KR20190065998A - Resin composition, cured film, semiconductor device and manufacturing method thereof - Google Patents

Abstract

(A) at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, other polyamides and copolymers thereof, (D) a resin containing a thermal crosslinking agent having three or more epoxy groups A resin composition comprising, as a composition, (E) a compound having a tertiary amide structure having a molecular weight of 60 or more and 1000 or less. It is possible to obtain a cured film which is excellent in storage stability and post-exposure delay stability and which can be cured by a heat treatment at a low temperature while exhibiting a high chemical resistance and also shows a decrease in device characteristics after a reliability test of a device to which the cured film is applied The present invention provides a resin composition containing

Description

Resin composition, cured film, semiconductor device and manufacturing method thereof

The present invention relates to a resin composition. More particularly, the present invention relates to a resin composition suitably used for a surface protective film such as a semiconductor device, an interlayer insulating film, an insulating layer of an organic electroluminescent device, and the like.

Conventionally, a planarizing film of a surface protective film or an interlayer insulating film of a semiconductor element, an insulating layer of an organic electrolytic element, or a thin film transistor (hereinafter referred to as a TFT) substrate includes a polyimide resin excellent in heat resistance, electrical insulation, Or a polyamide-imide resin has been widely used.

In such applications, resin compositions are generally formed by spin coating or slit coating. For this reason, various solvents have been conventionally used in resin compositions and have been selected and applied in consideration of solubility, coating properties, storage stability, developability, and the like (Patent Documents 1, 2, and 3).

When a coating film of a polyimide precursor, a polybenzoxazole precursor or a polyamideimide precursor is subjected to dehydration ring closure by heating to obtain a cured film containing polyimide, polybenzoxazole or polyamideimide, High-temperature firing is required. From the viewpoint that the memory device used in recent years and the mold resin used in the production of the semiconductor package are weak to the high-temperature process, the surface protective film or the interlayer insulating film is preferably subjected to baking at a temperature of 250 DEG C or lower, more preferably 200 DEG C or lower A curable resin composition is required.

As a resin composition capable of being cured at a low temperature, a resin composition containing a resin such as polyimide, polybenzoxazole, polybenzimidazole, and polybenzothiazole and a heat crosslinking agent (Patent Document 4), an alkali soluble polyamideimide, , A positive photosensitive polyimide resin composition containing a solvent and a crosslinking agent (Patent Document 5), a positive photosensitive polyimide resin composition containing an alkali soluble polyimide, a quinone diazide compound, a heat crosslinking agent, a thermal acid generator and an adhesion improver (Patent Document 6) and the like are known.

Japanese Patent No. 4911248 Japanese Patent Application Laid-Open No. 2015-232688 WO2015 / 046332 Japanese Patent Laid-Open No. 2007-16214 Japanese Patent Application Laid-Open No. 2007-240554 Japanese Patent Application Laid-Open No. 2013-72935

However, the resin compositions described in the patent documents have problems in terms of storage stability, delay stability after exposure, chemical resistance in a heat treatment at a low temperature, and device characteristics after a reliability test.

The present invention solves the above-mentioned problems associated with the prior art, and it is possible to obtain a cured film which is excellent in storage stability and post-exposure delay stability, can be cured by a heat treatment at a low temperature while exhibiting high chemical resistance, And it is an object of the present invention to provide a resin composition capable of suppressing deterioration of device characteristics after a reliability test of a device to which a film is applied.

The present invention has the following configuration.

(A) at least one resin selected from polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, other polyamides and copolymers thereof, (D) a heat crosslinking agent having three or more epoxy groups, And (E) a compound having a tertiary amide structure having a molecular weight of 60 or more and 1000 or less.

(2) A cured film obtained by curing the resin composition.

(3) a step of applying the resin composition on a substrate and drying to form a resin film, an exposure step of exposing the resin film, a developing step of developing the exposed resin film, and a heat treatment step of heating the developed resin film Of the cured film.

(4) A semiconductor device having a metal wiring and an insulating film, the semiconductor device having the cured film as an insulating film.

(5) The semiconductor device according to (4), further comprising a semiconductor chip, wherein the metal wiring is electrically connected to the semiconductor chip.

(6) The semiconductor device according to (5), wherein the semiconductor chip is sealed with a sealing resin, the insulating film is disposed as an interlayer insulating film on the semiconductor chip and the sealing resin, and the metal interconnection is disposed on the interlayer insulating film. Device.

(7) stacking a plurality of metal wiring and a rewiring layer including the cured film on a supporting substrate on which an attaching material is disposed;

A step of arranging a semiconductor chip and a sealing resin thereon to manufacture a semiconductor package,

And then peeling the support substrate and the semiconductor package therefrom.

