JP2022022578A - Resin composition, cured film, method for producing cured film, semiconductor device and organic el display device - Google Patents

Abstract

To provide a resin composition that shows a small change in sensitivity due to PED (post exposure bake delay effect) and can give a patterned cured film with small loss of thermal weight and a good shape.SOLUTION: A resin composition contains resin (a), nano diamond particles (b), and a photosensitive compound (c), the nano diamond particles (b) containing at least one selected from the group consisting of a carboxyl group, hydroxy group, ketone group and ether group.SELECTED DRAWING: None

Description

The present invention relates to a resin composition. More specifically, the present invention relates to a resin composition suitable for a surface protective film of a semiconductor device, an interlayer insulating film, an insulating layer of an organic electroluminescent (organic EL) device, a flattening layer, and the like.

Conventionally, polyimide resins and polybenzoxazole resins having excellent heat resistance and mechanical properties have been widely used as surface protective films and interlayer insulating films of semiconductor devices of electronic devices (see Patent Document 1). When polyimide or polybenzoxazole is used as a surface protective film or an interlayer insulating film, one of the methods for forming through holes and the like is etching using a positive photoresist. However, this method requires a step of applying and peeling the photoresist, which causes a problem that the step is complicated. Therefore, for the purpose of rationalizing the work process, a heat-resistant material to which photosensitivity has been imparted has been studied (see Patent Document 2).

On the other hand, the diameter of the silicon wafer, which is a substrate, is increasing year by year, and in recent years, the fan-out wafer level package that forms a rewiring structure on a sealing resin substrate or the like has been expanding.

Therefore, a heterocyclic compound is added to a photosensitive resin composition (see Patent Document 3) capable of suppressing thermal weight loss by adding silica fine particles to the photosensitive resin, and polybenzoxazole having an aliphatic group. , A photosensitive resin composition (see Patent Document 4) capable of obtaining adhesion to copper and high elongation is disclosed. Further, studies have been made to improve the elongation by adding an antioxidant and an epoxy resin to the polyimide resin (see Patent Document 5).

Japanese Unexamined Patent Publication No. 11-199557 Japanese Unexamined Patent Publication No. 11-24271 Japanese Unexamined Patent Publication No. 2018-36329 Japanese Unexamined Patent Publication No. 2010-96927 Japanese Unexamined Patent Publication No. 2010-77382

However, these resin compositions have a large change in sensitivity before and after the PED (Post Exposure bake Delay effect) process in the photolithography process, a large decrease in thermal weight of the cured film in the air, and a pattern shape of the cured film. There was one of the issues of being defective.

For this reason, in a rewiring structure where the photolithography process is long and barrier metal formation for metal wiring formation is repeated, such as a fan-out wafer level package on a glass substrate, which aims to reduce costs by using a large substrate. There was a problem with process stability.

In order to solve the above problems, the present invention
A resin composition containing (a) a resin, (b) nanodiamond particles, and (c) a photosensitive compound, wherein the (b) nanodiamond particles are a group consisting of a carboxyl group, a hydroxyl group, a ketone group, and an ether group. It is a resin composition containing one or more selected from the above.

Provided is a resin composition capable of obtaining a cured film having a small change in sensitivity before and after a PED (Post Exposure bake Delay effect) step, a small decrease in thermal weight of the cured film in air, and an excellent pattern shape of the cured film.

Hereinafter, the present invention will be described in detail.
The present invention is a resin composition containing (a) a resin, (b) nanodiamond particles and (c) a photosensitive compound, wherein the (b) nanodiamond particles have a carboxyl group, a hydroxyl group, a ketone group and an ether. It is a resin composition containing one or more selected from the group consisting of groups.

Since the resin composition of the present invention contains (b) nanodiamond particles and (c) a photosensitive compound, the sensitivity change before and after the PED (Post Exposure bake Delay effect) step is small, and the cured film is in the air. It is possible to obtain a cured film having a small thermal weight loss and an excellent pattern shape of the cured film.

This is because the nanodiamond particles have one or more selected from the group consisting of a carboxyl group, a hydroxyl group, a ketone group and an ether group, and thus interact with both (a) a resin and (c) a photosensitive compound. It is presumed that this is because the decomposition and reaction of the photosensitive compound during the PED process were suppressed, and the pattern shape change and the decrease in the thermal weight of the cured film due to shrinkage during curing were suppressed.

(A) The resin is a polyimide precursor, polyamide, polyimide, polybenzoxazole, polybenzoimidazole, polybenzoimidazole precursor, polybenzothiazole precursor, polybenzothiazole, and a copolymer thereof, polyamideimide resin, siloxane. Resin, acrylic polymer copolymerized with acrylic acid, novolak resin, resole resin, polystyrene resin, polyhydroxystyrene resin, and (a) a part of the aromatic ring of the resin and the hydrogen atom of the hydrocarbon are treated with a polyimide group and alkoxy. Examples include, but are not limited to, modified products having a cross-linking group such as a methyl group or an epoxy group introduced therein.

Among these, the resin (a) preferably contains at least one selected from the group consisting of a polyimide precursor, a polyamide, a polyimide, polybenzoxazole, and a copolymer thereof. When the resin composition contains (a) the resin, (b) the nanodiamond particles do not aggregate, (a) the resin and (c) the photosensitive compound interact appropriately, and the change in sensitivity before and after the PED step is suppressed. It is preferable because it can be done.

Polyamide contains the structure represented by the general formula (2), the polyimide precursor contains the structure represented by the general formula (3), polyimide contains the structure represented by the general formula (4), and polybenzoxazole. Includes the structure represented by the general formula (5).

Further, the resin (a) preferably contains a phenolic hydroxyl group. This is because (a) the phenolic hydroxyl group of the resin strongly interacts with (b) the nanodiamond particles, and the decrease in thermal weight of the cured film in the air can be suppressed.

Further, the resin (a) has a diamine residue having a phenolic hydroxyl group, and the content of the diamine residue having the phenolic hydroxyl group is 100 mol% of the total diamine residue in the resin (a). It is preferably 50 to 95 mol%.

(A) The resin has an appropriate polarity in the above range, and by being compatible with (b) nanodiamond particles, it interacts more strongly with (b) nanodiamond particles, so that the resin has a stronger interaction with the nanodiamond particles in the air of the cured film. It is preferable because it can suppress the decrease in thermal weight of.

Further, the resin (a) preferably has a structural unit represented by the general formula (1).

(In the general formula (1), R ¹ independently represents an alkylene group having 2 to 10 carbon atoms. A represents an integer of 1 ≦ a ≦ 60. * Represents a chemical bond.)
Since the structural unit represented by the general formula (1) in (a) interacts with the nanodiamond particles (b) and the reflow of the resin composition during curing is suppressed, a good pattern shape can be obtained. It is preferable because it can be used.

