WO2018043250A1

WO2018043250A1 - Photosensitive resin composition, cured film, organic el display device, semiconductor electronic component and semiconductor device

Info

Publication number: WO2018043250A1
Application number: PCT/JP2017/030144
Authority: WO
Inventors: 惇早坂; 洋平木内; 奥田　良治
Original assignee: 東レ株式会社
Priority date: 2016-08-29
Filing date: 2017-08-23
Publication date: 2018-03-08
Also published as: JPWO2018043250A1; JP7062953B2; TW201816514A

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, the present invention relates to a photosensitive resin composition suitably used for a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, and the like.

Conventionally, polyimide resins, polybenzoxazole resins, and the like that are excellent in heat resistance, mechanical properties, and the like have been widely used for surface protective films and interlayer insulating films of semiconductor elements of electronic devices. When polyimide or polybenzoxazole is used as a surface protective film or an interlayer insulating film, one method for forming a through hole or the like is etching using a positive photoresist. However, in this method, there is a problem that the process includes application and peeling of a photoresist and is complicated. Therefore, studies have been made on heat-resistant materials imparted with photosensitivity for the purpose of rationalizing work processes.

Polyimide and polybenzoxazole can obtain a thin film having excellent heat resistance and mechanical properties by thermally dehydrating and cyclizing their precursor coating film, but in that case, at a high temperature around 350 ° C. Requires heat treatment. However, for example, MRAM (Magnetic Resistive Random Access Memory), which is promising as a next-generation memory, is vulnerable to high-temperature processes. Therefore, even a surface protective film is cured by heat treatment at a low temperature of about 250 ° C. or lower. There is a need for polyimide resins and polybenzoxazole resins that provide performance comparable to cured films cured by heat treatment at a high temperature of around 350 ° C.

As a method for obtaining a polyimide-based resin and a polybenzoxazole-based resin that are cured by heat treatment at a low temperature, a method of adding a ring closure accelerator, an organic group that promotes ring closure at a low temperature in the unit structure, A method of using polyimide or polybenzoxazole which has been previously ring-closed after imparting alkali solubility is known.

Also, when the photosensitive resin composition is used for applications such as semiconductors, the cured film obtained by heat treatment remains as a permanent film in the device, so the physical properties as the cured film are very important. In order to ensure the reliability of the semiconductor package, adhesion with the material formed on the surface of the semiconductor chip is important. In particular, when used as an insulating film between wiring layers of a wafer level package, adhesion with a metal material used for electrodes, wiring, etc. is important.

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

In general, a heat-resistant resin is considered not to have high adhesion strength to a metal material due to its rigid main chain structure, and in particular, in the case of a cured film of a resin composition imparted with photosensitivity, the photosensitive resin constituting the resin composition Since additives such as an agent, a sensitizer, an acid generator and a dissolution regulator remain in the cured film even after heat curing, the adhesion strength is lower than those containing no additive. As these solutions, a positive photosensitive resin composition comprising an aqueous alkali soluble polymer, a photoacid generator, and a silane compound containing four or more specific functional groups directly bonded to an Al atom, Ti atom, or Si atom Products (see Patent Document 1), heat-resistant resin precursor compositions such as polyimide precursors, and specific amino compounds or thiol derivatives (see Patent Document 2) have been proposed.

Japanese Laid-Open Patent Publication No. 2008-276190 (page 1-3) Japanese Laid-Open Patent Publication No. 2007-39486 (page 1-3)

However, the photosensitive resin composition and the heat-resistant resin precursor composition described in

Patent Documents

1 and 2 generate an organic acid when used as a cured film, corrode metal wiring, especially copper, As a result, the adhesion may be reduced. Further, the cured film itself is decomposed by the generated organic acid, and the mechanical properties, particularly the elongation, may be lowered, resulting in lack of device reliability.

Accordingly, an object of the present invention is to provide a photosensitive resin composition that can provide a cured film having excellent adhesion to a metal material, particularly copper, even in heat treatment at a low temperature, and having a high elongation.

The photosensitive resin composition of this invention has the following structures. That is, it is a photosensitive resin composition 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 divalent to decavalent organic group, Y ¹ represents a divalent to tetravalent organic group, and Y ² represents an aliphatic group having 2 or more carbon atoms. A divalent organic group having a structure, wherein R ¹ and R ² represent hydrogen or an organic group having 1 to 20 carbon atoms, p, q, r, s, and t are 0 ≦ p ≦ 4, 0 ≦ q <= 4, 0 <= r <= 2, 0 <= s <= 4, 0 <= t <= 4 The integer in the range of 4 is represented, n1 and n2 are 1 <= n1 <= 500, 1 <= n2 <= 500, 0.05 <=. The integer satisfying the range of n1 / (n1 + n2) <1 and the arrangement of each repeating unit may be block-like or random.

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

FIG. 1 is an enlarged cross-sectional view of a pad portion of a semiconductor device having bumps. 2a to 2f are diagrams showing a detailed manufacturing method of a semiconductor device having bumps. 3a to 3f are explanatory views illustrating a method for manufacturing a semiconductor device in the RDL first method. FIG. 4 is a cross-sectional view showing an example of a TFT substrate.

The photosensitive resin composition of the present invention includes (A) an alkali-soluble resin having a structural unit represented by the general formula (1), and (B) a photocrosslinking agent. Preferably, (C) a compound having any one of oxygen atom, sulfur atom and nitrogen atom in the molecule, and / or (D) an organic solvent having a boiling point at 1013 hPa of 200 ° C. or higher and 260 ° C. or lower, and (E) a boiling point at 1013 hPa Contains an organic solvent having a temperature of 100 ° C. or higher and lower than 200 ° C. Hereinafter, the component (A), the component (B), the component (C), the component (D), and the component (E) may be omitted.

The cured film formed by curing the photosensitive resin composition of the present invention preferably reduces the generation of organic acid by using a specific (B) photocrosslinking agent and suppresses corrosion of metals, particularly copper. , Adhesion can be improved. Moreover, it is preferable to add (C) component, and interaction with copper increases further, As a result, adhesiveness with a copper substrate improves.

Further, as the reason for excellent elongation, the resin of (A) can easily be stretched by setting the diamine residue constituting the component (A), that is, Y ² to have 2 or more carbon atoms. As a result, a cured film obtained by curing the photosensitive resin composition becomes a high elongation material.

For this reason, the photosensitive resin composition of the present invention can obtain a cured film having high adhesion to a metal material, particularly copper, even in a heat treatment at a low temperature of 250 ° C. or less.

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 divalent to decavalent organic groups, preferably aliphatic carboxylic acid residues.
Y ¹ is a divalent to tetravalent organic group, preferably an organic group having an aromatic group, 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, preferably an aliphatic diamine residue.
R ¹ and R ² represent hydrogen or an organic group having 1 to 20 carbon atoms.
P, q, r, s, and t represent integers in the ranges of 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 2, 0 ≦ s ≦ 4, and 0 ≦ t ≦ 4. n1 and n2 are integers satisfying the ranges 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) The alkali-soluble resin is an alkali-soluble polyamide having an organic group derived from an aliphatic diamine and having a repeating unit represented by the general formula (1), and X ¹ (COOH) ₂ or X ² ( A dicarboxylic acid having a structure of (COOH) ₂ , or a dicarboxylic acid derivative having a structure of X ¹ (COZ) ₂ or X ² (COZ) ₂ (COZ represents an acid derivative of a carboxyl group) and Y ¹ ( It is a polyamide that can be obtained by polycondensation of bisaminophenol and diamine having the structure of NH ₂ ) ₂ (OH) ₂ and Y ² (NH ₂ ) ₂ . Here, the two groups of amino group and hydroxyl group of the bisaminophenol are in the ortho positions to each other, and this polyamide is dehydrated and ring-closed by heating at about 250 ° C. to 400 ° C. The phenol moiety may change to benzoxazole. The base polymer of the photosensitive resin composition of the present invention may or may not be closed after heat curing.

(A) The alkali-soluble resin has a value of n1 / (n1 + n2) in the general formula (1) of 0.05 or more, preferably 0.5 or more, from the viewpoint of solubility in an alkali solution. It is more preferably 7 or more, and further preferably 0.8 or more. Further, from the viewpoint of low stress properties, the value of n1 / (n1 + n2) is less than 1, and more preferably 0.95 or less.

Examples of the dicarboxylic acid having a structure of X ¹ (COOH) ₂ or X ² (COOH) ₂ include the case where X ¹ and X ² are aromatic groups selected from the following structural formulas. It is not limited.

(In the formula, A represents — (direct bond), —O—, —S—, —SO ₂ —, —COO—, —OCO—, —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, (It has a divalent group selected from the group consisting of —C (CF ₃ ) ₂ —.)

As the dicarboxylic acid derivative having the structure of X ¹ (COZ) ₂ and X ² (COZ) ₂ , Z is a group selected from an organic group having 1 to 12 carbon atoms or a halogen element. A selected group is preferred.

(In the formula, Zb and Zc include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, a trifluoromethyl group, a halogen group, a phenoxy group, and a nitro group. Not limited.)

In the present invention, from the viewpoint that a cured film having higher elongation can be obtained, X ¹ and X ² in the general formula (1) are structural units represented by the general formulas (2) to (4), respectively. It is preferable to have at least one of them.

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

Examples of the dicarboxylic acid having the structure represented by the general formulas (2) to (4) include dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, and tetrafluorosuccinic acid. Methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2, 2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, octafluoroadipic acid, pimelic acid, 2,2, 6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexade Fluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosandioic acid, heneicosandioic acid Acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosandioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid , Diglycolic acid, and the like, but are not limited thereto. In the component (A) used in the present invention, the dicarboxylic acid having a structure of X ¹ (COOH) ₂ or X ² (COOH) ₂ is preferably succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid , Sebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosandioic acid Acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosandioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid , But is not limited to diglycolic acid.

