hydrogen atom is substituted with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, or the like, but is not limited thereto.

The end capping agent that can be used in the present invention can be easily detected by the following method. For example, an alkali-soluble resin into which a terminal blocking agent has been introduced is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component, which are structural units, which are analyzed by gas chromatography (GC) or NMR. The end capping agent used in the invention can be easily detected. Apart from this, it can also be easily detected by directly measuring the alkali-soluble resin component into which the end-capping agent has been introduced, by pyrolysis gas chromatograph (PGC), infrared spectrum and ¹³ C-NMR spectrum.

  Although the heat resistant resin of this invention is synthesize | combined by the following method, for example, it is not limited to this.

  First, a compound obtained by substituting an active carboxylic acid group for a dicarboxylic acid, or an acid dianhydride, a diamine compound represented by the general formula (1), and other copolymerization components at room temperature, possibly at an elevated temperature, Dissolve in an organic solvent and then heat to polymerize. From the viewpoint of the stability of the solution at the time of reaction, it is preferable that the order of dissolution is performed first with a highly soluble diamine compound. Thereafter, in some cases, other copolymerization components are added, and an acid or acid anhydride to be used as a terminal blocking agent is added for polymerization.

  When introducing the diamine having an aliphatic group other than the diamine compound represented by the general formula (1), the reaction is preferably performed at -20 to 200 ° C.

  The polyimide precursor structure is a structure derived from an acid anhydride in the polymerization method. In the case of an amic acid ester, the polyimide precursor structure is obtained by reacting a carboxylic acid with an esterifying agent after the polymerization.

  The heat-resistant resin of the present invention preferably contains polyimide. For example, the polyimide obtains an imide precursor using a method for producing a structure represented by the general formula (9), and this is −20. A method of polymerizing at ˜200 ° C., a method of closing all imide rings of the imide precursor using a known imidization reaction method, a method of stopping the imidation reaction in the middle and introducing a part of the imide structure, Can be synthesized using a method of introducing a part of the imide structure by mixing the polyimide precursor with a closed ring imide polymer in which all of the imide rings of the imide precursor are closed.

  The benzoxazole used in the present invention can be synthesized by using, for example, a method of obtaining a polybenzoxazole precursor and heating and closing the ring at 150 to 350 ° C., or adding an acidic catalyst and closing the ring. . Examples of the organic solvent used for polymerizing the resin include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N, N ′. -Dimethylpropylene urea, N, N-dimethylisobutyric acid amide, amides of methoxy-N, N-dimethylpropionamide, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α- Cyclic esters such as methyl-γ-butyrolactone, carbonates such as ethylene carbonate and propylene carbonate, glycols such as triethylene glycol, phenols such as m-cresol and p-cresol, acetophenone, 1,3-dimethyl-2 -Imidazolidinone, sulfolane, Methyl sulfoxide, tetrahydrofuran, dimethyl sulfoxide, propylene glycol monomethyl ether acetate, but and ethyl lactate are not limited thereto.

  It is preferable that the heat-resistant resin of the present invention is polymerized by the above-described method, then poured into a large amount of water or a mixed solution of methanol and water, precipitated, filtered, dried and isolated. The drying temperature is preferably 40 to 100 ° C, more preferably 50 to 80 ° C. By this operation, unreacted monomers and oligomer components such as dimers and trimers are removed, and the film characteristics after thermosetting can be improved.

In the present invention, the imidization rate can be easily determined by, for example, the following method. First, the infrared absorption spectrum of the polymer is measured, and the presence of an absorption peak (near 1780 cm ^−1, near 1380 cm ⁻¹ ) of the imide structure due to polyimide is confirmed. Next, the polymer was heat-treated at 350 ° C. for 1 hour, an infrared absorption spectrum was measured using a sample having an imidization rate of 100%, and the peak intensity around 1380 cm ⁻¹ of the resin before and after the heat treatment was compared, thereby performing heat treatment. The content of imide groups in the pre-resin is calculated to determine the imidization rate. The imidation rate is preferably 50% or more, and more preferably 80% or more, because the change in the ring closure rate during thermosetting is suppressed and the effect of reducing the stress is obtained.

In the present invention, the oxazolation rate can be easily determined by, for example, the following method. First, the infrared absorption spectrum of the polymer is measured, and the presence of an absorption peak (near 1570 cm ^−1, near 1050 cm ⁻¹ ) of the imide structure attributed to polyimide is confirmed. Next, the polymer was heat-treated at 350 ° C. for 1 hour, an infrared absorption spectrum was measured using a sample having an oxazolation rate of 100%, and the peak intensity in the vicinity of 1570 cm ⁻¹ of the resin before and after the heat treatment was compared. The content of oxazole groups in the pre-resin is calculated to determine the oxazolation rate. Since the change in the ring closure rate during thermosetting is suppressed and the effect of reducing the stress is obtained, the oxazolation rate is preferably 50% or more, and more preferably 80% or more.

  The heat resistant resin of the present invention can be used as a resin composition.

  It is preferable to use a resin composition containing the heat resistant resin of the present invention, (b) a photosensitive compound, and (c) a solvent.

  Among these, (b) the resin composition using the photoacid generator as the photosensitive compound can be used as a positive photosensitive resin composition (positive photosensitive varnish).

  Moreover, the resin composition using the photopolymerizable compound as the photosensitive compound (b) can be used as a negative photosensitive resin composition (negative photosensitive varnish).

  Both types of photosensitive compounds are used depending on the application.

  Since the positive photosensitive composition generally has a higher resolution than the negative photosensitive composition, it is preferably used for the purpose of forming a fine processed pattern.

  As the photoacid generator of the positive photosensitive resin composition, a quinonediazide compound is preferably used.

  As quinonediazide compounds, quinonediazide sulfonic acid is ester-bonded to a polyhydroxy compound, quinonediazide sulfonic acid is sulfonamide-bonded to a polyamino compound, and quinonediazide sulfonic acid is ester-bonded and / or sulfonamide to a polyhydroxypolyamino compound. Examples include those that are combined. Although all the functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds may not be substituted with quinonediazide, it is preferable that 40 mol% or more of the entire functional groups are substituted with quinonediazide on average. . By using such a quinonediazide compound, a positive photosensitive resin composition that is sensitive to i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp, which is a general ultraviolet ray. Can be obtained.

  Specific examples of the polyhydroxy compound 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, Methylenetris-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 (above, trade name, manufactured by Honshu Chemical Industry), 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 (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.), 2 , 6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, book Chemical Co., Ltd.), there may be mentioned a novolak resin, but are not limited to.

  Specific examples of the polyamino compound include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4. Examples thereof include, but are not limited to, '-diaminodiphenyl sulfide.

  Specific examples of the polyhydroxypolyamino compound include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3′-dihydroxybenzidine, but are not limited thereto. .

  Among these, it is preferable that a quinonediazide compound contains an ester with a phenol compound and a 4-naphthoquinonediazidesulfonyl group. Thereby, high sensitivity and higher resolution can be obtained by i-line exposure.