In the resin (a), in the general formulas (2) to (5), Y ¹ to Y ³ independently represent divalent organic groups, and Y ⁴ is a tetravalent organic group having 1 to 100 carbon atoms. Is shown. X ¹ and X ⁴ represent divalent organic groups having 1 to 100 carbon atoms, and X ² and X ³ independently represent tetravalent organic groups having 1 to 100 carbon atoms. R represents hydrogen or a monovalent organic group having 1 to 100 carbon atoms having 1 to 20 carbon atoms.

In the above general formulas (2) and (5), X ¹ and X ⁴ represent divalent organic groups having 2 or more carbon atoms and having 1 to 100 carbon atoms, and represent acid residues. X ¹ and X ⁴ can be preferably used as aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid and bis (carboxyphenyl) propane, cyclobutanedicarboxylic acid, cyclohexanedicarboxylic acid and adipic acid. , Octafluoroadipic acid, 3-methyladipic acid, octafluoroadipic acid, pimelic acid, 2,2,6,6-tetramethylpimeric acid, sveric acid, dodecafluorosveric acid, azelaic acid, sevacinic acid, hexadeca Adicarboxylic acids such as fluorosevacinic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecandioic acid and Further, there are residues such as dicarboxylic acid represented by the following general formula, tricarboxylic acid such as trimellitic acid and trimesic acid, and a part of the aromatic ring of these acid residues and the hydrogen atom of the hydrocarbon. It may be an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, or one substituted with a halogen atom or the like.

In the above structure, * indicates a binding site of a carboxyl group.

In producing a resin, when performing polycondensation, for example, a carboxylic acid group of an acid having residues of X ¹ and X ⁴ is a group that activates the reactivity of the carboxylic acid group as shown in the following formula (hereinafter referred to as a group). , May be referred to as an active group.) May be used.

In the formula, X and Y independently include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, a trifluoromethyl group, a halogen group, a phenoxy group, a nitro group and the like. , Not limited to these.

Among these, the active group is preferably an active group other than the chloride compound. By using an active group other than the chloride compound, chlorine ions in the obtained resin can be reduced and peeling from the metal substrate due to the presence of chloride ions can be prevented. Further, it is more preferable to use a diimidazolide compound as the active group. Since the leaving group of the diimidazolide compound becomes a water-soluble imidazole, the obtained resin can be reprecipitated or washed with water.

Y1 to Y3 in the general formulas (2) to ( ⁴ ) represent divalent organic groups having ¹ to 100 carbon atoms, and Y4 in the general formula (5) has a ^tetravalent carbon number of 1 to 100. Indicates an organic group, Y ¹ to Y ³ represent an organic group derived from a diamine residue, and Y ⁴ represents an organic group derived from a diamine residue having a hydroxyl group at the ortho position of two sets of amino groups.

Examples of the diamine residues of Y ¹ to Y ³ 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, 2,2'-ditrifluoromethyl- 5,5'-Dihydroxyl-4,4'-diaminobiphenyl, bis (3-amino-4-hydroxyphenyl) fluorene, 2,2'-bis (trifluoromethyl) -5,5'-dihydroxybenzidine, 3 , 4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3 , 4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2 , 6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether, 1 , 4-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4 , 4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2', 3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3', 4, 4'-Tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, ethylenediamine, 1,3-diaminopropane, 2-methyl-1,3 -Propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,1 2-Diaminododecane, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,2-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1, 4-bis (aminomethyl) cyclohexane, 4,4'-methylenebis (cyclohexylamine), 4,4'-methylenebis (2-methylcyclohexylamine), 1,2-bis (2-aminoethoxy) ethane, KH-511 , ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, THF-100, THF-140, THF-170, RE-600, RE -900, RE-2000, RP-405, RP-409, RP-2005, RP-2009, RT-1000, HE-1000, HT-1100, HT-1700, (trade name, manufactured by HUNTSMAN Co., Ltd.) A compound in which a part of the hydrogen atom of these aromatic rings or hydrocarbons is replaced with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, or the like, or a diamine having the structure shown below, etc. Known diamine residues can be mentioned, but are not limited thereto.

Examples of the amine residue of Y4 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, 2,2'-ditrifluoromethyl-5,5 '-Dihydroxyl-4,4'-diaminobiphenyl, bis (3-amino-4-hydroxyphenyl) fluorene, 2,2'-bis (trifluoromethyl) -5,5'-dihydroxybenzidine and their fragrances Remains of known diamines such as compounds in which a part of hydrogen atoms of a group ring or hydrocarbon is replaced with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, or a diamine having the structure shown below. Groups can be mentioned, but are not limited to these.
In the above structure, n is an integer of 1 to 10, preferably 1 to 5, respectively.

The resin (a) preferably contains a phenolic hydroxyl group, and examples thereof include polyimide precursors, polyamides, polyimides, and known resins such as polybenzoxazole, polyhydroxystyrene resin, and novolak resin, which have a hydroxyl group. Not limited to this.
Among these, the resin (a) preferably has a diamine residue having a phenolic hydroxyl group.

It has a diamine residue having a phenolic hydroxyl group, and the content of the diamine residue having the phenolic hydroxyl group is 50 to 95 mol% with respect to 100 mol% of the total diamine residue in the resin (a). It is preferable to have. Examples of the diamine residue having a phenolic hydroxyl group 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) ) Residues of hydroxyl group-containing diamine residues such as fluorene and compounds in which some of the hydrogen atoms of these aromatic rings are replaced with alkyl groups having 1 to 10 carbon atoms, fluoroalkyl groups, halogen atoms, etc. The basis can be mentioned, but it is not limited to this.

It is more preferable that the resin (a) has a structural unit represented by the general formula (1). The structural unit represented by the general formula (1) is 1,2-bis (2-aminoethoxy) ethane, KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176. , D-200, D-400, D-2000, THF-100, THF-140, THF-170, RE-600, RE-900, RE-2000, RP-405, RP-409, RP-2005, RP -It is preferable that it is a residue of a diamine such as 2009, RT-1000, HE-1000, HT-1100, HT-1700, (trade name, manufactured by HUNTSMAN Co., Ltd.).

The number average molecular weight of the structural unit represented by the general formula (1) is preferably 150 or more and 2,000 or less. The number average molecular weight of the structural unit represented by the general formula (1) is preferably 150 or more, more preferably 600 or more, still more preferably 900 or more, because flexibility and elasticity can be obtained. Further, the number average molecular weight of the structural unit represented by the general formula (1) is preferably 2,000 or less, more preferably 1,800 or less, and more preferably 1,800 or less because the solubility in an alkaline solution can be maintained. More preferably 500 or less.

The content of the structural unit represented by the general formula (1) is 5 to 40 mol% with respect to 100 mol% of the total diamine residues of the resin (a), because high reflow resistance can be obtained. Is preferable.

Further, in order to improve the adhesion to the silicon substrate, the resin (a) may be copolymerized with an aliphatic group having a siloxane structure. Specific examples of the diamine component include those obtained by copolymerizing 1 to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, and the like.

