TW201816514A - Photosensitive resin composition, cured film, organic el display device, semiconductor electronic component and semiconductor device - Google Patents

Abstract

Provided is a photosensitive resin composition which forms a cured film that exhibits excellent adhesion to a metal material, especially to copper even during heat treatments at low temperatures, while having a high degree of elongation. This photosensitive resin composition is characterized by containing (A) an alkali-soluble resin having a structural unit represented by general formula (1) and (B) a photo-crosslinking agent. (In general formula (1), each of X1 and X2 represents an organic group having a valence of 2-10; Y1 represents an organic group having a valence of 2-4; Y2 represents a divalent organic group having an aliphatic structure with 2 or more carbon atoms; each of R1 and R2 represents a hydrogen atom or an organic group having 1-20 carbon atoms; each of p, q, r, s and t represents an integer satisfying 0 ≤ p ≤ 4, 0 ≤ q ≤ 4, 0 ≤ r ≤ 2, 0 ≤ s ≤ 4 and 0 ≤ t ≤ 4; each of n1 and n2 represents an integer satisfying 1 ≤ n1 ≤ 500, 1 ≤ n2 ≤ 500 and 0.05 ≤ n1/(n1 + n2) < 1; and the repeating units may be arranged in blocks or randomly).

Description

   Photosensitive resin composition, cured film, organic EL display device, semiconductor electronic component, semiconductor device   

The present invention relates to a photosensitive resin composition, a cured film using the same, an organic EL display device, a semiconductor electronic component, and a semiconductor device. More specifically, it relates to a photosensitive resin composition suitable for a surface protection film of a semiconductor element, an interlayer insulating film, and an insulating layer of an organic electric field light emitting element.

Conventionally, polyimide-based resins and polybenzones, which are excellent in heat resistance and mechanical properties, have been widely used as surface protective films or interlayer insulating films of semiconductor devices of electronic devices. An azole resin and the like. Use polyimide or polybenzo When the azole is used as a surface protective film or an interlayer insulating film, one of the formation methods of the through holes and the like is etching using a positive photoresist. However, the steps of this method include coating or peeling of the photoresist, which has complicated problems. Therefore, in order to rationalize the operation steps, a heat-resistant material that has been provided with photosensitivity is being reviewed.

Polyimide or polybenzo The azole system can thermally dehydrate and close the coatings of the precursors to obtain films with excellent heat resistance and mechanical properties. However, in this case, a heat treatment at a high temperature of about 350 ° C is usually required. However, for example, MRAM (Magnetoresistive Random Access Memory), which is promising as a new-generation memory, cannot withstand high-temperature programs, so polyimide resins and polybenzo The azole-based resin is hardened by a heat treatment at a low temperature of about 250 ° C or lower even on a surface protective film, and a cured film hardened by a heat treatment at a high temperature of about 350 ° C which is not inferior to the conventional performance can be obtained.

Polyimide-based resins and polybenzoxenes that are hardened by heat treatment at low temperatures Methods for azole-based resins are known: the addition of ring-closing accelerators, or the introduction of organic groups that promote ring-closing at low temperatures in the unit structure; or after imparting alkali solubility, using polyimide or polyimide that has been closed Benzo Azole method and so on.

When the photosensitive resin composition is used in applications such as semiconductors, the cured film system obtained by heat treatment is left in the device as a permanent film, so the physical properties of the cured film are very important. In order to ensure the reliability of the semiconductor package, the adhesion with the material formed on the surface of the semiconductor wafer is important. In particular, when it is used for an insulation film or the like between wiring layers of a wafer-level package, adhesion to a metal material used for electrodes, wiring, or the like becomes important.

However, the resin composition containing the resin which can be hardened by heat treatment at a low temperature has a problem that the adhesion of the metal used as a wiring material is low.

Heat-resistant resins are generally considered to have low adhesion strength to metal materials due to their rigid main chain structure, especially in the case of hardened films of resin compositions that have been provided with light sensitivity. Additives such as photosensitizers, sensitizers, acid generators, and dissolution adjusters also remain in the cured film after heat curing, so the adhesive strength is lower than those without additives. As a solution to these problems, there has been proposed a positive-type photosensitive resin composition containing an alkali aqueous solution-soluble polymer, a photoacid generator, and containing four or more directly bonded to Al atoms, Ti atoms, and Si atoms. Silane compound with specific functional group (refer to Patent Document 1); or a heat-resistant resin precursor composition including a heat-resistant resin precursor such as a polyimide precursor and a specific amine compound or thiol Derivatives (see Patent Document 2).

Prior art literature Patent literature

Patent Document 1 Japanese Patent Application Laid-Open No. 2008-276190 (p.1-3)

Patent Document 2 Japanese Patent Laid-Open No. 2007-39486 (p.1-3)

However, when the photosensitive resin composition or the heat-resistant resin precursor composition described in Patent Documents 1 and 2 forms a cured film, an organic acid is generated, and the metal wiring is corroded, especially copper. As a result, the adhesion is reduced. Happening. In addition, the cured film itself is decomposed by the organic acid generated, and the mechanical properties, especially the elongation are reduced, and the reliability of the device may be insufficient.

Then, the objective of this invention is to provide the photosensitive resin composition which can obtain the hardened film which is excellent in adhesiveness with a metal material, especially copper, and has high elongation even in the heat processing at low temperature.

The photosensitive resin composition of this invention has the following structures. That is, a photosensitive resin composition characterized by including (A) an alkali-soluble resin having a structural unit represented by the general formula (1), and (B) a photocrosslinking agent.

(In the general formula (1), X ¹ and X ² represent a 2- to 10-valent organic group, Y ¹ represents a 2- to 4-valent organic group, and Y ² represents a divalent compound having an aliphatic structure having 2 or more carbon atoms. Organic group, R ¹ and R ² represent hydrogen or an organic group having 1 to 20 carbon atoms; p, q, r, s, and t represent 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 2, 0 ≦ Integers in the range of s ≦ 4, 0 ≦ t ≦ 4; n1 and n2 are integers in the range of 1 ≦ n1 ≦ 500, 1 ≦ n2 ≦ 500, and 0.05 ≦ n1 / (n1 + n2) <1, each The arrangement of the repeating unit may be a block or a random one).

The photosensitive resin composition of the present invention can obtain a cured film having excellent adhesion to a metal material, especially copper, and a high elongation even in a heat treatment at low temperature.

1‧‧‧ silicon wafer

2‧‧‧ aluminum (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‧‧‧ cutting line

10‧‧‧solder bump

11‧‧‧Support substrate (glass substrate, silicon wafer)

12‧‧‧ electrode pad (Cu)

13‧‧‧ insulating film

14‧‧‧Metal wiring (Cu)

15‧‧‧Cu column

16‧‧‧solder bump

17‧‧‧Semiconductor wafer

18‧‧‧TFT (thin film transistor)

19‧‧‧ Wiring

20‧‧‧TFT insulating layer

21‧‧‧ flattening layer

22‧‧‧ITO (transparent electrode)

23‧‧‧ substrate

24‧‧‧ contact hole

25‧‧‧ Insulation

FIG. 1 is an enlarged cross-sectional view showing a pad portion of a semiconductor device having bumps.

2a to 2f of FIG. 2 are diagrams showing a detailed manufacturing method of a semiconductor device having a bump.

3a to 3f of FIG. 3 are explanatory diagrams illustrating a method of fabricating a semiconductor device in the RDL priority method.

FIG. 4 is a cross-sectional view showing an example of a TFT substrate.

Implementation of the invention

The photosensitive resin composition of this invention contains the said (A) alkali-soluble resin which has a structural unit represented by General formula (1), and (B) a photocrosslinking agent. A compound containing (C) at least one of an oxygen atom, a sulfur atom, and a nitrogen atom in the molecule and / or (D) an organic solvent having a boiling point of 1013 hPa of 200 ° C or higher and 260 ° C or lower is preferred. ) An organic solvent having a boiling point at 1013 hPa of 100 ° C or higher and lower than 200 ° C. In the following, the components (A), (B), (C), (D), and (E) may be omitted.

The cured film obtained by curing the photosensitive resin composition of the present invention preferably reduces the generation of organic acids by using a specific (B) photocrosslinking agent, and suppresses the corrosion of metals, especially copper, to be a cured film. Those with excellent adhesion. Moreover, it is preferable to add the component (C) and further increase the interaction with copper, and as a result, the adhesion to the copper substrate is improved.

The reason why the elongation is excellent is that the resin of (A) has a skeleton that is easily stretched when the number of carbons of the diamine residue (ie, Y ² ) constituting the component (A) is 2 or more. As a result, a cured film obtained by curing the photosensitive resin composition becomes a highly stretchable material.

Therefore, the photosensitive resin composition of the present invention can obtain a cured film having a high adhesion to a metal material, especially copper, even when subjected to a heat treatment at a low temperature of 250 ° C or lower.

The (A) alkali-soluble resin of the present invention has a structural unit represented by the general formula (1).

In the general formula (1), X ¹ and X ² are 2- to 10-valent organic groups, and are preferably aliphatic carboxylic acid residues.

Y ¹ is a 2- to 4-valent organic group, preferably an organic group having an aromatic group, and more preferably an organic group having a phenyl group.

Y ² is a divalent organic group having an aliphatic structure having 2 or more carbon atoms, and is preferably an aliphatic diamine residue.

R ¹ and R ² represent hydrogen or an organic group having 1 to 20 carbon atoms.

In addition, p, q, r, s, and t represent integers in a range of 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 2, 0 ≦ s ≦ 4, and 0 ≦ t ≦ 4. n1 and n2 are integers in a range of 1 ≦ n1 ≦ 500, 1 ≦ n2 ≦ 500, and 0.05 ≦ n1 / (n1 + n2) <1. The arrangement of each repeating unit may be block or random.

(A) Alkali-soluble resin is an alkali-soluble polyamine having an organic group derived from an aliphatic diamine and having a repeating unit represented by the aforementioned general formula (1), which may have X ¹ (COOH) ₂ or A dicarboxylic acid having a structure of X ² (COOH) ₂ or a dicarboxylic acid derivative having a structure of X ¹ (COZ) ₂ or X ² (COZ) ₂ (and an acid derivative having COZ representing a carboxyl group), and Y Polyamine obtained by polycondensing a bisaminophenol and a diamine having a structure of ¹ (NH ₂ ) ₂ (OH) ₂ and Y ² (NH ₂ ) ₂ . Here, the amine group and the hydroxyl group of the two groups of the bisaminophenol are ortho positions to each other, and the polyamidoamine is heated at about 250 ° C to 400 ° C to dehydrate and close the ring. Will change to benzo The case of azole. The base polymer of the photosensitive resin composition of the present invention may be closed-loop or closed-loop after heat curing.

(A) For alkali-soluble resins, in terms of the solubility of the alkali solution, in the general formula (1), the value of n1 / (n1 + n2) is 0.05 or more, preferably 0.5 or more, particularly preferably 0.7 or more, particularly More preferably, it is 0.8 or more. From the viewpoint of low stress, the value of n1 / (n1 + n2) is less than 1, and preferably 0.95 or less.