  1-50 mass parts is preferable with respect to 100 mass parts of resin, and, as for content of the quinonediazide compound used for the photosensitive resin composition of this invention, 10-40 mass parts is more preferable. By making the content of the quinonediazide compound within this range, it is possible to achieve higher sensitivity by obtaining the contrast between the exposed part and the unexposed part, and there is no residue generated when the content is high. preferable. Furthermore, you may add a sensitizer etc. as needed.

  The content of the photopolymerizable compound in the resin composition of the present invention is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the heat resistant resin, and 5 to 150 parts by mass from the viewpoint of compatibility. Is more preferable. By making content of a photopolymerizable compound into 5 mass parts or more, the elution of the exposure part at the time of image development can be prevented, and the resin composition with a high residual film rate after image development can be obtained. Moreover, the whitening of the film | membrane at the time of film formation can be suppressed because content of a photopolymerizable compound shall be 200 mass parts or less.

  Moreover, it is preferable that the resin composition of this invention contains the compound represented by following General formula (13).

  By containing the compound represented by the general formula (13), it is possible to improve the elongation characteristics of the cured film after the reliability evaluation and the adhesion to the metal material.

  The compound represented by the general formula (13) acts as an antioxidant to suppress oxidative deterioration of the aliphatic group or phenolic hydroxyl group of the heat-resistant resin. Moreover, metal oxidation can be suppressed by the antirust effect | action to a metal material.

In General Formula (13), R ¹⁶ represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, and R ¹⁸ represents an organic group having 2 or more carbon atoms. R ¹⁷ represents a 1 to 4 valent organic group containing at least one of an alkylene group having 2 or more carbon atoms, an O atom, and an N atom. Since k represents an integer of 1 to 4 and can act on the heat-resistant resin and the metal material at the same time, k is more preferably an integer of 2 to 4. R ¹⁸ includes alkyl group, alkylene group, cycloalkyl group, alkoxy group, alkyl ether group, alkylsilyl group, alkoxysilyl group, aryl group, aryl ether group, carboxyl group, carbonyl group, allyl group, vinyl group, complex Examples thereof include a cyclic group, —O—, —NH—, —NHNH—, a combination thereof, and the like, and may further have a substituent. Of these, alkyl ether and —NH— are preferable from the viewpoint of solubility in a developer and metal adhesion, and —NH from the viewpoint of interaction with a heat-resistant resin and metal complex formation. -Is more preferable.

  Examples of the compound represented by the general formula (13) include the following, but are not limited to the following structures.

  Moreover, 0.1-10 mass parts is preferable with respect to heat resistant resin, and, as for the addition amount of the compound represented by General formula (13), 0.5-5 mass parts is more preferable. When the added amount is less than 0.1 parts by mass, it is difficult to obtain the effect of improving the elongation properties after reliability and the adhesion to the metal material. When the added amount is more than 10 parts by mass, the interaction with the photosensitive agent is difficult. There is a risk of lowering the sensitivity of the resin composition.

  The resin composition of the present invention preferably further contains (d) a compound having two or more groups of at least any one of alkoxymethyl groups and methylol groups.

  (D) A compound having two or more of at least any one of an alkoxymethyl group and a methylol group (hereinafter sometimes abbreviated as (d) compound) is a compound that acts as a thermal crosslinking agent.

  By having at least two of these groups, it is possible to form a crosslinked structure by condensation reaction with the resin and the same kind of molecules. By using in combination with a photoacid generator or a photopolymerization initiator, a wider range of designs is possible to improve sensitivity and mechanical properties of the cured film.

  Preferred examples of such a compound include, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML- PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DMLBisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMO -BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark) MX-290, NIKALAC MX-280, NIKACALAC MX- 270, NIKACALAC MX-279, NIKACALAC MW-100LM, NIKACALAC MX-750LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.). Two or more of these may be contained. Among these, when HMOM-TPHAP and MW-100LM are added, reflow at the time of curing hardly occurs and the pattern becomes a high rectangle, which is more preferable.

  (D) The addition amount of the compound having at least two alkoxymethyl groups or methylol groups is preferably 10 to 60 parts by mass and more preferably 20 to 40 parts by mass with respect to the heat resistant resin. When the addition amount is more than 10 parts by mass, the crosslink density by the thermal crosslinking agent is high, so that the chemical resistance of the cured film is improved, and when it is less than 60 parts by mass, sufficient flexibility is obtained. This is preferable because high elongation can be obtained.

  The resin composition of the present invention can further improve elongation and reduce stress by containing a thermal crosslinking agent having a structural unit represented by the following general formula (14).

In General Formula (14), R ²⁰ and R ²¹ each independently represent a hydrogen atom or a methyl group. R ¹⁹ is a divalent organic group having an alkylene group having 2 or more carbon atoms, and may be linear, branched, or cyclic.

R ¹⁹ is an alkyl group, cycloalkyl group, alkoxy group, alkyl ether group, alkylsilyl group, alkoxysilyl group, aryl group, aryl ether group, carboxyl group, carbonyl group, allyl group, vinyl group, heterocyclic group, These may be combined, and may further have a substituent.

  Since the thermal crosslinking agent itself has a flexible alkylene group and a rigid aromatic group, it is possible to improve elongation and reduce stress while having heat resistance. Examples of the crosslinking group include, but are not limited to, an acrylic group, a methylol group, an alkoxymethyl group, and an epoxy group. Among these, an epoxy group is preferable because it can react with the phenolic hydroxyl group of the heat-resistant resin to improve the heat resistance of the cured film and can react without dehydration.

  Examples of the compound represented by the general formula (14) include, but are not limited to, the following structures.

(In the formula, n ₂ is an integer of 1 to 5, and n ₃ is an integer of 1 to 20.)
Among the above structures, n ₂ is preferably 1 to 2 and n ₃ is preferably ₃ to 7 from the viewpoint of achieving both heat resistance and elongation improvement.

  Moreover, you may contain the low molecular compound which has a phenolic hydroxyl group in the range which does not make the shrinkage | contraction residual film ratio after hardening small as needed. Thereby, the development time can be shortened.

  Examples of these compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP- CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP BIR-BIPC-F (trade name, manufactured by Asahi Organic Materials Co., Ltd.) and the like. Two or more of these may be contained.

  The content of the low molecular compound having a phenolic hydroxyl group is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the heat resistant resin.

  The resin composition of the present invention preferably contains (c) a solvent.

  (C) As a solvent, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, 1,3- Polar aprotic solvents such as dimethyl-2-imidazolidinone, N, N′-dimethylpropyleneurea, N, N-dimethylisobutyric acid amide, methoxy-N, N-dimethylpropionamide, tetrahydrofuran, dioxane, propylene glycol monomethyl Ethers, ethers such as propylene glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3- Esters such as chill-3-methoxybutyl acetate, ethyl lactate, methyl lactate, diacetone alcohol, 3-methyl-3-alcohols such as methoxy butanol, toluene, aromatic hydrocarbons such as xylene. Two or more of these may be contained.