Further, in the above general formula ( ³ ) having a polyimide precursor structure and the general formula (4) having a polyimide structure, X2 to X3 represent residues of ^acid dianhydride, and have a tetravalent carbon number of 1. ~ 100 organic groups.

Specific examples of the acid dianhydride residue include pyromellitic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3', 4'-. Biphenyltetracarboxylic acid dianhydride, 2,2', 3,3'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2', 3 , 3'-Benzophenone tetracarboxylic acid 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) methanedi Anhydrous, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfonate dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1, 2,5,6-naphthalenetetracarboxylic acid dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorenic acid dianhydride, 9,9-bis {4- (3,4-dicarboxyphenoxy) ) Phenyl} fluorenic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylene Aromatic tetracarboxylic acid dianhydride, such as tetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 3,3', 4,4'-diphenylsulfone Tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetra Carboxylic acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3 -Cyclohexene-1,2-dicarboxylic acid dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic acid dianhydride, bicyclo [2.2.2] octo-7-en-2,3,5 , 6-Tetracarboxylic acid dianhydride, 2,3,4,5-tetracarboxylic acid dianhydride, 3,5,6-tricarboxy-2-norbornan acetate dianhydride, 1,3,3a, 4 , 5,9b-Hexahydro-5 ( Tetrahydro-2,5-dioxo-3-franyl) naphtho [1,2-c] furan-1,3-dione and acid dianhydride having the structure shown in the following formula, and their aromatic rings and hydrocarbons. Residues such as compounds in which a part of a hydrogen atom is replaced with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, or the like can be mentioned, but the present invention is not limited thereto.

R of the general formula (3) represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. From the viewpoint of solubility in an alkaline developer and solution stability of the obtained photosensitive resin composition, it is preferable that 10 mol% to 90 mol% of hydrogen atoms are used with respect to 100 mol% of the total R.

(A) The molar ratio of the structures represented by the general formulas (2) to (5) in the resin is calculated from the molar ratio of the monomers used at the time of polymerization, or by using a nuclear magnetic resonance apparatus (NMR). , The obtained resin, the photosensitive resin composition, the polyamide structure and the imide precursor structure in the cured film, and the method for detecting the peak of the imide structure can be confirmed.

The resin (a) preferably has a weight average molecular weight in the range of 3,000 to 200,000. In this range, since appropriate solubility in an alkaline developer can be obtained, high contrast between the exposed portion and the unexposed portion can be obtained, and a desired pattern can be formed. From the viewpoint of solubility in an alkaline developer, 100,000 or less is more preferable, and 50,000 or less is more preferable. Further, from the viewpoint of improving elongation, 1.0000 or more is preferable. Here, the molecular weight can be measured by gel permeation chromatography (GPC) and converted from a standard polystyrene calibration curve.

(A) The resin may be sealed at the end of the main chain with another end-capping agent such as monoamine, monocarboxylic acid, acid anhydride, or monoactive ester compound.
The introduction ratio of the terminal encapsulant is preferably 0.1 mol% or more with respect to all the amine components in order to suppress the increase in the weight average molecular weight of the resin of the present invention and the decrease in the solubility in the alkaline solution. More preferably, it is 5 mol% or more. Further, in order to suppress deterioration of the mechanical properties of the cured film obtained by lowering the weight average molecular weight of the polyamide resin, the content is preferably 60 mol% or less, more preferably 50 mol% or less. Further, a plurality of terminal encapsulants may be reacted to introduce a plurality of different end groups.

Specifically, as monoamine as a terminal sealant, aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 2-aminobenzoic acid, 3-aminobenzoic acid , 4-Aminobenzoic acid, 4-Aminosalicylic acid, 5-Aminosalicylic acid, 6-Aminosalicylic acid, 2-Aminobenzenesulfonic acid, 3-Aminobenzenesulfonic acid, 4-Aminobenzenesulfonic acid, 3-Amino-4,6 -Dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like can be used. Two or more of these may be used.

The monocarboxylic acid as the terminal encapsulant and the monoactive ester compound are 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene and phthalic anhydride. , Maleic anhydride, Nasic acid anhydride, Cyclohexanedicarboxylic acid anhydride, Acid anhydrides such as 3-hydroxyphthalic acid anhydride, Dicarboxylic acid phthalic acid, Maleic acid, Nasic acid, Cyclohexanedicarboxylic acid, 3-Hydroxyphthalic acid Acid, 5-norbornen-2,3-dicarboxylic acid, tricarboxylic acid, trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene , 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-dicarboxynaphthalene and one of the carboxyl groups of dicarboxylic acids and N-hydroxybenzotriazole, imidazole, N-hydroxy-5-norbornene- Active ester compounds obtained by reaction with 2,3-dicarboxyimide, and some of the hydrogen atoms of these aromatic rings and hydrocarbons are represented by alkyl groups, fluoroalkyl groups, halogen atoms, etc. having 1 to 10 carbon atoms. Substituted compounds and the like can be used. Two or more of these may be used.

(A) The resin is synthesized, for example, by the following method, but the resin is not limited thereto.
First, a compound in which a dicarboxylic acid is replaced with an active carboxylic acid group, or an acid dianhydride, a diamine compound, or another copolymerization component is dissolved in an organic solvent at room temperature, and in some cases at a higher temperature, and then heated. And polymerize. From the viewpoint of the stability of the solution during the reaction, it is preferable to dissolve the highly soluble diamine compound first. Then, in some cases, another copolymerization component is added, and an acid or an acid anhydride as an end-capping agent is added to polymerize.

The polyimide precursor structure has an acid anhydride residue in the above polymerization method, and in the case of an amic acid ester, it can be obtained by reacting the remaining carboxylic acid with an esterifying agent after the above polymerization.

In the polyimide, for example, an acid dianhydride, a diamine compound, and in some cases other components are dissolved in an organic solvent, and then heated at about 40 ° C. to 60 ° C. for polymerization, and then an esterifying agent is added in some cases. In addition, a method of obtaining an imide precursor and polymerizing the imide precursor at 70 to 200 ° C., a method of closing all the imide rings of the imide precursor using a known imidization reaction method, and stopping the imidization reaction in the middle. Then, a method of partially introducing the imide structure, and further, a method of partially introducing the imide structure by mixing the imide polymer having a closed ring in which all the imide rings of the imide precursor are closed and the polyimide precursor. It can be used and synthesized.

For polyamide, for example, a method in which a dicarboxylic acid chloride and a diamine compound are mixed at 0 ° C to 15 ° C, other components are dissolved in an organic solvent, and then heated at about 40 ° C to 100 ° C to polymerize. , A compound in which a dicarboxylic acid is replaced with an active group, or a diamine compound, in some cases, another component is mixed in an organic solvent at 40 ° C to 60 ° C, and then heated at about 60 ° C to 100 ° C for polymerization. Can be synthesized.

For benzoxazole, for example, a method of obtaining a polyamide having an organic group derived from a diamine residue having a hydroxyl group at the ortho position of two sets of amino groups and polymerizing this at 150 to 250 ° C., and adding an acidic catalyst to close the ring. It can be synthesized by using the method of making it.