Examples of the dicarboxylic acid having a structure of X ¹ (COOH) ₂ or X ² (COOH) ₂ include a case where X ¹ and X ² are aromatic groups selected by the following structural formula, but Limited by these.

(In the formula, A has a member selected from-(direct bonding), -O-, -S-, -SO _2- , -COO-, -OCO-, -CONH-, -NHCO-, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -the divalent base of the group).

In a dicarboxylic acid derivative having a structure of X ¹ (COZ) ₂ and X ² (COZ) ₂ , Z is an organic group having 1 to 12 carbon atoms or a group selected from a halogen element, preferably from the following: The selected basis of the structural formula.

(In the formula, Zb and Zc include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a third butyl group, a trifluoromethyl group, a halogen group, a phenoxy group, and a nitro group. These are limited).

In the present invention, each of X ¹ and X ² in the general formula (1) preferably has a structural unit represented by the general formulae (2) to (4) in terms of obtaining a cured film having a higher elongation. At least either of them.

(In the general formulae (2) to (4), R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ⁵ represents an organic group having 1 to 5 carbon atoms containing an oxygen atom or a sulfur atom. Group, n3 represents an integer in the range of 1 to 20. * represents a chemical bond).

Examples of the dicarboxylic acid having a structure represented by the general formulae (2) to (4) include dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, and di-n-butylmalonic acid. , Succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid Acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylpentane Diacid, adipic acid, octafluoroadipate, 3-methyladipate, octafluoroadipate, pimelic acid, 2,2,6,6-tetramethylpimelate, suberic acid, Dodecafluorosuberic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, fifteen Oxalic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosenedioic acid, behenedioic acid, behenedioic acid, behenic acid Trioxane, docosaedioic acid, pentadecanedioic acid, hexacosane carboxylic acid, icosane carboxylic acid, octacosane carboxylic acid, icosane carboxylic acid, icosane Diacid, thirty Mono-methylene diacid, dodecanedioic acid, diethylene glycol acid and the like are not limited thereto. In the component (A) used in the present invention, as the dicarboxylic acid having a structure of X ¹ (COOH) ₂ or X ² (COOH) ₂ , succinic acid, glutaric acid, adipic acid, and pimelic acid are preferred. , Suberic acid, azelaic acid, sebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanoic acid, hexadecanedioic acid , Heptadecanedioic acid, octadecenedioic acid, nonadecanedioic acid, eicosenedioic acid, behenedioic acid, behenedioic acid, behenedioic acid, behenate Diacid, pentadecanedioic acid, hexacosadecanedioic acid, heptadecanedioic acid, octacosadecanedioic acid, icosanedioedioic acid, sescanedioic acid, sesquitenedioic acid , Dodecanedioic acid, diethylene glycol acid, but not limited to these.

Examples of the aminophenol having a structure of Y ¹ (NH ₂ ) ₂ (OH) ₂ in the general formula (1) include bis (3-amino-4-hydroxyphenyl) hexafluoropropane and bis ( 3-amino-4-hydroxyphenyl) fluorene, bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methane, bis (3-amino- Hydroxy-containing diamines such as 4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, bis (3-amino-4-hydroxyphenyl) fluorene, and the like. Moreover, you may use combining these 2 or more types of diamine components.

In a diamine having a structure of Y ² (NH ₂ ) ₂ , Y ² has an aliphatic structure, preferably an aliphatic diamine residue, and more preferably an alkylene oxide structural unit represented by the general formula (5) By.

(In the general formula (5), R ⁶ to R ⁹ each independently represent an alkylene group having 2 to 10 carbon atoms, and a, b, and c each represent 0 ≦ a ≦ 20, 0 ≦ b ≦ 20, 0 ≦ c ≦ For integers in the range of 20, the arrangement of each repeating unit can be block or random; * means chemical bonding).

In the component (A) used in the present invention, the diamine having a structural unit represented by the general formula (5) as Y ² includes, for example, ethylenediamine, 1,3-diaminopropane, and 2-methyl. -1,3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diamine Hexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diamine Undecane, 1,12-diaminododecane, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,2- Bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 4,4'-methylenebis (Cyclohexylamine), 4,4'-methylenebis (2-methylcyclohexylamine), KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D -200, D-400, D-2000, THF-100, THF-140, THF-170, RE-600, RE-900, RE-2000, RP-405, RP-409, RP-2005, RP-2009 , RT-1000, HE-1000, HT-1100, HT-1700, (the above trade names, manufactured by HUNTSMAN), etc., as long as they include an alkylene oxide structure, there is no limitation, 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-, -NHCONH-, etc.

In the component (A) used in the present invention, in the general formula (1), when the molecular weight of the structural unit represented by Y ² is 150 or more, the polyamide structure of the component (A) becomes soft and becomes When hardened, the film becomes highly extensible. In addition, since the component (A) is soft, the stress on the wafer when the cured film is formed can be reduced, and the residual stress of the cured film and the substrate can be reduced. As a result, adhesion can be improved. In addition, by introducing a soft base having low ultraviolet absorption, i-ray permeability is increased, and high sensitivity can be achieved at the same time. In the general formula (1), the molecular weight of the structural unit represented by Y ² is preferably 150 or more, more preferably 600 or more, and even more preferably 900 or more. When the molecular weight is 2,000 or less, it is preferable to maintain the solubility in an alkaline solution, more preferably 1800 or less, and even more preferably 1500 or less. The molecular weight is more preferably 600 or more and 1,800 or less, and particularly preferably 900 or more and 1,500 or less. This can further improve the elongation and sensitivity.

The molecular weight of the Y ² component in the general formula (1) of the resin of the component (A) can be obtained by measuring the molecular weight of a diamine monomer containing a Y ² structure, for example, by LC-MS or the like as a main signal.

In addition, the component (A) used in the present invention can copolymerize a diamine having a Y ² (NH ₂ ) ₂ structure, and also copolymerize other diamines. Examples of other diamines include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4 , 4'-diaminodiphenylmethane, 3,4'-diaminodiphenylphosphonium, 4,4'-diaminodiphenylphosphonium, 3,4'-diaminodiphenylsulfide Compounds, 4,4'-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, phenylyne, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalene Diamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) fluorene, bis (3-aminophenoxyphenyl) fluorene, bis (4-aminophenoxy) diamine Benzene, bis {4- (4-aminophenoxy) 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, 3,3', 4,4 ' -Aromatic diamines such as tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl; or the like A compound in which a part of the hydrogen atom of an aromatic ring is substituted with an alkyl group having 1 to 10 carbon atoms or a fluoroalkyl group, a halogen atom, etc. Represented by the structure (in the formula, * represents a chemical bonding) or the like, but these are not defined. The other diamine copolymerized can be used as it is, or it can be used as the corresponding diisocyanate compound and trimethylsilyldiamine. Moreover, you may use combining these 2 or more types of diamine components.

In addition, an aliphatic group having a siloxane structure may be copolymerized within a range that does not reduce heat resistance, and adhesion to a substrate may be improved. Specifically, as the diamine component, bis (3-aminopropyl) tetramethyldisilazane and bis (p-aminophenyl) octamethyl are copolymerized at 1 to 15 mole%. Pentasiloxane and others. When the copolymerization is more than 1 mol%, it is better at the point of improving the adhesion with the substrate such as a silicon wafer, and when it is 15 mol% or less, it is preferable at the point of not reducing the solubility in the alkaline solution. .

In addition, in order to improve the storage stability of the photosensitive resin composition, the resin of the component (A) is preferably a main chain blocked with a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monofluorinated compound, or a single active ester compound. End. In addition, by blocking the terminal of the resin with a terminal blocking agent having a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a vinyl group, an ethynyl group, or an allyl group, it is possible to easily dissolve the resin in an alkaline solution or obtain the obtained resin. The mechanical properties of the cured film are adjusted to a preferable range. The introduction ratio of the terminal blocking agent is preferably 0.1 mol% or more, and particularly preferably 5 mol% or more, relative to the total amine component, so as to increase the molecular weight of the resin of the (A) component and suppress the resin in an alkaline solution. The solubility in medium is reduced; preferably 60 mol% or less, and particularly preferably 50 mol% or less, in order to reduce the molecular weight of the resin of the component (A) and suppress the reduction of the mechanical properties of the resulting cured film. By reacting plural terminal blocking agents, plural different terminal groups can be introduced.

As the monoamine, M-600, M-1000, M-2005, M-2070 (the above trade names, manufactured by HUNTSMAN) are preferred, aniline, 2-ethynylaniline, 3-ethynylaniline, 4- Ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4 -Aminonaphthalene, 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-aminobenzene Formic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3- Aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminosulfide Phenol, 3-aminothiophenol, 4-aminothiophenol and the like. Two or more of these may be used.

As the acid anhydride, monocarboxylic acid, monophosphonium compound, and single active ester compound, phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, and 3-hydroxy-o-benzene are preferred. Acid anhydrides such as dicarboxylic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxyl Monocarboxylic groups such as -5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, etc. Acids and these carboxylic groups are monochlorinated compounds which are chlorinated with terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxylic acid Carboxynaphthalenes, 1,7-dicarboxynaphthalenes, 2,6-dicarboxynaphthalenes and other dicarboxylic acids have only one carboxyl group monochlorinated by chlorination, and the monofluorinated compound and N-hydroxybenzotriene Azole or imidazole, N-hydroxy-5-nor An active ester compound obtained by the reaction of ene-2,3-dicarboxyphosphonium imine and the like. Two or more of these may be used.

The terminal blocking agent introduced into the resin of the component (A) used in the present invention can be easily detected by the following method. For example, a resin in which a terminal blocking agent is introduced is dissolved in an acidic solution, and the amine component and the acid anhydride component of the constituent units are decomposed, and the gas chromatography (GC) or NMR measurement is performed on the resin, thereby easily detecting the Terminal blocking agent used in the invention. In addition, the resin component to which the terminal blocking agent has been introduced can also be easily detected by directly measuring it with a thermal decomposition gas chromatograph (PGC) or an infrared spectrum and a ¹³ C-NMR spectrum.

If the component (A) used in the present invention includes a structure represented by the general formula (1), it may be copolymerized with other structures such as polyimide. Here, the component (A) may have another structure, but is preferably a structural unit represented by the general formula (1) in an amount of 10 to 100 mole%.

The component (A) in the present invention preferably has a weight average molecular weight of 5,000 to 50,000. By setting the weight average molecular weight to 5,000 or more in terms of polystyrene measured by GPC (gel permeation chromatography), the bending resistance after curing can be improved. On the other hand, by setting the weight average molecular weight to 50,000 or less, the developability of the alkali solution can be improved. In order to obtain mechanical characteristics, it is more preferably 20,000 or more. In addition, when two or more kinds of alkali-soluble polyamines are contained, the weight average molecular weight of at least one kind may be in the above range.

The solvent (hereinafter, also referred to as a polymerization solvent) used in the polymerization of the component (A) is not particularly limited as long as it is a tetracarboxylic dianhydride and a diamine capable of dissolving a raw material monomer. Examples include: N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazoline Ketones, N, N'-dimethylpropaneurea, N, N-dimethylisobutyric acid amidoamine, methoxy-N, N-dimethylpropanamide amidines; γ-butane Cyclic esters such as lactones, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone; ethyl carbonate, carbonic acid Carbonic acid esters such as propylene esters; glycols such as triethylene glycol; phenols such as m-cresol and p-cresol; acetophenone, cyclobutane, dimethylarsin, etc. In order to dissolve the resin after the reaction, it is preferable to use 100 parts by mass or more, more preferably 150 parts by mass of the polymerization solvent with respect to 100 parts by mass of the obtained resin. 1,900 parts by mass or less is used, and more preferably 950 parts by mass or less is used.

