JP2018036329A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that can reduce development residues in pattern formation, gives a cured film with a low coefficient of thermal linear expansion, and has high sensitivity.SOLUTION: A photosensitive resin composition contains (A) an alkali-soluble resin containing one or more selected from polyimide, polybenzoxazole, polyamide-imide, a precursor thereof, and a copolymer thereof, (B) an inorganic fine particle with an average particle size of 0.001 μm or more and 0.1 μm or less, (C) a photoacid generator, (D) a solvent, and (E) a metal element. The (E) metal element includes one or more metal element selected from Na and K, and the content of the (E) metal element is 1.0 ppm or more and 300.0 ppm or less relative to the total solid content excluding the (D) solvent.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition. More specifically, the present invention relates to a photosensitive resin composition suitable for a surface protective film on the surface of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, and the like.

  Resins typified by polyimide and polybenzoxazole have excellent heat resistance and electrical insulation, and are therefore used for surface protective films of semiconductor elements, interlayer insulating films, insulating layers of organic electroluminescent elements, and the like. In recent years, with the miniaturization of semiconductor elements, surface protection films, interlayer insulating films, and the like are required to have a resolution of several μm level. For this reason, in such applications, photosensitive polyimide resin compositions and photosensitive polybenzoxazole resin compositions that can be finely processed are often used.

  A surface protective film of a general semiconductor device is laminated on a semiconductor element formed on a substrate and a passivation film typified by Si or SiN is formed thereon. Further, the correlation insulating film is laminated on the surface in order to maintain insulation between the wirings formed on the semiconductor element.

  In recent years, a circular wafer having a diameter of 300 mm or a square substrate having a panel size of 400 mm or more has been used due to the increase in size of the substrate. In the conventional photosensitive polyimide resin composition, when the substrate is large, in the thermal cycle test, shrinkage stress is generated due to the difference in the coefficient of thermal expansion with the substrate, and the substrate warp or the resin film peels off from the wiring. It may occur. In order to solve this, a method of reducing the thermal linear expansion coefficient by adding inorganic fine particles has been proposed (for example, Patent Document 1).

  Moreover, the method of making a thermal linear expansion coefficient low by adding an inorganic fine particle to the photosensitive resin composition containing a quinonediazide compound and alkali-soluble resin is proposed (for example, patent document 2).

  In addition, a resin composition containing an acrylic resin, an epoxy resin, and a polyurethane resin with improved dispersibility between the fine particles and the resin has been proposed (for example, Patent Document 3).

JP2015-128198A JP 2002-357898 A JP 2011-27842 A

  However, the resin composition containing inorganic fine particles as described in Patent Document 1 is not provided with photosensitivity and sometimes cannot be finely processed.

  Further, in the method of reducing the thermal expansion coefficient by adding inorganic fine particles to a photosensitive resin composition containing a quinonediazide compound and an alkali-soluble resin as described in Patent Document 2, the method after development with an alkali developer is used. In some cases, residues derived from inorganic fine particles are generated in the pattern opening.

  Furthermore, in the resin composition as described in Patent Document 3, there is a difficulty in solving the problem of reducing the thermal expansion coefficient without impairing the insulating properties required for a semiconductor device.

  Accordingly, an object of the present invention is to provide a photosensitive resin composition capable of obtaining a cured film having a low coefficient of thermal linear expansion (hereinafter abbreviated as CTE), being highly sensitive, and capable of reducing development residue during pattern formation. And

In order to solve the above problems, the photosensitive resin composition of the present invention has the following constitution. That is, (A) an alkali-soluble resin containing at least one selected from polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof, and (B) an average particle size of 0.001 μm or more , 0.1 μm or less inorganic fine particles, (C) a photoacid generator, (D) a solvent, and (E) a metal element,
The (E) metal element contains one or more metal elements selected from Na and K, and the content of the (E) metal element is 1 with respect to the total solid content excluding the (D) solvent. It is a photosensitive resin composition characterized by being 0.0 ppm or more and 300.0 ppm or less.

The photosensitive resin composition of the present invention is highly sensitive and not only can reduce development residues during pattern formation, but also can provide a cured film having a low CTE.

It is a schematic sectional drawing of the semiconductor device which has a resin film of this invention.

The present invention relates to an alkali-soluble resin containing one or more selected from (A) polyimide, polybenzoxazole, polyamideimide, a precursor thereof, and a copolymer thereof, and (B) an average particle size of 0.1. Containing inorganic fine particles of 001 μm or more and 0.1 μm or less, (C) a photoacid generator, (D) a solvent, and (E) a metal element,
The (E) metal element contains one or more metal elements selected from Na and K, and the content of the (E) metal element is 1 with respect to the total solid content excluding the (D) solvent. It is a photosensitive resin composition characterized by being 0.0 ppm or more and 300.0 ppm or less.

  (A) An alkali-soluble resin containing at least one selected from polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof is soluble in an aqueous solution of an alkaline compound. Examples of such resins include, but are not limited to, polyimide, polybenzoxazole, polyamideimide, precursors thereof, copolymers thereof, phenol resins, polyhydroxystyrene, acrylic resins, and polysiloxanes. Among these, from the viewpoint of heat resistance, it is preferable to include one or more selected from polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof.

  The alkali-soluble resin containing one or more selected from (A) polyimide, polybenzoxazole, polyamideimide, their precursors, and their copolymers is represented by the general formulas (1) and (2). It is preferable to have at least one of the structural units.

(In General Formula (1), R ¹ represents a tetravalent organic group having 4 to 40 carbon atoms. R ² represents a divalent organic group having 20 to 100 carbon atoms. N ₁ represents ₁₀ to 100,000. Indicates an integer within the range of.)

(In General Formula (2), R ¹ represents a tetravalent organic group having 4 to 40 carbon atoms. R ² represents a divalent organic group having 20 to 100 carbon atoms. R ³ represents hydrogen or carbon number 1. And n ₂ represents an integer in the range of 10 to 100,000, and p and q represent integers satisfying 0 ≦ p + q ≦ 6.
Also, it is shown in the formula (1) and (2), R ¹ is a monocyclic or fused polycyclic alicyclic structure, a tetravalent organic group having 4 to 40 carbon atoms. The monocyclic or condensed polycyclic alicyclic structure in R ¹ preferably contains one or more organic groups selected from the following general formulas (3) to (6).

(In General Formulas (3) to (6), R ^{4 to} R ⁴⁹ each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 3 carbon atoms. In the organic group, a hydrogen atom contained in the organic group may be substituted with a halogen atom.)
Moreover, R < ¹ > in General formula (1) and (2) is an organic group derived from the acid dianhydride used as a raw material of resin.

  Specific examples of the acid dianhydride containing a tetravalent organic group having 4 to 40 carbon atoms and having a monocyclic or condensed polycyclic alicyclic structure used in the present invention include 1, 2, 3 , 4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3 Examples include compounds such as 4-cyclobutanetetracarboxylic dianhydride and 1,2,4,5-cyclohexanetetracarboxylic dianhydride.

In general formulas (1) and (2), as a preferable structure of a tetravalent organic group having 4 to 40 carbon atoms having ^{1 to} 4 aromatic rings in R ¹ , pyromellitic acid, 3, 3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′- Benzophenone tetracarboxylic acid, 2,2 ′, 3,3′-benzophenone tetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 2,2-bis (2,3-dicarboxy) Phenyl) hexafluoropropane, 1,1-bis (3,4-dicarboxyphenyl) ethane, 1,1-bis (2,3-dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, Screw (2,3 Dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7 -Structures obtained by removing carboxyl groups from aromatic tetracarboxylic acids such as naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, and hydrogen Examples include a structure in which 1 to 4 atoms are substituted with 1 to 20 carbon atoms, a fluoroalkyl group, an alkoxyl group, an ester group, a nitro group, a cyano group, a fluorine atom, or a chlorine atom.

Alicyclic structure monocyclic or fused polycyclic in R ^1, when the general formula (1) and the R ¹ in (2) was 100 mole%, improving high elongation of the pattern processability of the film If it is 10 mol% or more from a viewpoint, it is more preferable if it is 30 mol% or more. From the viewpoint of obtaining an appropriate dissolution rate in the developer, it is preferably 80 mol% or less, more preferably 60 mol% or less.

Further, R ² in the general formulas (1) and (2) preferably has an organic group having a polyether structure represented by the following general formula (7).

(In the general formula (7), R ^{50 to} R ⁵³ represent a tetravalent organic group having 1 to 10 carbon atoms, and R ^{54 to} R ⁶¹ represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. , Y and z each independently represent an integer of 0 to 12, where x + y + z is an integer of 1 to 30.)
R ² in the general formulas (1) and (2) is an organic group derived from a diamine used as a raw material for the resin.

Specific examples of the diamine containing an organic group having a polyether structure used in the present invention include “Jeffamine” (registered trademark) HK-511, ED-600, ED-900, ED-2003, and EDR-148. , EDR-176, D-200, D-400, D-2000, D-4000, “Elastamine” (registered trademark) RP-409, RP-2009, RT-1000, HT-1100, HE-1000, HT- An aliphatic diamine such as 1700 (trade name, manufactured by HUNTSMAN Co., Ltd.) can be used. Having a polyether structure is preferable because flexibility is imparted and thus the elongation is improved, and the elastic modulus is lowered to suppress warping of the wafer. These characteristics are effective in multilayers and thick films.
The number average molecular weight of the structural unit represented by the general formula (7) is preferably 150 or more and 2,000 or less. The number average molecular weight of the structural unit represented by the general formula (7) is preferably 150 or more, more preferably 600 or more, and further preferably 900 or more, because flexibility and stretchability can be obtained. Further, the number average molecular weight of the structural unit represented by the general formula (7) is preferably 2,000 or less, more preferably 1,800 or less, more preferably 1,800 or less, because the solubility in an alkaline solution can be maintained. More preferably, it is 500 or less.
Polyether structure represented by the general formula (7) has the general formula (1) and (2) when the a ^{R 2} 100 mole% of it is preferably from 10 to 80 mol%. If it is 10 mol% or more, flexibility, low stress, and good dispersibility in fine particles are obtained, and 20 mol% or more is more preferable. Moreover, if it is 80 mol% or less, it is preferable at the point that the suitable melt | dissolution rate with respect to a developing solution is obtained, and it is more preferable that it is 50 mol% or less.

Further, as R ¹ in the general formulas (1) and (2), by further containing an organic group having a fluorine atom, water repellency is imparted to the resin, and permeation from the surface of the film is suppressed during alkali development. This is preferable. By suppressing the penetration from the surface of the film, it is possible to obtain a resin film having a high residual film ratio in which there is no development residue in the processing pattern. These characteristics are important in realizing thick film processing. When the total amount of R ¹ is 100 mol%, the organic group having a fluorine atom has an effect of preventing the penetration of the interface if it is 20 mol% or more, and if it is 90 mol% or less, an appropriate dissolution rate in the developer. Is preferable, and it is more preferable to contain 40 mol%-60 mol%.