Examples of the organic solvent used for resin polymerization include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N, N'. -Dimethylpropylene urea, N, N-dimethylisobutyric acid amide, methoxy-N, N-dimethylpropionamide amides, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α- Cyclic esters such as methyl-γ-butylolactone, carbonates such as ethylene carbonate and propylene carbonate, glycols such as triethylene glycol, phenols such as m-cresol and p-cresol, acetophenone, 1,3-dimethyl-2. -Includes, but is not limited to, imidazolidinone, sulfolane, dimethylsulfoxide, tetrahydrofuran, dimethylsulfoxide, propylene glycol monomethyl ether acetate, ethyl lactate and the like.

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

The resin composition of the present invention contains (b) nanodiamond particles.
(B) The nanodiamond particles include one or more selected from the group consisting of a carboxyl group, a hydroxyl group, a ketone group and an ether group. By containing the (b) nanodiamond particles, it interacts with both the (a) resin and (c) the photosensitive compound, suppresses the decomposition and reaction of the photosensitive compound during the PED process, and at the time of curing. It is possible to suppress the change in pattern shape due to shrinkage and the decrease in thermal weight of the cured film.

Preferably, (b) the nanodiamond particles are nanodiamond particles produced by the detonation method (detonation nanodiamond particles). The primary particle size of the explosive nanodiamond particles is a single digit nanometer, and such a configuration provides high transparency in the visible light region for the resin layer or film formed from the photosensitive composition. Is suitable.

As the detonation method of nanodiamond particles, an air-cooled detonation method and a water-cooled detonation method are known, and the air-cooled detonation method nanodiamond particles are preferable. Air-cooled detonation nanodiamond particles are suitable because the primary particles tend to be smaller than water-cooled detonation nanodiamond particles. Further, more preferably, the air-cooled detonation nanodiamond particles in the coexistence with the atmosphere, that is, the nanodiamonds produced by the detonation method under the condition of being air-cooled and coexisting with a gas having an atmospheric composition (including a significant amount of oxygen). It is a diamond particle. The detonation method, which is air-cooled and carried out under the condition that a gas having an atmospheric composition coexists, contains one or more selected from the group consisting of a carboxyl group, a hydroxyl group, a ketone group and an ether group on the surface of the primary particle (1). b) Suitable for producing nanodiamond particles.

Specifically, the product name is V-diamond (manufactured by Vision Development Co., Ltd.), the product name is Nanodiamond (particle size: <10 nm) (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and the product name is Nanodiamond (particle size: <10 nm) (Carboxyl-model). ) (Manufactured by Tokyo Kasei Kogyo Co., Ltd.), trade name: monodisperse nanodiamond particles (trade name, manufactured by Merck), trade name: Nanodiamond NMP dispersion (solid content concentration: 1%) (manufactured by Daicel Co., Ltd.), etc. , Not limited to this.

Since the change in sensitivity before and after the PED step can be suppressed, the content of the (b) nanodiamond particles in the resin composition is preferably 1 to 70 parts by weight with respect to 100 parts by weight of the (c) photosensitive compound. It is more preferably 3 to 30 weight.
It is presumed that when the nanodiamond particles are mixed in an appropriate range, the decomposition and reaction of the photosensitive compound during the PED process can be suppressed.

Since the nanodiamond particles (b) can obtain a cured film having an excellent pattern shape, it is preferable that the nanodiamond particles have an amorphous layer on the surface thereof, and the amorphous layer is surface-modified with a phenolic hydroxyl group. It is considered that this is because the phenolic hydroxyl group interacts with the resin and the photosensitive compound to suppress the pattern shape change due to the rapid shrinkage during curing. Specifically, the product name is V-diamond (manufactured by Vision Development Co., Ltd.), the product name is Nanodiamond (particle size: <10 nm) (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and the product name is monodisperse nanodiamond particles (product name, manufactured by Merck). ), Product name Nanodiamond NMP dispersion (solid content concentration 1%) (manufactured by Daicel Co., Ltd.), etc., but is not limited thereto.

The resin composition of the present invention further contains (c) a photosensitive compound.
(C) The resin composition containing a photoacid generator as a photosensitive compound can be used as a positive photosensitive resin composition (positive photosensitive varnish). Further, (c) the resin composition containing the photopolymerizable compound and the initiator as the photosensitive compound can be used as a negative type photosensitive resin composition (negative type photosensitive varnish).

(C) The photosensitive compound preferably contains a naphthoquinone diazide compound because a cured film having an excellent pattern shape can be obtained.
It is considered that this is because the naphthoquinone diazide compound interacts with both the resin (a) and the nanodiamond particles (b) to suppress the pattern shape change due to the rapid shrinkage during curing.

The naphthoquinone diazide compound includes a polyhydroxy compound with an ester bond of quinone diazide sulfonic acid, a polyamino compound with a sulfonamide bond of quinone diazide sulfonic acid, and a polyhydroxypolyamino compound with a quinone diazide sulfonic acid ester-bonded and / or sulfone. Examples thereof include amide-bonded compounds. All the functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds may not be substituted with quinonediazide, but it is preferable that 40 mol% or more of all the functional groups are substituted with quinonediazide on average. .. By containing such a naphthoquinone diazide compound, a positive photosensitive resin composition that is sensitive to i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp which is a general ultraviolet ray. You can get things.

Specifically, as the polyhydroxy compound, 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, Methyltris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (trade name, manufactured by Honshu Kagaku Kogyo), BIR-OC, BIP-PC, BIR-PC, BIR -PTBP, BIRO-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry), 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, manufactured by Honshu Chemical Industry Co., Ltd.), novolak resin and the like can be mentioned, but the present invention is not limited thereto.

Specifically, as the polyamino compound, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4 '-Diaminodiphenyl sulfide and the like can be mentioned, but the present invention is not limited thereto.

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

Among these, it is preferable that the naphthoquinone diazide compound contains an ester with a phenol compound and a 4-naphthoquinone diazidosulfonyl group. As a result, high sensitivity and higher resolution can be obtained by i-line exposure.

The content of the naphthoquinone diazide compound contained in the resin composition is preferably 1 part by weight or more, more preferably 10 parts by weight or more, preferably 50 parts by weight or less, and 40 parts by weight, based on 100 parts by weight of the total resin in the resin composition. More preferably, it is by weight or less. By setting the content of the naphthoquinone diazide compound in this range, the difference in the dissolution rate between the exposed part and the unexposed part with respect to the developing solution becomes high, so that the sensitivity can be made higher, and it occurs when the content is high. It is preferable because no residue is observed. Further, a sensitizer or the like may be added as needed.

When the resin composition contains a photopolymerizable compound and an initiator, it is a negative-type photosensitive resin composition that is insolubilized by light.
The photopolymerizable compound contains a polymerizable unsaturated functional group. Examples of the polymerizable unsaturated functional group include unsaturated double bond functional groups such as vinyl group, allyl group, acryloyl group and methacryloyl group, and unsaturated triple bond functional groups such as propargyl. Among these, a group selected from a conjugated vinyl group, an acryloyl group and a methacryloyl group is preferable in terms of polymerizable property.