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

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

(In the general formula (5), R ⁶ to R ⁹ each independently represents an alkylene group having 2 to 10 carbon atoms, and a, b and c are 0 ≦ a ≦ 20 and 0 ≦ b ≦ 20, respectively. It represents an integer in the range of 0 ≦ c ≦ 20, and the arrangement of each repeating unit may be block or random. * Indicates a chemical bond.)

In the component (A) used in the present invention, examples of the diamine having a structural unit represented by the general formula (5) as Y ² include ethylenediamine, 1,3-diaminopropane, 2-methyl-1,3-propanediamine. 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9 -Diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,2-bis (Aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) E) 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, (trade name, manufactured by HUNTSMAN Co., Ltd.), etc. -S-, -SO-, -SO _2- , -NH-, -NCH _3- , -N (CH ₂ CH ₃ ) A bond such as —, —N (CH ₂ CH ₂ CH ₃ ) —, —N (CH (CH ₃ ) ₂ ) —, —COO—, —CONH—, —OCONH—, —NHCONH— may be included.

In the component (A) used in the present invention, the molecular structure of the structural unit represented by Y ² in the general formula (1) is 150 or more, so that the polyamide structure of the component (A) becomes flexible and cured. High elongation when formed into a film. Furthermore, since the component (A) becomes flexible, the stress on the wafer when the cured film is formed can be relaxed, and the residual stress between the cured film and the substrate is reduced. As a result, the adhesion can be improved. In addition, the introduction of a low UV-absorbing flexible group improves i-ray transmission and can simultaneously achieve high sensitivity. In the general formula (1), the molecular weight of the structural unit represented as Y ² is preferably 150 or more, more preferably 600 or more, and still more preferably 900 or more. Moreover, if molecular weight is 2,000 or less, it is preferable at the point which maintains the solubility to an alkaline solution, 1800 or less is more preferable, and 1500 or less is further more preferable. The molecular weight is more preferably 600 or more and 1,800 or less, and further preferably 900 or more and 1,500 or less. Thereby, elongation and a sensitivity can be raised more.

The molecular weight of Y ² component in the general formula (1) of the resin of component (A) with respect to the diamine monomer containing Y ² structure, for example to measure such in LC-MS, can be obtained as the molecular weight of the main signal.

Moreover, used in the present invention component (A), in addition diamine having a structure of Y _₂ ^(NH 2) 2, it may be copolymerized with other diamines. Examples of other diamines include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4 , 4'-diaminodiphenylsulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, m-phenylenediamine, p-phenylenediamine 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4 -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', Aromatic diamines such as 4,4′-tetramethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, and hydrogen atoms of these aromatic rings And compounds having a structure shown below (in the formula, * indicates a chemical bond), etc., in which a part of is substituted with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group or a halogen atom. Yes, but not limited to . Other diamine to be copolymerized can be used as it is or as a corresponding diisocyanate compound or trimethylsilylated diamine. Moreover, you may use combining these 2 or more types of diamine components.

In addition, an aliphatic group having a siloxane structure may be copolymerized within a range where the heat resistance is not lowered, and the adhesion to the substrate can be improved. Specifically, examples of the diamine component include those obtained by copolymerizing 1 to 15 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like. In the case of copolymerization of 1 mol% or more, it is preferable from the viewpoint of improving the adhesion to a substrate such as a silicon wafer, and in the case of 15 mol% or less, the solubility in an alkaline solution is not lowered.

In order to improve the storage stability of the photosensitive resin composition, the resin of component (A) is end-capped with a main chain terminal such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound, etc. It is preferable to seal with a stopper. In addition, by sealing the terminal of the resin with a terminal sealing 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, the dissolution rate of the resin in an alkaline solution and the resulting curing can be obtained. The mechanical properties of the membrane can be easily adjusted to a preferred range. The introduction ratio of the end-capping agent is preferably 0.1 mol% in order to prevent the molecular weight of the resin of the component (A) from being increased and the solubility in an alkaline solution from being lowered with respect to the total amine component. More preferably, it is 5 mol% or more, and preferably 60 mol% or less, particularly preferably 50 mol in order to suppress a decrease in mechanical properties of the cured film obtained by lowering the molecular weight of the resin of component (A). % Or less. A plurality of different end groups may be introduced by reacting a plurality of end-capping agents.

Monoamines include M-600, M-1000, M-2005, M-2070 (above trade name, manufactured by HUNTSMAN Co., Ltd.), 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-amino Naphthalene, 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- Minonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfone Acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3- Aminothiophenol, 4-aminothiophenol and the like are preferable. Two or more of these may be used.

Acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, etc., as acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene Monocarboxylic acids such as 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, Monoacid chloride compounds in which these carboxyl groups are converted to acid chlorides, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxyl Monoacid chloride compounds in which only one carboxyl group of dicarboxylic acids such as naphthalene and 2,6-dicarboxynaphthalene is acid chloride, monoacid chloride compounds and N-hydroxybenzotriazole, imidazole, N-hydroxy-5-norbornene- Active ester compounds obtained by reaction with 2,3-dicarboximide are preferred. Two or more of these may be used.

Moreover, the terminal blocker introduce | transduced into resin of (A) component used for this invention can be easily detected with the following method. For example, a resin having a terminal blocking agent introduced therein is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component as structural units, and this is measured by gas chromatography (GC) or NMR measurement. The end-capping agent used in the present invention can be easily detected. Apart from this, the resin component into which the end-capping agent has been introduced can also be easily detected by directly measuring it with a pyrolysis gas chromatograph (PGC), infrared spectrum and ¹³ C-NMR spectrum.

In addition, the component (A) used in the present invention may be copolymerized with another structure such as polyimide as long as it includes the structure represented by the general formula (1). Here, the component (A) may have other structures, but preferably has 10 to 100 mol% of the structural unit represented by the general formula (1).

The component (A) in the present invention preferably has a weight average molecular weight of 5,000 or more and 50,000 or less. By setting the weight average molecular weight to 5,000 or more in terms of polystyrene by GPC (gel permeation chromatography), the folding resistance after curing can be improved. On the other hand, when the weight average molecular weight is 50,000 or less, developability with an alkaline solution can be improved. In order to obtain mechanical properties, 20,000 or more is more preferable. Moreover, when 2 or more types of alkali-soluble polyamide are contained, at least 1 type of weight average molecular weight should just be the said range.

The solvent used in the polymerization of the component (A) (hereinafter referred to as a polymerization solvent) is not particularly limited as long as it can dissolve the tetracarboxylic dianhydrides and diamines that are raw material monomers. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N, N′-dimethylpropyleneurea, N, N-dimethyliso Cyclic esters such as butyramide, methoxy-N, N-dimethylpropionamide amides, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone And carbonates such as ethylene carbonate and propylene carbonate; glycols such as triethylene glycol; phenols such as m-cresol and p-cresol; acetophenone, sulfolane and dimethyl sulfoxide. The polymerization solvent is preferably used in an amount of 100 parts by mass or more, more preferably 150 parts by mass or more in order to dissolve the resin after the reaction with respect to 100 parts by mass of the obtained resin. Therefore, it is preferable to use 1,900 parts by mass or less, and more preferably 950 parts by mass or less.

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

(B-1) Photoinitiators include, for example, benzophenones such as benzophenone, Michler's ketone, 4,4, -bis (diethylamino) benzophenone, 3,3,4,4, -tetra (t-butylperoxycarbonyl) benzophenone And benzylidenes such as 3,5-bis (diethylaminobenzylidene) -N-methyl-4-piperidone and 3,5-bis (diethylaminobenzylidene) -N-ethyl-4-piperidone, 7-diethylamino-3-thenonylcoumarin 4,6-dimethyl-3-ethylaminocoumarin, 3,3-carbonylbis (7-diethylaminocoumarin), 7-diethylamino-3- (1-methylbenzimidazolyl) coumarin, 3- (2-benzothiazolyl) -7- Coumarins such as diethylaminocoumarin, 2-t- Anthraquinones such as tilanthraquinone, 2-ethylanthraquinone, 1,2-benzanthraquinone, benzoins such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, ethylene glycol di (3-mercaptopropionate), 2-mercapto Mercaptos such as benzthiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N- (p-chlorophenyl) glycine, N- ( Glycines such as 4-cyanophenyl) glycine, 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o (methoxycarbo Oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, bis (α-iso Nitrosopropiophenone oxime) isophthal, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime), OXE02 (trade name, manufactured by Ciba Specialty Chemicals), NCI Oximes such as -831 (trade name, manufactured by ADEKA Corporation), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-methyl-1 [4- (methylthio) Α-aminoalkylphenones such as phenyl] -2-morpholinopropan-1-one, 2,2′-bis (o-chlorophene) Le) -4,4 ', 5,5'-tetraphenyl biimidazole, and the like. Of these, the above oximes are preferable, and 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-) is particularly preferable. Benzoyl) oxime, bis (α-isonitrosopropiophenoneoxime) isophthal, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime), OXE02, NCI-831 is there. These may be used alone or in combination of two or more.

Among these, the above benzophenones, glycines, mercaptos, oximes, α-aminoalkylphenones, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl A combination selected from biimidazoles is preferred from the viewpoint of photoreaction.

(B-1) The content of the photoinitiator is preferably 0.1 to 60 parts by mass, more preferably 0.2 to 40 parts by mass with respect to 100 parts by mass of the total amount of the component (A). When it is 0.1 part by mass or more, it is preferable in that sufficient radicals are generated by light irradiation and the sensitivity is improved, and when it is 60 parts by mass or less, the light non-irradiated part is cured by generation of excessive radicals. Alkali developability is improved.