  Specific examples of the compound having a fluorine atom include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, compounds in which these aromatic rings are substituted with an alkyl group or a halogen atom, and amides. An aromatic acid dianhydride such as an acid dianhydride having a group can be mentioned. (A) The alkali-soluble resin is preferably a resin containing a structure derived from these compounds.

  In addition, the alkali-soluble resin containing one or more selected from (A) polyimide, polybenzoxazole, polyamideimide, a precursor thereof, and a copolymer thereof has a hydroxyl group concentration of 1.80 mmol / g or more 6 It is preferable that it is 30 mmol / g or less. Among the alkali-soluble resins containing at least one selected from the above-mentioned (A) polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof, the dispersibility of polyimide and fine particles is particularly poor. It has been known. From the viewpoint of dispersibility with respect to the fine particles, 1.80 mmol / g or more is preferable, and 1.85 mmol or more is more preferable. Moreover, 6.30 mmol / g or less is preferable from a viewpoint that the suitable melt | dissolution rate with respect to a developing solution is obtained, and 5.00 mmol / g or less is more preferable. The hydroxyl group concentration of the alkali-soluble resin containing one or more selected from (A) polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof is (A) polyimide, polybenzoxazole. , Polyamideimide, precursors thereof, and copolymers thereof, the ratio of hydroxyl groups contained in 1 g of alkali-soluble resin containing at least one selected from the group consisting of “number of hydroxyl groups / unit of alkali-soluble resin” Per molecular weight ". (A) In the case of containing a plurality of alkali-soluble resins including one or more selected from polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof, the load of the content weight ratio thereof It can be calculated by averaging.

(A) The hydroxyl group of the alkali-soluble resin containing one or more selected from polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof is preferably a phenolic hydroxyl group. In the general formulas (1) and (2), it is preferable that at least one of R ¹ and R ² is an organic group having a phenolic hydroxyl group. Due to the presence of phenolic hydroxyl group, moderate solubility in alkaline developer is obtained, and it interacts with the photosensitizer to suppress solubility in the unexposed areas, thus improving the remaining film ratio and increasing sensitivity. Become. Moreover, since a phenolic hydroxyl group contributes also to reaction with a crosslinking agent, it is preferable also at the point from which high heat resistance is acquired.

  Specifically, as the compound having a phenolic hydroxyl group, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride or a compound in which these aromatic rings are substituted with an alkyl group or a halogen atom, and Aromatic acid dianhydrides such as acid dianhydrides having an amide group, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3- Amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, bis (3 -Amino-4-hydroxyphenyl) fluorene-containing diamines such as fluorene, and these Some of the hydrogen atoms of the aromatic ring include an alkyl group and a fluoroalkyl group having 1 to 10 carbon atoms, compounds substituted with a halogen atom, and the like. (A) The alkali-soluble resin containing one or more selected from polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof is a resin including a structure derived from these compounds. Is preferred.

  A diamine having a polyether structure having 20 to 100 carbon atoms and a hydroxyl group concentration of 1.80 mmol / g or more and 6.30 mmol / g or less (A) polyimide, polybenzoxazole, polyamideimide, and their precursors And an alkali-soluble resin containing at least one selected from the copolymers thereof, the dispersion with fine particles is good, the CTE is low, and there is no tack or development residue during development. The photosensitive resin composition is obtained.

  These characteristics are particularly useful in a rewiring application of a semiconductor device used as an interlayer insulation film between metal wirings and used in a noise filter of an inductor device.

  Further, the photosensitive resin composition of the present invention may contain a structure derived from other acid dianhydrides and diamines in addition to the above acid dianhydrides and diamines within a range not deteriorating the above-mentioned characteristics. .

  Specific examples of other dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetra Carboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3 '-Benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1, 1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride Bis (2,3-dicarbox Phenyl) methane dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic Acid dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid Aromatic tetracarboxylic dianhydrides such as dianhydrides, or compounds in which the hydrogen atoms of these compounds are substituted with alkyl groups or halogen atoms, or 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3 -Cyclohexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic acid dianhydride, bicyclo [2.2.2] octo-7-e -2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 3,5,6-tricarboxy-2-norbornane acetic dianhydride, 3 , 4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride such as alicyclic, semi-alicyclic tetracarboxylic dianhydride or alkyl of the hydrogen atom of these compounds And a compound substituted with a group or a halogen atom, and an acid dianhydride having an amide group. These can be used in combination with two or more acid dianhydrides containing an alicyclic structure having 4 to 40 carbon atoms.

  Specific examples of other diamines include bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, and bis (3-amino-4-hydroxyphenyl) propane. Bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, bis (3-amino-4-hydroxyphenyl) Hydroxyl group-containing diamines such as fluorene, sulfonic acid-containing diamines such as 3-sulfonic acid-4,4′-diaminodiphenyl ether, thiol group-containing diamines such as dimercaptophenylenediamine, 3,4′-diaminodiphenyl ether, 4,4 ′ -Diaminodiphenyl ether, 3,4'- Aminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, 1,4 -Bis (4-aminophenoxy) benzene, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3- Aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2′-dimethyl-4 , 4'-Diaminobiphenyl, 2,2 -Diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2 ', 3,3' -Tetramethyl-4,4'-diaminobiphenyl, 3,3 ', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'- Aromatic diamines such as diaminobiphenyl, compounds in which some of the hydrogen atoms of these aromatic rings are substituted with alkyl groups having 1 to 10 carbon atoms, fluoroalkyl groups, halogen atoms, cyclohexyl diamine, methylene bis cyclohexyl amine And alicyclic diamines. These diamines can be used as they are or as the corresponding diisocyanate compounds and trimethylsilylated diamines. Moreover, you may use combining these 2 or more types of diamine components.

  Among these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4, 4'-diaminodiphenylsulfide, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2 -Bis [4- (4-aminophenoxy) phenyl] propane, 2,2- Scan (3-amino-4-hydroxyphenyl) hexafluoropropane or compounds of these aromatic rings substituted with an alkyl group or a halogen atom, and the like diamines having an amide group as preferred. These are used alone or in combination of two or more.

  Further, an aliphatic group having a siloxane structure may be introduced as long as the heat resistance is not lowered, and the adhesion to the substrate can be improved. Specific examples of the diamine component include those obtained by copolymerizing 1 to 15 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like.

  In applications where heat resistance is required, it is preferable to use an aromatic diamine in an amount of 50 mol% or more of the total diamine.

In the general formulas (1) and (2), n ₁ and n ₂ can be easily determined by measuring the weight average molecular weight (Mw) by gel permeation chromatography (GPC), light scattering method, X-ray small angle scattering method, etc. Can be calculated. When the molecular weight of the repeating unit is M and the weight average molecular weight of the polymer is Mw, n = Mw / M. The number of repetitions n in the present invention refers to a value calculated using the simplest GPC (gel permeation chromatography) measurement in terms of polystyrene.

  (A) The weight average molecular weight of the alkali-soluble resin containing at least one selected from polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof is in terms of polystyrene by gel permeation chromatography. It is preferably in the range of 3,000 to 80,000, and more preferably in the range of 8,000 to 50,000. If it is this range, a thick film can be formed easily.

  Moreover, (A) alkali-soluble resin containing 1 or more types chosen from a polyimide, polybenzoxazole, a polyamideimide, those precursors, and those copolymers is monoamine, an acid anhydride, acid chloride, monocarboxylic The terminal may be sealed with a terminal sealing agent such as an acid. By sealing the terminal of the resin with a terminal sealing agent having a hydroxyl group, carboxyl group, sulfonic acid group, thiol group, vinyl group, ethynyl group or allyl group, the dissolution rate of the resin in an alkaline aqueous solution can be easily within a preferred range. Can be adjusted. The terminal blocking agent is preferably used in an amount of 0.1 to 60 mol%, more preferably 5 to 50 mol%, based on the total amine component of the resin.

  Specific examples of end capping agents include monoamines such as 3-aminophenylacetylene, 4-aminophenylacetylene, 3,5-diethynylaniline, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 3,4-diethynyl. Monocarboxylic acids such as benzoic acid and 3,5-diethynylbenzoic acid, acid anhydrides such as maleic anhydride and 5-norbornene-2,3-dicarboxylic acid anhydride, and the carboxyl group of the monocarboxylic acid was acid chlorided Compounds obtained by acid chloride of one carboxyl group of dicarboxylic acids such as compounds and maleic acid, active ester compounds obtained by reacting monoacid chloride compounds with N-hydroxy-5-norbornene-2,3-dicarboximide, etc. In addition to an end-capping agent having an unsaturated bond of 5-amino-8-hydroxyquinoline, 1-hydride Roxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-amino Naphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy -6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2- Aminobenzenesulfonic acid, 3-aminobenzenesulfone Acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-amino Monoamines such as thiophenol, phthalic anhydride, cyclohexanedicarboxylic anhydride, acid anhydrides such as 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercap Monocarboxylic acids such as -5-carboxynaphthalene, 3-carboxybenzenesulfonic acid and 4-carboxybenzenesulfonic acid, and monoacid chloride compounds in which these carboxyl groups are converted to acid chloride, terephthalic acid, phthalic acid, cyclohexanedicarboxylic acid, 1 , 5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,6-dicarboxynaphthalene monoacid chloride compound in which only one carboxyl group of dicarboxylic acids such as acid chloride is converted, Examples thereof include end capping agents having no unsaturated bond such as an active ester compound obtained by reacting a monoacid chloride compound with N-hydroxybenzotriazole. Moreover, it can use as terminal blocker which has an unsaturated bond by substituting the hydrogen bond of the terminal blocker which does not have these unsaturated bonds with a vinyl group.

The resin having at least one of the structural units represented by the general formulas (1) and (2) can be produced according to known methods for producing polyimides and polyimide precursors. For example, (I) a method of reacting a tetracarboxylic dianhydride having an R ¹ group with a diamine compound having an R ² group and a monoamino compound as a terminal blocking agent under low temperature conditions, (II) an R ¹ group A diester obtained by having a tetracarboxylic dianhydride and an alcohol, and then reacting in the presence of a diamine compound having an R ² group, a monoamino compound as a terminal blocking agent and a condensing agent, (III) R ¹ group Examples include a method in which a diester is obtained from a tetracarboxylic dianhydride having an alcohol and an alcohol, and then the remaining two carboxyl groups are acid chlorideed and reacted with a diamine compound having an R ² group and a monoamino compound as a terminal blocking agent. be able to. The resin polymerized by the above method is preferably put into a large amount of water or a methanol / water mixture, precipitated, filtered, dried and isolated. By this precipitation operation, unreacted monomers and oligomer components such as dimers and trimers are removed, and film properties after thermosetting are improved. Moreover, after imidating the polyimide precursor and ring-closing polyimide, after obtaining said polyimide precursor, it can synthesize | combine using the method of making a well-known imidation reaction.