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

Preferred photopolymerizable compounds include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylol. Propanetriacrylate, trimethylolpropanedimethacrylate, trimethylolpropanetrimethacrylate, styrene, α-methylstyrene, 1,2-dihydronaphthalene, 1,3-diisopropenylbenzene, 3-methylstyrene, 4-methylstyrene, 2 -Vinylnaphthalene, butyl acrylate, butyl methacrylate, isobutyl acrylate, hexyl acrylate, isooctyl acrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate. , Neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol di Methacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecanediacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate , 2-Hydroxyethyl acrylate, 2-Hydroxyethyl methacrylate, 1,3-diacryloyloxy-2-hydroxypropane, 1,3-dimethacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, 2,2,6,6-tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinylacrylate, N-methyl-2,2,6,6-tetramethylpi Peridinyl methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl acrylate, ethylene oxide modified bisphenol A diacrylate , Ethylene oxide-modified bisphenol A dimethacrylate, N-vinylpyrrolidone, N-vinylcaprolactam and the like. These may be used alone or in combination of two or more.

Of these, those that can be particularly preferably used are 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecanediacrylate, isobornyl acrylate, isobornyl methacrylate, and pentaerythritol tri. Acrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, 2,2,6 , 6-Tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl acrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, N-methyl-2, Examples thereof include 2,6,6-tetramethylpiperidinyl acrylate, ethylene oxide-modified bisphenol A diacrylate, ethylene oxide-modified bisphenol A dimethacrylate, N-vinylpyrrolidone, and N-vinylcaprolactam.

The content of the photopolymerizable compound is preferably 5 to 200 parts by weight, more preferably 5 to 150 parts by weight from the viewpoint of compatibility with respect to 100 parts by weight of the resin (a). By setting the content of the photopolymerizable compound to 5 parts by weight or more, it is possible to prevent elution of the exposed portion during development and obtain a resin composition having a high residual film ratio after development. Further, by setting the content of the photopolymerizable compound to 200 parts by weight or less, whitening of the film during film formation can be suppressed.

The polymerization initiator is not particularly limited as long as it is a compound that generates an active radical during pattern exposure, but for example, an azo compound, an azido compound, a diazo compound, an o-quinone diazide compound, an organic peroxide, and benzophenones. , Biscmarin, bisimidazole compound, titanosen compound, organic thiol compound, halogenated hydrocarbon compound, trichloromethyltriazine compound, iodonium salt compound, onium salt compound such as sulfonium salt compound and the like.

Further, the resin composition of the present invention preferably contains a compound having an alkoxymethyl group. Examples of the alkoxymethyl group-containing compound include, but are not limited to, the following compounds.

(B) It is preferable to use nanodiamond particles and a compound having an alkoxymethyl group in combination because heat shrinkage can be suppressed.

The amount of the compound having an alkoxymethyl group added is preferably 10 parts by weight or more, more preferably 20 parts by weight or more, based on 100 parts by weight of the resin (a). Further, 60 parts by weight or less is preferable, and 40 parts by weight or less is more preferable. In the above range, since the cross-linking density by the thermal cross-linking agent is high, the chemical resistance of the cured film can be improved, and sufficient flexibility can be obtained, so that high elongation can be obtained, which is preferable.

Further, the resin composition may contain a heat-crosslinking agent having an epoxy group, an acrylic group, an oxetane group or a methylol group in order to improve chemical resistance and heat resistance.

The resin composition of the present invention may contain an antioxidant. The antioxidant is an antioxidant added to suppress oxidation, but in the present invention, the antioxidant means one having no cross-linking group. Since the antioxidant does not have a cross-linking group, it can act not only on the site where the cross-linking group can react but also on the entire membrane.

The content of the antioxidant with respect to 100 parts by weight of the resin (a) is preferably in the range of 0.1 to 10 parts by weight.

Examples of the antioxidant include benzotriazole, organic phosphorus, and an antioxidant having a hindered phenol structure. Among these, an antioxidant having a hindered phenol structure is preferable because it is excellent in solubility and storage stability during development, and a high-resolution resin composition can be obtained as well as in-plane film thickness and pattern uniformity.

Further, if necessary, a small molecule compound having a phenolic hydroxyl group may be contained within a range that does not reduce the shrinkage residual film ratio after curing. As a result, the development time can be shortened.

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

The content of the small molecule compound having a phenolic hydroxyl group is preferably 1 to 40 parts by weight with respect to 100 parts by weight of the total resin.

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

Among these, the resin composition of the present invention preferably contains a surfactant of an acrylic polymer. Since the surfactant of the acrylic polymer has low compatibility with the resin (a), it tends to be unevenly distributed on the film surface of the cured film, and as a result, the wettability of the cured film can be improved. Therefore, the barrier metal can be uniformly wet-etched in the plane, and wiring having excellent dimensional uniformity can be formed, which is preferable.

Specific examples include Polyflow manufactured by Kyoeisha Chemical Co., Ltd. The surface active agent of the acrylic polymer is preferably (a) contained in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight of the resin.

Other surfactants include "Florard" (registered trademark) manufactured by Sumitomo 3M Ltd., D.
Fluorosurfactants such as "Megafuck" (registered trademark) manufactured by IC Co., Ltd., "Sulflon" (registered trademark) manufactured by Asahi Glass Co., Ltd., KP341 manufactured by Shin-Etsu Chemical Co., Ltd., Chisso Co., Ltd. Examples thereof include organic siloxane surfactants such as DBE manufactured by Kyoeisha Chemical Co., Ltd., "Polyflow" (registered trademark) manufactured by Kyoeisha Chemical Co., Ltd., "Glanol" (registered trademark), and BYK manufactured by Big Chemie Co., Ltd.

Further, in order to enhance the adhesiveness to the substrate, trimethoxyaminopropylsilane, trimethoxyepoxysilane, trimethoxyvinylsilane, trimethoxythiolpropyl as silicon components in the resin composition of the present invention within a range that does not impair storage stability. It may contain a silane coupling agent such as silane. The preferable content of the silane coupling agent is (a) 0.01 to 5 parts by weight with respect to 100 parts by weight of the resin.

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

The viscosity of the resin composition of the present invention is preferably 2 to 5,000 mPa · s at 25 ° C. The viscosity can be measured using an E-type rotational viscometer. By adjusting the solid content concentration so that the viscosity is 2 mPa · s or more, it becomes easy to obtain a desired film thickness. On the other hand, when the viscosity is 5,000 mPa · s or less, it becomes easy to obtain a highly uniform coating film. A resin composition having such a viscosity can be easily obtained, for example, by setting the solid content concentration to 5 to 60% by weight.