  (C) The content of the solvent (in order to dissolve the composition with respect to 100 parts by mass of the heat resistant resin, it is preferable to contain 100 parts by mass or more, and to form a coating film having a thickness of 1 μm or more, It is preferable to contain 500 parts by mass or less.

  The resin composition of the present invention is a surfactant, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, ketones such as cyclohexanone and methyl isobutyl ketone for the purpose of improving the wettability with the substrate. , Ethers such as tetrahydrofuran and dioxane may be contained.

  In addition, in order to enhance the adhesion to the substrate, the resin composition of the present invention includes, as a silicon component, trimethoxyaminopropylsilane, trimethoxyepoxysilane, trimethoxyvinylsilane, trimethoxythiolpropyl as long as storage stability is not impaired. A silane coupling agent such as silane may be contained. The preferable content of the silane coupling agent is 0.01 to 5 parts by mass with respect to 100 parts by mass of the heat resistant resin.

  The resin composition of the present invention preferably has another alkali-soluble resin in addition to the heat-resistant resin of the present invention. Specifically, a siloxane resin, an acrylic polymer copolymerized with acrylic acid, a novolac resin, a resole resin, a polyhydroxystyrene resin, and a modified product in which a crosslinking group such as a methylol group, an alkoxymethyl group or an epoxy group is introduced, Examples thereof include copolymer polymers thereof. Such a resin is soluble in an alkaline solution such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, and sodium carbonate. By containing these alkali-soluble resins, the properties of each alkali-soluble resin can be imparted while maintaining the adhesion and excellent sensitivity of the cured film.

  Among them, in addition to improving the sensitivity, since the rate of change in shrinkage before and after curing is low, it is possible to reduce stress, so that novolak resins, resole resins, polyhydroxystyrene resins, methylol groups, alkoxymethyl A phenolic resin such as a modified body into which a crosslinking group such as a group or an epoxy group is introduced is preferred.

  As preferable content of these resin, it is 15-150 mass parts more preferably 5-200 mass parts with respect to 100 mass parts of heat resistant resins of this invention.

  Furthermore, the resin composition of the present invention may contain a dissolution regulator within a range that does not increase the shrinkage after curing. As the dissolution regulator, any compound can be preferably used as long as it is a compound generally used as a solubility regulator in a positive resist, such as a polyhydroxy compound, a sulfonamide compound, and a urea compound. In particular, a polyhydroxy compound which is a raw material for synthesizing a quinonediazide compound is preferably used.

  Moreover, the resin composition of this invention is a negative type insolubilized with light, when a photopolymerizable compound is mix | blended. A photopolymerizable compound contains a polymerizable unsaturated functional group. Examples of the polymerizable unsaturated functional group include unsaturated double bond functional groups such as vinyl group, allyl group, acryloyl group and methacryloyl group, and unsaturated triple bond functional groups such as propargyl. Among these, a group selected from a conjugated vinyl group, an acryloyl group, and a methacryloyl group is preferable in terms of polymerizability.

  The number of the functional groups contained is preferably 1 to 4 from the viewpoint of stability, and the groups may not be the same. The photopolymerizable compound preferably has a number average molecular weight of 30 to 800. When the number average molecular weight is in the range of 30 to 800, the compatibility with the polyamide is good and the stability of the resin composition solution is good.

  Preferred photopolymerizable compounds include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylol. Propane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, styrene, α-methylstyrene, 1,2-dihydronaphthalene, 1,3-diisopropenylbenzene, 3-methylstyrene, 4-methylstyrene, 2 -Vinyl naphthalene, butyl acrylate, butyl methacrylate, isobutyl acrylate, hexyl acetate Rate, isooctyl acrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol di Acrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tri Cyclodecanediacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetra Methacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-diacryloyloxy-2-hydroxypropane, 1,3-dimethacryloyloxy-2-hydroxy Propane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, 2,2,6,6-tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl acrylate, N- Methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl acrylate, ethylene oxide modified bisphenol A diacrylate , Ethylene oxide-modified bisphenol A dimethacrylate, N-vinylpyrrolidone, N-vinylcaprolactam and the like. These may be used alone or in combination of two or more.

  Among these, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, isobornyl acrylate, isobornyl methacrylate, pentaerythritol tris are particularly preferable. Acrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, 2,2,6 , 6-Tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl acetate Relate, N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl acrylate, ethylene oxide modified bisphenol A diacrylate, ethylene oxide modified bisphenol A dimethacrylate, N-vinyl pyrrolidone, N-vinyl caprolactam, etc. are mentioned.

  The viscosity of the resin composition of the present invention is preferably 2 to 5,000 mPa · s. The viscosity can be measured using an E-type rotational viscometer (for example, product name “VISCOMETER TV-22”, manufactured by TOKI SANGYO). By adjusting the solid content concentration so that the viscosity is 2 mPa · s or more, it becomes easy to obtain a desired film thickness. On the other hand, if the viscosity is 5,000 mPa · s or less, it becomes easy to obtain a highly uniform coating film. The resin composition having such a viscosity can be easily obtained by setting the solid content concentration to 5 to 60% by mass, for example.

  Next, a method for forming a resin sheet from the resin composition of the present invention, a method for forming a cured film obtained by curing the resin composition or the resin sheet, and a method for forming a relief pattern of the cured film will be described.

  First, the resin composition of the present invention is applied to a substrate. As substrates, silicon wafers, ceramics, gallium arsenide, organic circuit boards, inorganic circuit boards, composite substrates of silicon wafers and sealing resins such as epoxy resins, and circuit constituent materials are arranged on these boards Examples include, but are not limited to: Examples of organic circuit boards include: glass substrate copper-clad laminates such as glass cloth and epoxy copper-clad laminates, composite copper-clad laminates such as glass nonwoven fabrics and epoxy copper-clad laminates, temporary carrier substrates, polyetherimide Examples thereof include heat-resistant / thermoplastic substrates such as resin substrates, polyetherketone resin substrates and polysulfone resin substrates, polyester copper-clad film substrates, and polyimide copper-clad film substrates. Examples of inorganic circuit boards include glass substrates, alumina substrates, aluminum nitride substrates, ceramic substrates such as silicon carbide substrates, and metal substrates such as aluminum base substrates and iron base substrates. Examples of circuit components include conductors containing metals such as silver, gold and copper, resistors containing inorganic oxides, low dielectrics containing glass materials and / or resins, resins and high Examples thereof include high dielectric materials containing dielectric constant inorganic particles, insulators containing glass-based materials, and the like. Application methods include spin coating using spinner, spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure coater, screen coater, slit die coater. Or the like. Moreover, although a coating film thickness changes with application methods, solid content concentration of composition, viscosity, etc., it is normally applied so that the film thickness after drying is 0.1 to 150 μm.

  When it is set as a resin sheet and a resin sheet having photosensitivity, it can be formed by drying and then peeling.

  In order to enhance the adhesion between the substrate such as a silicon wafer and the resin composition, the substrate can be pretreated with the above-mentioned silane coupling agent. For example, a solution obtained by dissolving 0.5 to 20% by mass of a silane coupling agent in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. Surface treatment is performed by spin coating, dipping, spray coating, steam treatment or the like. In some cases, a heat treatment is subsequently performed at 50 ° C. to 300 ° C. to advance the reaction between the substrate and the silane coupling agent.