(B-2) The photopolymerizable compound is preferably a compound having an unsaturated carbon-carbon bond, that is, a polymerizable unsaturated compound. Examples thereof include unsaturated double bond functional groups such as vinyl group, allyl group, acryloyl group, methacryloyl group and / or unsaturated triple bond functional groups such as propargyl group. Among them, conjugated vinyl groups and acryloyl groups A methacryloyl group is preferred in terms of polymerizability.

Also, the number of functional groups contained is preferably 1 to 4 from the viewpoint of stability, and they may not be the same group.

(B-2) The number average molecular weight of the photopolymerizable compound is not particularly limited, but the number average molecular weight is preferably 800 or less because of good compatibility with the polymer and the reactive diluent. The number average molecular weight is preferably 30 or more for the purpose of suppressing the solubility in the developer after exposure.

(B-2) Specific examples of the polymerizable unsaturated compound include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and trimethylol. Propanediacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, styrene, α-methylstyrene, 1,2-dihydronaphthalene, 1,3-diisopropenylbenzene, 3-methylstyrene, 4-methylstyrene, 2-vinylnaphthalene, butyl acrylate, butyl methacrylate, isobutyl acrylate, hex Acrylate, isooctyl acrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol Diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol- Tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol Tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-diacryloyloxy-2-hydroxypropane, 1,3-dimethacryloyloxy-2 -Hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, 2,2,6,6-tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl acrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl acrylate, ethylene oxide modified bisphenol A diaquo Rate, ethylene oxide-modified bisphenol A dimethacrylate, N- vinylpyrrolidone, etc. N- vinyl caprolactam. These may be used alone or in combination of two or more.

Of these, 1,9-nonanediol dimethacrylate, 1,10-decandiol dimethacrylate, dimethylol-tricyclodecane diacrylate, isobornyl acrylate, isobornyl methacrylate, pentaerythritol triacrylate, penta Erythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, 2,2,6,6- Tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl 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, Examples thereof include N-vinyl pyrrolidone and N-vinyl caprolactam.

(B-2) The content of the polymerizable unsaturated compound is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the component (A). For the purpose of suppressing the solubility in the developer after exposure, Part or more is more preferable, and 20 parts by mass or less is more preferable for the purpose of obtaining a highly perpendicular pattern shape.

The photosensitive resin composition of the present invention can contain (C) a compound having at least 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 metal, particularly copper, and by containing this, the adhesion between the heat-cured film and the metal material is greatly improved.

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 each} represents an oxygen atom, a sulfur atom, or a nitrogen atom, and at least one of R ¹⁰ to R ¹² represents a sulfur atom. R ¹⁰ represents an oxygen atom or a sulfur atom when l is 0, and a nitrogen atom when l is 1. m and n are integers of 1 to 2, u and v are 0 R ¹¹ and R ^{12 each} represents an oxygen atom or a sulfur atom when u and v are 0, and represents a nitrogen atom when u and v are 1. R ¹³ to R ¹⁷ are each independently selected. Represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.)
R ¹³ to R ¹⁵ are hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, alkyl ether group, alkylsilyl group, alkoxysilyl group, aryl group, aryl ether group, carboxyl group, carbonyl group, allyl group, vinyl A group, a heterocyclic group, a combination thereof, and the like, and may further have a substituent. R ¹³ to R ¹⁷ may form a ring with groups adjacent to each other.

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 with respect to 100 parts by mass of the component (A), and more preferably 3 parts by mass or more for the purpose of suppressing solubility in the developer after exposure. 20 mass parts or less are more preferable from a viewpoint of storage stability.

Furthermore, the photosensitive resin composition of the present invention preferably contains (D) an organic solvent having a boiling point of 200 ° C. or more and 260 ° C. or less at 1013 hPa, and (E) an organic solvent having a boiling point of 1013 hPa or more and 100 ° C. or more and less than 200 ° C. Well, the content of the organic solvent having a boiling point in the (D) 1013 hPa of 200 ° C. or more and 260 ° C. or less is 5% by mass or more and 70% by mass or less, and the boiling point in the (E) 1013 hPa is 100 ° C. or more and 200 ° C. The content of the organic solvent at a temperature lower than 0 ° C. is preferably 30% by mass or more and 95% by mass or less with respect to the total amount of the organic solvent.

(D) By containing an organic solvent having a boiling point at 1013 hPa of 200 ° C. or more and 260 ° C. or less, a decrease in fluidity due to drying of the photosensitive resin composition at the time of coating and the subsequent drying step is alleviated, and a step portion of the substrate The embedding property can be improved. The boiling point of component (D) at 1013 hPa is preferably 200 ° C. or higher, since it can mitigate a decrease in fluidity due to drying of the coating film at the time of coating and in the drying step. It is preferable at the point which suppresses the residual of the organic solvent to a conductive resin film, More preferably, it is 250 degrees C or less.

In the present invention, the content of the component (D) is 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 component (D) is preferably 5% by mass or more, more preferably 15% by mass or more, and further preferably 30% by mass or more in that a sufficient step filling effect can be obtained by the presence of a high boiling point solvent. On the other hand, the content of the component (D) is preferably 70% by mass or less from the viewpoint that the boiling point of the solvent contained in the photosensitive resin composition can be maintained to such an extent that it does not require time for the drying step. 60 mass% or less is more preferable and 50 mass% or less is still more preferable at the point which can suppress the residual | survival of the organic solvent to a film | membrane.

The component (D) is preferably one that dissolves the resin of the component (A). Specifically, 1,3-dimethyl-2-imidazolidinone (boiling point 220 ° C.), N, N-dimethylpropyleneurea (boiling point 246 ° C.), 3-methoxy-N, N-dimethylpropionamide (boiling point 216 ° C.) ), Deltavalerolactone (boiling point 230 ° C.), gamma butyrolactone (boiling point 203 ° C.), N-methyl-2-pyrrolidone (boiling point 204 ° C.), and the like.

The photosensitive resin composition of the present invention preferably contains (E) an organic solvent having a boiling point at 1013 hPa of 100 ° C. or higher and lower than 200 ° C. In addition to the component (D), the organic solvent having a boiling point at 1013 hPa of 100 ° C. or more and less than 200 ° C. 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 situation where the resin component (A) is dissolved and the solid content is precipitated can be avoided.

In the present invention, the content of the component (E) is 30% by mass to 95% by mass with respect to the total amount of the organic solvent, and the total of the component (D) and the component (E) is 100% by mass with respect to the total amount of the organic solvent. It is as follows. The content of the component (E) is preferably 30% by mass or more, more preferably 40% by mass or more, in that the boiling point of the solvent contained in the photosensitive resin composition can be maintained to such an extent that it does not require time for the drying step. 50 mass% or more is more preferable. On the other hand, the content of the component (E) is preferably 95% by mass or less, more preferably 85% by mass or less, and more preferably 70% by mass or less in that a sufficient step filling effect can be obtained by combining with the component (D). Further preferred.

By combining the (D) component and the (E) component as the organic solvent, the effect of improving the level difference embedding accompanying maintaining the fluidity of the photosensitive resin composition at the time of coating and the subsequent drying step is remarkably exhibited.

As the component (E), those capable of dissolving the resin of the component (A) are preferable. Specifically, ethyl lactate (boiling point 154 ° C.), butyl lactate (boiling point 186 ° C.), dipropylene glycol dimethyl ether (boiling point 171 ° C.), diethylene glycol dimethyl ether (boiling point 162 ° C.), diethylene glycol ethyl methyl ether (boiling point 176 ° C.), diethylene glycol Diethyl ether (bp 189 ° C.), 3-methoxybutyl acetate (bp 171 ° C.), ethylene glycol monoethyl ether acetate (bp 160 ° C.), diacetone alcohol (bp 166 ° C.), N-cyclohexyl-2-pyrrolidone (bp 154) ° C), N, N-dimethylformamide (boiling point 153 ° C), N, N-dimethylacetamide (boiling point 165 ° C), dimethyl sulfoxide (boiling point 189 ° C), propylene glycol monomethyl ether acetate (Boiling point 146 ° C.), N, N-dimethylisobutyric acid amide (boiling point 175 ° C.), ethylene glycol monomethyl ether (boiling point 124 ° C.), propylene glycol monomethyl ether (boiling point 120 ° C.) and other alkylene glycol monoalkyl ethers, propyl acetate ( Alkyl acetates such as butyl acetate (boiling point 125 ° C.), isobutyl acetate (boiling point 118 ° C.), ketones such as methyl isobutyl ketone (boiling point 116 ° C.), methyl propyl ketone (boiling point 102 ° C.), butyl Examples include alcohols such as alcohol (boiling point 117 ° C.) and isobutyl alcohol (boiling point 108 ° C.). From the viewpoints of storage stability and viscosity stability of the photosensitive resin composition, ethyl lactate, diethylene glycol ethyl methyl ether, N, N-dimethylisobutyric acid amide, or propylene glycol monomethyl ether is more preferable.

The boiling point of organic solvents at 1013 hPa (under atmospheric pressure) is described in the literature of “CRC Handbook of Chemistry and Physics” and “Aldrich Handbook of Fine Chemical and Laboratory Equipment”. The boiling point of an organic solvent not described in the known literature can be measured by a commercially available boiling point measuring device, for example, FP81HT / FP81C (manufactured by METTLER TOLEDO).

The content of the total amount of the 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 (A). It is preferable that it is 50 parts by mass or more from the viewpoint that the polymer dissolves in the organic solvent without precipitation, and more preferably 100 parts by mass or more. It is preferable that it is 2000 parts by mass or less in that it can be controlled to have a viscosity suitable for coating, and more preferably 1500 parts by mass.