The method for producing the resin composition of the present invention is exemplified. For example, a method of putting the components (a) to (c) and, if necessary, other components in a glass flask or a stainless steel container and stirring and dissolving them with a mechanical stirrer, a method of dissolving by ultrasonic waves, and a planetary stirring defoaming method. Examples thereof include a method of stirring and dissolving with an apparatus. Among them, a method of stirring and dissolving with a mechanical stirrer or the like is preferable.
Then, it is preferable to filter with a filter having a pore size of 0.1 μm to 5 μm in order to remove foreign matter.

The cured film of the present invention is obtained by curing the resin film by applying the resin composition to the substrate and heat-treating it to promote the thermal cross-linking reaction. Crosslinking can improve heat resistance and chemical resistance. As the method of this heat treatment, a method of raising the temperature stepwise or a method of selecting a certain temperature range and continuously raising the temperature for 5 minutes to 5 hours can be selected. As an example of the former, there is a method of heat-treating at 130 ° C. and 200 ° C. for 30 minutes each. As an example of the latter, there is a method of linearly raising the temperature from room temperature to 400 ° C. over 2 hours.

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

First, the resin composition of the present invention is applied to a substrate. The boards include silicon wafers, ceramics, gallium arsenic, organic circuit boards, inorganic circuit boards, composite boards of silicon wafers and sealing resins such as epoxy resins, sealing resin boards, and circuit configurations on these boards. Examples include, but are not limited to, those in which materials are arranged. Examples of organic circuit boards include glass substrate copper-clad laminates such as glass cloth and epoxy copper-clad laminates, composite copper-clad laminates such as glass non-woven fabrics and epoxy copper-clad laminates, temporary carrier substrates, and polyetherimide. Examples thereof include heat-resistant and thermoplastic substrates such as resin substrates, polyether ketone resin substrates, polysulfon-based resin substrates, and flexible substrates such as polyester copper-clad film substrates and polyimide copper-clad film substrates. Examples of the inorganic circuit board include a glass substrate, an alumina substrate, an aluminum nitride substrate, a ceramic substrate such as a silicon carbide substrate, an aluminum base substrate, and a metal substrate such as an iron base substrate. Examples of circuit constituent materials are conductors containing metals such as silver, gold and copper, resistors containing inorganic oxides, low dielectrics containing glass materials and / or resins, resins and highs. Dielectric constants Examples include high dielectrics containing inorganic particles and insulators containing glass-based materials. As the coating method, rotary coating using a spinner, spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure coater, screen coater, slit die coater. There are methods such as ter. The coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the film thickness after drying is 0.1 to 150 μm.

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

Next, the substrate on which the resin composition is applied is dried to obtain a resin film. Drying is preferably carried out in the range of 50 ° C. to 150 ° C. for 1 minute to several hours using an oven, a hot plate, infrared rays or the like.

Next, the resin film is irradiated with chemical rays through a mask having a desired pattern and exposed. The chemical rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc., but in the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) of mercury lamps. ..

To form a pattern, after exposure, a developer is used to develop the exposed area in the case of the positive type and the unexposed area in the case of the negative type. The developing solution includes tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, and dimethyl. A solution of an alkaline compound such as aminoethylmethacrylate, cyclohexylamine, ethylenediamine and hexamethylenediamine is preferable.

In the present invention, it is particularly preferable to use an alkaline aqueous solution as the developing solution. After the alkaline development step, it is preferable because the minute surface roughness and the uniform wettability in the surface are improved, and the wiring having excellent dimensional uniformity can be formed.

In some cases, an alkaline solution containing a polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, or dimethylacrylamide, methanol, ethanol, isopropanol, etc. Alcohols, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone may be added alone or in combination of several kinds. Development can be carried out by a method such as spraying the above-mentioned developer on the film surface, immersing it in the developer, applying ultrasonic waves while immersing it, or spraying the developer while rotating the substrate. After development, it is preferable to rinse with water. Here, too, 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.

After the development, a heat treatment is performed to allow the thermal cross-linking reaction to proceed, thereby curing the resin film to obtain a cured film. Crosslinking can improve heat resistance and chemical resistance. As the method of this heat treatment, a method of raising the temperature stepwise or a method of selecting a certain temperature range and continuously raising the temperature for 5 minutes to 5 hours can be selected. As an example of the former, there is a method of heat-treating at 130 ° C. and 200 ° C. for 30 minutes each. As an example of the latter, there is a method of linearly raising the temperature from room temperature to 400 ° C. over 2 hours. The cure conditions in the present invention are preferably 150 ° C. or higher and 350 ° C. or lower.

Further, the method for producing a cured film of the present invention preferably includes a step of performing a dry etching process on the cured film obtained by heat treatment. By performing the dry etching process, it is possible to improve minute surface roughness on the cured film and improve the adhesion to the barrier metal due to the anchor effect.

Examples of the dry etching step of the present invention include plasma etching and reactive ion etching. Reactive ion etching is preferable from the viewpoint that a high anchoring effect can be obtained because etching with high anisotropy is possible in the cured film. The reactive gas used for dry etching is not particularly limited, and reactive gases such as tetrafluoromethane, trifluoromethane, oxygen, nitrogen, tetrachloromethane, carbon monoxide, and carbon dioxide are used alone or in combination of two or more. Be done. Further, an inert gas such as helium or argon may be mixed. Among these, it is preferable that the reactive gas has oxygen because the surface energy of the cured film can be improved and the adhesion to the barrier metal can be improved. The RF output is preferably 200 W or more and 1500 W or less, and the pressure is preferably 5 to 80 Pa.

The amount of film sag of the cured film etched by the dry etching step is preferably 0.1 to 0.5 μm.

The semiconductor device of the present invention is a semiconductor device provided with the cured film.

The organic EL display device of the present invention is an organic EL display device provided with the cured film. Preferably, it is an organic EL display device including the cured film as an insulating layer or a flattening layer.

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

(1) PED sensitivity change rate processing method (i)
(C) For a positive photosensitive resin composition to which a naphthoquinone diazide compound is added as a photosensitive compound, a varnish is applied onto two 8-inch silicon wafers and a developing device ACT-8 (Tokyo Electron Limited). ) Was applied by a spin coating method so that the film thickness was 10 μm, and prebaking was performed at 120 ° C. for 3 minutes. These wafers were set with a reticle with a circular via pattern cut on an exposure machine i-line stepper DSW-8000 (manufactured by GCA), and exposed in ² steps of 10 mJ / cm with an exposure amount of 0 to 1500 mJ / cm ² . ..
One sheet is immediately after exposure and the other sheet is left for 24 hours (PED step), and then using the ACT-8 developer, a 2.38 wt% tetramethylammonium aqueous solution (hereinafter TMAH, Tama Chemical Industry Co., Ltd.) The developer was repeatedly developed twice with a discharge time of 10 seconds and a paddle time of 40 seconds by a paddle method, then rinsed with pure water and then shaken off to dry to obtain a developing film. The exposure amount at which the exposed portion was completely eluted was defined as the sensitivity, and the difference in sensitivity between the two wafers was defined as the PED sensitivity change rate.