Hereinafter, an example of a method for producing a polyimide precursor will be described as a preferred example of (I).
First, a diamine compound having an R ² group is dissolved in a polymerization solvent. To this solution, a tetracarboxylic dianhydride having an R ¹ group in a substantially equimolar amount with the diamine compound is gradually added. Using a mechanical stirrer, the mixture is stirred at -20 to 100 ° C, preferably 10 to 50 ° C for 0.5 to 100 hours, more preferably 2 to 24 hours. When using terminal blocker, after adding tetracarboxylic dianhydride, after stirring at -20-100 degreeC, Preferably 10-50 degreeC for 0.1-24 hours, terminal blocker is gradually used. You may add and you may make it react at once.

  The polymerization solvent is not particularly limited as long as it can dissolve tetracarboxylic dianhydrides and diamines which are raw material monomers. For example, N, N-dimethylformamide, N, N-dimethylacetamide, amides of N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α -Cyclic esters such as methyl-γ-butyrolactone, carbonates such as ethylene carbonate and propylene carbonate, glycols such as triethylene glycol, phenols such as m-cresol and p-cresol, acetophenone, 1,3-dimethyl- Examples include 2-imidazolidinone, sulfolane, dimethyl sulfoxide, and the like.

  If the polymerization solvent is 100 parts by mass or more with respect to 100 parts by mass in total of the tetracarboxylic dianhydride, the diamine compound, and the monoamino compound that is the terminal blocking agent used in the polymerization reaction, there is no precipitation of raw materials and resins. The reaction can be performed, and if it is 1900 parts by mass or less, the reaction proceeds quickly, and 150 to 950 parts by mass is more preferable.

The (A) alkali-soluble resin may contain a phenol resin.
A phenol resin is obtained by polycondensing phenols and aldehydes by a well-known method. You may contain combining 2 or more types of phenol resins.

Preferred examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3 , 5-trimethylphenol, 3,4,5-trimethylphenol and the like. In particular, phenol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol or 2,3,5-trimethylphenol are preferable. Two or more of these phenols may be used in combination. From the viewpoint of solubility in an alkaline developer, m-cresol is preferable, and a combination of m-cresol and p-cresol is also preferable. That is, the resin having a phenolic hydroxyl group preferably includes an m-cresol residue, or a cresol novolak resin containing an m-cresol residue and a p-cresol residue. At this time, the molar ratio of m-cresol residue to p-cresol residue in the cresol novolak resin (m-cresol residue / p-cresol residue, m / p) is preferably 1.8 or more. If it is this range, the moderate solubility to an alkali developing solution will be shown, and favorable sensitivity will be obtained. More preferably, it is 4 or more.

  Preferred examples of the aldehydes include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, salicylaldehyde and the like. Of these, formalin is particularly preferred. Two or more of these aldehydes may be used in combination. The amount of the aldehyde used is preferably 0.6 mol or more, more preferably 0.7 mol or more, and preferably 3.0 mol or less, with respect to 1.0 mol of phenols, from the viewpoint of pattern processability. More preferable is 5 mol or less.

In the polycondensation reaction between phenols and aldehydes, an acidic catalyst is usually used. Examples of the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, p-toluenesulfonic acid, and the like. The usage-amount of these acidic catalysts is 1 * 10 < ^-5 > ^-5 * 10 < ^-1 > mol normally with respect to 1 mol of phenols. In the polycondensation reaction, water is usually used as a reaction medium. However, when a heterogeneous system is formed from the beginning of the reaction, a hydrophilic solvent or a lipophilic solvent is used as the reaction medium. Examples of the hydrophilic solvent include alcohols such as methanol, ethanol, propanol, butanol and propylene glycol monomethyl ether, and cyclic ethers such as tetrahydrofuran and dioxane. Examples of the lipophilic solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. The amount of the reaction medium used is usually 20 to 1,000 parts by mass per 100 parts by mass of the reaction raw material.

  The reaction temperature of the polycondensation can be appropriately adjusted according to the reactivity of the raw materials, but is usually 10 to 200 ° C. As a polycondensation reaction method, phenols, aldehydes, acidic catalysts, etc. are charged all at once and reacted, or phenols, aldehydes, etc. are added as the reaction proceeds in the presence of acidic catalysts, etc. Can be adopted as appropriate. After completion of the polycondensation reaction, in order to remove unreacted raw materials, acidic catalyst, reaction medium, etc. present in the system, the reaction temperature is generally increased to 130 to 230 ° C., and volatile components are reduced under reduced pressure. The resin having a phenolic hydroxyl group is removed.

  In the present invention, the polystyrene-reduced weight average molecular weight (Mw) of the phenol resin is preferably 2,000 or more and 15,000 or less, more preferably 3,000 or more and 10,000 or less. Within this range, a good pattern shape can be obtained after thermosetting while having high sensitivity and high resolution.

  In the present invention, examples of the phenol resin include a resol resin and a novolac resin, and a novolac resin is preferable from the viewpoint of high sensitivity and storage stability.

  In the present invention, the (A) alkali-soluble resin may contain polyhydroxystyrene. Examples of the polyhydroxystyrene include aromatic vinyl compounds having a phenolic hydroxyl group such as p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol, And it can obtain by polymerizing aromatic vinyl compounds, such as styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, alone or in a combination of two or more. As the aromatic vinyl compound having a phenolic hydroxyl group, p-hydroxystyrene and / or m-hydroxystyrene is preferably used, and styrene is preferably used as the aromatic vinyl compound. The polystyrene-converted weight average molecular weight (Mw) of the polyhydroxystyrene is preferably 3,000 or more from the viewpoint of forming an unexposed portion pattern without eluting it. Moreover, 60,000 or less is preferable from a viewpoint of maintaining the alkali solubility which can reduce the residue of an exposure part, and 25,000 or less are more preferable.

  The polystyrene-converted weight average molecular weight (Mw) is a value calculated using GPC (gel permeation chromatography) measurement based on polystyrene.

The photosensitive resin composition of the present invention contains (B) inorganic fine particles.
The (B) inorganic fine particles having an average particle size of 0.001 μm or more and 0.1 μm or less are preferably subjected to hydrophilic or hydrophobic treatment and have organic groups on the surface of the fine particles. From the viewpoint of reducing development residue during pattern processing, it is preferable to have a hydrophilic organic group on the surface of the fine particles, and it is more preferable to have one or more organic groups selected from a hydroxyl group, a carboxyl group, and a sulfonyl group. By having said organic group, stability with respect to an alkali developing solution can be improved, and a development residue can be reduced.

In the present invention, the organic group on the surface of the fine particles can be confirmed using an FT-IR analyzer. Specifically, a peak derived from the hydroxyl group near 3650 cm ^-1, 1740 cm ^-1 or near 1400cm near ^-1 or 1250cm near ^-1 or peak attributable to the carboxyl group of 920cm around ^-1, near 940 cm ^-1 It can be confirmed that the surface of the fine particle is modified with each organic group by a peak derived from the sulfonyl group.
(B) The average particle diameter of the inorganic fine particles having an average particle diameter of 0.001 μm or more and 0.1 μm or less is preferably 0.010 μm or more from the viewpoint of dispersibility when mixed as a resin composition. More preferably, it is 0.08 μm or less from the viewpoint of resolution and sensitivity. The average particle diameter in the present invention is a value measured by the BET method.

  The content of the inorganic fine particles (B) having an average particle diameter of 0.001 μm or more and 0.1 μm or less is 10 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the total solid content excluding the (D) solvent. Preferably there is. 10 mass parts or more are preferable from a viewpoint of reducing CTE, and 20 mass parts or more are more preferable. Moreover, 90 mass parts or less are preferable from a viewpoint of maintaining the mechanical characteristics of a cured film, and 80 mass parts or less are more preferable.

  Moreover, (B) Content of the inorganic fine particle whose average particle diameter is 0.001 micrometer or more and 0.1 micrometer or less is 5 from a viewpoint of reducing CTE with respect to 100 mass parts of total amounts of the photosensitive resin composition containing a solvent. It is preferably at least 7 parts by mass and more preferably at least 7 parts by mass. Moreover, 30 mass parts or less are preferable from a viewpoint of the dispersibility of the inorganic fine particle in a varnish, and 28 mass parts or less are more preferable.

In this invention, the effect of reducing CTE is acquired by containing the inorganic fine particle of the said range.
The photosensitive resin composition of the present invention contains (D) a solvent. The content of the inorganic fine particles (B) having an average particle diameter of 0.001 μm or more and 0.1 μm or less is 5 mass from the viewpoint of lowering CTE with respect to 100 mass parts of the total amount of the photosensitive resin composition containing a solvent. Part or more is preferable, and 10 parts by mass or more is more preferable. Moreover, from a viewpoint of suppressing aggregation in normal temperature storage, 30 mass parts or less are preferable, and 25 mass parts or less are more preferable.
Examples of the inorganic fine particles (B) having an average particle diameter of 0.001 μm or more and 0.1 μm or less include, for example, metal oxide fine particles such as alumina, silica, magnesia, ferrite, aluminum oxide, zirconium oxide, talc, mica, Examples thereof include silicates such as kaolin and zeolite, and fine particles such as barium sulfate, calcium carbonate and fullerene. The fine particles are used alone or in combination of two or more. Silica is preferred from the viewpoint of lowering the CTE while maintaining the insulating properties. Silica can be synthesized by, for example, a gas phase method, a sol-gel method, an RF plasma method, or the like. In order to disperse the inorganic ultrafine particles synthesized by the vapor phase method in a solvent, it can be dispersed to primary particles by using a known dispersing method, a bead mill, a kneading method, a high-pressure homogenizer, etc. in combination with a dispersant. The content of (B) inorganic fine particles in the cured film or varnish can be quantified by a known method. The inorganic fine particles in the present invention are quantified by measuring the strength of the element derived from the inorganic fine particles contained in the cured film or varnish using a fluorescent X-ray analyzer, and calculating with reference to the inorganic fine particles dispersed at a specified concentration. The

  The photosensitive resin composition of this invention has photosensitivity by containing the (C) photo-acid generator. That is, (C) the photoacid generator has a characteristic that an acid is generated by light irradiation, and the solubility of the light irradiation portion in an alkaline aqueous solution increases. (C) Photoacid generators include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts, and the like. Among these, (A) an excellent dissolution inhibiting effect when used in combination with an alkali-soluble resin containing at least one selected from polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof. From the viewpoint of expressing quinonediazide compound, it is preferably used.

  The quinonediazide compound has a quinonediazide sulfonic acid bonded to a polyhydroxy compound with an ester, a quinonediazide sulfonic acid bonded to a polyamino compound, and a quinonediazide sulfonic acid bonded to the polyhydroxypolyamino compound with an ester bond or sulfonamide bond. And those in which a sulfonic acid of quinonediazide is ester-bonded and sulfonamide-bonded to a polyhydroxypolyamino compound. Although all the functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, it is preferable that 50 mol% or more of the entire functional groups are substituted with quinonediazide. When the substitution with quinonediazide is 50 mol% or more, the solubility in an alkali developer is not excessively high, a contrast with an unexposed portion is obtained, and a desired pattern can be obtained. By using such a quinonediazide compound, a positive photosensitive resin composition or a photosensitive film that is sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp, which is a general ultraviolet ray. Can be obtained. Such compounds may be used alone or in combination of two or more. Further, by using two types of photoacid generators, the ratio of the dissolution rate between the exposed part and the unexposed part can be increased, and as a result, a highly sensitive photosensitive resin composition can be obtained.

  Polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP -IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ , TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR -PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.) ), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, Honshu Chemical Industry Co., Ltd.) and the like, but are not limited thereto.

  Polyamino compounds are 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl. Examples thereof include, but are not limited to, sulfhydrides.

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

  In the present invention, quinonediazide is preferably a 5-naphthoquinonediazidosulfonyl group or a 4-naphthoquinonediazidesulfonyl group.

  The 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure.

  The 5-naphthoquinone diazide sulfonyl ester compound has an absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure.

  In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength to be exposed. In addition, a naphthoquinone diazide sulfonyl ester compound in which a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group are used in the same molecule can be obtained, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound. Can also be used as a mixture.

  The molecular weight of the quinonediazide compound of the present invention is preferably in the range of 300 to 3,000. When the molecular weight of the quinonediazide compound is larger than 5,000, the quinonediazide compound is not sufficiently thermally decomposed in the subsequent heat treatment, so that the heat resistance of the resulting film is lowered, the mechanical properties are lowered, the adhesiveness is lowered, etc. Problems can arise.

  The quinonediazide compound used in the present invention is synthesized from a specific phenol compound by the following method. For example, a method of reacting 5-naphthoquinonediazide sulfonyl chloride and a phenol compound in the presence of triethylamine can be mentioned. Examples of the method for synthesizing a phenol compound include a method in which an α- (hydroxyphenyl) styrene derivative is reacted with a polyhydric phenol compound under an acid catalyst.

  Among the (C) photoacid generators used in the present invention, those that moderately stabilize the acid component generated by exposure are preferably sulfonium salts, phosphonium salts, or diazonium salts. Since the photosensitive resin composition of the present invention is used as a permanent film, it is not preferable from the environment that phosphorus or the like remains, and it is necessary to consider the color tone of the film. Among these, a sulfonium salt is preferable. Used. Particularly preferred is a triarylsulfonium salt, which can suppress changes in the color tone of the film.

  (C) Content of a photo-acid generator becomes like this. Preferably it is 0.01-50 mass parts with respect to 100 mass parts of total amounts of (A) alkali-soluble resin. Among these, the quinonediazide compound has a preferable range of 3-40 mass parts. In addition, the compound selected from sulfonium salts, phosphonium salts, and diazonium salts is preferably in the range of 0.05 to 40 parts by mass, and more preferably in the range of 0.1 to 30 parts by mass. (C) By making content of a photo-acid generator into this range, high sensitivity can be achieved. Furthermore, you may contain a sensitizer etc. as needed.

  The photosensitive resin composition of the present invention contains (D) a solvent. Solvents include polar aprotic solvents such as γ-butyrolactone, ethers such as tetrahydrofuran, dioxane, and propylene glycol monomethyl ether, dialkylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether. , Acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, ketones such as N, N-dimethylformamide, N, N-dimethylacetamide, acetates such as 3-methoxybutyl acetate, ethylene glycol monoethyl ether acetate, ethyl acetate , Esters such as propylene glycol monomethyl ether acetate and ethyl lactate, toluene, The solvents such as aromatic hydrocarbons such as Ren alone or in combination may be used.

  In the photosensitive resin composition of the present invention, (D) the content of the solvent is such that (A) polyimide, polybenzoxazole, polyamideimide, precursors thereof, 50 mass parts or more are preferable with respect to 100 mass parts of alkali-soluble resin containing 1 or more types chosen from a polymer, and 100 mass parts or more are more preferable. Moreover, 2000 mass parts or less are preferable at the point from which the resin film used as the film thickness which functions as a protective film is obtained, and 1500 mass parts or less are more preferable.

  The photosensitive resin composition of the present invention contains (E) a metal element. By containing one or more kinds of metal elements selected from Na and K, it contains (A) one or more kinds selected from polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof. The dispersibility of the alkali-soluble resin and (B) inorganic fine particles having an average particle diameter of 0.001 μm or more and 0.1 μm or less can be improved, and the residue after development of the exposed portion in pattern processing can be reduced. (E) The content of the metal element is preferably 1.0 ppm or more, more preferably 2.0 ppm or more, from the viewpoint of reducing the development residue with respect to the total solid content excluding the solvent (D). Moreover, 300.0 ppm or less is preferable from a viewpoint of a reliability test, and 250.0 ppm or less is more preferable.

  The metal element selected from Na and K easily forms ions, and the photosensitive resin composition used for the insulating film has an insulating property in a reliability test under a high temperature and high humidity condition and a withstand voltage test under a room temperature condition. Lowers and causes electrical failure. Therefore, it is preferable that it is 300.0 ppm or less. Further, by containing 1.0 ppm or more of the metal element, the surface of the fine particles is charged by the ionized metal, and the dispersibility of the inorganic fine particles in the photosensitive resin composition is improved, so that the solubility in the developer is improved. Therefore, it is considered that development residue reduction is achieved.

  For the above reasons, the content of the solid content excluding the solvent (D) is in the range of 1.0 ppm or more and 300.0 ppm or less, so that the development residue is reduced and the insulating film functions well as an insulating film Can be obtained.

  The photosensitive resin composition of the present invention may contain (F) a crosslinking agent. (F) The crosslinking agent is preferably a compound containing an alkoxymethyl group. (F) As a crosslinking agent, the compound represented by General formula (8) is preferable. The compound represented by the general formula (8) has an alkoxymethyl group, and the alkoxymethyl group undergoes a crosslinking reaction in a temperature range of 150 ° C. or higher. Therefore, by containing the compound, the polyimide precursor or the polybenzoxazole precursor can be crosslinked by heat and cured by heat treatment to obtain a better pattern shape. In addition, a compound having two or more alkoxymethyl groups is preferable for increasing the crosslinking density, and a compound having four or more alkoxymethyl groups is more preferable from the viewpoint of increasing the crosslinking density and further improving chemical resistance. Moreover, from the viewpoint of maintaining the mechanical properties of the thermosetting film, it is preferable to have at least one compound having 6 or more alkoxymethyl groups.

(In the general formula (8), R ⁶² represents a 1 to 4 valent organic group. R ⁶³ may be the same or different, and represents an alkyl group having 1 to 4 carbon atoms. R is an integer of 1 to 4) S represents an integer of 1 to 4.)
Specific examples of the compound (F) include the following compounds, but are not limited thereto. Moreover, you may contain 2 or more types of these.

  (F) From the viewpoint of increasing the crosslinking density and further improving chemical resistance and mechanical properties, the content of the crosslinking agent is (A) polyimide, polybenzoxazole, polyamideimide, their precursors, and their co-weights. 1 mass part or more is preferable with respect to 100 mass parts of alkali-soluble resin containing 1 or more types chosen from coalescence, and 20 mass parts or less are preferable from a viewpoint of storage stability.

  The photosensitive resin composition of this invention can contain the (G) silane compound, and can improve adhesiveness with a base substrate. (G) Specific examples of the silane compound include N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, and N-phenyl. Aminobutyltrimethoxysilane, N-phenylaminobutyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-acryl Roxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and the structure shown below It can be mentioned that the silane compound is not limited thereto. Two or more of these may be contained.

  (G) The content of the silane compound is based on 100 parts by mass of an alkali-soluble resin containing one or more selected from (A) polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof. From the viewpoint of adhesiveness, 0.01 parts by mass or more is preferable, and from the viewpoint of heat resistance, 15 parts by mass or less is preferable.

  Moreover, the photosensitive resin composition of this invention can contain the compound which has (H) phenolic hydroxyl group except a phenol resin and polyhydroxystyrene. By containing a compound having a phenolic hydroxyl group, the resulting photosensitive resin composition hardly dissolves in an alkali developer before exposure, and easily dissolves in an alkali developer upon exposure. And development is easy in a short time. (H) Particularly preferred compounds as the compound having a phenolic hydroxyl group include Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P (trade name, Honshu Chemical Industry Co., Ltd.) BIR-PC, BIR-PTBP, BIR-BIPC-F (trade name, available from Asahi Organic Materials Co., Ltd.), and the like.

  (H) Since the content of the compound having a phenolic hydroxyl group is small in film loss due to development and can be easily developed in a short time, (A) polyimide, polybenzoxazole, polyamideimide, precursors thereof, and 3 parts by mass or more is preferable with respect to 100 parts by mass of the alkali-soluble resin containing one or more kinds selected from these copolymers, and 40 parts by mass or less is preferable in terms of heat resistance and mechanical properties.

  If necessary, for the purpose of improving the wettability between the photosensitive resin composition and the substrate, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone, methyl isobutyl ketone, etc. May also contain ethers such as ketones, tetrahydrofuran and dioxane. Further, inorganic particles such as silicon dioxide and titanium dioxide, polyimide powder, and the like can also be contained.

The photosensitive resin composition of this invention may contain (I) acrylate compound as needed.
In the present invention, the (I) acrylate compound refers to a compound having an acryloyl group or a methacryloyl group. (I) The acrylate compound includes a monofunctional acrylate and a polyfunctional acrylate. The monofunctional acrylate refers to a compound having at least one of acryloyl group and methacryloyl group. For example, acrylic acid ester, methacrylic acid ester, acrylamide, methacrylamide, etc. can be mentioned. In addition, the polyfunctional acrylate compound refers to a compound having at least one of acryloyl group and methacryloyl group.

  The photosensitive resin composition of the present invention is heat-treated after pattern processing. When used as a positive photosensitive resin composition, the acrylate compound reacts with the heat-polymerized or alkali-soluble resin between the acrylate compounds and crosslinks to improve the elongation of the cured film. When used as a negative photosensitive resin composition, acrylates are photopolymerized by exposure during pattern processing, thereby forming a network structure with an alkali-soluble resin.

  In the case of a monofunctional acrylate compound, curing of the film by the crosslinking reaction does not proceed sufficiently, and the effect of improving the elongation is low, so that it is preferably a polyfunctional acrylate.