The photosensitive resin composition of this invention contains (B) photocrosslinking agent. (B) The photocrosslinking agent is a negative type which is hardened by light, and preferably contains (b-1) a photoinitiator and (b-2) a photopolymerizable compound.

Examples of the (b-1) photoinitiator include diphenyl ketone, Michelin, 4,4, -bis (diethylamino) diphenyl ketone, 3,3,4, Diphenyl ketones such as 4, -tetrakis (third butylperoxycarbonyl) diphenyl ketone or 3,5-bis (diethylaminobenzylidene) -N-methyl-4-piperidine Benzenes such as ketones, 3,5-bis (diethylaminobenzylidene) -N-ethyl-4-piperidone; 7-diethylamino-3-nonylcoumarin , 4,6-dimethyl-3-ethylaminocoumarin, 3,3-carbonylbis (7-diethylaminocoumarin), 7-diethylamino-3- (1 -Methylbenzimidazolyl) coumarin, 3- (2-benzothiazolyl) -7-diethylaminocoumarin, and other coumarins; 2-third butyl anthraquinone, 2 -Anthraquinones such as ethyl anthraquinone and 1,2-benzoanthraquinone; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc. Alcohol bis (3-mercaptopropionate), 2-mercaptobenzothiazole, 2-mercaptobenzo Thiols, 2-mercaptobenzimidazole, etc .; N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N- (p-chlorophenyl) glycine , N- (4-cyanophenyl) glycine and other glycine acids; 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1 , 2-propanedione-2- (o- (methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1, 2-propanedione-2- (o-benzylidene) oxime, bis (α-isonitrosophenylacetone oxime) isophthalic acid, 1,2-octanedione-1- [4- (phenylthio Phenyl] phenyl] -2- (o-benzylidene oxime), OXE02 (trade name, made by CIBA Special Chemicals (Stock)), NCI-831 (trade name, made by ADEKA (Stock)), etc. 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butane-1-2-methyl-1 [4- (methylthio) phenyl] -2- Α-Aminoalkylphenones such as morpholinylpropane-1-one; 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole and the like. Among these, the aforementioned oximes are preferred; particularly preferred are 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propane Dione-2- (o-benzylidene) oxime, bis (α-isonitrosophenylacetone oxime) isophthalic acid, 1,2- Dione 1- [4- (phenylthio) phenyl] -2- (o-benzoyl oxime), OXE02, NCI-831. These lines may be alone or in combination use of two or more species.

Among these, from the viewpoint of photoreaction, it is more suitable to use the above-mentioned diphenyl ketones, glycine acids, mercapto groups, oximes, α-aminoalkyl phenones, 2,2 ' -The selected combination of bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole.

The content of the (b-1) photoinitiator is preferably 0.1 to 60 parts by mass, and more preferably 0.2 to 40 parts by mass with respect to 100 parts by mass of the total amount of the component (A). If it is 0.1 parts by mass or more, sufficient free radicals are generated by light irradiation and the sensitivity is increased. If it is 60 parts by mass or less, no light-irradiated portion is hardened due to excessive radicals. , Alkali imaging increased.

The (b-2) photopolymerizable compound is preferably a compound having an unsaturated carbon-carbon bond, that is, a polymerizable unsaturated compound. For example, unsaturated double bond functional groups such as vinyl, allyl, allyl acryl, methacryl and the like, and / or unsaturated triple bond functional groups such as propargyl, among these, Conjugated vinyl, acrylfluorenyl, and methacrylfluorenyl are preferred in terms of polymerizability.

In addition, the number of the functional group is preferably 1-4 from the viewpoint of stability, and each of them may be a different group.

(b-2) The number average molecular weight of the photopolymerizable compound is not particularly limited, but from the viewpoint of good compatibility with the polymer and the reactive diluent, the number average molecular weight is preferably 800 or less. For the purpose of suppressing the solubility in the developing solution after exposure, the number average molecular weight is preferably 30 or more.

Specific examples of (b-2) polymerizable unsaturated compounds include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and diethylene glycol dimethacrylate. , Triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, Trimethylolpropane trimethacrylate, styrene, α-methylstyrene, 1,2-dihydronaphthalene, 1,3-diisopropenylbenzene, 3-methylstyrene, 4-methyl Styrene, 2-vinylnaphthalene, butyl acrylate, butyl methacrylate, isobutyl acrylate, hexyl acrylate, isooctyl acrylate, isopropyl acrylate Esters, methacrylate Ester, cyclohexyl methacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate Ester, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate Ester, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate Ester, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-dipropenyloxy-2-hydroxypropane, 1,3 -Dimethacryloxy-2-hydroxypropane, Methylenebispropenylamine, N, N-Dimethyacrylamide, N-Methylmethacrylamide, 2,2,6,6- Tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl acrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate Ester, N-methyl-2,2,6,6-tetramethylpiperidinyl propylene Acrylate, ethylene oxide modified bisphenol A diacrylate, ethylene oxide modified bisphenol A dimethacrylate, N- vinyl pyrrolidone, N- vinyl caprolactam and the like. These can be used alone or in combination of two or more kinds.

Among these, particularly preferred are 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, Acrylic iso Esters, methacrylate Ester, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, methylene bisacrylamide, N, N-Dimethacrylamide, N-Methylmethacrylamide, 2,2,6,6-tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidine 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.

The content of the (b-2) polymerizable unsaturated compound is preferably 1 to 40 parts by mass relative to 100 parts by mass of the component (A), and is more preferably for the purpose of suppressing the solubility in the developing solution after exposure. It is 3 parts by mass or more for the purpose of obtaining a highly vertical pattern shape, and more preferably 20 parts by mass or less.

The photosensitive resin composition of the present invention may contain (C) a compound having at least any one of an oxygen atom, a sulfur atom, and a nitrogen atom in the molecule. The component (C) in the present invention is a compound that interacts with a metal, particularly copper, and by containing this, the adhesion between the film and the metal material after heat curing is greatly increased.

The component (C) in the present invention is preferably a compound represented by the general formula (6).

(In the general formula (6), R ¹⁰ to R ¹² represent any of an oxygen atom, a sulfur atom, or a nitrogen atom, and at least one of R ¹⁰ to R ¹² represents a sulfur atom; l represents 0 or 1; R ¹⁰ is an oxygen or sulfur atom when l is 0; nitrogen is an atom when l is 1; m and n are integers of 1 to 2; u and v are 0 or 1; R ¹¹ and R ¹² are when u, When v is 0, it represents an oxygen atom or a sulfur atom, and when u and v are 1, it represents a nitrogen atom; R ¹³ to R ¹⁷ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms).

Examples of R ¹³ to R ¹⁵ include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an arylether group, a carboxyl group, A carbonyl group, an allyl group, a vinyl group, a heterocyclic group, a combination thereof, and the like may further have a substituent. In addition, R ¹³ to R ¹⁷ may form a ring by adjacent groups.

Examples of the compound represented by the general formula (6) include the following, but are not limited to the following structures.

The content of the component (C) is preferably 1 to 40 parts by mass relative to 100 parts by mass of the component (A). The purpose is to suppress the solubility in the developing solution after exposure, and more preferably 3 parts by mass or more. From the viewpoint of preservation stability, it is more preferably 20 parts by mass or less.

Furthermore, the photosensitive resin composition of the present invention may preferably contain (D) an organic solvent having a boiling point of 1013 hPa at 200 ° C or higher and 260 ° C or lower and (E) a boiling point at 1013 hPa of 100 ° C or higher and lower than 200 ° C. Organic solvent, and the content of the organic solvent with the boiling point of 1013 hPa above 200 ° C and below 260 ° C may be 5% by mass or more and 70% by mass or less with respect to the total amount of the organic solvent. The content of the organic solvent having a boiling point at 1013 hPa of 100 ° C. or higher and less than 200 ° C. may be 30% by mass or more and 95% by mass or less.

By containing (D) an organic solvent having a boiling point of 200 ° C or higher and 260 ° C or lower at 1013 hPa, the drying of the photosensitive resin composition due to drying can be eased during coating and subsequent drying steps, and the substrate can be improved. The step difference is embedded. Regarding the boiling point of the component (D) at 1013 hPa, if it is 200 ° C or higher, it is preferable to reduce the fluidity reduction caused by drying of the coating film at the time of coating and drying step. If it is 260 ° C or lower, The point of suppressing the residual of the organic solvent in the photosensitive resin film after firing is more preferable, and more preferably 250 ° C or lower.

In this invention, content of (D) component is 5 mass% or more and 70 mass% or less with respect to the whole amount of an organic solvent. At the point where a sufficient step difference embedding effect can be obtained by the presence of a high boiling point solvent, the content of the (D) component is preferably 5 mass% or more, more preferably 15 mass% or more, and even more preferably 30 mass% or more. . On the other hand, in order to maintain the boiling point of the solvent contained in the photosensitive resin composition to such an extent that the drying step is not time-consuming, the content of the (D) component is preferably 70% by mass or less. The point at which the organic solvent remains in the photosensitive resin film after firing is more preferably 60% by mass or less, and even more preferably 50% by mass or less.

As (D) component, the resin which melt | dissolved the said (A) component is preferable. Specific examples include 1,3-dimethyl-2-imidazolinone (boiling point 220 ° C), N, N-dimethylbutyral urea (boiling point 246 ° C), and 3-methoxy-N , N-dimethylpropanamide (boiling point 216 ° C), δ-valerolactone (boiling point 230 ° C), γ-butyrolactone (boiling point 203 ° C), N-methyl-2-pyrrolidone (boiling point 204 ° C) and so on.

The photosensitive resin composition of the present invention preferably contains (E) an organic solvent having a boiling point of 100 ° C. or higher and lower than 200 ° C. at 1013 hPa. By containing (D) component and (E) an organic solvent having a boiling point of 100 ° C. or higher and lower than 200 ° C. at 1013 hPa, the organic solvent can be removed from the coating film in a short time in the drying step. On the other hand, if the boiling point at 1013 hPa is 100 ° C. or higher, the dissolution of the resin component of the aforementioned (A) proceeds, and a situation such as analysis of solid components can be avoided.

In the present invention, the content of the (E) component is 30% by mass or more and 95% by mass or less with respect to the total amount of the organic solvent, and the total of the (D) component and the (E) component is 100% by mass or less with respect to the total amount of the organic solvent. The content of the (E) component is preferably 30% by mass or more, more preferably 40% by mass or more, so that the boiling point of the solvent contained in the photosensitive resin composition is maintained to such an extent that the drying step is not time-consuming. It is preferably at least 50% by mass. On the other hand, from the point that a sufficient step difference embedding effect can be obtained by combining with the (D) component, the content of the (E) component is preferably 95% by mass or less, more preferably 85% by mass or less, especially It is preferably 70% by mass or less.