  Next, the substrate obtained by applying or laminating the resin composition or the resin sheet on the substrate is dried to obtain a resin film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like in the range of 50 ° C. to 150 ° C. for 1 minute to several hours.

  Next, the resin film is irradiated with actinic radiation through a mask having a desired pattern and exposed. As the actinic radiation used for exposure, there are ultraviolet rays, visible rays, electron beams, X-rays and the like. In the present invention, it is preferable to use i rays (365 nm), h rays (405 nm), and g rays (436 nm) of a mercury lamp. .

  In order to form a pattern, after exposure, a developing solution is used to remove an exposed portion in the case of a positive type and an unexposed portion in the case of a negative type.

  Developers include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl A solution of an alkaline compound such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine or hexamethylenediamine is preferred. In some cases, these alkaline solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added singly or in combination. Good. Development can be performed by spraying the developer onto the coating surface, immersing in the developer, applying ultrasonic waves while immersing, or spraying the developer while rotating the substrate. After development, it is preferable to rinse with water. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.

  After the development, a temperature of 150 ° C. to 500 ° C. is applied to advance the thermal crosslinking reaction. Crosslinking can improve heat resistance and chemical resistance. As a method for this heat treatment, a method of selecting a temperature and increasing the temperature stepwise, or a method of selecting a certain temperature range and continuously increasing the temperature for 5 minutes to 5 hours can be selected. As an example of the former, there is a method in which heat treatment is performed at 130 ° C. and 200 ° C. for 30 minutes each. An example of the latter is a method of linearly raising the temperature from room temperature to 400 ° C. over 2 hours.

  The curing condition in the present invention is preferably 150 ° C. or higher and 350 ° C. or lower. However, since the present invention provides a cured film particularly excellent in low-temperature curability, 160 ° C. or higher and 250 ° C. or lower is more preferable. 160 ° C. or more and 200 ° C. or less is more preferable in view of the influence of

  A cured film obtained by curing the resin composition or resin sheet of the present invention or a relief pattern of the cured film can be used as follows.

  That is, it can be used as an organic EL display device that is disposed on at least one of the planarization layer on the driving circuit and the first electrode.

  Further, it can be used as a semiconductor electronic component or a semiconductor device arranged as an interlayer insulating film between rewirings.

  Further, it can be used as a semiconductor electronic component or a semiconductor device arranged as an interlayer insulating film between rewirings on a sealing resin substrate on which a silicon chip is arranged.

  Furthermore, it can be used as a semiconductor electronic component or a semiconductor device arranged as an interlayer insulating film of an adjacent substrate made of two or more kinds of materials.

  In using a cured film or a cured pattern of a cured film obtained by curing the resin composition or resin sheet of the present invention for a semiconductor electronic component or a semiconductor device, specifically, a semiconductor passivation film, a surface protection film of a semiconductor element It is suitably used for applications such as interlayer insulating films, interlayer insulating films for multilayer wiring for high-density mounting, and insulating layers for organic electroluminescent elements. Of course, the present invention is not limited to this, and various structures can be adopted.

  Next, an application example using the resin composition or resin sheet of the present invention to a semiconductor device having bumps will be described with reference to the drawings (Application Example 1).

  FIG. 1 is an enlarged cross-sectional view of a pad portion of a semiconductor device having a bump according to the present invention. As shown in FIG. 1, a passivation film 3 is formed on an input / output aluminum (hereinafter, Al) pad 2 in a silicon wafer 1, and a via hole is formed in the passivation film 3. Further, an insulating film 4 is formed thereon as a pattern made of the resin composition of the present invention, and further, a metal (Cr, Ti, etc.) film 5 is formed so as to be connected to the Al pad 2 and the metal is formed by electrolytic plating or the like. Wiring (Al, Cu, etc.) 6 is formed. The metal film 5 etches the periphery of the solder bump 10 to insulate between the pads. A barrier metal 8 and a solder bump 10 are formed on the insulated pad. The resin composition of the insulating film 7 can be processed with a thick film in the scribe line 9. When a flexible component is introduced into the resin composition, since the wafer warpage is small, exposure and wafer transportation can be performed with high accuracy. In addition, since the resin of the present invention is also excellent in high extensibility, since the resin itself is deformed, stress from the sealing resin can be relieved even during mounting, so that damage to bumps, wirings, and low-k layers can be reduced. And a highly reliable semiconductor device can be provided.

  Next, a detailed method for manufacturing the semiconductor device is described with reference to FIGS. As shown in 2a of FIG. 2, an input / output Al pad 2 and a passivation film 3 are formed on the silicon wafer 1, and an insulating film 4 is formed as a pattern of the resin composition of the present invention. Subsequently, as shown in 2b of FIG. 2, a metal (Cr, Ti, etc.) film 5 is formed so as to be connected to the Al pad 2, and as shown in 2c of FIG. 2, the metal wiring 6 is formed by a plating method. Form a film. Next, as shown in 2d 'of FIG. 2, the resin composition of the present invention is applied, and the insulating film 7 is formed in a pattern as shown in 2d of FIG. 2 through a photolithography process. A wiring (so-called rewiring) can be further formed on the insulating film 7. In the case of forming a multilayer wiring structure having two or more layers, a multilayer wiring in which rewiring of two or more layers is separated by an interlayer insulating film obtained from the resin composition of the present invention by repeating the above steps. A structure can be formed. At this time, the formed insulating film comes into contact with various chemicals a plurality of times, but the insulating film obtained from the resin composition of the present invention is excellent in adhesion and chemical resistance. A multilayer wiring structure can be formed. There is no upper limit to the number of layers in the multilayer wiring structure, but 10 or fewer layers are often used.

  Next, as shown in 2e and 2f of FIG. 2, a barrier metal 8 and a solder bump 10 are formed. Then, the wafer is diced along the last scribe line 9 and cut into chips.

  Next, application example 2 to the semiconductor device having bumps using the resin composition of the present invention will be described with reference to the drawings.

  FIG. 3 is an enlarged cross-sectional view of a pad portion of a semiconductor device having an insulating film of the present invention, and shows a structure called a fan-out wafer level package (fan-out WLP). Similar to the first application example, the silicon wafer 1 on which the Al pad 2 and the passivation film 3 are formed is diced and cut into chips, and then sealed with a resin 11. Over this sealing resin 11 and the chip, an insulating film 4 is formed as a pattern of the resin composition of the present invention, and further, a metal (Cr, Ti, etc.) film 5 and a metal wiring 6 are formed. Thereafter, a barrier metal 8 and a solder bump 10 are formed in the opening of the insulating film 7 formed on the sealing resin outside the chip. The fan-out WLP is provided with an extended portion using a sealing resin such as epoxy resin around the semiconductor chip, rewiring from the electrode on the semiconductor chip to the extended portion, and mounting a solder ball on the extended portion. This is a semiconductor package that secures the necessary number of terminals. In the fan-out WLP, wiring is installed so as to straddle the boundary line formed by the main surface of the semiconductor chip and the main surface of the sealing resin. That is, an interlayer insulating film is formed on a base material made of two or more materials such as a semiconductor chip provided with metal wiring and a sealing resin, and wiring is formed on the interlayer insulating film.