  (I) As a preferable example of an acrylate compound, Shin Nakamura Chemical Co., Ltd. NK ester series 1G, 2G, 3G, 4G, 9G, 14G, 23G, BG, HD, NPG, 9PG, 701, BPE-100, BPE-200, BPE-500, BPE-1300, A-200, A-400, A-600, A-HD, A-NPG, APG-200, APG-400, APG-700, A-BPE-4, 701A, TMPT, A-TMPT, A-TMM-3, A-TMM-3L, A-TMMT, A-9300, ATM-4E, ATM-35E, ATM-4P, AD-TMP, AD-TMP-L, A-DPH etc. are mentioned. In addition, Kyoeisha Chemical Co., Ltd. light ester series P-1M, P-2M, EG, 2EG, 3EG, 4EG, 9EG, 14EG, 1.4BG, NP, 1.6HX, 1.9ND, 1.10DC, G -101P, G-201P, DCP-M, BP-2EM, BP-4EM, BP-6EM, TMP, etc. are mentioned. Moreover, Kyoeisha Chemical Co., Ltd. "Light acrylate" (trademark) series 3EG-A, 4EG-A, 9EG-A, 14EG-A, TMGA-250, NP-A, MPD-A, 1.6HX-A , BEPG-A, 1.9ND-A, MOD-A, DCP-A, BP-4EA, BP-4PA, BA-134, BP-10EA, HPP-A, TMP-A, TMP-3EO-A, TMP -6EO-3A, PE-3A, PE-4A, DPE-6A and the like. Moreover, Kyoeisha Chemical Co., Ltd. epoxy ester series 40EM, 70PA, 200PA, 80MFA, 3002M, 3002A, 3000M, 3000A etc. are mentioned. In addition, "Aronix" (registered trademark) series M-203, M-208, M-210, M-211B, M-215, M-220, M-225, M-240, M- manufactured by Toa Gosei Co., Ltd. 243, M-245, M-260, M-270, M-305, M-309, M-310, M-313, M-315, M-320, M-325, M-350, M-360, M-402, M-408, M-450 etc. are mentioned. In addition, “KAYARAD” (registered trademark) series R-526, NPGDA, PEG400DA, MANDA, R-167, HX-220, HX-620, R-551, R-712, R-604 manufactured by Nippon Kayaku Co., Ltd. , R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, T-1420 (T), RP-1040, and the like. Also, “Blemmer” (registered trademark) series GMR-H, GAM, PDE-50, PDE-100, PDE-150, PDE-200, PDE-400, PDE-600, PDE-1000, manufactured by NOF Corporation. ADE-200, ADE-400, PDP-400, ADP-200, ADP-400, PDT-650, ADT-250, PDBE-200, PDBE-250, PDBE-450, PDBE-1300, ADBE-200, ADBE- 250, ADBE-450 and the like. Further, MBAA manufactured by MRC Unitech Co., Ltd. can be mentioned. You may contain 2 or more types of these compounds.

  Among the above (I) acrylate compounds, acrylate compounds having a molecular weight of 100 or more and 2,000 or less are preferable. A cured film having a high elongation can be obtained when the molecular weight is 100 or more, and a resin composition having moderate alkali solubility and high compatibility with an alkali-soluble resin can be obtained when the molecular weight is 2,000 or less. Can do.

  The manufacturing method of the photosensitive resin composition of this invention is illustrated. For example, (A) an alkali-soluble resin containing one or more selected from polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof, (B) an average particle size of 0.001 μm or more, Inorganic fine particles of 0.1 μm or less, (C) photoacid generator, (D) solvent, (E) one or more metal elements selected from Na and K, and other components, if necessary, made of glass flask or stainless steel And a method of stirring and dissolving with a mechanical stirrer, a method of dissolving with ultrasonic waves, a method of stirring and dissolving with a planetary stirring deaerator, and the like. Here, (E) one or more metal elements selected from Na and K may be contained in advance in (B) inorganic fine particles.

  The viscosity of the photosensitive composition is preferably 5 to 10,000 mPa · s. Moreover, you may filter with the filter of 0.1 micrometer-5 micrometers pore size in order to remove a foreign material.

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

  A photosensitive resin composition is applied onto a substrate. As the substrate, a silicon wafer, ceramics, gallium arsenide, metal, glass, metal oxide insulating film, silicon nitride, ITO, or the like is used, but is not limited thereto. Examples of the coating method include spin coating, spray coating, roll coating, and slit die coating. In the present invention, a particularly advantageous effect can be obtained in coating by a spin coating method. Moreover, although a coating film thickness changes with application methods, solid content concentration of composition, viscosity, etc., it is normally applied so that the film thickness after drying becomes 5 to 30 μm. It is preferably 2 μm or more from the viewpoint of chemical resistance in the flux treatment. Moreover, it is preferable that it is 15 um or less from the point of adhesiveness with the metal wiring after a flux process.

  Next, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like at 50 to 150 ° C. for 1 minute to several hours.

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

  In order to form a pattern of a heat resistant resin from the photosensitive resin film, the exposed portion may be removed using a developer after exposure. The developer is an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylamino An aqueous solution of a compound exhibiting alkalinity such as ethyl 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, One or more alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone may be added. After development, it is preferable to rinse with water. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.

  After development, a temperature of 200 to 500 ° C. is applied to convert it to a heat resistant resin film. This heat treatment is generally carried out for 5 minutes to 5 hours by selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature. For example, heat treatment at 130 ° C., 200 ° C., and 320 ° C. for 30 minutes each, method of linearly increasing the temperature from room temperature to 320 ° C. over 2 hours, charging at a high temperature of 200 ° C. over 2 hours The method of raising temperature linearly can be mentioned. At this time, the heating temperature is preferably 150 ° C. or higher and 320 ° C. or lower, and more preferably 180 ° C. or higher and 250 ° C. or lower.

  Next, the photosensitive film formed from the photosensitive resin composition of this invention is demonstrated. The photosensitive film of the present invention preferably has a support film. (A) An alkali-soluble resin containing one or more selected from polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof, (B) an average particle diameter of 0.001 μm or more, and 0.0. A photosensitive resin composition containing inorganic fine particles of 1 μm or less, (C) a photoacid generator, (D) a solvent, (E) one or more metal elements selected from Na and K, and the like is applied onto a support film. Then, by drying this, a photosensitive film having a photosensitive layer on the support film can be obtained.

  The support film is not particularly limited, but 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 film 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.

  Moreover, in order to protect the surface, the photosensitive film of this invention may have a protective film on a film | membrane. Thereby, the photosensitive film 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 film.

  (A) An alkali-soluble resin containing one or more selected from polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof, (B) an average particle diameter of 0.001 μm or more, and 0.0. A photosensitive resin composition containing inorganic fine particles of 1 μm or less, (C) a photoacid generator, (D) a solvent, (E) one or more metal elements selected from Na and K, and the like is applied to a support film, The photosensitive layer can be formed by spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure coater, screen coater, slit die coater, etc. The method by is mentioned. In addition, the coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but it is usually preferable that the film thickness of the photosensitive layer obtained after drying is 0.5 μm or more and 100 μm or less. Moreover, it is more preferable that they are 3 micrometers or more and 40 micrometers or less.

  An oven, a hot plate, infrared rays, or the like can be used for drying. The drying temperature and the drying time may be in a range where the solvent can be volatilized, and it is preferable to appropriately set a range in which the resin film material for a semiconductor is in an uncured or semi-cured state. Specifically, it is preferable to carry out from 1 minute to several tens of minutes in the range of 40 ° C to 120 ° C. Moreover, you may heat up in steps combining these temperatures, for example, you may heat-process at 50 degreeC, 60 degreeC, and 70 degreeC for 1 minute each.

  Next, a method for manufacturing a semiconductor device using a photosensitive film will be described. When the photosensitive film has a protective film, it is first peeled off. A photosensitive film and a board | substrate are made to oppose, and it bonds together by thermocompression bonding, transfers a photosensitive film to a board | substrate, and laminates. Next, the support film is peeled off to obtain a photosensitive coating. The thermocompression bonding can be performed by a heat press process, a heat laminating process, a heat vacuum laminating process, or the like. The temperature for thermocompression bonding and lamination is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, from the viewpoint of adhesion to the substrate and embedding. In order to prevent the photosensitive film from being cured at the time of thermocompression bonding and the resolution of pattern formation in the exposure / development process from being deteriorated, the temperature of thermocompression bonding is preferably 150 ° C. or less, and preferably 120 ° C. or less. More preferred. Moreover, you may carry out under reduced pressure in order to remove a bubble at the time of thermocompression bonding.

  Moreover, after laminating the photosensitive film on the substrate, the support film is peeled off from the photosensitive film in a temperature range of 0 ° C. or higher and 100 ° C. or lower.

  Examples of the substrate to be used include, but are not limited to, silicon wafers, ceramics, gallium arsenide, organic circuit substrates, inorganic circuit substrates, and substrates on which circuit constituent materials are arranged.

  Examples of organic circuit boards include glass-based 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, Examples include heat-resistant / thermoplastic substrates such as ether 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 materials include conductors containing metals such as gold, silver and copper, resistors containing inorganic oxides, low dielectrics containing glass materials, resins, etc., resins and high dielectric constants Examples thereof include high dielectric materials containing inorganic particles and insulators containing glass-based materials.

  Next, the photosensitive film formed by the above method is irradiated with actinic radiation through a mask having a desired pattern and exposed. As the actinic radiation used for exposure, there are ultraviolet rays, visible rays, electron beams, X-rays and the like. In the present invention, it is preferable to use i rays (365 nm), h rays (405 nm), and g rays (436 nm) of a mercury lamp. . In the photosensitive film, when the support film is a material transparent to these light beams, the exposure may be performed after peeling the support film from the photosensitive film, or the exposure may be performed without peeling. . When exposure is performed without peeling, the support film is peeled after exposure and before development.

  In order to form a pattern, after exposure, an unexposed portion is removed using a developer. Developers include tetramethylammonium aqueous solution, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl An aqueous solution of a compound showing alkalinity such as aminoethyl 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 performed by spraying the developer on the surface with the photosensitive coating, immersing in the developer, applying ultrasonic waves while immersing, or spraying the developer while rotating the substrate. it can. The development conditions such as the development time and the temperature of the development step developer may be any conditions that allow the unexposed areas to be removed. In order to process fine patterns and remove residues between patterns, unexposed areas It is preferable to perform further development after the removal.

  After the development, rinsing with water may be performed. 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.

  When the resolution of the pattern at the time of development is improved and the allowable range of development conditions is increased, a step of performing a baking process before development can be incorporated. As this temperature, the range of 50-180 degreeC is preferable, and the range of 60-120 degreeC is especially more preferable. The time is preferably 5 seconds to several hours.

  After forming the pattern, a cured film is obtained by applying a temperature of 120 ° C. to 500 ° C. This heat treatment is carried out for 5 minutes to 5 hours by selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature. As an example, heat treatment is performed at 130 ° C., 200 ° C., and 320 ° C. for 30 minutes each. Alternatively, a method such as linearly raising the temperature from room temperature to 320 ° C. over 2 hours can be mentioned. At this time, the heating temperature is preferably 150 ° C. or higher and 320 ° C. or lower, and more preferably 180 ° C. or higher and 250 ° C. or lower.

  The thickness of the cured film is preferably 0.5 μm or more and more preferably 2 μm or more in order to improve insulation. Further, from the viewpoint of reducing the warpage of the substrate due to residual stress, it is preferably 100 μm or less, and more preferably 40 μm or less.

  From the viewpoint of dispersibility, the content of the metal element in the cured film formed from the photosensitive resin composition or the photosensitive film of the present invention is preferably 1.0 ppm or more, and more preferably 2.0 ppm or more. Moreover, 300.0 ppm or less is preferable from a viewpoint of a reliability test, and 250.0 ppm or less is more preferable.