As an organic solvent, by combining the (D) component and the (E) component, as the fluidity of the photosensitive resin composition is maintained at the time of coating and the subsequent drying step, the effect of improving the step embedding property can be significantly achieved. .

As (E) component, the resin which melt | dissolved the said (A) component is preferable. Specific examples include ethyl lactate (boiling point: 154 ° C), butyl lactate (boiling point: 186 ° C), dipropylene glycol dimethyl ether (boiling point: 171 ° C), and diethylene glycol dimethyl ether (boiling point: 162 ° C). ), Diethylene glycol ethyl methyl ether (boiling point 176 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), 3-methoxybutyl acetate (boiling point 171 ° C), ethylene glycol monoethyl ether Ether acetate (boiling point 160 ° C), diacetone alcohol (boiling point 166 ° C), N-cyclohexyl-2-pyrrolidone (boiling point 154 ° C), N, N-dimethylformamidine (boiling point 153 ° C) ), N, N-Dimethylacetamide (boiling point 165 ° C), Dimethylarsine (boiling point 189 ° C), propylene glycol monomethyl ether acetate (boiling point 146 ° C), N, N-dimethylisopropyl Alkyl glycol monoalkyl ethers such as ammonium butyrate (boiling point 175 ° C), ethylene glycol monomethyl ether (boiling point 124 ° C), propylene glycol monomethyl ether (boiling point 120 ° C); propyl acetate (boiling point 102 ℃), butyl acetate (boiling point 125 ℃), isobutyl acetate (boiling point 118 ℃) and other alkyl acetates; methyl isobutyl ketone (boiling point 116 ℃), methylpropyl ketone (boiling point 102 ℃) Ketones and the like; alcohols such as butanol (boiling point 117 ° C), isobutanol (boiling point 108 ° C) and the like. From the viewpoints of storage stability and viscosity stability of the photosensitive resin composition, ethyl lactate or diethylene glycol ethyl methyl ether, N, N-dimethylisobutyrate, propylene glycol, and the like are more preferable. Monomethyl ether.

The boiling point of organic solvents at 1013 hPa (atmospheric pressure) is described in the CRC Handbook of Chemistry and Physics or the Aldrich Handbook of Fine Chemical and Laboratory Equipment. In the literature. The boiling point of an organic solvent which is not described in a well-known literature can be measured with a commercially available boiling point measuring device, for example, FP81HT / FP81C (made by Mettler-Toledo).

The content of the entire organic solvent of the present invention is preferably 50 parts by mass to 2000 parts by mass with respect to 100 parts by mass of the resin of the component (A). When it is 50 parts by mass or more, it is preferable that the polymer can be dissolved without precipitation in an organic solvent, and more preferably 100 parts by mass or more. If it is 2000 parts by mass or less, it is preferable to control the viscosity suitable for coating, and more preferably 1500 parts by mass.

The photosensitive resin composition of the present invention may optionally contain a low-molecular compound having a phenolic hydroxyl group within a range that does not reduce the shrinkage residual film rate after curing. By containing a low-molecular compound having a phenolic hydroxyl group, adjustment of alkali solubility during pattern processing becomes easy.

In order to exhibit the aforementioned effect, the content of the low-molecular compound having a phenolic hydroxyl group is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the component (A). From the viewpoint of maintaining characteristics, it is preferably 30 parts by mass or less, and more preferably 15 parts by mass or less.

The photosensitive resin composition of this invention may contain (F) a thermal crosslinking agent as needed. As the thermal cross-linking agent, a compound having at least 2 alkoxymethyl and / or hydroxymethyl groups, a compound having at least 2 epoxy groups and / or oxetanyl groups is preferably used, but not limited to these Limited. By containing these compounds, upon curing after patterning, a condensation reaction with the component (A) is caused to form a crosslinked structure, and mechanical properties such as the elongation of the cured film are increased. In addition, two or more types of thermal crosslinking agents may be used, thereby enabling a wider range of designs.

Preferred examples of the compound having at least two alkoxymethyl and / or methylol groups 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, DML-BisOCHP-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, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (The above trade names, Honshu Chemical Industry (Stock system); "NIKALAC" (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (the above trade names, Sanwa Chemical ( Share) system), which can be obtained by various companies. It may contain two or more of these.

Further, as preferable examples of the compound having at least two epoxy groups and / or oxetanyl groups, for example, bisphenol A type epoxy resin, bisphenol A type oxetan resin, bis Phenol F-type epoxy resin, bisphenol F-oxetanyl resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polymethyl (glycidoxypropyl) siloxane Polysiloxanes containing epoxy groups are not limited thereto. Specific examples include "EPICLON" (registered trademark) 850-S, EPICLON HP-4032, EPICLON HP-7200, EPICLON HP-820, EPICLON HP-4700, EPICLON EXA-4710, EPICLON HP-4770, EPICLON EXA-859CRP, EPICLON EXA-1514, EPICLON EXA-4880, EPICLON EXA-4850-150, EPICLON EXA-4850-1000, EPICLON EXA-4816, EPICLON EXA-4822 (The above trade names, Dainippon Ink Chemical Industry (Stock) (Manufactured); "Rikaresin" (registered trademark) BEO-60E (commercial name, New Japan Physical and Chemical (stock) system); EP-4003S, EP-4000S (commercial name, ADEKA (stock) system), etc., can be obtained from various companies. It may contain two or more of these.

The content of the (F) thermal crosslinking agent used in the present invention is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 3 parts by mass or more with respect to 100 parts by mass of the (A) component. From the viewpoint of maintaining mechanical properties such as elongation, it is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, particularly preferably 100 parts by mass or less, even more preferably 70 parts by mass or less, and particularly preferably 40 parts by mass or less .

The photosensitive resin composition of the present invention may contain a surfactant for the purpose of improving the wettability with the substrate, if necessary; esters such as ethyl lactate or propylene glycol monomethyl ether acetate; alcohols such as ethanol ; Ketones such as cyclohexanone, methyl isobutyl ketone; tetrahydrofuran, two Ethers such as alkanes.

The preferable content of the compound used for the purpose of improving wettability with the substrate is 0.001 part by mass or more with respect to 100 parts by mass of the component (A). From the viewpoint of obtaining a moderate film thickness, It is preferably 1800 parts by mass or less, and more preferably 1500 parts by mass or less.

The photosensitive resin composition of the present invention may contain inorganic particles. Preferred specific examples include, but are not limited to, silicon oxide, titanium oxide, barium titanate, alumina, and talc.

From the viewpoint of photosensitivity, the average primary particle diameter of these inorganic particles is preferably 1 nm to 100 nm, and more preferably 10 nm to 60 nm. Each particle diameter of these inorganic particles can be measured by a scanning electron microscope, such as a scanning electron microscope JSM-6301NF made by Japan Electronics Co., Ltd. In addition, the average primary particle diameter can be calculated by measuring the diameter of 100 particles randomly selected from the photograph, and calculating the arithmetic mean.

In addition, in order to improve the adhesion to the silicon substrate, trimethoxyaminopropylsilane, trimethoxyepoxysilane, trimethoxyvinylsilane, and trimethoxyoxide may be contained within a range that does not impair storage stability. Silane coupling agents such as thiol and propylsilane.

The preferable content of these compounds used to improve the adhesion to the silicon substrate is 0.01 parts by mass or more relative to 100 parts by mass of the (A) component, and it is preferable from the viewpoint of maintaining mechanical properties such as elongation. It is 5 parts by mass or less.

The viscosity of the photosensitive resin composition of the present invention is preferably 2 to 5000 mPa · s. By adjusting the solid content concentration so that the viscosity becomes 2 mPa · s or more, a desired film thickness can be easily obtained. On the other hand, if the viscosity is 5000 mPa · s or less, a coating film with high uniformity is easily obtained. A resin composition having such a viscosity can be easily obtained by making the solid content concentration into 5 to 60% by mass, for example.

Next, a method for forming a resin pattern using the photosensitive resin composition of the present invention will be described.

The photosensitive resin composition of the present invention is coated on a substrate. As the substrate, a wafer of silicon, ceramics, gallium arsenide, or the like, or a metal on which electrodes or wirings are formed is not limited. Examples of the coating method include spin coating, spray coating, and roll coating using a spinner. The coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the film thickness after drying becomes 0.1 to 150 μm.

In order to improve the adhesion between a substrate such as a silicon wafer and a photosensitive resin composition, the substrate may be pretreated with the aforementioned silane coupling agent. For example, by dissolving 0.5 to 20 in solvents such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate. A solution prepared by mass% of a silane coupling agent is subjected to surface treatment by spin coating, dipping, spray coating, steam treatment, or the like. Depending on the circumstances, a heat treatment at 50 to 300 ° C. is then performed to perform a reaction between the substrate and the silane coupling agent.

Next, a method for forming a photosensitive resin pattern using the photosensitive resin composition of the present invention will be described. The method for producing a relief pattern of a cured film of the present invention includes the steps of: coating a photosensitive resin composition on a substrate, or laminating a photosensitive resin sheet on a substrate, and drying to form a photosensitive resin film; Alternatively, a step of exposing the photosensitive resin film using a direct drawing device; a step of developing the exposed photosensitive resin film with an alkali solution; and a step of heating the photosensitive resin film after development.

First, a method for forming a photosensitive resin composition film on a substrate using the photosensitive resin composition of the present invention or a photosensitive sheet formed therefrom will be described.

When a photosensitive resin composition is used, a varnish containing the photosensitive resin composition is first applied to a substrate. Examples of the coating method include spin coating, spray coating, roll coating, slit coating, and screen printing using a spinner. The coating film thickness varies depending on the coating method, the solid content concentration and viscosity of the resin composition, but it is generally preferred to apply the film so that the film thickness after drying becomes 0.5 μm or more and 100 μm or less. Next, the substrate coated with the photosensitive resin composition varnish was dried to obtain a photosensitive resin composition film. For the drying system, an oven, a hot plate, or infrared rays can be used. The drying temperature and the drying time may be in a range in which the organic solvent can be volatilized, and it is preferable to set a range in which the photosensitive resin composition film is in an unhardened or semi-hardened state. Specifically, it is preferably performed in a range of 50 to 150 ° C for 1 minute to several hours.

On the other hand, when making the photosensitive resin composition of this invention into a photosensitive resin sheet, it is preferable to apply | coat to a support film, and to dry it, and to form a photosensitive resin sheet. The supporting film used is not particularly limited, but various commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film can be used. On the joint surface of the support film and the photosensitive resin sheet, in order to improve adhesion and peelability, a surface treatment such as polysiloxane, a silane coupling agent, an aluminum chelating agent, and polyurea may be applied. The thickness of the support film is not particularly limited, but is preferably in the range of 10 to 100 μm from the viewpoint of workability. The photosensitive resin composition applied on the support film is subjected to a drying step. From the viewpoint of drying properties, the drying temperature is preferably 50 ° C or higher, and from the viewpoint of not impairing the sensitivity, it is preferably 150 ° C or lower. At this time, the film thickness of the photosensitive resin sheet is preferably 5 m or more from the viewpoint of the step embedding property at the time of lamination, and is preferably 150 m or less from the viewpoint of the uniformity of the film thickness.