  In addition, the fan-out WLP is disposed as an interlayer insulating film between rewirings on a support substrate on which a temporary bonding material is disposed, and after a silicon chip and a sealing resin are disposed on the support substrate, the temporary bonding material is disposed on the support substrate. There is a type of package that is created in the process of peeling the substrate and the rewiring. In this type of package, a glass substrate or the like that is more likely to warp than a silicon wafer is often used as a support substrate, and therefore it is preferable that the insulating film has low stress.

  In addition to this, in a semiconductor package of a type in which a semiconductor chip is embedded in a recess formed in a glass epoxy resin substrate, wiring is installed so as to straddle the boundary line between the main surface of the semiconductor chip and the main surface of the printed circuit board. . Also in this aspect, an interlayer insulating film is formed on a base material made of two or more materials, and wiring is formed on the interlayer insulating film. The cured film formed by curing the resin composition of the present invention has high elongation and high adhesion to a semiconductor chip provided with metal wiring, and also has high adhesion to the sealing resin to an epoxy resin or the like. Therefore, it is suitably used as an interlayer insulating film provided on a substrate made of two or more materials.

  Further, in the fan-out WLP, rewiring has been miniaturized. The cured film of the resin composition of the present invention is suitable for fine rewiring because it has a high metal adhesion even for a wiring in which the width of the metal wiring and the distance between adjacent wirings are 5 μm or less. Next, an application example 3 of the inductor device to a coil component using the resin composition of the present invention will be described with reference to the drawings. 4 is a cross-sectional view of a coil component having an insulating film of the present invention. As shown in FIG. 3, an insulating film 13 is formed on the substrate 12, and an insulating film 14 is formed thereon as a pattern. As the substrate 12, ferrite or the like is used. The resin composition of the present invention may be used for either the insulating film 13 or the insulating film 14. A metal (Cr, Ti, etc.) film 15 is formed in the opening of this pattern, and a metal wiring (Ag, Cu, etc.) 16 is formed thereon by plating. The metal wiring 16 (Ag, Cu, etc.) is formed on the spiral. The function as a coil can be given by repeating the steps 13 to 16 a plurality of times and laminating them. Finally, the metal wiring 16 (Ag, Cu, etc.) is connected to the electrode 18 by the metal wiring 17 (Ag, Cu, etc.) and sealed with the sealing resin 19.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited by these examples. First, an evaluation method in each example and comparative example will be described. For the evaluation, a resin composition (hereinafter referred to as varnish) filtered in advance with a 1 μm polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) was used.

(1) Weight average molecular weight measurement The molecular weight of the heat-resistant resin was measured using a GPC (gel permeation chromatography) apparatus Waters 2690-996 (manufactured by Nihon Waters Co., Ltd.) and the developing solvent was N-methyl-2-pyrrolidone (hereinafter NMP The weight average molecular weight (Mw) was calculated in terms of polystyrene.

(2) Ring closure rate and polyimidation rate of polyhydroxyamide In the calculation of the ring closure rate in this example, a varnish was spin-coated on a silicon wafer and dried at 120 ° C. for 3 minutes to obtain a coating film having a thickness of 5 μm. It was. Furthermore, this coating film is heated at 180 ° C. for 10 minutes or at 300 to 350 ° C. for 10 minutes to obtain a cured film (cured film (A) heated at 180 ° C., cured film (B) heated at 300 to 350 ° C.). Obtained. The infrared absorption spectra of these cured film (A) and cured film (B) were measured, and the absorbance of the peak due to the oxazole ring stretching vibration near 1570 cm ⁻¹ was determined. The ring closure rate of the cured film (A) was calculated with the ring closure rate of the polyhydroxyamide of the cured film (B) as 100%.

  Since the solubility at the time of thermosetting is suppressed and an effect of high chemical resistance is obtained, the ring closure rate of polyhydroxyamide is preferably 50% or more.

Moreover, about the imidation rate, the light absorbency of the peak resulting from the CN stretching vibration near the absorption peak (1377 cm < ^-1 >) of the imide structure resulting from a polyimide was calculated | required. The imidization rate of the cured film (A) was calculated with the imidization rate of the cured film (B) as 100%.

  The imidation rate is preferably 50% or more, and more preferably 80% or more, because the solubility during thermosetting is suppressed and the effect of high chemical resistance is obtained.

(3) Evaluation of chemical resistance Varnish was applied on a 6-inch silicon wafer. Using a coating and developing apparatus Mark-7, the film thickness after prebaking at 120 ° C. for 3 minutes was adjusted to 11 μm. The coating method used was a spin coating method. After pre-baking, using an inert oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.), the temperature was raised to 180 ° C. at 3.5 ° C./min with an oxygen concentration of 20 ppm or less, and heat treatment was performed at 180 ° C. for 1 hour. Was done. When the temperature became 50 ° C. or lower, the wafer was taken out, measured for film thickness, and then immersed in a solvent for resist stripping solution ST-120 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 60 ° C. for 30 minutes. After the wafer taken out from the solvent is washed with pure water, the film thickness is measured again. If the absolute value of the change rate exceeds 20% or the cured film is peeled off (C), within 20% Thus, a value exceeding 10% was acceptable (B), and a value within 10% was regarded as good (A).

(4) Evaluation of elongation (high elongation)
The varnish was applied and prebaked on an 8-inch silicon wafer by spin coating using a coating / developing apparatus ACT-8 so that the film thickness after pre-baking at 120 ° C. for 3 minutes was 11 μm, and then an inert oven CLH- Using 21CD-S (manufactured by Koyo Thermo System Co., Ltd.), the temperature was raised to 180 ° C. at 3.5 ° C./min with an oxygen concentration of 20 ppm or less, and heat treatment was performed at 180 ° C. for 1 hour. When the temperature became 50 ° C. or lower, the wafer was taken out and immersed in 45% by mass of hydrofluoric acid for 5 minutes to peel off the resin composition film from the wafer. This film was cut into strips having a width of 1 cm and a length of 9 cm, and using Tensilon RTM-100 (manufactured by Orientec Co., Ltd.) at a room temperature of 23.0 ° C. and a humidity of 45.0% RH, a tensile rate of 50 mm / The sample was pulled in minutes and the elongation at break was measured. The measurement was performed on 10 strips per specimen, and the average value of the top 5 points was obtained from the results. An elongation at break value of 90% or more is very good (A), 70% or more and less than 90% is good (B), 40% or more and less than 70% is acceptable (C), 40 Less than% was regarded as insufficient (D).