The photosensitive resin composition of the present invention may contain a low molecular compound having a phenolic hydroxyl group as long as it does not reduce the shrinkage residual film ratio after curing. By containing the low molecular weight compound having a phenolic hydroxyl group, it is easy to adjust the alkali solubility during pattern processing.

The content of the low molecular weight compound having a phenolic hydroxyl group that is preferable for the purpose of manifesting the effect is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more with respect to 100 parts by mass of the component (A). From the viewpoint of maintaining mechanical properties such as elongation, it is preferably 30 parts by mass or less, more preferably 15 parts by mass or less.

The photosensitive resin composition of the present invention may contain a thermal crosslinking agent (F) as necessary. As the thermal crosslinking agent, a compound having at least two alkoxymethyl groups and / or methylol groups and a compound having at least two epoxy groups and / or oxetanyl groups are preferably used, but are not limited thereto. By containing these compounds, a condensation reaction is caused with the component (A) during curing after patterning to form a crosslinked structure, and mechanical properties such as elongation of the cured film are improved. Further, two or more kinds of thermal cross-linking agents may be used, which enables a wider range of designs.

Preferred examples of the compound having at least two alkoxymethyl groups 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, T OM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), “NIKACALAC” ( Registered trademarks) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKACALAC MX-750LM (above, trade names, manufactured by Sanwa Chemical Co., Ltd.) Is available from Two or more of these may be contained.

Preferred examples of the compound having at least two epoxy groups and / or oxetanyl groups include, for example, bisphenol A type epoxy resins, bisphenol A type oxetanyl resins, bisphenol F type epoxy resins, bisphenol F type oxetanyl resins, propylene glycol diesters. Examples thereof include, but are not limited to, epoxy group-containing silicones such as glycidyl ether, polypropylene glycol diglycidyl ether, and polymethyl (glycidyloxypropyl) siloxane. Specifically, “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-859P EPICLON EXA-1514, EPICLON EXA-4880, EPICLON EXA-4850-150, EPICLON EXA-4850-1000, EPICLON EXA-4816, EPICLON EXA-4822 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.) “Lika Resin” (registered trademark) BEO-60E (trade name, manufactured by Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S (trade names, Co., Ltd.) ADEKA), and the like, are available from each company. Two or more of these may be contained.

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, further preferably 3 parts by mass with respect to 100 parts by mass of the component (A). 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, still more preferably 100 parts by mass or less, still more preferably 70 parts by mass or less, and particularly preferably 40 parts by mass. It is below mass parts.

The photosensitive resin composition of the present invention includes surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone, methyl for the purpose of improving the wettability with the substrate as necessary. Ketones such as isobutyl ketone and ethers such as tetrahydrofuran and dioxane may be contained.

The preferable content of the compound used for the purpose of improving the wettability with these substrates is 0.001 part by mass or more with respect to 100 parts by mass of the component (A), preferably from the viewpoint of obtaining an appropriate film thickness. It is 1800 parts by mass or less, 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, talc and the like.

The average primary particle size of these inorganic particles is preferably from 1 nm to 100 nm, more preferably from 10 nm to 60 nm, from the viewpoint of photosensitivity. The individual particle diameters of these inorganic particles can be measured with a scanning electron microscope, for example, a scanning electron microscope manufactured by JEOL Ltd., JSM-6301NF. The average primary particle diameter can be calculated by measuring the diameter of 100 particles randomly selected from the photograph and obtaining the arithmetic average thereof.

It also contains a silane coupling agent such as trimethoxyaminopropyl silane, trimethoxy epoxy silane, trimethoxy vinyl silane, trimethoxy thiol propyl silane as long as storage stability is not impaired in order to enhance adhesion to the silicon substrate. May be.

The preferable content of the compound used for enhancing the adhesion to these silicon substrates is 0.01 parts by mass or more with respect to 100 parts by mass of the component (A), which is preferable from the viewpoint of maintaining mechanical properties such as elongation. 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 is 2 mPa · s or more, it becomes easy to obtain a desired film thickness. On the other hand, when the viscosity is 5000 mPa · s or less, it becomes easy to obtain a highly uniform coating film. A resin composition having such a viscosity can be easily obtained, for example, by setting the solid content concentration to 5 to 60% by mass.
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 applied to the substrate. As the substrate, a wafer made of silicon, ceramics, gallium arsenide, or the like on which a metal is formed as an electrode or wiring is used, but is not limited thereto. Examples of the application method include spin coating using a spinner, spray coating, and roll coating. 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 is 0.1 to 150 μm.

In order to enhance the adhesion between a substrate such as a silicon wafer and the photosensitive resin composition, the substrate can be pretreated with the above-described silane coupling agent. For example, a solution obtained by dissolving 0.5 to 20% by mass of a silane coupling agent in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. Surface treatment is performed by spin coating, dipping, spray coating, steam treatment or the like. In some cases, a heat treatment at 50 to 300 ° C. is then performed to advance the 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. A method for producing a relief pattern of a cured film according to the present invention includes a step of applying a photosensitive resin composition on a substrate or laminating a photosensitive resin sheet on a substrate and drying to form a photosensitive resin film, a mask Or a step of exposing the photosensitive resin film using a direct drawing apparatus, a step of developing the exposed photosensitive resin film with an alkaline solution, and a heat treatment step of 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 comprising the same will be described.
When using the photosensitive resin composition, first, a varnish made of the photosensitive resin composition is applied on the substrate. Examples of the coating method include spin coating using a spinner, spray coating, roll coating, slit coating, and screen printing. Further, the coating film thickness varies depending on the coating technique, the solid content concentration and the viscosity of the resin composition, etc., but it is usually preferable that the coating film thickness is 0.5 μm or more and 100 μm or less after drying. Next, the substrate coated with the photosensitive resin composition varnish is dried to obtain a photosensitive resin composition film. For drying, an oven, a hot plate, infrared rays, or the like can be used. The drying temperature and drying time may be in a range where the organic solvent can be volatilized, and it is preferable to appropriately set a range in which the photosensitive resin composition film is in an uncured or semi-cured state. Specifically, it is preferably performed in the range of 50 to 150 ° C. for 1 minute to several hours.

On the other hand, when the photosensitive resin composition of the present invention is used as a photosensitive resin sheet, it is preferably applied to a support film and dried to form a photosensitive resin sheet. Although the support film to be used is not particularly limited, various commercially available films such as a polyethylene terephthalate (PET) film, a polyphenylene sulfide film, and a polyimide film can be used. The bonding surface between the support film and the photosensitive resin sheet may be subjected to a surface treatment such as silicone, a silane coupling agent, an aluminum chelating agent, or polyurea in order to improve adhesion and peelability. 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 coated on the support film undergoes a drying process. The drying temperature is preferably 50 ° C. or higher from the viewpoint of drying properties, and is preferably 150 ° C. or lower from the viewpoint of not impairing photosensitivity. At this time, the film thickness of the photosensitive resin sheet is preferably 5 μm or more from the viewpoint of step embedding during lamination, and is preferably 150 μm or less from the viewpoint of film thickness uniformity.

Moreover, in order to protect the surface, the photosensitive resin sheet of this invention may have a protective film on a sheet | seat. Thereby, the photosensitive resin sheet surface can be protected from contaminants such as dust and dust in the atmosphere.
Examples of the protective film include polyolefin films and polyester films. The protective film preferably has a small adhesive force with the photosensitive resin sheet.

The obtained photosensitive resin sheet is bonded to the substrate. As the substrate, a wafer made of silicon, ceramics, gallium arsenide, or the like on which a metal is formed as an electrode or wiring is used, but is not limited thereto. When the photosensitive resin sheet has a protective film, it is peeled off, and the photosensitive resin sheet and the substrate are opposed to each other and bonded together by thermocompression bonding to obtain a photosensitive resin composition film. The thermocompression bonding can be performed by a heat press process, a heat laminating process, a heat vacuum laminating process, or the like. The bonding temperature is preferably 40 ° C. or higher from the viewpoint of adhesion to the substrate and embedding. Further, the bonding temperature is preferably 150 ° C. or lower in order to prevent the photosensitive resin sheet from being cured at the time of bonding and deteriorating the resolution of pattern formation in the exposure / development process.

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, is an organic material having a boiling point of 200 to 260 ° C. at (D) 1013 hPa in the cured film. The amount of the solvent is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, preferably 1% by mass or less, more preferably 0.5% by mass with respect to the total mass of the cured film. It may be the following. By making the component (D) 0.005% by mass or more, the adhesion to the copper substrate is further improved, and by making it 1% by mass or less, the component (D) itself becomes outgas so as not to impair the reliability. Can be. The mass% of the component (D) in the cured film is determined by measuring the mass of the collected cured film by the purge-and-trap method, the TPD-MS method, etc., and determining the value as the alkali-soluble resin (A). By calculating from the specific gravity of the component, the mass% of the compound in the cured film can be calculated.

In either case, the photosensitive resin composition is applied on a substrate and dried to form a photosensitive resin film, or the photosensitive resin sheet is laminated on the substrate and dried to form a photosensitive resin film. Examples of substrates used include glass substrates, silicon wafers, ceramics, gallium arsenide, organic circuit substrates, inorganic circuit substrates, and those in which circuit materials are arranged on these substrates. It is not limited to. Examples of organic circuit boards include: glass substrate copper-clad laminates such as glass cloth / epoxy copper-clad laminates, composite copper-clad laminates such as glass nonwoven fabrics / epoxy copper-clad laminates, polyetherimide resin substrates, polyethers Examples include heat-resistant / thermoplastic substrates such as ketone resin substrates and polysulfone resin substrates, polyester copper-clad film substrates, and polyimide copper-clad film substrates. Examples of the inorganic circuit board include ceramic substrates such as an alumina substrate, an aluminum nitride substrate, and a silicon carbide substrate, and metal substrates such as an aluminum base substrate and an iron base substrate. Examples of circuit components include conductors containing metals such as silver, gold and copper, resistors containing inorganic oxides, low dielectrics containing glass materials and / or resins, resins and high Examples thereof include high dielectric materials containing dielectric constant inorganic particles, insulators containing glass-based materials, and the like.