In order to protect the surface, the photosensitive resin sheet of the present invention may have a protective film on the sheet. Thereby, it is possible to prevent contaminations such as dust or dirt in the atmosphere, and to protect the surface of the photosensitive resin sheet.

Examples of the protective film include polyolefin films and polyester films. The protective film is preferably one having a small adhesion to the photosensitive resin sheet.

The obtained photosensitive resin sheet was bonded to a substrate. As the substrate, a wafer of ceramics, gallium arsenide, or the like, or a metal on which electrodes or wirings are formed is not limited. When the photosensitive resin sheet has a protective film, it is peeled off, the photosensitive resin sheet is opposed to the substrate, and the photosensitive resin sheet is bonded by hot pressing to obtain a photosensitive resin composition film. The thermocompression bonding system can be performed by a thermocompression process, a thermal lamination process, a thermal vacuum lamination process, or the like. From the standpoint of adhesion to the substrate and embedding property, the bonding temperature is preferably 40 ° C or higher. In addition, in order to prevent the photosensitive resin sheet from being hardened at the time of bonding and the resolution of the pattern formation in the exposure and development steps from being deteriorated, the bonding temperature is preferably 150 ° C or lower.

The photosensitive resin sheet formed from the photosensitive resin composition of the present invention, or a cured film obtained by curing the photosensitive resin composition. The (D) in the cured film has a boiling point of 1013 hPa at 200 ° C or higher and 260 ° C or lower. The amount of the solvent may be preferably 0.005 mass% or more, more preferably 0.01 mass% or more, and more preferably 1 mass% or less, and more preferably 0.5 mass% or less with respect to the total mass of the cured film. By setting the (D) component to 0.005% by mass or more, the adhesion to the copper substrate is further improved, and by setting the component (D) to 1% by mass or less, the (D) component itself can be exhausted without impairing reliability. The mass% of the (D) component in the cured film can be measured by a purge and trap method or a TPD-MS method on the collected cured film. The mass of the compound can be determined from an alkali-soluble resin ( A) Calculate the value of the specific gravity of the component, and calculate the mass% of the compound in the cured film.

A step of applying a photosensitive resin composition on a substrate and drying to form a photosensitive resin film, or a step of laminating a photosensitive resin sheet on a substrate and drying to form a photosensitive resin film, which is used in either case The substrates include, but are not limited to, glass substrates, silicon wafers, ceramics, gallium arsenide, organic circuit substrates, inorganic circuit substrates, and those constituting circuits on such substrates. Etc. limited. Examples of the organic circuit board include glass substrates, copper-clad laminates such as glass cloth, epoxy copper-clad laminates, composite copper-clad laminates such as glass nonwovens, epoxy-clad copper-clad laminates, etc. Flexible substrates such as heat-resistant and thermoplastic substrates such as amine resin substrates, polyetherketone resin substrates, and polyfluorene-based resin substrates, polyester copper-clad film substrates, and polyimide copper-clad film substrates. Examples of the inorganic-based circuit substrate include ceramic substrates such as alumina substrates, aluminum nitride substrates, and silicon carbide substrates, and metal-based substrates such as aluminum-based substrates and iron-based substrates. Examples of circuit constituent materials include conductors containing metals such as silver, gold, and copper; resistors containing inorganic oxides; low dielectric materials containing glass-based materials and / or resins; resins or high dielectric materials High dielectrics such as dielectric constant inorganic particles, insulators containing glass-based materials, etc.

Next, on the photosensitive resin film formed by the above method, exposure is performed by irradiating chemical rays through a mask having a desired pattern, or using a direct drawing device without exposing the mask. The chemical rays used for exposure include ultraviolet rays, visible rays, electron rays, X-rays, YAG lasers, etc., but in the present invention, i-line (365 nm), h-line (405 nm), and g-line ( 436nm). In the photosensitive sheet, when the support is made of a transparent material for such light, the support may be exposed without peeling the support from the photosensitive sheet.

In order to form a pattern, after exposure, a developing solution is used to remove unexposed portions. As the developing solution, an aqueous solution of tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, and methylamine are preferable. , Dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine, etc. Aqueous solution of sexual compounds. In some cases, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and dimethylformamide may be contained in these alkaline aqueous solutions. Polar solvents such as methylene, γ-butyrolactone, dimethylacrylamide, alcohols such as methanol, ethanol, isopropanol, esters such as ethyl lactate, propylene glycol monomethyl ether acetate, etc. One or a combination of ketones such as pentanone, cyclohexanone, isobutyl ketone, methyl isobutyl ketone, and the like.

The development can be performed by spraying the above-mentioned developing solution on the film surface; immersing in the developing solution; or applying ultrasonic while dipping; spraying the developing solution while rotating the substrate. The conditions during development such as the development time or the temperature of the developing solution during the development step are conditions that can remove the unexposed portions. In order to process fine patterns or remove residues between the patterns, it is preferable to The unexposed area is removed before development.

It can also be rinsed with water after development. Here, alcohols such as ethanol and isopropanol, esters such as ethyl lactate, propylene glycol monomethyl ether acetate, and the like may be added to water and subjected to a rinse treatment.

When the resolution of the pattern during development is increased or the tolerance of the development conditions is increased, a step of baking treatment may be incorporated before the development. This temperature is preferably in the range of 50 to 180 ° C, and particularly preferably in the range of 80 to 150 ° C. The time is preferably 5 seconds to several hours.

After the pattern is formed, from the viewpoint of reducing the residual solvent, volatile matter, and water in the photosensitive resin film, it can be dried by heating in the range of 70 to 150 ° C. The time is preferably 1 minute to several hours.

The thus obtained substrate on which the patterned photosensitive resin film is formed is subjected to a temperature of 150 ° C to 450 ° C to form a cured film. This heat treatment is carried out by selecting a temperature and increasing the temperature stepwise, or selecting a certain temperature range and continuously increasing the temperature, and performing the heating for 5 minutes to 10 hours. As an example, there are a method of performing heat treatment at 110 ° C and 250 ° C for 60 minutes each, a method of linearly increasing temperature by taking 2 hours from room temperature to 220 ° C, and the like. At this time, since the high-temperature heating or the repetition thereof may change the electrical characteristics of the device or increase the warpage of the substrate, the heat treatment is preferably performed at 250 ° C or lower. Further, in order to impart chemical resistance by crosslinking or to obtain an interaction between the adhesion improving agent and the substrate, the heat treatment is more preferably performed at 150 ° C or higher. The photosensitive resin composition in the present invention can obtain a cured film excellent in adhesion even at a low temperature firing at 250 ° C or lower.

The cured film obtained by curing the photosensitive resin composition or photosensitive sheet of the present invention can be used in semiconductor devices or semiconductor electronic components. The semiconductor device referred to in the present invention means a memory device (memory) or a device represented by a central processing unit (CPU), which is connected to a semiconductor wafer by a multilayer wiring called a redistribution layer, and is sealed with an epoxy resin or the like. Made of resin. Here, the so-called semiconductor wafer refers to a Si wafer or the like having circuit elements. The term "semiconductor electronic component" as used in the present invention refers to a device (surface acoustic wave filter), inductance, or conductance that takes out a specific frequency. The term "semiconductor device" as used in the present invention refers to all devices that can function by utilizing the characteristics of semiconductor elements. An electro-optical device or a semiconductor circuit substrate having a semiconductor element connected to the substrate, a plurality of semiconductor elements laminated, and an electronic device including these are all included in the semiconductor device. In addition, electronic components such as multilayer wiring boards for connecting semiconductor elements are also included in semiconductor devices. Specifically, it can be applied to passivation films of semiconductors, surface protection films of semiconductor elements, interlayer insulating films between semiconductor elements and wiring, interlayer insulating films between plural semiconductor elements, and interlayer wiring of high-density assembly multilayer wiring. Interlayer insulation films, insulation layers of organic electric field light-emitting elements, and the like are not limited in this way, and can be used for a variety of applications.

Next, an application example in which the photosensitive resin composition of the present invention is applied to a semiconductor device having bumps will be described using drawings. FIG. 1 is an enlarged sectional view of a pad portion of a semiconductor device having bumps. As shown in FIG. 1, in a silicon wafer 1, a passivation film 3 is formed on an Al pad 2 for input, and a through hole is formed in the passivation film 3. Furthermore, an insulating film 4 formed using the photosensitive resin composition of the present invention is formed thereon, and a metal film 5 composed of Cr, Ti, or the like is formed so as to be connected to the Al pad 2. The periphery of the solder bump 10 of the metal film 5 is etched to insulate the solder pads. A barrier metal 8 and a solder bump 10 are formed on the insulated solder pads. When a soft component is introduced into the photosensitive resin composition, since the warpage of the wafer is small, exposure or wafer transportation can be performed with high accuracy. Also, polyimide resin or polybenzo The azole resin is also excellent in mechanical properties and can relieve stress from the sealing resin during assembly, so it can prevent damage to the low-k layer (low dielectric constant layer), and can provide a highly reliable semiconductor device.

Next, a detailed manufacturing method of a semiconductor device having bumps will be described. In the step 2a of FIG. 2, the photosensitive resin composition of the present invention is coated on the silicon wafer 1 on which the Al pad 2 and the passivation film 3 are formed, and a photolithography step is performed to form a patterned insulating film 4. . Next, in step 2b, a metal film 5 is formed by a sputtering method. As shown in FIG. 2C, the metal wiring 6 is formed on the metal film 5 by a plating method. Next, as shown in 2d 'of FIG. 2, the photosensitive resin composition of the present invention is applied and subjected to a photolithography step to form an insulating film 7 having a pattern shown in FIG. 2d. At this time, the photosensitive resin composition of the insulating film 7 is subjected to thick film processing in the cutting line 9. Wiring (so-called rewiring) may be further formed on the insulating film 7. When a multilayer wiring structure having two or more layers is to be formed, the multilayer wiring structure in which two or more layers of rewiring are separated by an interlayer insulating film obtained from the photosensitive resin composition of the present invention can be formed by repeating the above steps. At this time, the formed insulating film comes into contact with various chemical liquids several times. However, since the insulating film obtained from the photosensitive resin composition of the present invention is excellent in adhesion and chemical resistance, it can form a good multilayer wiring structure. . There is no upper limit on the number of layers in a multilayer wiring structure, but most of them use less than 10 layers.

Next, as shown in 2e and 2f of FIG. 2, a barrier metal 8 and a solder bump 10 are formed. Then, each wafer is cut by cutting along the cutting line 9. When the insulating film 7 is not patterned in the dicing line 9 or residues remain, cracks and the like may occur during dicing, which affects the reliability of the wafer. Therefore, if the present invention can provide pattern processing excellent in thick film processing, it is very desirable in order to obtain high reliability of a semiconductor device.