<Synthesis Example 1 Synthesis of Diamine Compound (A-1) Represented by General Formula (1)>
Under a nitrogen stream, lithium chloride (5.31 g, 0.125 mol) and 2-amino-4-nitrophenol (16.21 g, 0.105 mol) were added to a 500 ml eggplant flask and dissolved in 300 mL of dehydrated NMP at room temperature. I let you. While this was cooled in a dry ice-isopropanol bath, dodecanedioic acid dichloride (13.3 g, 0.050 mol) was added dropwise. After the dropwise addition, the reaction solution was further stirred at room temperature for 1 hour and poured into 1.5 L of water. The obtained precipitate was collected by filtration, and further washed with 1.5 L of water three times in total. The obtained solid was dried in a ventilated oven at 50 ° C. for 3 days to obtain a dinitro compound (24.9 g, 98%).

Subsequently, 10.0 g of the obtained dinitro compound was dissolved in 100 ml of a mixed solution of tetrahydrofuran / N, N-dimethylformamide (9/1 v / v), 2 g of 5% palladium-carbon was added, and the resulting mixture was kept under hydrogen for 8 hours. Stir. After completion of the reaction, the catalyst was filtered and poured into 2 L of water. The obtained precipitate was filtered and further washed with 2 L of water, and then the obtained solid was dried in a ventilated oven at 50 ° C. for 3 days to obtain the desired diamine (A-1) (8.3 g, 94). %).
FT-IR (KBr), ν (cm ⁻¹ ): 3363, 3244, 2914, 2850, 1647, 1603, 1545, 1508, 1460, 1284, 1223, 1201, 1184, 1107. ¹ H-NMR (270 MHz, DMSO, δ, ppm, 40 ° C.): 9.13 (s, 2H), 8.52 (s, 2H), 6.88 (s, 2H), 6.56 (d, 2H), 6.24 (d, 2H), 4.51 (br, 4H), 2.35 (t, 4H), 1.58-1.28 (m, 16H).

<Synthesis Example 2 Synthesis of Diamine Compound (A-2) Represented by General Formula (1)>
Under a nitrogen stream, lithium chloride (5.31 g, 0.125 mol) and 2-amino-5-nitrophenol (16.21 g, 0.105 mol) were added to a 500 ml eggplant flask and dissolved in 300 mL of dehydrated NMP at room temperature. I let you. While this was cooled in a dry ice-isopropanol bath, dodecanedioic acid dichloride (13.3 g, 0.050 mol) was added dropwise. After the dropwise addition, the reaction solution was further stirred at room temperature for 1 hour and poured into 1.5 L of water. The obtained precipitate was collected by filtration, and further washed with 1.5 L of water three times in total. The obtained solid was dried in a ventilated oven at 50 ° C. for 3 days to obtain a dinitro compound (24.8 g, 98%).

Subsequently, 10.0 g of the obtained dinitro compound was dissolved in 100 ml of a mixed solution of tetrahydrofuran / N, N-dimethylformamide (9/1 v / v), 2 g of 5% palladium-carbon was added, and the resulting mixture was kept under hydrogen for 8 hours. Stir. After completion of the reaction, the catalyst was filtered and poured into 2 L of water. The obtained precipitate was filtered and further washed with 2 L of water, and then the obtained solid was dried in a ventilated oven at 50 ° C. for 3 days to obtain the desired diamine (A-2) (8.2 g, 94). %).
FT-IR (KBr), ν (cm ⁻¹ ): 3373, 3288, 2935, 2850, 1647, 1616, 1539, 1516, 1471, 1448, 1412, 1381, 1329, 1292, 1223, 1174, 1119. ¹ H-NMR (270 MHz, DMSO, δ, ppm, 40 ° C.): 9.29 (s, 2H), 9.12 (s, 2H), 6.98 (d, 2H), 6.10 (s, 2H), 6.01 (d, 2H), 4.77 (br, 4H), 2.30 (t, 4H), 1.57-1.28 (m, 16H).

<Synthesis Example 3 Synthesis of Diamine Compound (A-3) Represented by General Formula (1)>
Under a nitrogen stream, lithium chloride (5.31 g, 0.125 mol) and 2-amino-5-nitrophenol (16.21 g, 0.105 mol) were added to a 500 ml eggplant flask and dissolved in 300 mL of dehydrated NMP at room temperature. I let you. While this was cooled in a dry ice-isopropanol bath, sebacic acid dichloride (12.0 g, 0.050 mol) was added dropwise. After the dropwise addition, the reaction solution was further stirred at room temperature for 1 hour and poured into 1.5 L of water. The obtained precipitate was collected by filtration, and further washed with 1.5 L of water three times in total. The obtained solid was dried in a ventilated oven at 50 ° C. for 3 days to obtain a dinitro compound (23.2 g, 98%).

Subsequently, 10.0 g of the obtained dinitro compound was dissolved in 100 ml of a mixed solution of tetrahydrofuran / N, N-dimethylformamide (9/1 v / v), 2 g of 5% palladium-carbon was added, and the resulting mixture was kept under hydrogen for 8 hours. Stir. After completion of the reaction, the catalyst was filtered and poured into 2 L of water. The obtained precipitate was filtered and further washed with 2 L of water, and then the obtained solid was dried in a ventilated oven at 50 ° C. for 3 days to obtain the desired diamine (A-2) (8.3 g, 95). %).
FT-IR (KBr), ν (cm ⁻¹ ): 3373, 3288, 2935, 2850, 1647, 1616, 1539, 1516, 1471, 1448, 1412, 1381, 1329, 1292, 1223, 1174, 1119. ¹ H-NMR (270 MHz, DMSO, δ, ppm, 40 ° C.): 9.29 (s, 2H), 9.12 (s, 2H), 6.98 (d, 2H), 6.10 (s, 2H), 6.01 (d, 2H), 4.77 (br, 4H), 2.30 (t, 4H), 1.57-1.28 (m, 12H).

<Synthesis Example 4 Synthesis of Polyimide Precursor (I)>
Under a dry nitrogen stream, 22.1 g (0.050 mol) of (A-1) obtained in Synthesis Example 1 was dissolved in 80 g of N-methyl-2-pyrrolidone (NMP). To this, 14.0 g (0.045 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (hereinafter sometimes abbreviated as ODPA) is added together with 10 g of NMP, and 1 at 40 ° C. Reacted for hours. Thereafter, 1.64 (0.010 mol) of 5-norbornene-2,3-dicarboxylic anhydride (hereinafter sometimes abbreviated as NA) is added as a terminal blocking agent, and further at 40 ° C. for 1 hour. Reacted. Thereafter, a solution obtained by diluting 12.5 g (0.110 mol) of N, N′-dimethylformamide dimethylacetal with 15 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40 ° C. for 2 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 50 ° C. for 3 days to obtain polyimide precursor (I). The weight average molecular weight was 32,100.

<Synthesis Example 5 Synthesis of Polyimide Precursor (II)>
Under a dry nitrogen stream, 22.1 g (0.050 mol) of (A-2) obtained in Synthesis Example 2 was dissolved in 80 g of N-methyl-2-pyrrolidone (NMP). ODPA 14.0g (0.045mol) was added here with NMP10g, and it was made to react at 40 degreeC for 1 hour. Thereafter, NA1.64 (0.010 mol) was added as a terminal blocking agent, and the mixture was further reacted at 40 ° C. for 1 hour. Thereafter, a solution obtained by diluting 12.5 g (0.110 mol) of N, N′-dimethylformamide dimethylacetal with 15 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40 ° C. for 2 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 50 ° C. for 3 days to obtain polyimide precursor (II). The weight average molecular weight was 35,400.