Next, the photosensitive resin film formed by the above method is irradiated with actinic radiation through a mask having a desired pattern and exposed, or exposed directly without using a mask using a drawing apparatus. Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, YAG lasers, etc., but in the present invention, such as i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) of mercury lamps. It is preferable to use ultraviolet rays. In the photosensitive sheet, when the support is made of a material transparent to these rays, the exposure may be performed without peeling the support from the photosensitive sheet.

To form a pattern, after exposure, the unexposed area is removed using a developer. As developer, aqueous solution of tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol An aqueous solution of a compound exhibiting alkalinity such as dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable. In some cases, these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, Contains alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone alone or in combination of several kinds Good.

Development can be carried out by spraying the developer on the coating surface, immersing in the developer, applying ultrasonic waves while immersing, or spraying the developer while rotating the substrate. The development conditions such as the development time and the temperature of the development step developer may be any conditions that can remove the unexposed areas. In order to process fine patterns or remove residues between patterns, It is preferable to further develop after the portion has been removed.

Rinsing with water may be performed after development. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.

If the pattern resolution at the time of development is improved or the allowable range of development conditions is increased, a process of baking before development may be incorporated. This temperature is preferably in the range of 50 to 180 ° C, and more preferably in the range of 80 to 150 ° C. The time is preferably 5 seconds to several hours.

After the pattern formation, from the viewpoint of reducing the solvent, volatile matter, and water remaining in the photosensitive resin film, heat drying may be performed in the range of 70 to 150 ° C. The time is preferably 1 minute to several hours.

The substrate on which the patterned photosensitive resin film thus obtained is formed is cured at a temperature of 150 ° C. to 450 ° C. This heat treatment is carried out for 5 minutes to 10 hours by selecting the temperature and increasing the temperature stepwise or by selecting a certain temperature range and continuously increasing the temperature. As an example, a method of performing heat treatment at 110 ° C. and 250 ° C. for 60 minutes each, a method of linearly raising the temperature from room temperature to 220 ° C. over 2 hours, and the like can be mentioned. At this time, it is preferable that the heat treatment be performed at 250 ° C. or lower because there is a risk that the electrical characteristics of the element may change due to high-temperature heating or repetition thereof, and warping of the substrate may increase. In addition, in order to impart chemical resistance by crosslinking and 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 provide a cured film having excellent adhesion even at low temperature baking of 250 ° C. or lower.

The cured film obtained by curing the photosensitive resin composition or photosensitive sheet of the present invention can be used for semiconductor devices and semiconductor electronic components. The semiconductor device referred to in the present invention refers to a device represented by a storage device (memory) or a central processing unit (CPU), in which semiconductor chips are connected by a multilayer wiring called a rewiring layer, and a sealing resin such as epoxy Packaged using. Here, the semiconductor chip refers to a Si wafer having circuit elements. The semiconductor electronic component referred to in the present invention refers to a device (surface acoustic wave filter) for extracting a specific frequency, an inductor, and a conductor. The semiconductor device referred to in the present invention refers to all devices that can function by utilizing the characteristics of semiconductor elements. An electro-optical device and a semiconductor circuit substrate in which a semiconductor element is connected to a substrate, a stack of a plurality of semiconductor elements, and an electronic device including these are all included in the semiconductor device. Further, electronic components such as a multilayer wiring board for connecting semiconductor elements are also included in the semiconductor device. Specifically, a semiconductor passivation film, a surface protection film of a semiconductor element, an interlayer insulating film between a semiconductor element and a wiring, an interlayer insulating film between a plurality of semiconductor elements, and an interlayer between wiring layers of a multilayer wiring for high-density mounting Although used suitably for uses, such as an insulating film and an insulating layer of an organic electroluminescent element, it is not restricted to this but can be used for various uses.

Next, application examples of the photosensitive resin composition of the present invention to a semiconductor device having bumps will be described with reference to the drawings. FIG. 1 is an enlarged cross-sectional view of a pad portion of a semiconductor device having bumps. As shown in FIG. 1, a passivation film 3 is formed on an input / output Al pad 2 in a silicon wafer 1, and a via hole is formed in the passivation film 3. Further, an insulating film 4 formed using the photosensitive resin composition of the present invention is formed thereon, and further a metal film 5 made of Cr, Ti or the like is formed so as to be connected to the Al pad 2. Yes. By etching the periphery of the solder bump 10 of the metal film 5, the pads are insulated from each other. A barrier metal 8 and a solder bump 10 are formed on the insulated pad. When a flexible component is introduced into the photosensitive resin composition, since the warpage of the wafer is small, exposure and transportation of the wafer can be performed with high accuracy. In addition, polyimide resin and polybenzoxazole resin also have excellent mechanical properties, so stress from the sealing resin can be relaxed even during mounting, preventing damage to the low-k layer (low dielectric constant layer) and high reliability. The semiconductor device can be provided.

Next, a detailed method for creating a semiconductor device having bumps will be described. 2A, the photosensitive resin composition of the present invention is applied to the silicon wafer 1 on which the Al pad 2 and the passivation film 3 are formed, and a patterned insulating film 4 is formed through a photolithography process. To do. Next, in the step 2b, the metal film 5 is formed by the sputtering method. As shown in 2c of FIG. 2, a metal wiring 6 is formed on the metal film 5 by a plating method. Next, as shown by 2d 'in FIG. 2, the photosensitive resin composition of the present invention is applied, and an insulating film 7 is formed as a pattern as shown in 2d of FIG. 2 through a photolithography process. At this time, the photosensitive resin composition of the insulating film 7 is subjected to thick film processing in the scribe line 9. A wiring (so-called rewiring) can be further formed on the insulating film 7. In the case of forming a multilayer wiring structure having two or more layers, by repeating the above process, two or more layers of rewiring were separated by an interlayer insulating film obtained from the photosensitive resin composition of the present invention. A multilayer wiring structure can be formed. At this time, the formed insulating film will come into contact with various chemicals multiple times, but since the insulating film obtained from the photosensitive resin composition of the present invention is excellent in adhesion and chemical resistance, A good multilayer wiring structure can be formed. There is no upper limit to the number of layers in the multilayer wiring structure, but 10 or fewer layers are often used.

Next, as shown in 2e and 2f of FIG. 2, a barrier metal 8 and a solder bump 10 are formed. Then, the wafer is diced along the scribe line 9 and cut into chips. If the insulating film 7 has no pattern formed on the scribe line 9 or a residue remains, cracks or the like occur during dicing, which affects the reliability of the chip. For this reason, it is very preferable to provide pattern processing excellent in thick film processing as in the present invention in order to obtain high reliability of the semiconductor device.

Further, the photosensitive resin composition and photosensitive sheet of the present invention are also suitably used for fan-out wafer level packages (fan-out WLP). The fan-out WLP is provided with an extended portion using a sealing resin such as epoxy resin around the semiconductor chip, rewiring from the electrode on the semiconductor chip to the extended portion, and mounting a solder ball on the extended portion. This is a semiconductor package that secures the necessary number of terminals. In the fan-out WLP, wiring is installed so as to straddle the boundary line formed by the main surface of the semiconductor chip and the main surface of the sealing resin. That is, an interlayer insulating film is formed on a base material composed of two or more materials such as a semiconductor chip provided with metal wiring and a sealing resin, and wiring is formed on the interlayer insulating film. In addition to this, in a semiconductor package of a type in which a semiconductor chip is embedded in a recess formed in a glass epoxy resin substrate, wiring is installed so as to straddle the boundary line between the main surface of the semiconductor chip and the main surface of the printed circuit board. . Also in this aspect, an interlayer insulating film is formed on a substrate composed of two or more materials, and wiring is formed on the interlayer insulating film. The cured film formed by curing the photosensitive resin composition or photosensitive sheet of the present invention has a high adhesion to a semiconductor chip provided with metal wiring, and also has a high adhesion to an epoxy resin or the like on a sealing resin. Therefore, it is suitably used as an interlayer insulating film provided on a substrate composed of two or more materials.

Also, a process such as a chip-first method or a RDL-first (Redistribution Layer-first) method is applied to the fan-out WLP.

In the chip first method, as described above, first, semiconductor chips are arranged at arbitrary intervals on the upper surface of a support wafer serving as a support, and the semiconductor chips are sealed with resin to obtain a sealed wafer (pseudo wafer). . Next, the support wafer is separated and removed from the sealing wafer, and a wiring layer is formed on the exposed surface of the sealing wafer. Then, a plurality of device packages are obtained by dividing the sealing wafer between the semiconductor chips.

In contrast, in the RDL first method, first, a wiring layer is formed on the upper surface of the supporting wafer, and a semiconductor chip is bonded to the wiring layer. Next, the semiconductor chip is sealed with resin to obtain a sealed wafer (pseudo wafer). Thereafter, the support wafer is separated and removed from the sealing wafer including the wiring layer, and the sealing wafer is divided between the semiconductor chips. In this RDL first method, a semiconductor chip can be bonded while avoiding a defective portion of the wiring layer, so that the yield is easily increased as compared with the chip first method.