The photosensitive resin composition or the photosensitive sheet of the present invention can also be applied to a fan-out type wafer level package (fan-out type WLP). The fan-out type WLP uses a sealing resin such as epoxy resin to provide an expansion portion around the semiconductor wafer. Rewiring is performed from the electrode on the semiconductor wafer to the expansion portion. The expansion portion is also provided with solder holes. A semiconductor package that secures the required number of terminals. In the fan-out type WLP, wiring is provided so as to cross the boundary line formed by the main surface of the semiconductor wafer and the main surface of the sealing resin. That is, an interlayer insulating film is formed on a substrate made of two or more materials such as a semiconductor wafer to which metal wiring is applied, and a sealing resin, and wiring is formed on the interlayer insulating film. In addition, in a semiconductor package of a type in which a semiconductor wafer is embedded in a recess formed on a glass epoxy substrate, wiring is provided so as to cross a boundary line between a main surface of the semiconductor wafer and a main surface of the printed substrate. In this aspect, an interlayer insulating film is also formed on a substrate made of two or more materials, and wiring is formed on the interlayer insulating film. The cured film obtained by curing the photosensitive resin composition or photosensitive sheet of the present invention has high adhesion to semiconductor wafers to which metal wiring is applied, and also has high adhesion to sealing resins such as epoxy resins. It is suitable for use as an interlayer insulating film provided on a substrate made of two or more materials.

In addition, in a fan-out WLP, processes such as a chip-first method or an RDL-first (Redistribution Layer-first) method can be applied.

The wafer priority method is as described above. First, semiconductor wafers are arranged at arbitrary intervals on a support wafer that becomes a support, and the semiconductor wafer is sealed with a resin to obtain a sealed wafer (pseudo wafer). Next, the support wafer is separated and removed from the sealed wafer, and a wiring layer is formed on the exposed sealed wafer surface. Then, the sealed wafer is divided between the semiconductor wafers, thereby obtaining a plurality of device packages.

In contrast, the RDL priority rule is that first, a wiring layer is formed on a support wafer, and a semiconductor wafer is bonded to this wiring layer. Next, the semiconductor wafer is sealed with a resin to obtain a sealed wafer (dummy wafer). Then, the support wafer is separated and removed from the sealed wafer including the wiring layer, and the sealed wafer is divided between the semiconductor wafers. This RDL priority method can avoid the defective part of the wiring layer and bond the semiconductor wafer, so it is easy to improve the yield compared with the wafer priority method.

Next, a method for preparing a semiconductor device in the RDL priority method will be described using FIG. 3. In FIG. 3A, a barrier metal such as Ti is formed on the support substrate 11 by sputtering, and a Cu seed (seed layer) is formed thereon by sputtering, and then an electrode pad is formed by the plating method. 12. In the subsequent step 3b, the photosensitive resin composition of the present invention is applied, and a photolithography step is performed to form a patterned insulating film 13. In the subsequent step 3c, the seed layer is formed again by the sputtering method, and the metal wiring 14 (rewiring layer) is formed by the plating method. Thereafter, in order to integrate the distance between the conducting portions of the semiconductor wafer and the distance between the metal wirings, the steps 3b and 3c are repeated to form a multilayer wiring structure as shown in 3d. Thereby, the cured film system of this invention is arrange | positioned as an interlayer insulation film between rewiring rooms. In the subsequent step 3e, the photosensitive resin composition of the present invention is applied again, and a photolithography step is performed to form a patterned insulating film, and then the Cu pillars 15 are formed by a plating method. Here, the distance between the Cu pillars is equal to the distance between the conducting portions of the semiconductor wafer. That is, in order to multilayer the redistribution layer while narrowing the metal wiring pitch, as shown in 3e of FIG. 3, the film thickness of the interlayer insulating film is to be an interlayer insulating film 1> interlayer insulating film 2> interlayer insulating film 3> interlayer Insulation film 4>. That is, a plurality of interlayer insulating films are laminated, and a semiconductor wafer is arranged slightly parallel thereto. The thickness of the interlayer insulating film arranged near the semiconductor wafer is thinner than the thickness of the interlayer insulating film arranged further away. In the subsequent step 3f, the semiconductor wafer 17 is connected through the solder bump 16 to obtain a semiconductor device having an RDL priority method with a multilayer wiring structure.

The photosensitive resin composition of the present invention is also suitable for an organic EL display device. The organic EL display device includes a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate. The planarizing layer on the driving circuit and / or the insulating layer on the first electrode are provided by the present invention. The invention consists of a cured film. The organic EL light-emitting material is likely to be deteriorated by moisture, which may cause adverse effects such as a reduction in the area ratio of the light-emitting portion with respect to the area of the light-emitting pixel. Driving and light emitting characteristics. If an active-matrix display device is listed as an example, the substrate is made of glass or various plastics, and has TFTs and wirings connecting the TFTs on the side of the TFTs. The substrates are flattened so as to cover the irregularities. Layer, and a display element is disposed on the planarization layer. The display element and the wiring system are connected through a contact hole formed in the planarization layer.

FIG. 4 is a cross-sectional view showing an example of a TFT substrate. On the substrate 23, a lower gate type or an upper gate type TFT (thin film transistor) 18 is arranged in a matrix shape to cover the TFT 18 to form a TFT insulating layer 20. A wiring 19 connected to the TFT 18 is provided on the TFT insulating layer 20. Further, a planarization layer 21 is provided on the TFT insulating layer 20 in a state where the wiring 19 is buried. A contact hole 24 reaching the wiring 19 is provided in the planarization layer 21. Then, an ITO (transparent electrode) 22 is formed on the planarization layer 21 in a state of being connected to the wiring 19 through the contact hole 24. Here, ITO22 is an electrode of a display element (for example, an organic EL element). Then, the insulating layer 25 is formed so as to cover the periphery of the ITO 22. The organic EL element may be a top-emission type that emits light from the side opposite to the substrate 23, or a bottom-emission type that takes out light from the substrate 23 side. In this way, an organic EL display device of the active matrix type in which the TFT 18 for driving the organic EL element is connected to each organic EL element is obtained.

Such an insulating layer 20, a planarizing layer 21, and / or an insulating layer 25 can be formed by the steps of forming a photosensitive resin film including the resin composition or resin sheet of the present invention as described above, and exposing the photosensitive resin film. A step of developing the exposed photosensitive resin film; and a step of heating the developed photosensitive resin film. By the manufacturing method having these steps, an organic EL display device can be obtained.

In the manufacture of semiconductor devices, for example, a semiconductor substrate formed by the above-mentioned wafer-first method and RDL-first method is a silicon substrate, which is a silicon substrate, a temporary substrate, and a silicon substrate, a glass substrate, Film, etc., to form a wafer processing body. Then, the non-circuit-forming surface (back surface) is polished to become a semiconductor circuit-forming substrate having a thickness of 1 μm to 100 μm.

Examples

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

    (1) determination of molecular weight    

The molecular weight of the resin of (A) component is a GPC (gel permeation chromatography) apparatus Waters 2690-996 (made by Japan WATERS Co., Ltd.), and N-methyl-2-pyrrolidone (hereinafter referred to as "NMP ”) Was measured as a developing solvent, and a weight average molecular weight (Mw) and a dispersion degree (PDI = Mw / Mn) in terms of polystyrene were calculated. The molecular weight of the Y ² component in the general formula (1) of the resin of the component (A) can be measured by LC-MS (Q Exactive, Thermo SCIENTIFIC, Inc.) for a diamine monomer containing a Y ² structure. Calculated as the molecular weight of the main signal.

    (2) Method for measuring film thickness    

After pre-baking, Lambda Ace STM-602 manufactured by Dainippon SCREEN Co., Ltd. was used. Polyimide was used as a reference. The pre-baking film was set to a refractive index of 1.629, and the cured film was set to 1.737. The refractive index was measured.

    (3-1) Evaluation of sensitivity (when a photosensitive resin film is directly formed from varnish)    

The varnish was spin-coated on an 8-inch silicon wafer using a coating and developing device ACT-8 so that the film thickness became 10 μm after pre-baking at 120 ° C for 3 minutes to obtain a photosensitive film. Sexual resin film. For this, exposure was performed using an exposure machine i-line step exposure apparatus NSR-2005i9C (manufactured by NIKON). After exposure, using an ACT-8 imaging device, a 2.38% by mass tetramethylammonium solution (manufactured by Tama Chemical Industry Co., Ltd.) was used, and the ejection time of the imaging solution was repeated twice by the liquid-covering method for 10 seconds and the liquid-covering time of 40. After developing in seconds, rinse with pure water, spin dry, and use the minimum exposure when the unexposed area is completely dissolved as the sensitivity. As a result, those with a sensitivity of 500mJ / cm ² or more or unexposed areas that were completely insoluble and residues were considered to be inadequate C, and those with a sensitivity of 300mJ / cm ² or more and less than 500mJ / cm ² were regarded as good B, and less than 300mJ / cm ^{2 was} regarded as very good A.

    (3-2) Evaluation of sensitivity (case where a photosensitive resin film is formed on a substrate after a photosensitive resin sheet is obtained from a varnish)    

The varnish was applied to a PET film having a thickness of 38 μm using a notched wheel roll coater (manufactured by Techno Smart, MODEL K202), and dried at 75 ° C. for 6 minutes. As a protective film, a PP film having a thickness of 10 μm was laminated. A photosensitive resin sheet was obtained. It adjusted so that the film thickness of the photosensitive resin sheet might be 10 micrometers. Using a lamination device ((Takatori, VTM-200M)), the peeling area was made under the conditions of a platform temperature of 80 ° C, a roll temperature of 80 ° C, a vacuum of 150 Pa, an attachment speed of 5 mm / sec, and an attachment pressure of 0.2 MPa Layer on a silicon wafer, peel off the support film, and form a photosensitive resin film. Then, as described in (3-1), the sensitivity evaluation is performed.

    (4) Adhesion test    

Adhesion tests with metal materials were performed by the following methods.

    <Production of cured film>    

Copper was sputter-plated on a silicon wafer to prepare a substrate (copper-sputtered substrate) having a metal material layer each having a thickness of 200 nm on the surface. On this substrate, a varnish was spin-coated using a spinner (manufactured by MIKASA), followed by a hot plate (D-SPIN manufactured by Dainippon SCREEN Co., Ltd.) and baked at 120 ° C for 3 minutes. A pre-baking film having a thickness of 8 μm was produced. Or, as described in the evaluation of sensitivity (3-2), a photosensitive resin sheet is prepared, and a photosensitive resin film is prepared so that the thickness becomes 8 μm. Then, the entire surface of the substrate was exposed using an exposure machine i-line step exposure apparatus NSR-2005i9C (manufactured by NIKON) at an exposure amount of 1000 mJ / cm ² . For these films, use a clean oven (CLH-21CD-S manufactured by Koyo Thermal Systems Co., Ltd.) under a nitrogen flow (oxygen concentration below 20 ppm) at 140 ° C for 30 minutes, then increase the temperature and cure at 220 ° C for 1 hour. To obtain a cured film.

    <Evaluation of adhesion characteristics>    

The substrate was divided into two, and for each substrate, a single-edged blade was used to introduce a checkerboard-like cut into the cured film at 2 mm intervals and 10 rows and 10 columns. Using one of the sample substrates, peeling off with a scotch tape, counting the number of mask peelings out of 100 masks, and evaluating the adhesion characteristics between the metal material and the cured film. For another sample substrate, a pressure cooker test (PCT) device (HAST CHAMBER EHS-211MD, manufactured by TABAI ESPEC) was used to perform PCT treatment at 121 ° C and 2 atmospheres for 400 hours, and then the above-mentioned peeling was performed. test. In the peel test for any of the substrates, the number of peelings was less than 10 as A (excellent), the number of 10 or more and less than 20 was B (good), and 20 or more was C (insufficient).