<Synthesis Example 6 Synthesis of Polyimide Precursor (III)>
Under a dry nitrogen stream, 20.7 g (0.050 mol) of (A-3) obtained in Synthesis Example 3 was dissolved in 80 g of N-methyl-2-pyrrolidone (NMP). To this, 14.0 g (0.045 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (ODPA) was added together with 10 g of NMP, and reacted at 40 ° C. for 1 hour. Thereafter, NA1.64 (0.010 mol) was added as a terminal blocking agent, and the mixture was further reacted at 40 ° C. for 1 hour. Thereafter, a solution obtained by diluting 12.5 g (0.110 mol) of N, N′-dimethylformamide dimethylacetal with 15 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40 ° C. for 2 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 50 ° C. for 3 days to obtain a polyimide precursor (III). The weight average molecular weight was 29,100.

<Synthesis Example 7 Synthesis of Polyhydroxyamide (IV)>
Under a dry nitrogen stream, 22.1 g (0.050 mol) of (A-2) obtained in Synthesis Example 2 was dissolved in 100 g of NMP. To this, acid A (13.5 g, 0.045 mol) and 5-norbornene-2,3-dicarboxylic acid anhydride 1.64 (0.010 mol) were added together with 25 g of NMP and reacted at 85 ° C. for 3 hours. It was. After completion of the reaction, the mixture was cooled to room temperature, acetic acid (13.2 g, 0.250 mol) 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 three times, and then dried in a ventilated dryer at 50 ° C. for 3 days to obtain polyhydroxyamide (IV). The weight average molecular weight was 37,100.

<Synthesis Example 8 Synthesis of Polyhydroxyamide-Polyimide Copolymer (V)>
Under a dry nitrogen stream, 22.1 g (0.050 mol) of (A-2) obtained in Synthesis Example 2 was dissolved in 100 g of NMP. To this, acid A (6.76 g, 0.023 mol), ODPA 6.98 g (0.023 mol) and NA1.64 (0.010 mol) were added together with NMP 25 g, and reacted at 85 ° C. for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, acetic acid (13.20 g, 0.250 mol) 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. The precipitate was collected by filtration, washed with water three times, and then dried for 3 days with a ventilating dryer at 50 ° C. to obtain a polyhydroxyamide-polyimide copolymer (V). The weight average molecular weight was 35,300.

<Synthesis Example 9 Synthesis of Polyhydroxyamide-Polyimide Copolymer (VI)>
Under a dry nitrogen stream, 11.1 g (0.025 mol) of (A-2) obtained in Synthesis Example 2 and 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as BAHF) (It may be omitted.) 9.16 g (0.025 mol) was dissolved in 100 g of NMP. To this, acid A (6.76 g, 0.023 mol), ODPA 6.98 g (0.023 mol) and NA1.64 (0.010 mol) were added together with NMP 25 g, and reacted at 85 ° C. for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, acetic acid (13.20 g, 0.250 mol) 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 three times, and then dried for 3 days in a ventilating dryer at 50 ° C. to obtain a polyhydroxyamide-polyimide copolymer (VI). Weight average molecular weight is 38,200, PDI is. 1.9.

<Synthesis Example 10 Synthesis of Polyhydroxyamide-Polyimide Copolymer (VII)>
11.1 g (0.025 mol) (A-2) obtained in Synthesis Example 2 under dry nitrogen stream, 7.33 g (0.020 mol) BAHF, RT-1000 (5.0 g, 0.005 mol) Was dissolved in 100 g of NMP. To this, acid A (6.76 g, 0.023 mol), ODPA 6.98 g (0.023 mol) and NA1.64 (0.010 mol) were added together with NMP 25 g, and reacted at 85 ° C. for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, acetic acid (13.2 g, 0.250 mol) 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 three times, and then dried for 3 days in a ventilating dryer at 50 ° C. to obtain a polyhydroxyamide-polyimide copolymer (VII). The weight average molecular weight was 38,200.

<Synthesis Example 11 Synthesis of Polyimide Precursor (VIII)>
Under a dry nitrogen stream, 18.3 g (0.050 mol) of BAHF was dissolved in 80 g of N-methyl-2-pyrrolidone (NMP). ODPA 14.0g (0.045mol) was added here with NMP10g, and it was made to react at 40 degreeC for 1 hour. Thereafter, NA1.64 (0.010 mol) was added as a terminal blocking agent, and the mixture was further reacted at 40 ° C. for 1 hour. Thereafter, a solution obtained by diluting 12.5 g (0.110 mol) of N, N′-dimethylformamide dimethylacetal with 15 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40 ° C. for 2 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 50 ° C. for 3 days to obtain a polyimide precursor (VIII). The weight average molecular weight was 29,900.

<Synthesis Example 12 Synthesis of Polyimide Precursor (IX)>
Under a dry nitrogen stream, 30.2 g (0.050 mol) of 2,2-bis [3- (3-aminobenzamido) -4-hydroxyphenyl] hexafluoropropane (hereinafter sometimes abbreviated as HFHA). It was dissolved in 80 g of N-methyl-2-pyrrolidone (NMP). ODPA 14.0g (0.045mol) was added here with NMP10g, and it was made to react at 40 degreeC for 1 hour. Thereafter, NA1.64 (0.010 mol) was added as a terminal blocking agent, and the mixture was further reacted at 40 ° C. for 1 hour. Thereafter, a solution obtained by diluting 12.5 g (0.11 mol) of N, N′-dimethylformamide dimethylacetal with 15 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40 ° C. for 2 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 50 ° C. for 3 days to obtain a polyimide precursor (IX). The weight average molecular weight was 29,200.

<Synthesis Example 13 Synthesis of Polyhydroxyamide (X)>
Under a dry nitrogen stream, 18.31 g (0.050 mol) of BAHF was dissolved in 100 g of NMP. To this, acid A (16.11 g, 0.045 mol) was added together with 25 g of NMP, and reacted at 85 ° C. for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, acetic acid (13.20 g, 0.25 mol) 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. The precipitate was collected by filtration, washed 3 times with water, and then dried for 3 days with a ventilating dryer at 50 ° C. to obtain polyhydroxyamide (X). The weight average molecular weight was 35,400.

<Synthesis Example 14 Synthesis of Polyhydroxyamide (XI)>
Under a dry nitrogen stream, 100 g of N-methylpyrrolidone was added, 18.3 g (0.050 mol) of BAHF was added, and dissolved by stirring at room temperature. Then, while maintaining the temperature of the reaction solution at −10 to 0 ° C., the acid B ( 12.0 g, 0.045 mol) was added dropwise over 10 minutes, and stirring was continued at room temperature for 3 hours. The reaction solution was poured into 1.5 liters of water, and the precipitate was collected, washed with pure water three times, and then dried for 3 days with a ventilating dryer at 50 ° C. to obtain polyhydroxyamide (XI). The weight average molecular weight was 32,400.