  The metal element selected from Na and K easily forms ions, and the photosensitive resin composition used for the insulating film has an insulating property in a reliability test under a high temperature and high humidity condition and a withstand voltage test under a room temperature condition. Lowers and causes electrical failure. Therefore, it is preferable that it is 300.0 ppm or less. Further, by containing 1.0 ppm or more of the metal element, the surface of the fine particles is charged by the ionized metal, and the dispersibility of the inorganic fine particles in the photosensitive resin composition is improved.

  The content of the metal element in the cured film in the present invention can be measured by dissolving the cured film using a chemical solution such as an acid and analyzing it using an ICP emission analyzer.

  The 5% thermal weight loss temperature of the cured film formed from the photosensitive resin composition or photosensitive film of the present invention is preferably 350 ° C. or higher from the viewpoint of heat resistance in the semiconductor device manufacturing process such as reflow. Moreover, it is preferable that it is 550 degrees C or less from a viewpoint of relieving the thermal stress concerning resin to a film | membrane.

From the viewpoint of insulation resistance, the volume resistance value of the cured film formed from the photosensitive resin composition of the present invention or the photosensitive film is preferably 1 × 10 ¹⁶ Ω · cm or more, and 5 × 10 ¹⁶ Ω · cm. From the viewpoint of obtaining a resin composition that can be patterned, it is more preferably 1 × 10 ²⁰ Ω · cm or less, and more preferably 5 × 10 ¹⁹ Ω · cm or less.

The cured film formed of the photosensitive resin composition or the photosensitive film of the present invention includes a semiconductor passivation film, a protective film for a semiconductor element, an interlayer insulating film for a multilayer wiring for high-density mounting, an insulating layer for an organic electroluminescent element, In particular, it is suitably used for applications such as rewiring of a semiconductor device that is used by being stacked in multiple layers as an interlayer insulating film between metal wirings and a noise filter of an inductor device.
Moreover, the photosensitive resin composition of this invention or the cured film which hardened | cured the photosensitive film can be used for a semiconductor electronic component or a semiconductor device in the state in which the relief pattern layer of this cured film was formed.

  Moreover, after arrange | positioning a cured film on a board | substrate with a film thickness of 2-40 micrometers as above-mentioned, and arrange | positioning a copper wiring on it, the cured film is further made into a film thickness of 2-40 micrometers as an insulating film between copper wiring. Thus, a semiconductor electronic component or a semiconductor device can be manufactured.

A preferred structure in the present invention is shown in FIG.
In general, a passivation film 2 is formed on the semiconductor element 1. The photosensitive resin composition according to the present invention is applied onto the passivation film 2 by spin coating, or a photosensitive film is laminated by thermocompression bonding, heat-dried using a hot plate or the like, and a pattern is formed through exposure and development. After the pattern formation of the photosensitive resin film, a cured film 3 is formed by performing a high temperature treatment process by curing. A metal wiring 4 is formed on the cured film 3 by a technique such as sputtering, vapor deposition, electroless plating, or electrolytic plating. Furthermore, in order to protect the metal wiring, the photosensitive resin composition according to the present invention is applied by spin coating, or the photosensitive film is laminated by thermocompression bonding, and is heated and dried using a hot plate or the like, through exposure and development. Form a pattern. After the resin film pattern is formed, a high temperature treatment process by curing is performed to form the cured film 5. By forming a cured film by the above method, a semiconductor device having a low CTE and high heat resistance, mechanical characteristics, and reliability can be provided.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated, this invention is not limited by these examples. In addition, evaluation of the photosensitive resin composition in an Example was performed with the following method.

<Content of metal element with respect to total solid content>
1 g of the photosensitive resin composition was diluted with NMP to 25 mL to prepare an NMP solution of the resin composition. The concentration of Na and K metal elements was measured using an atomic absorption photometer Z-2710 (manufactured by Hitachi High-Tech Science). The content of the metal element relative to the total solid content was calculated from the measured concentration.

<Measuring method of film thickness>
A Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. was used, and the film after pre-baking and development was measured at a refractive index of 1.629 based on polyimide.

<Measurement of imidation ratio of polyimide>
(A) The imidization ratio of an alkali-soluble resin containing one or more selected from polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof is obtained on a 6-inch silicon wafer. An N-methylpyrrolidone (hereinafter referred to as NMP) solution having a resin solid content concentration of 50% by mass is applied by spin coating, and then baked on a 120 ° C. hot plate (SKW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.) for 3 minutes. Then, a prebaked film having a thickness of 10 μm ± 1 μm was produced. This film was divided in half, and one side was placed in an inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.), raised to a curing temperature of 350 ° C. over 30 minutes, and heat-treated at 350 ° C. for 60 minutes. Then, it annealed until the inside of oven became 50 degrees C or less, and obtained the cured film. About the obtained cured film (X) and the film (Y) before curing, an infrared absorption spectrum was measured using a Fourier transform infrared spectrophotometer FT-720 (manufactured by Horiba, Ltd.). The peak intensity in the vicinity of 1377 cm ⁻¹ due to CN stretching vibration of the imide ring was determined, and the value of “peak intensity of the film (Y) before curing / peak intensity of the cured film (X)” was defined as the imidization ratio.

<Production of photosensitive resin film>
The varnish was applied onto an 8-inch silicon wafer by spin coating so that the film thickness T1 after application (film thickness after application) = 4.0 to 4.5 μm, and then hot plate (manufactured by Tokyo Electron Co., Ltd.) A photosensitive resin film was obtained by pre-baking at 100 ° C. for 3 minutes using a coating and developing apparatus ACT8).

<Exposure>
The reticle on which the pattern was drawn was set in an exposure machine (Union full-wavelength aligner PEM-6M), and the photosensitive resin film was exposed to a mixed wavelength light of g, h, i lines for a predetermined time.

<Development>
Using a developing device of ACT8 manufactured by Tokyo Electron Ltd., a 2.38 mass% aqueous solution of tetramethylammonium hydroxide was sprayed on the exposed film for 10 seconds at 50 revolutions. Then, it was left still for 0 second at 0 rotation. The developer was shaken off, and tetramethylammonium hydroxide was sprayed again and allowed to stand for 20 seconds. At this time, the development time X was adjusted so that the phenomenon of film thickness due to development was 1.5 μm. Thereafter, the substrate was rinsed with water at 400 rpm, shaken and dried for 10 seconds at 3,000 rpm.

<Sensitivity>
The exposure time was changed in the above exposure and development, and the minimum exposure amount (Eth) at which the 50 μm pad pattern after development opened to 50 μm was determined. The irradiation intensity of i-line at the minimum exposure amount necessary for opening the exposed portion was defined as Eth. If Eth is 350 mJ / cm ² or less, the pattern workability is good, and 200 mJ / cm ² or less is more preferable.

<Development residue>
The 50 μm pattern opening obtained by the above <evaluation of pattern workability> was observed with FE-SEM (manufactured by Hitachi, Ltd.), and the presence or absence of a residue was evaluated. 1 (good) when there is no residue in the pattern opening, 2 if the area of the residue relative to the area of the opening is less than 20%, 2 if it is 20% or more and less than 40%, 3 if it is 40% or more (Defect).

<Formation of cured film by heat treatment>
The photosensitive resin film obtained in the above <Preparation of photosensitive resin film> is 220 ° C. under an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.) under a nitrogen atmosphere and an oxygen concentration of 20 ppm or less. A heat treatment was performed for 60 minutes or 320 ° C. for 60 minutes to obtain a cured film.

<Content of metal element in cured film>
The cured film obtained by <Formation of cured film by heat treatment> was scraped off and added with aqua regia to dissolve. After diluting this, the content of the metal element was measured with an ICP issuance analyzer (ICPS-8100, manufactured by Shimadzu Corporation).

<5% weight loss temperature>
The cured film obtained by the above <Formation of cured film by heat treatment> was peeled off with a 46% by mass hydrofluoric acid aqueous solution to obtain a cured film (heat-resistant resin film). The cured film obtained by this method was cut out with a single blade so as to be 3 × 0.5 cm. This was measured by increasing the temperature at a rate of 10 ° C./min under a nitrogen stream at 80 mL / min using a thermogravimetry measuring instrument (TGA50 manufactured by Shimadzu Corporation). The 5% weight loss temperature is preferably 350 ° C. or higher, more preferably 360 ° C. or higher, and further preferably 370 ° C. or higher.

<Volume resistance>
The cured film obtained by the above <Formation of cured film by heat treatment> was peeled off with a 46% by mass hydrofluoric acid aqueous solution to obtain a cured film (heat-resistant resin film). The cured film obtained by this method was cut out with a single blade so as to be 7 × 7 cm. A volume resistance value was measured by applying a voltage of 25 V at 24 ° C. and RH 45% using an insulation resistance meter (manufactured by ADVANTEST, TR8601 HIGH MEGOHM METER). When the resistance value was 1 × 10 ¹⁶ Ω · cm or more, it was evaluated as “good”, and when it was 1 × 10 ¹⁶ Ω · cm or more, it was evaluated as “x” (defective).

<CTE> Coefficient of thermal linear expansion Using a differential scanning calorimeter (manufactured by Seiko Instruments, TMA / SS6100), the cured film of 3 × 0.5 cm obtained by the above <5% weight loss temperature measurement (evaluation of heat resistance)> Then, the temperature was increased from 25 ° C. to 400 ° C. at a rate of 10 ° C./min under the condition of 80 mL / min under a nitrogen stream. The thermal expansion coefficient from 50 ° C. to 150 ° C. was calculated as CTE. It is preferably 70 ppm or less, more preferably 55 ppm or less, and even more preferably 40 ppm or less.

<Migration test>
The varnish was applied on a comb-type copper wiring electrode (Walts-TEG ME0102JY) by spin coating so that the film thickness T1 after pre-baking (film thickness after application) = 11.0 to 17.0 μm was obtained. A photosensitive resin film was obtained by pre-baking at 100 ° C. for 3 minutes using a hot plate. Heat treatment was performed at 220 ° C., 60 minutes, or 320 ° C. for 60 minutes under a nitrogen atmosphere in an inert oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.) to obtain a cured film. .

Thereafter, using a HAST CHAMBER PM220 (manufactured by ETAC), a voltage of 3.5 V was applied to the cured film having a distance between copper wirings of 20 μm under the conditions of 130 ° C., RH 85%, 96 hours, and the resistance value was measured. Those having a resistance value of 1.0 × 10 ⁻⁷ Ω or more after 96 hours were evaluated as “Good” (Good), and those having a resistance value of less than 1.0 × 10 ⁻⁷ Ω were evaluated as “Poor” (Poor).