    (5) Elongation evaluation    

The varnish and pre-bake were applied by spin coating on an 8-inch silicon wafer using a coating and developing device ACT-8 so that the film thickness became 11 μm after pre-baking at 120 ° C for 3 minutes. grilled. Alternatively, as described in the evaluation of sensitivity (3-2), a photosensitive resin sheet is prepared, and a photosensitive resin film is prepared so that the thickness becomes 11 μm. Then, the entire surface of the substrate was exposed using an exposure machine i-line step exposure apparatus NSR-2005i9C (manufactured by NIKON) at an exposure amount of 1000 mJ / cm ² . Then, using an inert oven CLH-21CD-S (manufactured by Koyo Thermal Systems Co., Ltd.), the temperature was raised to 220 ° C at 3.5 ° C / min at an oxygen concentration of 20 ppm or less, and heat treatment was performed at 220 ° C for 1 hour. When the temperature became 50 ° C or lower, the wafer was taken out, and the film of the resin composition was peeled from the wafer by immersing it in 45% by mass of hydrofluoric acid for 5 minutes. This film was cut into a strip shape having a width of 1 cm and a length of 9 cm. Tensilon RTM-100 (manufactured by ORIENTEC) was used, and the drawing speed was 50 mm / min at a room temperature of 23.0 ° C and a humidity of 45.0% RH. Stretching was performed to measure the elongation at break point. The measurement was performed in 10 strips per specimen, and the average of the upper 5 points was obtained from the results. The value of the elongation at break point of 60% or more is regarded as A (excellent), the value of 30% or more and less than 60% is regarded as B (good), and the value of less than 30% is regarded as C (not sufficient).

    (6) Calculation of the total content of (D) component in the cured film    

Using a coating and developing device Mark-7 (manufactured by Tokyo Electron Co., Ltd.), the varnish was applied by spin coating on an 8-inch silicon wafer, and baked on a hot plate at 120 ° C for 3 minutes to produce a film thickness of 3.2. μm pre-baked film. Then, development was performed using the Mark-7 developing device using a 2.38% by mass tetramethylammonium hydroxide aqueous solution (manufactured by Tama Chemical Industry Co., Ltd.), rinsed with distilled water, and then spin-dried to place the flat film after the development on Under a nitrogen atmosphere, it was cured at 200 ° C for 60 minutes to obtain a cured film.

The film thickness of the obtained cured film was measured, and a 1 × 5 cm (area 5 cm ² ) was cut out from the sample, collected, and adsorbed and captured by a purge and supplement method. Specifically, the collected cured film was heated at 400 ° C. for 60 minutes using helium as a purge gas, and the separated components were collected in an adsorption tube.

The captured components were thermally desorbed using a thermal desorption device at 260 ° C for 15 minutes under primary desorption conditions and -27 ° C and 320 ° C for 5 minutes under secondary desorption conditions. Then, a GC-MS device 7890 / 5975C (manufactured by Agilent Corporation) was used. ), GC-MS analysis was performed under the conditions of column temperature: 40 ~ 300 ° C, carrier gas: helium (1.5mL / min), and scanning range: m / Z29 ~ 600. Using each component of the (D) component, a GC-MS analysis was performed under the same conditions as described above, a calibration curve was prepared, and the amount of gas generated was calculated.

The obtained value (μg) was divided by an area of 5 cm ² to obtain μg / cm ² . Divide the value by the value obtained by multiplying the specific gravity of the alkali-soluble resin (A) by the film thickness, and multiply by 100 to calculate the total content of the compound (D) in the cured film.

    [Synthesis example 1] Synthesis of alkali solution soluble resin (A-1)    

Under a stream of dry nitrogen, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as "BAHF") (25.64 g, 0.070 mole) was dissolved in 185 g of NMP. To this, 1,1 '-(4,4'-oxybenzylidene) diimidazole (hereinafter referred to as "PBOM") (17.20 g, 0.048 mol) was added together with 20 g of NMP and reacted at 85 ° C. 3 hour. Next, 1,12-diaminododecane (5.01 g, 0.025 mol) and 1,3-bis (3-aminopropyl) tetramethyldisilaxane (1.24 g, 0.0050 mol) were added. PBOM (14.33g, 0.044 mole) together with 30g of NMP, reacted at 85 ° C for 1 hour. Furthermore, as a terminal blocking agent, 5-nor The ene-2,3-dicarboxylic anhydride (3.94 g, 0.024 mole) together with 10 g of NMP was reacted at 85 ° C for 30 minutes. After the reaction was completed, the mixture was cooled to room temperature, and acetic acid (26.41 g, 0.50 mol) was added together with 58 g of NMP, followed by stirring at room temperature for 1 hour. After the stirring was completed, the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried with a ventilated dryer at 50 ° C for three days to obtain a powder of an alkali-soluble resin (A-1). When evaluated by the above method, the weight average molecular weight of the resin (A-1) was 33,000, and the PDI was 2.1.

    [Synthesis example 2] Synthesis of alkali-soluble resin (A-2)    

According to the aforementioned Synthesis Example 1, BAHF (25.64 g, 0.070 mole), PBOM (31.53 g, 0.088 mole), D-400 (10.00 g, 0.025 mole) containing propylene oxide structure, and 1,3-bis (3-Aminopropyl) tetramethyldisilazane (1.24g, 0.0050 mole), 5-nor The ene-2,3-dicarboxylic anhydride (3.94 g, 0.024 mole), acetic acid (26.41 g, 0.50 mole), and 300 g of NMP were carried out in the same manner to obtain a powder of an alkali-soluble resin (A-2). When evaluated by the above method, the weight average molecular weight of the resin (A-2) was 34,000, and the PDI was 2.2.

    [Synthesis example 3] Synthesis of alkali-soluble resin (A-3)    

According to Synthesis Example 1, BAHF (25.64g, 0.070 mole), PBOM (31.53g, 0.088 mole), and ED-600 (15.00g, 0.025 mole, HUNTSMAN) containing ethylene oxide and propylene oxide structures were used. (Product), 1,3-bis (3-aminopropyl) tetramethyldisilazane (1.24g, 0.0050 mole), 5-nor The ene-2,3-dicarboxylic anhydride (3.94 g, 0.024 mole), acetic acid (26.41 g, 0.50 mole), and 300 g of NMP were carried out in the same manner to obtain a powder of an alkali-soluble resin (A-3). As a result of evaluation by the above method, the weight average molecular weight of the resin (A-3) was 34,000, and the PDI was 2.3.

    [Synthesis example 4] Synthesis of alkali-soluble resin (A-4)    

According to Synthesis Example 1, BAHF (25.64g, 0.070 mole), PBOM (31.53g, 0.088 mole), and ED-900 (22.50g, 0.025 mole, HUNTSMAN) containing ethylene oxide and propylene oxide structures were used. (Product), 1,3-bis (3-aminopropyl) tetramethyldisilazane (1.24g, 0.0050 mole), 5-nor The ene-2,3-dicarboxylic anhydride (3.94 g, 0.024 mole), acetic acid (26.41 g, 0.50 mole), and 300 g of NMP were carried out in the same manner to obtain a powder of an alkali-soluble resin (A-4). When evaluated by the above method, the weight average molecular weight of the resin (A-4) was 41,000, and the PDI was 2.4.

    [Synthesis example 5] Synthesis of alkali-soluble resin (A-5)    

According to Synthesis Example 1, BAHF (12.82 g, 0.035 mole), 3,3'-diamino-4,4'-dihydroxydiphenylphosphonium (9.81 g, 0.035 mole), and PBOM (31.53 g) were used. , 0.088 mole), ED-900 (22.50 g, 0.025 mole, manufactured by HUNTSMAN), 1,3-bis (3-aminopropyl) tetramethyldisilaxane (1.24 g, 0.0050 mole) Ear), 5-drop The ene-2,3-dicarboxylic anhydride (3.94 g, 0.024 mol), acetic acid (26.41 g, 0.50 mol), and 300 g of NMP were performed in the same manner to obtain a powder of an alkali-soluble resin (A-5). The weight average molecular weight of the resin (A-5) was 51,000 and the PDI was 2.4 when evaluated by the method described above.

    [Synthesis example 6] Synthesis of alkali-soluble resin (A-6)    

According to the aforementioned Synthesis Example 1, BAHF (25.64g, 0.070 mole), PBOM (31.53g, 0.088 mole), RT-1000 (25.00g, 0.025 mole, HUNTSMAN) containing propylene oxide and a tetrahydrofuran structure were used. Made), 1,3-bis (3-aminopropyl) tetramethyldisilaxane (1.24g, 0.0050 mole), 5-nor The ene-2,3-dicarboxylic anhydride (3.94 g, 0.024 mole), acetic acid (26.41 g, 0.50 mole), and 300 g of NMP were carried out in the same manner to obtain a powder of an alkali-soluble resin (A-6). When evaluated by the above method, the weight average molecular weight of the resin (A-6) was 37,000, and the PDI was 1.8.

    [Synthesis Example 7] Synthesis of alkali-soluble resin (A-7)    

According to the aforementioned Synthesis Example 1, BAHF (27.47 g, 0.075 mol), PBOM (31.53 g, 0.088 mol), RT-1000 (20.00 g, 0.020 mol, HUNTSMAN (stock)), 1, 3-double (3-Aminopropyl) tetramethyldisilazane (1.24g, 0.0050 mole), 5-nor The ene-2,3-dicarboxylic anhydride (3.94 g, 0.024 mole), acetic acid (26.41 g, 0.50 mole), and 300 g of NMP were carried out in the same manner to obtain a powder of an alkali-soluble resin (A-7). The weight average molecular weight of the resin (A-7) was 44,000 and the PDI was 2.2 when evaluated by the method described above.

    [Synthesis Example 8] Synthesis of alkali-soluble resin (A-8)    

According to Synthesis Example 1, BAHF (25.64g, 0.070 mole), PBOM (31.53g, 0.088 mole), and ED-2003 (50.00g, 0.025 mole, HUNTSMAN) containing ethylene oxide and propylene oxide structures were used. (Product), 1,3-bis (3-aminopropyl) tetramethyldisilazane (1.24g, 0.0050 mole), 5-nor The ene-2,3-dicarboxylic anhydride (3.94 g, 0.024 mole), acetic acid (26.41 g, 0.50 mole), and 300 g of NMP were performed in the same manner to obtain a powder of an alkali-soluble resin (A-8). As a result of evaluation by the above method, the weight average molecular weight of the resin (A-8) was 52,000, and the PDI was 2.1.

    [Synthesis example 9] Synthesis of alkali-soluble resin (A-9)    

In a 0.2-liter flask equipped with a stirrer and a thermometer, 60 g of N-methylpyrrolidone was added, and 13.92 g (38 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added. , Stir to dissolve. Next, while maintaining the temperature at 0 to 5 ° C., 9.56 g (40 mmol) of sebacin dichloride was dropped over 10 minutes, and then stirring was continued for 60 minutes. The solution was poured into 3 liters of water, and the precipitate was recovered, washed three times with pure water, and then decompressed to obtain an alkali-soluble resin (A-9). (A-9) The weight-average molecular weight determined by GPC method standard polystyrene conversion was 31,600, and the degree of dispersion was 2.0.