Processing method (ii)
(C) For the negative-type photosensitive resin composition to which the initiator and the photopolymerizable compound are added as the photosensitive compound, varnish is applied onto an 8-inch silicon wafer and the developing apparatus ACT-8 (Tokyo Electron (Tokyo Electron). Co., Ltd.) was applied by a spin coating method so that the film thickness was 10.5 μm to 12 μm, and prebaking was performed at 120 ° C. for 3 minutes. These wafers were set with a reticle with a circular via pattern cut on an exposure machine i-line stepper DSW-8000 (manufactured by GCA), and exposed in ² steps of 10 mJ / cm with an exposure amount of 0 to 1500 mJ / cm ² . .. Immediately after exposure, one sheet is left for 24 hours, and then the developer is developed using the ACT-8 developer with a paddle method using a cyclopentanone with a developer discharge time of 10 seconds and a paddle time of 40 seconds. The process was repeated several times, then rinsed with pure water, shaken off and dried to obtain a developing film. The exposure amount at which the unexposed portion was completely eluted was defined as the sensitivity, and the difference in sensitivity between the two wafers was defined as the PED sensitivity change rate.

Regarding the developing films obtained by the processing methods (i) and (ii), those having a PED sensitivity change rate of more than 15% are defective (E), and those having a PED sensitivity change rate of 15% or less and exceeding 10% are acceptable (D), 10%. Those below 7% were considered acceptable (C), those below 7% and above 5% were good (B), and those below 5% were good (A).

(2) Thermal weight reduction The varnish was applied and prebaked on an 8-inch silicon wafer by a spin coating method using a coating developer ACT-8 so that the film thickness after prebaking at 120 ° C. for 3 minutes was 11 μm. After that, using the varnish oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.), the temperature was raised to 320 ° C. at 3.5 ° C./min at an oxygen concentration of 20 ppm or less, and heat treatment was performed at the curing temperature for 1 hour. rice field. When the temperature became 50 ° C. or lower, the wafer was taken out, slowly cooled, and then immersed in 45% by weight of hydrofluoric acid for 5 minutes to peel off the cured film of the resin composition from the wafer. The cured film obtained by this method was cut out with a single blade so as to have a size of 3 × 0.5 cm. This was measured by raising the temperature at a rate of 10 ° C./min under a condition of 80 mL / min under an air flow using a thermogravimetric reduction measuring machine (TGA50 manufactured by Shimadzu Corporation). Those with a 5% weight loss temperature of less than 350 ° C are considered defective (D), those with a temperature of 350 ° C or higher and lower than 360 ° C are acceptable (C), those with a weight loss temperature of 360 ° C or higher and lower than 370 ° C are good (B), and those with a temperature of 370 ° C are good (B). The above was regarded as good (A).

(3) Pattern shape (1) For the developing film developed immediately after exposure, which was created at the PED sensitivity change rate, the oxygen concentration was 20 ppm or less using the Inert Oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.). The temperature was raised to 320 ° C. at 3.5 ° C./min, and heat treatment was performed at the curing temperature for 1 hour. The obtained pattern was observed in cross section at a magnification of 5000 times using a scanning electron microscope (SEM, S-3000N manufactured by Hitachi High-Technologies Corporation). Those with a defect (D), those with a taper angle of 70 ° or less are good (C), those with a taper angle of 80 ° or less and exceeding 70 ° are good (B), those with a taper angle of 90 ° or less and exceeding 80 °. Was better (A).

The names or structures of the compounds used are shown below.

(Synthesis Example 1) Synthesis of Resin (A-1) 29.30 g (0.08 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as BAHF) under a dry nitrogen stream. ), 1,3-Bis (3-aminopropyl) tetramethyldisiloxane 1.24 g (0.005 mol), 4-aminophenol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 3.27 g (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a terminal encapsulant. 0.03 mol) was dissolved in 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP). To this, 31.2 g (0.1 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride (hereinafter referred to as ODPA, manufactured by Manac Inc.) was added together with 20 g of NMP, and the mixture was reacted at 60 ° C. for 1 hour. Then, the mixture was stirred at 180 ° C. for 4 hours. After the stirring was completed, the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80 ° C. for 20 hours to obtain a resin (A-1) as a polyimide resin.

(Synthesis Example 2) Synthesis of Resin (A-2) In a mixed solution containing 500 ml of tetrahydrofuran and 0.01 mol of sec-butyllithium as an initiator, pt-butoxystyrene and styrene are added in a molar ratio of 3: 1. In total, 20 g was added, and the mixture was polymerized with stirring for 3 hours. The polymerization termination reaction was carried out by adding 0.1 mol of methanol to the reaction solution.

The reaction mixture was then poured into methanol to purify the polymer and the precipitated polymer was dried to give a white polymer. Further, it is dissolved in 400 ml of acetone, a small amount of concentrated hydrochloric acid is added at 60 ° C., and the mixture is stirred for 7 hours, then poured into water to precipitate the polymer, deprotect the pt-butoxystyrene, convert it to hydroxystyrene, and wash it. After drying, a resin (A-2) was obtained as a polyhydroxystyrene resin which is a copolymer of purified p-hydroxystyrene and styrene.

(Synthesis Example 3) Synthesis of Resin (A-3) Under a dry nitrogen air flow, 30.23 g (0.05 mol) of HA was dissolved in 80 g of N-methyl-2-pyrrolidone (NMP). To this, 13.95 g (0.045 mol) of 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA) was added together with 10 g of NMP, and the mixture was reacted at 40 ° C. for 1 hour. Then, 1.64 g (0.01 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride (NA) was added as an end-capping agent, and the mixture was further reacted at 40 ° C. for 1 hour. Then, a solution of 12.50 g (0.11 mol) of N, N'-dimethylformamide dimethylacetal diluted with 15 g of NMP was added dropwise over 10 minutes. After the dropping, the mixture was stirred at 40 ° C. for 2 hours. After completion of the reaction, the solution was poured into 2 L of water and the precipitate of the polymer solid was collected by filtration. The polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-3) as a polyimide precursor.

(Synthesis Example 4) Synthesis of Resin (A-4) Place 4,4'-oxydiphthalic acid dianhydride (155.1 g, 0.5 mol) in a 2 liter volume separable flask and add 125 g of 2-hydroxyethyl methacrylate. 400 ml of γ-butyrolactone was added and stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generated by the reaction was completed, the mixture was allowed to cool to room temperature and left for 16 hours.

Next, under ice-cooling, a solution of 206.3 g of dicyclohexylcarbodiimide in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4'-diaminodiphenyl ether (95.0 g, 0). .48 mol) was suspended in 350 ml of γ-butyrolactone and added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and the mixture was stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. The obtained reaction solution was added to 3 L of ethyl alcohol to form a precipitate composed of a crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate the polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a resin (A-4) as a polyimide precursor.