Abbreviations and names of the compounds used in the examples and comparative examples are as follows.
PMDA-HH: 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride CBDA: cyclobutanetetracarboxylic dianhydride TDA-100: 3,4-dicarboxy-1,2,3,4-tetrahydro -1-Naphthalene succinic dianhydride ODPA: 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride 6FDA: 4,4′-hexafluoroisopropylidenediphthalic dianhydride BAHF: 2,2 -Bis (3-amino-4-hydroxyphenyl) hexafluoropropane ED-600: Jeffamine ED-600 (trade name, manufactured by HUNTSMAN Co., Ltd.)
DAE: 4,4′-diaminodiphenyl ether SiDA: 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane NMP: N-methyl-2-pyrrolidone MAP: 3-amino Phenol NA: 5-norbornene-2,3-dicarboxylic anhydride GBL: γ-butyrolactone (D) Solvent (a) in Examples
NaCl: sodium chloride Fe ₂ O ₃ : iron (III) oxide (manufactured by Sigma-Aldrich).

The (B) inorganic fine particles and (F) cross-linking agent used in each Example and Comparative Example are shown below.
(B) Inorganic fine particles MEK-EC-2130Y Average particle size 0.015 μm (silica sol, MEK dispersion concentration, 35%, manufactured by Nissan Chemical Industries)
MEK-EC-6150P average particle size 0.035 μm (silica sol, MEK dispersion concentration, 50%, manufactured by Nissan Chemical Co., Ltd.)
PL-2L PGME average particle size 0.016 μm (silica sol, PGME dispersion, concentration 25%, manufactured by Fuso Chemical)
ZR-010 average particle size 0.014 μm (zirconia sol, MEK dispersion, concentration 30%, manufactured by Solar)
MEK-AC-4130Y average particle size 0.045 μm (silica sol, MEK dispersion concentration, 30%, manufactured by Nissan Chemical Industries)
MEK-AC-5140Z average particle size 0.085 μm (silica sol, MEK dispersion concentration, 40%, manufactured by Nissan Chemical Industries)
Sciqas 0.2 μm Average particle size 0.20 μm (silica powder, manufactured by Sakai Chemical Industry)
(F) Crosslinking agent (a)

<Change of inorganic fine particle dispersion solvent>
Preparation of fine particle dispersion (a) GBL7.0 was added to 20.0 g of MEK-EC-2130Y. MEK was volatilized in a warm bath at 40 ° C. using a rotary evaporator and concentrated to 14.0 g to obtain a 50% fine particle dispersion (a).
Preparation of fine particle dispersion (b) GBL 10.0 was added to 20.0 g of MEK-EC-6150P. MEK was volatilized in a 40 ° C. warm bath using a rotary evaporator and concentrated to 20.0 g to obtain a 50% fine particle dispersion (b).
Preparation of fine particle dispersion (c) GBL10.0 was added to 40.0 g of PL-2L PGME. PGME was volatilized in a 40 ° C. warm bath using a rotary evaporator and concentrated to 20.0 g to obtain a 50% fine particle dispersion (c).
Preparation of fine particle dispersion (d) GBL10.0 was added to 33.3 g of ZR-010. MEK was volatilized in a 40 ° C. warm bath using a rotary evaporator and concentrated to 20.0 g to obtain a 50% fine particle dispersion (d).

Preparation of fine particle dispersion (e) GBL 6.0 was added to 20.0 g of MEK-AC-4130Y. MEK was volatilized in a warm bath at 40 ° C. using a rotary evaporator and concentrated to 12.0 g to obtain a 50% fine particle dispersion (e).

Preparation of fine particle dispersion (f) GBL 8.0 was added to 20.0 g of MEK-AC-5140Z. MEK was volatilized with a rotary evaporator in a warm bath at 40 ° C. and concentrated to 16.0 g to obtain a 50% fine particle dispersion (f).

Preparation of fine particle dispersion (g) 8.0 g of GBL was added to 8.0 g of Sciqas 0.2 μm and dispersed to obtain a 50% fine particle dispersion (g).

<Measurement of metal elements in inorganic fine particles>
The average particle size was measured by the BET method. A known method is used for the measurement by the BET method. (For example, patent document JP, 2016-33684, A)
The metal element in the inorganic fine particles was measured, and it was confirmed that the metal element was contained in the silica sol.
MEK-EC-2130Y: Na 1.1 ppm, Ca 1.6 ppm, K 4.9 ppm, Al 2.9 ppm, Fe 2.4 ppm
MEK-EC-6150P: Na 0.9 ppm, Ca 0.5 ppm, K 0.3 ppm, Al 2.2 ppm, Fe 1.0 ppm
PL-2L PGME: Na <0.1 ppm, Ca <0.1 ppm, K <0.1 ppm, Al <0.1 ppm, Fe 0.7 ppm
ZR-010 Na 7 ppm, Ca 15 ppm, K 3.2 ppm Al 5.1 ppm, Fe 3.0 ppm
MEK-AC-4130Y: Na 1.5ppm, Ca 2.4ppm, K 5.5ppm, Al 2.2ppm, Fe 3.0ppm
MEK-AC-5140Z: Na 1.6ppm, Ca 1.8ppm, K 4.9ppm, Al 3.3ppm, Fe 3.4ppm
Fine particle dispersion (g) (Sciqas 0.2 μm): Na 7.5 ppm, Ca 7.0 ppm, K 19.0 ppm, Al 3.3 ppm, Fe 3.4 ppm.

<Synthesis Example 1 Synthesis of quinonediazide compound (a)>
Under a dry nitrogen stream, TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 21.22 g (0.05 mol), 5-naphthoquinone diazide sulfonyl chloride 26.86 g (0.10 mol), 4-naphtho 13.43 g (0.05 mol) of quinonediazidesulfonyl chloride was dissolved in 50 g of 1,4-dioxane and brought to room temperature. Here, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise while confirming that the inside of the system was not 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (a) represented by the following formula.

<Synthesis Example 2 Synthesis of Phenol Resin (a)>
Under a dry nitrogen stream, 70.2 g (0.65 mol) of m-cresol, 37.8 g (0.35 mol) of p-cresol, 75.5 g of a 37 wt% aqueous formaldehyde solution (0.93 mol of formaldehyde), dioxalic acid After 0.63 g (0.005 mol) of hydrate and 264 g of methyl isobutyl ketone were charged into a 1 L flask, the 1 L flask was immersed in an oil bath, and a polycondensation reaction was performed for 4 hours while refluxing the reaction solution. Thereafter, the temperature of the oil bath is raised over 3 hours, and then the pressure in the 1 L flask is reduced to 40 to 67 hPa to remove volatile components, and the polymer solid of the phenol resin (a) is cooled to room temperature. Got. From GPC, the weight average molecular weight (Mw) was 3,500 (in terms of GPC polystyrene).

<Synthesis Example 3 Synthesis of Phenol Resin (b)>
To a mixed solution containing 500 ml of tetrahydrofuran and 0.01 mol of sec-butyllithium as an initiator, 20 g in total of pt-butoxystyrene and styrene in a molar ratio of 3: 1 was added, and polymerization was performed while stirring for 3 hours. I let you. The polymerization termination reaction was performed by adding 0.1 mol of methanol to the reaction solution. Next, in order to purify the polymer, the reaction mixture was poured into methanol, and the precipitated polymer was dried to obtain a white polymer. Furthermore, after dissolving in 400 ml of acetone, adding a small amount of concentrated hydrochloric acid at 60 ° C. and stirring for 7 hours, the mixture is poured into water, the polymer is precipitated, pt-butoxystyrene is deprotected and converted to hydroxystyrene, and washed. When dried, a purified copolymer of p-hydroxystyrene and styrene (hereinafter phenol resin (b)) was obtained. Moreover, the weight average molecular weight (Mw) was 3500 (GPC polystyrene conversion) by the analysis by GPC, and dispersion degree was (Mw / Mn) 2.80.

<Synthesis Example 4 Synthesis of Polymer A>
Under a dry nitrogen stream, 4.48 g (0.020 mol) of PMDA-HH and 11.11 g (0.025 mol) of 6FDA were dissolved in 100 g of NMP. MAP1.09g (0.010mol) was added here with NMP20g. Furthermore, BAHF11.90g (0.033mol), ED600 6.00g (0.010mol), DAE1.00g (0.005mol), SiDA0.62g (0.003mol) were added with NMP20g, and at 60 degreeC. The reaction was carried out for 1 hour and then stirred at 180 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polymer A powder.

<Synthesis Example 5 Synthesis of Polymer B>
Under a dry nitrogen stream, 1.12 g (0.005 mol) of PMDA-HH and 11.11 g (0.025 mol) of 6FDA were dissolved in 100 g of NMP. MAP1.09g (0.010mol) was added here with NMP20g. Furthermore, BAHF11.90g (0.033mol), ED600 6.00g (0.010mol), DAE1.00g (0.005mol), SiDA0.62g (0.003mol) were added with NMP20g, and at 60 degreeC. The reaction was carried out for 1 hour and then stirred at 180 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polymer B powder.

<Synthesis Example 6 Synthesis of Polymer C>
Under a dry nitrogen stream, 3.92 g (0.020 mol) of CBDA and 11.11 g (0.025 mol) of 6FDA were dissolved in 100 g of NMP. MAP1.09g (0.010mol) was added here with NMP20g. Furthermore, BAHF11.90g (0.033mol), ED600 6.00g (0.010mol), DAE1.00g (0.005mol), SiDA0.62g (0.003mol) were added with NMP20g, and at 60 degreeC. The reaction was carried out for 1 hour and then stirred at 180 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polymer C powder.

<Synthesis Example 7 Synthesis of Polymer D>
Under a dry nitrogen stream, 0.98 g (0.005 mol) of CBDA, 11.11 g (0.025 mol) of 6FDA and 4.65 g (0.015 mol) of ODPA were dissolved in 100 g of NMP. BAHF11.90g (0.033mol), DAE0.50g (0.003mol), ED600 7.50g (0.013mol), SiDA0.62g (0.003mol) were added with NMP20g here, 60 degreeC After stirring at 180 ° C. for 4 hours, 1.64 g (0.010 mol) of NA (5-norbornene-2,3-dicarboxylic acid anhydride) is added together with 10 g of NMP as an end-capping agent. And reacted at 60 ° C. for 1 hour. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polymer D powder.

<Synthesis Example 8 Synthesis of Polymer E>
Under a dry nitrogen stream, 0.98 g (0.005 mol) of CBDA, 4.50 g (0.015 mol) of TDA, and 11.11 g (0.025 mol) of 6FDA were dissolved in 100 g of NMP. BAHF11.90g (0.033mol), DAE0.50g (0.003mol), ED600 7.50g (0.013mol), SiDA0.62g (0.003mol) were added with NMP20g here, 60 degreeC Then, after stirring at 180 ° C. for 4 hours, 1.64 g (0.010 mol) of NA as a terminal blocking agent was added together with 10 g of NMP, and the mixture was reacted at 60 ° C. for 1 hour. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polymer E powder.

<Synthesis Example 9 Synthesis of Polymer F>
Under a dry nitrogen stream, 4.48 g (0.020 mol) of PMDA-HH and 11.11 g (0.025 mol) of 6FDA were dissolved in 100 g of NMP. MAP1.09g (0.010mol) was added here with NMP20g. Further, 15.57 g (0.043 mol) of BAHF, 1.00 g (0.005 mol) of DAE and 0.62 g (0.003 mol) of SiDA were added together with 20 g of NMP and reacted at 60 ° C. for 1 hour, and then at 180 ° C. for 4 hours. Stir. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polymer F powder.