    [Synthesis example 10] Synthesis of novolac resin (A-10)    

Under a dry nitrogen stream, m-cresol (70.2 g, 0.65 mole), p-cresol (37.8 g, 0.35 mole), a 37% by mass aqueous formaldehyde solution (75.5 g, (formaldehyde 0.93 mole), and oxalic acid dihydrate were added. (0.63 g, 0.005 mol) and 264 g of methyl isobutyl ketone, and then immersed in an oil bath to carry out a polycondensation reaction for 4 hours while refluxing the reaction solution. Then, it took 3 hours to raise the temperature of the oil bath Then, the pressure in the flask was reduced to 30 to 50 mmHg, the volatile matter was removed, and the dissolved resin was cooled to room temperature to obtain a powder of novolac resin (A-10). The resin was evaluated by the method described above, and the resin was obtained. The weight average molecular weight of (A-10) was 3,500, and the PDI was 2.8.

    [Synthesis Example 11] Synthesis of closed loop polyfluorene imine (A-11)    

Under a stream of dry nitrogen, BAHF (31.13 g, 0.085 mole), 1,3-bis (3-aminopropyl) tetramethyldisilaxane (1.24 g, 0.0050 mole), m-aminophenol ( 2.18 g, 0.020 mol) was dissolved in 250 g of NMP. To this was added 4,4'-oxydiphthalic anhydride (31.02 g, 0.10 mole) together with 50 g of NMP, and the mixture was reacted at 60 ° C for 1 hour, and then stirred at 200 ° C for 4 hours. After the stirring was completed, the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried with a ventilated dryer at 50 ° C. for three days to obtain a powder of a closed polyimide resin (A-11). Evaluation by the above method revealed that the weight average molecular weight of the resin (A-11) was 27,000, and the PDI was 2.0.

    [Examples 1 to 21, Comparative Examples 1, 2]    

Hereinafter, Example 1 will be described as an example for specific description. To 10 g of the obtained alkali-soluble resin (A-1), 1.5 g of the following (b-1-1) and (b-2) of the (b-1) photoinitiator as the (B) photocrosslinking agent was added. ) 3.0 g of the polymerizable unsaturated compound (b-1-2) below, and 0.5 g of the compound (C) having at least one of an oxygen atom and a sulfur atom nitrogen atom in the molecule (C- 1) As (D) 5 g of 3-methoxy-N, N-dimethylpropanamide (D-1) as an organic solvent having a boiling point of 200 ° C or higher and 260 ° C or lower at 1013 hPa, and (E) 15g of ethyl lactate (E-1), which is an organic solvent having a boiling point of 100 ° C or higher and lower than 200 ° C, at 1013 hPa to produce a varnish. As in Example 1, Examples 2 to 21, Comparative Examples 1 and 2 had the composition as shown in Table 1, and varnishes were produced.

The characteristics of the produced varnish were measured by the above-mentioned evaluation method. The results obtained are shown in Table 1. In addition, in the solvents of Examples 1 to 21 and Comparative Examples 1 and 2, 3-methoxy-N, N-dimethylpropylamine (D-1) was set to 5 g, and ethyl lactate (E- 1) It is implemented as 15 g.

This is shown in the table, and the production of the photosensitive resin film is described in the form column as being made from varnish or from sheet.

Alkali-soluble resins (A-1) to (A-9), novolac resins (A-10), and ring-closed polyimide (A-11): prepared according to Synthesis Examples 1 to 11 above

Photoinitiator (b-1-1): 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzophenyIxime) (OXE02, CIBA Special Chemistry (Stock) system)

Photoinitiator (b-1-2): NCI-831 (trade name, made by ADEKA (stock), structure not disclosed)

Polymerizable unsaturated compound (b-2-1): 1,9-nonanediol dimethacrylate

C-1 ~ C-5: The following formulas

D-1: 3-methoxy-N, N-dimethylpropanamide

E-1: ethyl lactate

Thermal crosslinking agent (F-1): NIKALAC MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.)

Claims (26)

A photosensitive resin composition characterized by comprising (A) an alkali-soluble resin having a structural unit represented by the general formula (1), and (B) a photocrosslinking agent; (In the general formula (1), X ¹ and X ² represent a 2- to 10-valent organic group, Y ¹ represents a 2- to 4-valent organic group, and Y ² represents a bivalent having an aliphatic structure having 2 or more carbon atoms. Organic group, R ¹ and R ² represent hydrogen or an organic group having 1 to 20 carbon atoms; p, q, r, s, and t represent 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 2, 0 ≦ Integers in the range of s ≦ 4, 0 ≦ t ≦ 4; n1 and n2 are integers in the range of 1 ≦ n1 ≦ 500, 1 ≦ n2 ≦ 500, and 0.05 ≦ n1 / (n1 + n2) <1, each The arrangement of the repeating unit may be a block or a random one). The photosensitive resin composition according to claim 1, wherein X ¹ and X ² in the general formula (1) each have at least any one of the structural units represented by the general formulas (2) to (4); (In the general formulae (2) to (4), R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ⁵ represents an organic group having 1 to 5 carbon atoms containing an oxygen atom or a sulfur atom. Group, n3 represents an integer in the range of 1 to 20; * represents a chemical bond). The photosensitive resin composition according to claim 1 or 2, wherein the Y ² series aliphatic diamine residue in the general formula (1). The photosensitive resin composition according to any one of claims 1 to 3, wherein Y ² in the general formula (1) has a structural unit represented by the general formula (5); (In the general formula (5), R ⁶ to R ⁹ each independently represent an alkylene group having 2 to 10 carbon atoms, and a, b, and c each represent 1 ≦ a ≦ 20, 0 ≦ b ≦ 20, 0 ≦ c ≦ For integers in the range of 20, the arrangement of each repeating unit can be block or random; * means chemical bonding). The photosensitive resin composition according to any one of claims 1 to 4, wherein Y ² in the general formula (1) has a molecular weight of 150 to 2,000.     The photosensitive resin composition according to any one of claims 1 to 5, wherein the (B) photocrosslinking agent includes (b-1) a photoinitiator and (b-2) a photopolymerizable compound.         The photosensitive resin composition according to claim 6, wherein the (b-2) photopolymerizable compound is a compound having an unsaturated carbon-carbon bond.         The photosensitive resin composition according to any one of claims 1 to 7, further comprising (C) a compound having at least any one of an oxygen atom, a sulfur atom, and a nitrogen atom in the molecule.     The photosensitive resin composition according to claim 8, wherein the compound (C) having at least one of an oxygen atom and a sulfur atom and a nitrogen atom in the molecule is a compound represented by the general formula (6); (In the general formula (6), R ¹⁰ to R ¹² represent any of an oxygen atom, a sulfur atom, or a nitrogen atom, and at least one of R ¹⁰ to R ¹² represents a sulfur atom; l represents 0 or 1; R ¹⁰ is an oxygen or sulfur atom when l is 0; nitrogen is an atom when l is 1; m and n are integers of 1 to 2; u and v are 0 or 1; R ¹¹ and R ¹² are when u, When v is 0, it represents an oxygen atom or a sulfur atom, and when u and v are 1, it represents a nitrogen atom; R ¹³ to R ¹⁷ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms).     The photosensitive resin composition according to any one of claims 1 to 9, further comprising (D) an organic solvent having a boiling point of 1013 hPa at 200 ° C or higher and 260 ° C or lower and (E) a boiling point at 1013 hPa of 100 ° C or higher and For organic solvents below 200 ° C, the content of the organic solvent with a boiling point of 1013 hPa above 200 ° C and below 260 ° C is 5 mass% to 70 mass% with respect to the total amount of the organic solvent. The content of the (E) organic solvent having a boiling point of 1013 hPa of 100 ° C or higher and lower than 200 ° C is 30% by mass or more and 95% by mass or less.         A photosensitive resin sheet formed from the photosensitive resin composition according to any one of claims 1 to 10.         A cured film obtained by curing a photosensitive resin composition according to any one of claims 1 to 10 or a photosensitive resin sheet according to claim 11.         For example, the cured film of claim 12, which contains 0.005 mass% or more and 1 mass% or less of (D) an organic solvent having a boiling point of 1013 hPa of 200 ° C or higher and 260 ° C or lower.         A method for producing a relief pattern of a cured film, comprising: coating the photosensitive resin composition according to any one of claims 1 to 10 on a substrate; or laminating the photosensitive resin sheet according to claim 11 on a substrate Step of forming a photosensitive resin film by drying, exposing the photosensitive resin film through a mask or using a direct drawing device, developing the exposed photosensitive resin film with an alkali solution, and A heat treatment step of the photosensitive resin film after development.         The method for producing an embossed pattern of a cured film according to claim 14, wherein the step of applying the resin composition on a substrate and drying to form a resin film includes a step of applying a slit nozzle to the substrate.         An organic EL display device is provided with at least one of a planarizing layer on a driving circuit and an insulating layer on a first electrode, and a hardened film as claimed in claim 12 or 13.         A semiconductor electronic part is provided with a hardened film as claimed in claim 12 or 13 as an interlayer insulating film between redistribution rooms.         The semiconductor electronic component according to claim 17, wherein the rewiring is a copper metal wiring, and the semiconductor wafer and the copper metal wiring are connected via a bump.         For example, the semiconductor electronic component of claim 17 or 18, wherein at least three or more redistribution layers including the copper metal wiring are arranged.         The semiconductor electronic part according to any one of claims 17 to 19, wherein the interlayer insulating film according to claim 17 is a plurality of laminated layers, and at the same time has a semiconductor wafer arranged slightly parallel to it, and the interlayer insulating film arranged near the semiconductor wafer The thickness is thinner than the thickness of the interlayer insulating film disposed at a distance.         A method for manufacturing a semiconductor electronic component, comprising the step of using a hardened film as claimed in claim 12 or 13 as an interlayer insulating film in a redistribution room, and arranging it on a support substrate provided with a temporary paste material, and disposing the semiconductor thereon. A step of wafer and sealing resin, and a step of peeling a support substrate provided with a temporary paste material and a step of rewiring.         A semiconductor device in which a cured film according to claim 12 or 13 is provided as an interlayer insulating film between redistribution wirings.         The semiconductor device according to claim 22, wherein the rewiring is a copper metal wiring, and the semiconductor wafer and the copper metal wiring are connected via a bump.         The semiconductor device according to claim 22 or 23, wherein at least three or more redistribution layers including the copper metal wiring are arranged.         For example, the semiconductor device of claim 22 to 24, wherein the interlayer insulating film of claim 22 is a plurality of laminated layers and has a semiconductor wafer arranged slightly parallel to it, and the thickness of the interlayer insulating film arranged near the semiconductor wafer is far away. The interlayer insulating film is configured to have a thinner thickness.         A method for manufacturing a semiconductor device, comprising the step of using a hardened film as claimed in claim 12 or 13 as an interlayer insulating film in a rewiring room, and arranging it on a supporting substrate provided with a temporary paste material, and disposing a semiconductor wafer thereon And sealing resin, and then the step of peeling the supporting substrate and the rewiring provided with the temporary bonding material.