Next, a method for manufacturing a semiconductor device in the RDL first method will be described with reference to FIG. 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 further formed thereon by sputtering, and then an electrode pad 12 is formed by plating. In the subsequent step 3b, the photosensitive resin composition of the present invention is applied, and a patterned insulating film 13 is formed through a photolithography process. Next, in step 3c, a seed layer is formed again by a sputtering method, and a metal wiring 14 (rewiring layer) is formed by a plating method. Thereafter, the

steps

3b and 3c are repeated in order to match the pitch of the conductive portion of the semiconductor chip and the pitch of the metal wiring to form a multilayer wiring structure as shown in 3d. Thereby, the cured film of this invention is arrange | positioned as an interlayer insulation film between rewiring. Next, in step 3e, the photosensitive resin composition of the present invention is applied again, and after a photolithography process, a patterned insulating film is formed, and then a Cu post 15 is formed by a plating method. Here, the pitch of the Cu posts is equal to the pitch of the conductive portions of the semiconductor chip. That is, in order to make the rewiring layer multilayer while narrowing the metal wiring pitch, as shown in 3e of FIG. 3, the thickness of the interlayer insulating film is as follows: interlayer insulating film 1> interlayer insulating film 2> interlayer insulating film 3> Interlayer insulating film 4>. That is, a plurality of interlayer insulating films are stacked, a semiconductor chip is disposed substantially parallel to the interlayer insulating film, and the thickness of the interlayer insulating film disposed near the semiconductor chip is the thickness of the interlayer insulating film disposed further away. It will be thinner. Then, in the step 3f, the semiconductor chip 17 is connected through the solder bumps 16 to obtain a semiconductor device by the RDL first method having a multilayer wiring structure.

The photosensitive resin composition of the present invention is also suitably used for an organic EL display device. The organic EL display device includes a drive circuit, a planarization layer, a first electrode, an insulating layer, a light emitting layer, and a second electrode on a substrate, and the planarization layer and / or the first electrode on the drive circuit. The insulating layer is made of the cured film of the present invention. Organic EL light-emitting materials are susceptible to deterioration due to moisture and may adversely affect the area ratio of the light-emitting portion relative to the area of the light-emitting pixels, but the cured film of the present invention has a low water absorption rate, so stable driving and light emission Characteristics are obtained. Taking an active matrix display device as an example, it has a TFT on a substrate made of glass, various plastics, etc., and a wiring located on a side portion of the TFT and connected to the TFT, and covers unevenness thereon. Thus, the planarization layer is provided, and the display element is provided on the planarization layer. The display element and the wiring are connected through a contact hole formed in the planarization layer.

FIG. 4 shows a cross-sectional view of an example of a TFT substrate. On the substrate 23, bottom gate type or top gate type TFTs (thin film transistors) 18 are provided in a matrix, and the TFT insulating layer 20 is formed so as to cover the TFTs 18. A wiring 19 connected to the TFT 18 is provided on the TFT insulating layer 20. Further, a planarizing layer 21 is provided on the TFT insulating layer 20 in a state where the wiring 19 is embedded. A contact hole 24 reaching the wiring 19 is provided in the planarization layer 21. An ITO (transparent electrode) 22 is formed on the planarizing layer 21 while being connected to the wiring 19 through the contact hole 24. Here, the ITO 22 serves as an electrode of a display element (for example, an organic EL element). An 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 emitted light from the side opposite to the substrate 23 or a bottom emission type that extracts light from the substrate 23 side. In this manner, an active matrix organic EL display device in which the TFT 18 for driving the organic EL element is connected to each organic EL element is obtained.

As described above, the insulating layer 20, the planarizing layer 21, and / or the insulating layer 25 are a step of forming a photosensitive resin film made of the resin composition or resin sheet of the present invention, a step of exposing the photosensitive resin film, It can form by the process of developing the exposed photosensitive resin film, and the process of heat-processing the developed photosensitive resin film. An organic EL display device can be obtained from the manufacturing method having these steps.

In the manufacture of semiconductor devices, for example, a silicon substrate that is a semiconductor circuit forming substrate manufactured by the chip first method or the RDL first method described above is used as a support substrate using a temporary bonding adhesive, a glass substrate, a film. The wafer processed body is formed by adhering to the above. Thereafter, the non-circuit forming surface (back surface) is polished to obtain a semiconductor circuit forming substrate having a thickness of 1 μm to 100 μm.

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

(1) Molecular weight measurement The molecular weight of the resin of component (A) was measured using a GPC (gel permeation chromatography) apparatus Waters 2690-996 (manufactured by Nippon Waters Co., Ltd.), and the developing solvent was N-methyl-2-pyrrolidone (hereinafter referred to as “the developing solvent”). The weight average molecular weight (Mw) and dispersity (PDI = Mw / Mn) were calculated in terms of polystyrene. The molecular weight of the Y ² component in the general formula (1) of the component (A) resin is measured by LC-MS (Q Exactive, Thermo SCIENTIFIC, Inc.) for the diamine monomer containing the Y ² structure. The molecular weight can be obtained.

(2) Measuring method of film thickness After pre-baking, Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. was used as the standard, the film after pre-baking was set to have a refractive index of 1.629, and the film after curing was The refractive index was measured as 1.773.

(3-1) Evaluation of sensitivity (in the case of using a photosensitive resin film directly from the varnish)
The varnish was coated on an 8-inch silicon wafer by spin coating using a coating / developing apparatus ACT-8 (manufactured by Tokyo Electron) so that the film thickness after pre-baking at 120 ° C. for 3 minutes was 10 μm. A resin film was obtained. This was exposed using an exposure machine i-line stepper NSR-2005i9C (manufactured by Nikon). After the exposure, using an ACT-8 developing device, a 2.38 mass% tetramethylammonium solution (manufactured by Tama Chemical Industry) was used for development with a developer discharge time of 10 seconds and a paddle time of 40 seconds. Repeated twice, rinsed with pure water, then shaken off and dried, and the minimum exposure when the unexposed area was completely dissolved was defined as sensitivity. As a result, the sensitivity is 500 mJ / cm ² or more, or the unexposed part is not completely dissolved and there is a residue C, and C is 300 mJ / cm ² or more and less than 500 mJ / cm ² is good B. A sample having a value of less than 300 mJ / cm ² was regarded as very good A.

(3-2) Evaluation of sensitivity (when a photosensitive resin sheet is obtained from a varnish and then a photosensitive resin film is formed on the substrate)
The varnish was coated on a PET film having a thickness of 38 μm using a comma roll coater (manufactured by Techno Smart Co., Ltd., MODEL K202), dried at 75 ° C. for 6 minutes, and then having a thickness of 10 μm as a protective film. A PP film was laminated to obtain a photosensitive resin sheet. The film thickness of the photosensitive resin sheet was adjusted to 10 μm. Using a laminating apparatus (manufactured by Takatori Co., Ltd., VTM-200M), the release surface was placed on a silicon wafer with a stage temperature of 80 ° C., a roll temperature of 80 ° C., a vacuum of 150 Pa, a sticking speed of 5 mm / sec, and a sticking pressure of 0 The film was laminated under the condition of 2 MPa, and the support film was peeled off to obtain a photosensitive resin film. Thereafter, the sensitivity was evaluated as described in (3-1).

(4) Adhesion test An adhesion test with a metal material was performed by the following method.
<Preparation of cure film>
Copper was sputtered onto a silicon wafer, and a substrate (copper sputter substrate) having a metal material layer formed with a thickness of 200 nm on the surface was prepared. On this substrate, varnish was applied by spin coating using a spinner (Mikasa Co., Ltd.) and then baked at 120 ° C. for 3 minutes using a hot plate (D-SPIN manufactured by Dainippon Screen Mfg. Co., Ltd.). Finally, a pre-baked film having a thickness of 8 μm was produced. Alternatively, a photosensitive resin sheet was prepared as described in (3-2) Evaluation of sensitivity, and a photosensitive resin film was prepared to have a thickness of 8 μm. Thereafter, the entire surface of the substrate was exposed at an exposure amount of 1000 mJ / cm ² using an exposure machine i-line stepper NSR-2005i9C (manufactured by Nikon Corporation). Using a clean oven (CLH-21CD-S manufactured by Koyo Thermo System Co., Ltd.), these membranes were heated at 140 ° C. for 30 minutes under a nitrogen stream (oxygen concentration of 20 ppm or less), then further heated to 220 ° C. Cured for 1 hour to obtain a cured film.

<Adhesion characteristics evaluation>
The substrate was divided into two, and each substrate was cut into 10 rows and 10 columns in a grid pattern at intervals of 2 mm using a single blade on the cured film. Of these, one sample substrate was used to count how many of the 100 cells were peeled by peeling with a cellophane tape, and the adhesion characteristics between the metal material and the cured film were evaluated. The other sample substrate was subjected to PCT treatment for 400 hours under a saturated condition of 121 ° C. and 2 atm using a pressure cooker test (PCT) apparatus (HAST CHAMBER EHS-212MD manufactured by Tabais Peeck Co., Ltd.). Thereafter, the above-described peeling test was performed. In any of the substrates, the number of peeled off in the peeling test was A (excellent) when 10 or less, and B (good) when 10 or more and 20 or less, and C (insufficient) when 20 or more.