  The diamines (A-1), (A-2), (A-3), BAHF, HFHA, acid A, and acid B used in the synthesis examples are as follows.

[Examples 1-7, Comparative Examples 1-4]
To 10 g of the above resins (I) to (XI), (b) 2.0 g of the photosensitive compound, 3.0 g of the compound (d) which is a thermal crosslinking agent, and (c) 20 g of γ-butyrolactone as a solvent were added to the varnish. Was made.

  The (b) photosensitive compound and the (d) compound used in the examples are as follows.

  Using the produced varnish, the characteristics were evaluated according to the method described above. Table 1 shows the composition of the resin used in Table 1, and Table 2 shows the result.

1 Silicon wafer 2 Al pad 3 Passivation film 4 Insulating film 5 Metal (Cr, Ti, etc.) film 6 Metal wiring (Al, Cu, etc.)
7 Insulating film 8 Barrier metal 9 Scribe line 10 Solder bump
11 Sealing resin 12 Substrate 13 Insulating film 14 Insulating film 15 Metal (Cr, Ti, etc.) film 16 Metal wiring (Ag, Cu, etc.)
17 Metal wiring (Ag, Cu, etc.)
18 Electrode 19 Sealing resin

Claims (18)

A diamine compound represented by the general formula (1).
(In General Formula (1), R ¹ and R ² represent a divalent aliphatic group. A represents a divalent aliphatic group, an alicyclic group, an aromatic group, or a plurality of aromatic groups in a single bond. A bonded divalent organic group or a plurality of aromatic groups are —O—, —S—, —CO—, —SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, or —C. (CF ₃ ) ₂ —: (where F is fluorine) represents a divalent organic group, and p and q are integers in the range of 0 to 3.) The diamine compound according to claim 1, which is represented by the general formula (1), wherein A in the general formula (1) is a divalent aliphatic group represented by the general formula (2) or the general formula (3). .
(In General Formula (1), R ¹ and R ² represent a divalent aliphatic group. A represents a divalent aliphatic group, an alicyclic group, an aromatic group, or a plurality of aromatic groups in a single bond. A bonded divalent organic group or a plurality of aromatic groups are —O—, —S—, —CO—, —SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, or —C. (CF ₃ ) ₂ —: (where F is fluorine) represents a divalent organic group, and p and q are integers in the range of 0 to 3.)
(In General Formula (2), R ^{3 to} R ⁶ each independently represent an alkylene group having 1 to 10 carbon atoms, and a, b, and c are 1 ≦ a ≦ 20, 0 ≦ b ≦ 20, 0, respectively. Represents an integer within the range of ≦ c ≦ 20, and the arrangement of repeating units may be block or random, provided that the structures shown in parentheses are different, and * indicates a chemical bond.)
(In General Formula (3), R ⁷ and R ⁸ are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms, n is an integer of 1 to 20, and * is a chemical bond. .)   A heat resistant resin having a structure derived from the diamine compound according to claim 1. The heat resistant resin of Claim 3 which has 1 or more types of structural units selected from General formula (4), General formula (5), and General formula (6).
(In the general formulas (4) to (6), B is an organic group represented by the general formula (7). X ¹ represents a divalent to hexavalent organic group, and X ² and X ³ are each independently 4 to 10-valent organic group, R represents hydrogen or an organic group having 1 to 20 carbon atoms, and p, q, and r are each independently an integer of 0 to 4.)
(In General Formula (7), R ⁹ and R ¹⁰ represent a divalent aliphatic group. C represents a divalent aliphatic group, an alicyclic group, an aromatic group, or a plurality of aromatic groups in a single bond. A bonded divalent organic group or a plurality of aromatic groups are —O—, —S—, —CO—, —SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, or —C. In the case of a divalent organic group bonded by (CF ₃ ) ₂ —: (where F is fluorine), s and t are integers in the range of 0 to 3. * is chemical Indicates binding.) The heat resistant resin according to claim 4, wherein C in the general formula (7) is a divalent aliphatic group represented by the general formula (2) or the general formula (3).
(In General Formula (2), R ^{3 to} R ⁶ each independently represent an alkylene group having 1 to 10 carbon atoms, and a, b, and c are 1 ≦ a ≦ 20, 0 ≦ b ≦ 20, 0, respectively. Represents an integer within the range of ≦ c ≦ 20, and the arrangement of repeating units may be block or random, provided that the structures shown in parentheses are different, and * indicates a chemical bond.)
(In General Formula (3), R ⁷ and R ⁸ are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms, n is an integer of 1 to 20, and * is a chemical bond. .)   The heat resistant resin according to any one of claims 3 to 5, comprising one or more kinds of resins selected from polyimide, polyamide, polybenzoxazole, precursors thereof, and copolymers thereof.   A resin composition comprising the heat resistant resin according to any one of claims 3 to 6, (b) a photosensitive compound, and (c) a solvent.   Furthermore, (d) The resin composition of Claim 7 containing the compound which has 2 or more of at least any one group among an alkoxymethyl group and a methylol group.   A resin sheet formed from the resin composition according to claim 7 or 8.   A cured film obtained by curing the resin composition according to claim 7 or 8, or the resin sheet according to claim 9.   A step of applying the resin composition according to claim 7 or 8 on a substrate or laminating the resin sheet according to claim 9 on the substrate and drying to form a resin film, and exposure through a mask A method for producing a relief pattern of a cured film, comprising: a step of developing, elution or removal of the irradiated portion with an alkaline solution and development, and a step of heat-treating the resin film after development.   The manufacturing method of the relief pattern of the cured film of Claim 11 with which the process of apply | coating the said resin composition on a board | substrate and drying and forming a resin film includes the process apply | coated on a board | substrate using a slit nozzle. .   An organic EL display device, wherein the cured film according to claim 10 is disposed on at least one of a planarization layer on a drive circuit and an insulating layer on a first electrode.   A semiconductor electronic component or a semiconductor device, wherein the cured film according to claim 10 is disposed as an interlayer insulating film between rewirings.   The semiconductor electronic component or the semiconductor device according to claim 14, wherein the rewiring is a copper metal wiring, and a distance between wirings adjacent to the width of the copper metal wiring is 5 μm or less.   A semiconductor electronic component or a semiconductor device, wherein the cured film according to claim 10 is disposed as an interlayer insulating film between rewirings on a sealing resin substrate on which a silicon chip is disposed.   A step of disposing the cured film according to claim 10 as an interlayer insulating film between rewirings on a support substrate on which a temporary attachment material is disposed, a step of disposing a silicon chip and a sealing resin thereon, and A method for manufacturing a semiconductor electronic component or a semiconductor device, comprising a step of peeling a rewiring from a support substrate on which a temporary attachment material is disposed.   The semiconductor electronic component or semiconductor device by which the cured film of Claim 10 is arrange | positioned as an interlayer insulation film of the adjacent board | substrate comprised with 2 or more types of materials.