<Synthesis Example 10 Synthesis of Polymer G>
Under a dry nitrogen stream, 4.48 g (0.020 mol) of PMDA-HH and 11.11 g (0.025 mol) of 6FDA were dissolved in 100 g of NMP. MAP1.09g (0.010mol) was added here with NMP20g. Furthermore, 4.58 g (0.013 mol) of BAHF, 21.00 g (0.035 mol) of ED600 and 0.62 g (0.003 mol) of SiDA were added together with 20 g of NMP, and reacted at 60 ° C. for 1 hour. Stir for hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polymer G powder.

<Synthesis Example 11 Synthesis of Polymer H>
Under a dry nitrogen stream, 4.48 g (0.020 mol) of PMDA-HH and 11.11 g (0.025 mol) of 6FDA were dissolved in 100 g of NMP. MAP1.09g (0.010mol) was added here with NMP20g. Furthermore, 0.92 g (0.003 mol) of BAHF, 27.00 g (0.045 mol) of ED600 and 0.62 g (0.003 mol) of SiDA were added together with 20 g of NMP, and reacted at 60 ° C. for 1 hour, and then at 180 ° C. for 4 hours. Stir for hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polymer H powder.

<Synthesis Example 12 Synthesis of Polymer I>
Under a dry nitrogen stream, 19.99 g (0.045 mol) of 6FDA was dissolved in 100 g of NMP. MAP1.09g (0.010mol) was added here with NMP20g. Furthermore, BAHF11.90g (0.033mol), ED600 6.00g (0.010mol), DAE1.00g (0.005mol), SiDA0.62g (0.003mol) were added with NMP20g, and at 60 degreeC. The reaction was carried out for 1 hour and then stirred at 180 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polymer I powder.

<Synthesis Example 13 Synthesis of Polymer J>
Under a dry nitrogen stream, 13.96 g (0.045 mol) of ODPA was dissolved in 119 g of N-methylpyrrolidone. MAP1.09g (0.010mol) was added here with NMP20g. Further, 11.72 g (0.032 mol) of BAHF and 3.48 g (0.014 mol) of SiDA were added and reacted at 60 ° C. for 1 hour and then at 200 ° C. for 6 hours. After completion of the reaction, the solution was cooled to room temperature and then poured into 2.5 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80 ° C. for 40 hours to obtain polymer J.

<Synthesis Example 14 Synthesis of Polymer K>
Under a dry nitrogen stream, 13.96 g (0.045 mol) of ODPA was dissolved in 119 g of N-methylpyrrolidone. MAP1.09g (0.010mol) was added here with NMP20g. Further, 11.72 g (0.032 mol) of BAHF and 3.48 g (0.014 mol) of SiDA were added together with 14 g of NMP, followed by stirring at 20 ° C. for 1 hour and then at 40 ° C. for 2 hours. Thereafter, a solution prepared by diluting 7.14 g (0.06 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40 ° C. for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 50 ° C. for 72 hours to obtain a polymer K as a polyimide precursor.

<Synthesis Example 15 Synthesis of Polymer L>
9.85 g (0.020) of a dicarboxylic acid derivative (DEDC derivative) obtained by reacting 1 mol of diphenyl ether-4,4′-dicarboxylic acid dichloride (DEDC) with 2 mol of 1-hydroxybenzotriazole in a dry nitrogen stream. Mol) and 9.16 g (0.025 mol) of BAHF were dissolved in 100 g of NMP. Further, 1.64 g (0.010 mol) of NA and 10 g of NMP were added and dissolved, followed by stirring at 75 ° C. for 12 hours to complete the reaction. After completion of the reaction, the solution was poured into 3 L of a solution of water / methanol = 3/1 (volume ratio), and the polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 20 hours to obtain a polybenzoxazole precursor polymer L.

[Example 1]
Weighing 10.0 g of polymer J, 1.4 g of quinonediazide compound (a), and 2.0 g of cross-linking agent (a) and dissolving in 3.0 g of GBL, adding an inorganic fine particle dispersion, varnish of the photosensitive resin composition Got. Each evaluation test was performed as described above using the obtained varnish.

[Examples 2 to 26]
A varnish was prepared in the same manner as in Example 1 except that (A) alkali-soluble resin, (B) inorganic fine particles or other additives were changed as shown in Tables 1 and 2, and each evaluation test was performed. The evaluation results are shown in Tables 3 and 4.

[Comparative Examples 1-8]
In Comparative Example 1, the inorganic fine particle dispersion (b) is the inorganic fine particle dispersion (c), the amount of the photoacid generator is 1.4 g, and the comparative example 2 is the amount of the polymer J of 10 g is 17 g. The amount of the liquid 20 g was 6 g, the amount of the photoacid generator 1.4 g was 1.8 g, and Comparative Example 3 was the inorganic fine particle dispersion (b) was the inorganic fine particle dispersion (a). 1.8 g of 4 g and 0.024 g of NaCl were added. In Comparative Example 4, 10 g of polymer J was 20 g, 20 g of inorganic fine particle dispersion was 0 g, and 1.4 g of photoacid generator was 1.8 g. In Comparative Example 5, 10 g of polymer J is 20 g of polymer L, 20 g of inorganic fine particle dispersion is 0 g, 1.4 g of photoacid generator is 1.8 g, and Comparative Example 6 is 10 g of polymer J. 0 g, inorganic fine particle dispersion (b) 20 g, inorganic fine particle dispersion (a) 40 g, light The amount of the acid generator 1.4 g was 1.8 g, Comparative Example 7 was added with 0.001 g of Fe ₂ O ₃ , and Comparative Example 8 was the inorganic fine particle dispersion (b) as the inorganic fine particle dispersion (g). Except for the above, a varnish was prepared and evaluated in the same manner as in Example 1. The composition of the varnish is shown in Table 2, and the evaluation results are shown in Tables 3 and 4.

  Here, Comparative Examples 1 and 2 have a large amount of development residue because the total metal element content of (E) Na and K is small, while Comparative Example 3 contains (E) the total metal element content of Na and K. Volume resistance and migration were poor because of the large amount. Moreover, since Comparative Example 4 with only polyimide and Comparative Example 5 with only PBO precursor did not contain inorganic fine particles, the CTE was high. In Comparative Example 6 containing no resin (polyimide, PBO precursor), patterning was not possible. Since Comparative Example 7 did not contain (E) Na and K, there were many development residues. In Comparative Example 8, the particle size of the inorganic fine particles was as large as 0.2 μm, and light was dispersed, so that there were many development residues.

DESCRIPTION OF SYMBOLS 1 Semiconductor element 2 Passivation film 3 Cured film 4 Metal wiring 5 Cured film

Claims (20)

(A) an alkali-soluble resin containing at least one selected from polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof; and (B) an average particle size of 0.001 μm or more, 0 Containing inorganic fine particles of 1 μm or less, (C) a photoacid generator, (D) a solvent, and (E) a metal element,
The (E) metal element contains one or more metal elements selected from Na and K, and the content of the (E) metal element is 1 with respect to the total solid content excluding the (D) solvent. A photosensitive resin composition having a concentration of 0.0 ppm to 300.0 ppm. The photosensitive resin composition according to claim 1, wherein the (B) inorganic fine particles have one or more organic groups selected from a hydroxyl group, a carboxyl group, and a sulfonyl group on the surface of the fine particles. The photosensitive resin composition of Claim 1 or 2 whose content of the said (B) inorganic fine particle is 10 mass parts or more and 90 mass parts or less with respect to 100 mass parts of total solid content except the said (D) solvent. object. The photosensitive resin composition in any one of Claims 1-3 in which the said (A) alkali-soluble resin has at least any one among the structural units represented by General formula (1) and (2).
(In General Formula (1), R ¹ represents a tetravalent organic group having 4 to 40 carbon atoms. R ² represents a divalent organic group having 20 to 100 carbon atoms. N ₁ represents ₁₀ to 100,000. Indicates an integer within the range of.)
(In General Formula (2), R ¹ represents a tetravalent organic group having 4 to 40 carbon atoms. R ² represents a divalent organic group having 20 to 100 carbon atoms. R ³ represents hydrogen or carbon number 1. And n ₂ represents an integer in the range of 10 to 100,000, and p and q represent integers satisfying 0 ≦ p + q ≦ 6. The divalent organic group having 20 to 100 carbon atoms in R ² of the general formulas (1) and (2) has a polyether structure, and the content of the polyether structure is based on all structural units of R ² The photosensitive resin composition of Claim 4 which is 10-80 mol%. The photosensitive resin composition according to claim 5, wherein the polyether structure is represented by the general formula (7).
(In the general formula (7), R ^{50 to} R ⁵³ represent a tetravalent organic group having 1 to 10 carbon atoms, and R ^{54 to} R ⁶¹ represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. , Y and z each independently represent an integer of 0 to 12, where x + y + z is an integer of 1 to 30.) The photosensitive resin composition in any one of Claims 1-6 whose hydroxyl group concentration of the said (A) alkali-soluble resin is 1.80 mmol / g or more and 5.50 mmol / g or less. The photosensitive according to any one of claims 1 to 7, wherein the content of the (B) inorganic fine particles is 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the total amount of the photosensitive resin composition containing a solvent. Resin composition. The photosensitive resin composition according to claim 1, wherein the (B) inorganic fine particles are silica fine particles. The photosensitive resin composition in any one of Claims 1-9 whose said (C) photo-acid generator is a naphthoquinone diazide compound. The photosensitive film formed from the photosensitive resin composition in any one of Claims 1-10. A cured film obtained by curing the photosensitive resin composition according to claim 1. A cured film obtained by curing the photosensitive film according to claim 11. (E) Content of metal element is 1.0 ppm or more and 300.0 ppm or less, The cured film of Claim 12 or 13 characterized by the above-mentioned. The cured film in any one of Claims 12-14 whose 5% thermogravimetric reduction temperature is 350 degreeC or more and 550 degrees C or less. The cured film according to claim 12, which has a volume resistance value of 1 × 10 ¹⁶ Ω · cm or more and 1 × 10 ²⁰ Ω · cm or less. The interlayer insulation film or semiconductor protective film in which the cured film in any one of Claims 12-16 was arrange | positioned. A method for producing a semiconductor electronic component or a semiconductor device using the photosensitive resin composition according to any one of claims 1 to 10 or the photosensitive film according to claim 11.
A method for manufacturing a semiconductor electronic component or a semiconductor device, comprising: a step of forming a pattern through an ultraviolet irradiation step and a development step; and a step of forming a relief pattern layer of a cured film by heating. A semiconductor electronic component or a semiconductor device comprising the relief pattern layer of the cured film according to claim 12. A semiconductor electronic component or a semiconductor device, wherein the cured film according to claim 12 is disposed as an interlayer insulating film between rewirings.