(Synthesis Example 5) Synthesis of Resin (A-5) Under a dry nitrogen air flow, 13.6 g (0.0225 mol) of HA and 4,4'-diaminodiphenyl ether (5.5 g, 0.275 mol) were added to N-methyl-. It was dissolved in 80 g of 2-pyrrolidone (NMP). To this, 13.95 g (0.045 mol) of 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA) was added together with 10 g of NMP, and the mixture was reacted at 40 ° C. for 1 hour. Then, 1.64 g (0.01 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride (NA) was added as an end-capping agent, and the mixture was further reacted at 40 ° C. for 1 hour. Then, a solution of 12.50 g (0.11 mol) of N, N'-dimethylformamide dimethylacetal diluted with 15 g of NMP was added dropwise over 10 minutes. After the dropping, the mixture was stirred at 40 ° C. for 2 hours. After completion of the reaction, the solution was poured into 2 L of water and the precipitate of the polymer solid was collected by filtration. The polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a resin (A-5) as a polyimide precursor.

(Synthesis Example 6) Synthesis of Resin (A-6) BAHF (11.9 g, 0.033 mol), RT-1000 (15.0 g, 0.015 mol), 1,3-bis (under a dry nitrogen air flow). 3-Aminopropyl) tetramethyldisiloxane (0.62 g, 0.0025 mol),) was dissolved in 100 g of NMP. To this, acid A (14.26 g, 0.048 mol) and 5-norbornene-2,3-dicarboxylic acid (0.41 g, 0.0025 mol) were added together with NMP 25 g, and the mixture was reacted at 85 ° C. for 3 hours. .. After completion of the reaction, the mixture was cooled to room temperature, and the same procedure was carried out using acetic acid (13.20 g, 0.25 mol) and NMP 150 g to obtain a resin (A-6) as a polyamide.

Hereinafter, each component used in Examples and Comparative Examples is shown below.
GBL: γ-butyl lactone (B-1) nanodiamond particles: nanodiamond NMP dispersion (solid content concentration 1%) (manufactured by Daicel Corporation). The surface of the nanodiamond particles has an amorphous layer, and the amorphous layer is surface-modified with a phenolic hydroxyl group.
(B-2) Nanodiamond particles: Nanodiamond (particle size: <10 nm) (Carboxyl-modified) (manufactured by Tokyo Kasei Co., Ltd.) NMP dispersion (solid content concentration 1%). Nanodiamond particles contain a carboxyl group.
(B'-1) Silica fine particles: MEK-EC-2130Y (manufactured by Nissan Chemical Industries, Ltd.) NMP dispersion (solid content concentration 1%)
(C-1), (C-2), (C-3), and (D-1) are compounds represented by the following chemical formulas, respectively.

[Examples 1 to 8, 10 to 11, Comparative Examples 1, 3, 4]
In the composition shown in Table 1, (a) the resin (A-1) to (A-6) 10 g, (D-1) 3 g, and (c) the photosensitive compound (C-1) 4 g. , 5.0 g of solvent GBL was blended, and (c) the nanodiamond particles had a solid content ratio of 3 g with respect to the photosensitive compound (b) as the weight ratio (b) nanodiamond particles shown in Table 1. A varnish of a positive photosensitive resin composition was prepared by blending 5.0 g of GBL.

Regarding Table 1, when Example 1 is taken as an example, when the weight ratio of (b) to (c) is 75%,
(B) Since 3 g of nanodiamond particles is used, 300 g of the dispersion liquid (B-1) is blended.
[Example 9, Comparative Example 5,]
(A) As the resin, 10 g of the above resin (A-2), (D-1) 3 g, (c) as the photosensitive compound (C-2) 2.0 g, (C-3) 2.0 g, solvent GBL 5. 0 g is blended, and (c) the photosensitive compound is blended so that (b) the nanodiamond particles (B-1) have a solid content ratio of the weight ratio shown in Table 1, and the negative type photosensitive is blended. A varnish of the resin composition was prepared.
[Comparative Example 2]
In the composition shown in Table 1, (a) the resin (A-1) is 10 g, (D-1) 3 g, (c) the photosensitive compound is (C-1) 4 g, and the solvent GBL 5.0 g. (C) Silica fine particles (B'-1) were blended with the photosensitive compound so as to have a solid content ratio of 75% to prepare a varnish of a positive photosensitive resin composition.

[Comparative Example 6]
In the composition shown in Table 1, as the resin (a), 10 g of the above resin (A-1), 3 g of (D-1), 5.0 g of the solvent GBL (b) and 300 g of the dispersion liquid of nanodiamond particles (B-1). (A solid content of 3.0 g was blended to prepare a varnish of a resin composition.

[Comparative Example 7]
(D-1) 3 g, (c) 2.0 g of (C-2) as a photosensitive compound, and (C-3) 2.0 g are blended, and (b) nanodiamond is blended with respect to (c) the photosensitive compound. The particles (B-1) were blended so as to have a solid content ratio of 75% by weight to prepare a varnish of a negative photosensitive resin composition.

Table 1 shows the evaluation results of the obtained resin composition.

Claims (12)

A resin composition containing (a) a resin, (b) nanodiamond particles and (c) a photosensitive compound, wherein the (b) nanodiamond particles are a group consisting of a carboxyl group, a hydroxyl group, a ketone group and an ether group. A resin composition containing one or more selected from the above. The resin composition according to claim 1, wherein the content of the (b) nanodiamond particles is 1 to 70 parts by weight with respect to 100 parts by weight of the (c) photosensitive compound. The resin composition according to claim 1 or 2, wherein the resin (a) comprises at least one selected from the group consisting of a polyimide precursor, a polyamide, a polyimide, a polybenzoxazole, and a copolymer thereof. (A) The resin composition according to any one of claims 1 to 3, wherein the resin contains a phenolic hydroxyl group. The resin composition according to any one of claims 1 to 4, wherein the nanodiamond particles (b) have an amorphous layer on the surface thereof, and the amorphous layer is surface-modified with a phenolic hydroxyl group. The resin composition according to any one of claims 1 to 5, wherein the (c) photosensitive compound contains a naphthoquinone diazide compound. The resin (a) has a diamine residue having a phenolic hydroxyl group, and the content of the diamine residue having the phenolic hydroxyl group is 100 mol% of the total diamine residue in the resin (a). , 50-95 mol%, according to any one of claims 1-6. The resin composition according to any one of claims 1 to 6, wherein the resin (a) has a structural unit represented by the general formula (1).

(In the general formula (1), R ¹ independently represents an alkylene group having 2 to 10 carbon atoms. A represents an integer of 1 ≦ a ≦ 60. * Represents a chemical bond.) A cured film obtained by curing the resin composition according to any one of claims 1 to 8. A step of applying the resin composition according to any one of claims 1 to 8 to a substrate and drying to form a resin film, a step of exposing, a step of developing, and a heat treatment of the developed resin film. A method for producing a cured film, which comprises a step of making a cured film. A semiconductor device comprising the cured film according to claim 9. An organic EL display device comprising the cured film according to claim 9.