(5) Evaluation of elongation The varnish was applied and prebaked on an 8-inch silicon wafer by spin coating using a coating / developing apparatus ACT-8 so that the film thickness after prebaking at 120 ° C. for 3 minutes was 11 μm. . Alternatively, a photosensitive resin sheet was prepared as described in (3-2) Evaluation of sensitivity, and a photosensitive resin film was prepared to have a thickness of 11 μm. Thereafter, the entire surface of the substrate was exposed at an exposure amount of 1000 mJ / cm ² using an exposure machine i-line stepper NSR-2005i9C (manufactured by Nikon Corporation). Then, using an inert oven CLH-21CD-S (manufactured by Koyo Thermo System 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. It was. When the temperature became 50 ° C. or lower, the wafer was taken out and immersed in 45% by mass of hydrofluoric acid for 5 minutes to peel off the resin composition film from the wafer. This film was cut into strips having a width of 1 cm and a length of 9 cm, and using Tensilon RTM-100 (manufactured by Orientec Co., Ltd.) at a room temperature of 23.0 ° C. and a humidity of 45.0% RH, a tensile rate of 50 mm / The sample was pulled in minutes and the elongation at break was measured. The measurement was performed on 10 strips per specimen, and the average value of the top 5 points was obtained from the results. The elongation at break value of 60% or more was designated as A (excellent), 30% or more and less than 60% as B (good), and less than 30% as C (insufficient).

(6) Calculation of the total content of component (D) in the cured film Using a coating and developing apparatus Mark-7 (manufactured by Tokyo Electron Ltd.), varnish was applied on an 8-inch silicon wafer by spin coating. Baked on a hot plate at 120 ° C. for 3 minutes to produce a pre-baked film having a thickness of 3.2 μm. Thereafter, using the Mark-7 developing device, development was performed using a 2.38 mass% tetramethylammonium aqueous solution (manufactured by Tama Chemical Industry Co., Ltd.), rinsed with distilled water, shaken off, dried, and developed. The back solid film was cured at 200 ° C. for 60 minutes in a nitrogen atmosphere to obtain a cured film.

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

The collected components are thermally desorbed using a thermal desorption apparatus at a primary desorption condition of 260 ° C. for 15 minutes, a secondary adsorption desorption condition of −27 ° C. and 320 ° C. for 5 minutes, and then a GC-MS apparatus 7890. / 5975C (manufactured by Agilent), GC-MS analysis was performed under the conditions of column temperature: 40 to 300 ° C., carrier gas: helium (1.5 mL / min), scan range: m / Z 29 to 600. The amount of gas generated was calculated by preparing a calibration curve by GC-MS analysis of each component (D) under the same conditions as described above.

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

Synthesis Example 1 Synthesis of Alkaline Solution-Soluble Resin (A-1) 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as “BAHF”) under a dry nitrogen stream 25.64 g, 0.070 mol) was dissolved in 185 g of NMP. To this was added 1,1 ′-(4,4′-oxybenzoyl) diimidazole (hereinafter referred to as “PBOM”) (17.20 g, 0.048 mol) together with 20 g of NMP, and at 85 ° C. for 3 hours. Reacted. Subsequently, 1,12-diaminododecane (5.01 g, 0.025 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (1.24 g, 0.0050 mol), PBOM (14. 33 g, 0.044 mol) was added together with 30 g of NMP and reacted at 85 ° C. for 1 hour. Further, 5-norbornene-2,3-dicarboxylic acid anhydride (3.94 g, 0.024 mol) was added as a terminal blocking agent together with 10 g of NMP and reacted at 85 ° C. for 30 minutes. After completion of the reaction, the mixture was cooled to room temperature, acetic acid (26.41 g, 0.50 mol) was added together with 58 g of NMP, and the mixture was stirred at room temperature for 1 hour. After stirring, the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried for 3 days in a ventilator at 50 ° C. to obtain an alkali-soluble resin (A-1) powder. As a result of evaluation by the above method, the resin (A-1) had a weight average molecular weight of 33,000 and PDI of 2.1.

[Synthesis Example 2] Synthesis of Alkali-Soluble Resin (A-2) According to Synthesis Example 1, BAHF (25.64 g, 0.070 mol), PBOM (31.53 g, 0.088 mol), and propylene oxide structure are included. D-400 (10.00 g, 0.025 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (1.24 g, 0.0050 mol), 5-norbornene-2,3-dicarboxylic acid An alkali-soluble resin (A-2) powder was obtained in the same manner using anhydride (3.94 g, 0.024 mol), acetic acid (26.41 g, 0.50 mol), and NMP 300 g. As a result of evaluation by the above method, the resin (A-2) had a weight average molecular weight of 34,000 and PDI of 2.2.

[Synthesis Example 3] Synthesis of Alkali-Soluble Resin (A-3) According to Synthesis Example 1, BAHF (25.64 g, 0.070 mol), PBOM (31.53 g, 0.088 mol), ethylene oxide and propylene oxide structures ED-600 (15.00 g, 0.025 mol, manufactured by HUNTSMAN), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (1.24 g, 0.0050 mol), 5- The same procedure was carried out using norbornene-2,3-dicarboxylic acid anhydride (3.94 g, 0.024 mol), acetic acid (26.41 g, 0.50 mol), and 300 g of NMP to obtain an alkali-soluble resin (A-3). A powder was obtained. As a result of evaluation by the above method, the resin (A-3) had a weight average molecular weight of 34,000 and PDI of 2.3.

[Synthesis Example 4] Synthesis of Alkali-Soluble Resin (A-4) According to Synthesis Example 1, BAHF (25.64 g, 0.070 mol), PBOM (31.53 g, 0.088 mol), ethylene oxide and propylene oxide structures ED-900 (22.50 g, 0.025 mol, manufactured by HUNTSMAN), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (1.24 g, 0.0050 mol), 5- The same procedure was carried out using norbornene-2,3-dicarboxylic anhydride (3.94 g, 0.024 mol), acetic acid (26.41 g, 0.50 mol), and 300 g of NMP to obtain an alkali-soluble resin (A-4). A powder was obtained. As a result of evaluation by the above methods, the resin (A-4) had a weight average molecular weight of 41,000 and PDI of 2.4.

Synthesis Example 5 Synthesis of Alkali-Soluble Resin (A-5) According to Synthesis Example 1, BAHF (12.82 g, 0.035 mol), 3,3′-diamino-4,4′-dihydroxydiphenyl sulfone (9 .81 g, 0.035 mol), PBOM (31.53 g, 0.088 mol), ED-900 (22.50 g, 0.025 mol, manufactured by HUNTSMAN), 1,3-bis (3-amino) Propyl) tetramethyldisiloxane (1.24 g, 0.0050 mol), 5-norbornene-2,3-dicarboxylic anhydride (3.94 g, 0.024 mol), acetic acid (26.41 g, 0.50 mol) ) And NMP 300 g in the same manner to obtain an alkali-soluble resin (A-5) powder. As a result of evaluation by the above method, the resin (A-5) had a weight average molecular weight of 51,000 and PDI of 2.4.

[Synthesis Example 6] Synthesis of Alkali-Soluble Resin (A-6) According to Synthesis Example 1, BAHF (25.64 g, 0.070 mol), PBOM (31.53 g, 0.088 mol), propylene oxide and tetramethylene RT-1000 containing an oxide structure (25.00 g, 0.025 mol, manufactured by HUNTSMAN), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (1.24 g, 0.0050 mol), The same procedure was carried out using 5-norbornene-2,3-dicarboxylic anhydride (3.94 g, 0.024 mol), acetic acid (26.41 g, 0.50 mol), and 300 g of NMP, and an alkali-soluble resin (A-6 ) Was obtained. As a result of evaluation by the above method, the resin (A-6) had a weight average molecular weight of 37,000 and PDI of 1.8.

Synthesis Example 7 Synthesis of Alkali-Soluble Resin (A-7) According to Synthesis Example 1, BAHF (27.47 g, 0.075 mol), PBOM (31.53 g, 0.088 mol), RT-1000 (20 0.000 g, 0.020 mol, manufactured by HUNTSMAN), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (1.24 g, 0.0050 mol), 5-norbornene-2,3-dicarboxylic acid The same procedure was performed using acid anhydride (3.94 g, 0.024 mol), acetic acid (26.41 g, 0.50 mol), and 300 g of NMP to obtain an alkali-soluble resin (A-7) powder. As a result of evaluation by the above method, the resin (A-7) had a weight average molecular weight of 44,000 and PDI of 2.2.

[Synthesis Example 8] Synthesis of Alkali-Soluble Resin (A-8) According to Synthesis Example 1, BAHF (25.64 g, 0.070 mol), PBOM (31.53 g, 0.088 mol), ethylene oxide and propylene oxide structure ED-2003 (50.00 g, 0.025 mol, manufactured by HUNTSMAN), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (1.24 g, 0.0050 mol), 5- The same procedure was carried out using norbornene-2,3-dicarboxylic anhydride (3.94 g, 0.024 mol), acetic acid (26.41 g, 0.50 mol), and 300 g of NMP, and the alkali-soluble resin (A-8) A powder was obtained. 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 charged, and 2,2-bis (3-amino-4 -Hydroxyphenyl) hexafluoropropane (13.92 g, 38 mmol) was added and dissolved by stirring. Subsequently, 9.56 g (40 mmol) of sebacic acid dichloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5 ° C., and stirring was continued for 60 minutes. The solution was poured into 3 liters of water, and the precipitate was collected, washed with pure water three times, and then decompressed to obtain an alkali-soluble resin (A-9). The weight average molecular weight determined by GPC standard polystyrene conversion of (A-9) was 31,600, and the degree of dispersion was 2.0.

Synthesis Example 10 Synthesis of Novolak Resin (A-10) m-cresol (70.2 g, 0.65 mol), p-cresol (37.8 g, 0.35 mol), 37% by mass under a dry nitrogen stream An aqueous formaldehyde solution (75.5 g, (formaldehyde 0.93 mol), oxalic acid dihydrate (0.63 g, 0.005 mol), and 264 g of methyl isobutyl ketone were charged, and then immersed in an oil bath. The polycondensation reaction was carried out for 4 hours while refluxing, and then the temperature of the oil bath was raised over 3 hours, and then the pressure in the flask was reduced to 30-50 mmHg to remove volatiles and dissolution. The resulting resin was cooled to room temperature to obtain a novolak resin (A-10) powder, and as a result of evaluation by the above method, the resin (A-10) had a weight average molecular weight of 3,500 and a PDI of 2 .8 Was Tsu.

Synthesis Example 11 Synthesis of Ring-Closed Polyimide (A-11) BAHF (31.13 g, 0.085 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (1. 24 g, 0.0050 mol) and m-aminophenol (2.18 g, 0.020 mol) were dissolved in 250 g of NMP. To this, 4,4′-oxydiphthalic anhydride (31.02 g, 0.10 mol) was added together with 50 g of NMP, reacted at 60 ° C. for 1 hour, and then stirred at 200 ° C. for 4 hours. After stirring, the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried for 3 days with a ventilator at 50 ° C. to obtain a powder of a closed ring polyimide resin (A-11). As a result of evaluation by the above method, the resin (A-11) had a weight average molecular weight of 27,000 and PDI of 2.0.

[Examples 1 to 21, Comparative Examples 1 and 2]
Example 1 will be described below in detail as an example. 10 g of the obtained alkali-soluble resin (A-1) (B-1) 1.5 g of (b-1) photoinitiator (b-1) as a photocrosslinking agent, and (b-2) polymerizability 3.0 g of the following (b-1-2) as an unsaturated compound, and (C) 0.5 g of the following (C-1) is added as a compound having at least an oxygen atom or a sulfur atom or nitrogen atom in the molecule. (D) 5 g of 3-methoxy-N, N-dimethylpropionamide (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) a boiling point of 100 ° C. or higher and 200 ° C. at 1013 hPa. A varnish was prepared by adding 15 g of ethyl lactate (E-1) as a less organic solvent. In the same manner as in Example 1, varnishes according to the compositions shown in Table 1 were prepared in Examples 2 to 21 and Comparative Examples 1 and 2.
The characteristics of the produced varnish were measured by the above evaluation method. The obtained results are shown in Table 1. The solvents of Examples 1 to 21 and Comparative Examples 1 and 2 were all prepared with 5 g of 3-methoxy-N, N-dimethylpropionamide (D-1) and 15 g of ethyl lactate (E-1).
Here, in the column of the form, the photosensitive resin film is produced by distinguishing whether it is produced from a varnish or a sheet.
Alkali-soluble resins (A-1) to (A-9), novolak resin (A-10), closed ring polyimide (A-11): prepared in Synthesis Examples 1 to 11 Photoinitiator (b-1-1) : 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime) (OXE02, manufactured by Ciba Specialty Chemicals)
Photoinitiator (b-1-2): NCI-831 (trade name, manufactured by ADEKA Corporation, structure not disclosed)
Polymerizable unsaturated compound (b-2-1): 1,9-nonanediol dimethacrylate C-1 to C-5:

D-1: 3-methoxy-N, N-dimethylpropionamide E-1: Ethyl lactate Thermal cross-linking agent (F-1): NIKACALAC MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.)

DESCRIPTION OF SYMBOLS 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 Scribe line 10 Solder bump 11 Support substrate (glass substrate, silicon wafer)
12 electrode pad (Cu)
13 Insulating film 14 Metal wiring (Cu)
15 Cu post 16 Solder bump 17 Semiconductor chip 18 TFT (thin film transistor)
19 Wiring 20 TFT insulation layer 21 Flattening layer 22 ITO (transparent electrode)
23 Substrate 24 Contact hole 25 Insulating layer

Claims

A photosensitive resin composition 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 divalent to decavalent organic group, Y 1 represents a divalent to tetravalent organic group, and Y 2 represents an aliphatic group having 2 or more carbon atoms. A divalent organic group having a structure, wherein R 1 and R 2 represent hydrogen or an organic group having 1 to 20 carbon atoms, p, q, r, s, and t are 0 ≦ p ≦ 4, 0 ≦ q <= 4, 0 <= r <= 2, 0 <= s <= 4, 0 <= t <= 4 The integer in the range of 4 is represented, n1 and n2 are 1 <= n1 <= 500, 1 <= n2 <= 500, 0.05 <=. (An integer satisfying the range of n1 / (n1 + n2) <1 and the arrangement of each repeating unit may be block or random.)
The photosensitive resin composition according to claim 1, wherein X 1 and X 2 in the general formula (1) each have at least one of the structural units represented by the general formulas (2) to (4). .

(In the general formulas (2) to (4), R 3 and R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 5 represents a carbon number containing an oxygen atom or a sulfur atom. 1 to 5 represents an organic group, and n3 represents an integer within the range of 1 to 20. * represents a chemical bond.)
The photosensitive resin composition according to claim 1, wherein Y 2 in the general formula (1) is an aliphatic diamine residue.
The photosensitive resin composition according to claim 1, 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 represents an alkylene group having 2 to 10 carbon atoms, and a, b and c are 1 ≦ a ≦ 20, 0 ≦ b ≦ 20, It represents an integer in the range of 0 ≦ c ≦ 20, and the arrangement of each repeating unit may be block or random. * Indicates a chemical bond.)
The photosensitive resin composition according to claim 1, wherein Y 2 in the general formula (1) has a molecular weight of 150 or more and 2,000 or less.
6. The photosensitive resin composition according to claim 1, wherein the (B) photocrosslinking agent comprises (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 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 or 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 each represents an oxygen atom, a sulfur atom, or a nitrogen atom, and at least one of R 10 to R 12 represents a sulfur atom. R 10 represents an oxygen atom or a sulfur atom when l is 0, and a nitrogen atom when l is 1. m and n are integers of 1 to 2, u and v are 0 R 11 and R 12 each represents an oxygen atom or a sulfur atom when u and v are 0, and represents a nitrogen atom when u and v are 1. R 13 to R 17 are each independently selected. Represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.)
And (D) an organic solvent having a boiling point at 1013 hPa of 200 ° C. or higher and 260 ° C. or lower, and (E) an organic solvent having a boiling point at 1013 hPa of 100 ° C. or higher and lower than 200 ° C.,
The content of the organic solvent having a boiling point of 200 to 260 ° C. in (D) 1013 hPa is 5 to 70% by mass with respect to the total amount of the organic solvent, and the boiling point in 1013 hPa of 100 to 200 ° C. The photosensitive resin composition according to any one of claims 1 to 9, wherein the content of the organic solvent at a temperature lower than 0 ° C is 30% by mass or more and 95% by mass or less based on the total amount of the organic solvent.
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 the photosensitive resin composition according to any one of claims 1 to 10 or the photosensitive resin sheet according to claim 11.
The cured film according to claim 12, comprising 0.005 mass% or more and 1 mass% or less of an organic solvent having a boiling point of 200C to 260C in (D) 1013 hPa.
A photosensitive resin composition according to any one of claims 1 to 10 is applied onto a substrate, or the photosensitive resin sheet according to claim 11 is laminated on a substrate and dried to form a photosensitive resin film. A step of exposing the photosensitive resin film through a mask or directly using a drawing apparatus, a step of developing the exposed photosensitive resin film with an alkaline solution, and heating of the photosensitive resin film after development. The manufacturing method of the relief pattern of a cured film including a process process.
The manufacturing method of the relief pattern of the cured film of Claim 14 with which the process of apply | coating the said resin composition on a board | substrate and drying and forming a resin film includes the process apply | coated on a board | substrate using a slit nozzle. .
14. An organic EL display device, wherein the cured film according to claim 12 or 13 is disposed on at least one of a planarizing layer on a drive circuit and an insulating layer on a first electrode.
A semiconductor electronic component in which the cured film according to claim 12 or 13 is disposed as an interlayer insulating film between rewirings.
The semiconductor electronic component according to claim 17, wherein the rewiring is a copper metal wiring, and the semiconductor chip and the copper metal wiring are further connected via a bump.
The semiconductor electronic component according to claim 17 or 18, wherein at least three or more rewiring layers made of the copper metal wiring are arranged.
A plurality of interlayer insulating films according to claim 17 are stacked, and a semiconductor chip is disposed substantially parallel to the interlayer insulating film, and the thickness of the interlayer insulating film disposed near the semiconductor chip is disposed far away. 20. The semiconductor electronic component according to claim 17, wherein the thickness is smaller than the thickness of the interlayer insulating film.
A step of disposing the cured film according to claim 12 or 13 as an interlayer insulating film between rewirings on a support substrate on which a temporary attachment material is disposed, and a step of disposing a semiconductor chip and a sealing resin thereon Then, the manufacturing method of a semiconductor electronic component including the process of peeling a support substrate with which temporary sticking material was arrange | positioned, and rewiring.
14. A semiconductor device, wherein the cured film according to claim 12 or 13 is disposed as an interlayer insulating film between rewirings.
23. The semiconductor device according to claim 22, wherein the rewiring is a copper metal wiring, and the semiconductor chip and the copper metal wiring are further connected via bumps.
24. The semiconductor device according to claim 22, wherein at least three or more rewiring layers made of the copper metal wiring are arranged.
A plurality of interlayer insulating films according to claim 22 are stacked, and the semiconductor chip has a semiconductor chip disposed substantially parallel to the interlayer insulating film, and the thickness of the interlayer insulating film disposed near the semiconductor chip is disposed far away. 25. The semiconductor device according to claim 22, wherein the thickness of the interlayer insulating film is thinner.
A step of disposing the cured film according to claim 12 or 13 as an interlayer insulating film between rewirings on a support substrate on which a temporary attachment material is disposed, and a step of disposing a semiconductor chip and a sealing resin thereon Then, the manufacturing method of a semiconductor device including the process of peeling a support substrate with which temporary sticking material was arrange | positioned, and rewiring.