According to the resin composition of the present invention, it is possible to obtain a cured film which is excellent in storage stability and post-exposure delay stability and can be cured by a heat treatment at a low temperature while having a high chemical resistance, It is possible to suppress the deterioration of the device characteristics in the future.

1 is an enlarged cross-sectional view of a put portion of a semiconductor device having bumps.
2 is a diagram showing a detailed manufacturing method of a semiconductor device having bumps.
3 is a cross-sectional view of a manufacturing process of an example of the semiconductor device of the present invention.
4 is a view showing a method of manufacturing a semiconductor device in an RDL first.
5 is a cross-sectional view of a coil part of an inductor device which is an example of the semiconductor device of the present invention.
6 is a cross-sectional view of an example of a TFT substrate.

(A) at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, other polyamide and copolymers thereof; (D) (E) a resin composition comprising a compound having a tertiary amide structure having a molecular weight of 60 or more and 1000 or less. (A), (D) and (E), respectively.

The component (A) is preferably an alkali-soluble resin. The alkali solubility in the present invention means that a solution prepared by dissolving a resin in? -Butyrolactone is applied onto a silicon wafer and prebaked at 120 占 폚 for 4 minutes to form a prebaked film having a film thickness of 10 占 퐉 占 0.5 占 퐉, The prebake film is immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution having a temperature of 23 +/- 1 deg. C for 1 minute and then rinsed with pure water, the dissolution rate of the prebake film is 50 nm / It says.

At least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, other polyamides and copolymers thereof as the component (A) has a high heat resistance, It is suitably used as a flattening film, an insulating layer, a partition wall, a protective film, and an interlayer insulating film particularly used for an organic light emitting device, a display device, and a semiconductor device.

(A) will be described. The polyimide is not particularly limited as long as it has an imide ring. The polyimide precursor is not particularly limited as long as it has a structure to become a polyimide having an imide ring by dehydrating and ring-closing, and polyamide acid, polyamide acid ester, or the like can be used. The polybenzoxazole is not particularly limited as long as it has a benzoxazole ring. The polybenzoxazole precursor is not particularly limited as long as it has a structure to become a polybenzoxazole having a benzoxazole ring by dehydration ring closure, and polyhydroxyamide and the like can be used. The other polyamides are polyamides having a structure other than the polyimide precursor and the polybenzoxazole precursor, and are not particularly limited as long as they have an amide structure in the molecule. The above polymers may be contained in two or more kinds, and resins obtained by copolymerizing these may be used.

More preferably used as the component (A) are polyimide, polyimide precursor or polybenzoxazole precursor. As the polyimide, a resin having a structural unit represented by the following general formula (1) is preferable. As the polyimide precursor and the polybenzoxazole precursor, a resin having a structural unit represented by the following general formula (2) is preferable.

In the general formula (1), V represents an organic group having 4 to 10 valences, and W represents an organic group having 2 to 8 valences. p and q each represent an integer within the range of 0 to 6; It is preferable that p + q > 0 so that the component (A) has alkali solubility. R ¹ represents a group selected from a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group and a thiol group, and when p is 2 or more, a plurality of R ^{1 s} may be the same or different. R ² represents a group selected from a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group and a thiol group, and when q is 2 or more, a plurality of R ^{2 s} may be the same or different.

In the general formula (2), X and Y each independently represent a 2 to 8-valent organic group having at least 2 carbon atoms. R ³ and R ⁴ each independently represent hydrogen or an organic group having 1 to 20 carbon atoms. r and s each represent an integer within the range of 0 to 4, and t and u represent an integer within the range of 0 to 2, respectively. It is preferable that r + s + t + u > 0 in order to make the component (A) have alkali solubility. In the case of the polyimide precursor in the general formula (2), it is preferable that the polyimide precursor has a structure in which t> 0, a carboxy group or a carboxy ester group at the ortho position of the amide group, and dehydrocondensation to form an imide ring. In the case of the polybenzoxazole precursor in the general formula (2), it is preferable that the polybenzoxazole precursor has a structure in which s > 0, a hydroxyl group is present at the ortho position of the amide group and the benzoxazole ring is formed by dehydration cyclization Do. Also, as the other polyamide, a polyamide having a structure represented by the general formula (2) (except for a polyimide precursor and a polybenzoxazole precursor) can be preferably used.

 The component (A) preferably has 5 to 100,000 structural units represented by the general formula (1) or (2) in one molecule, more preferably 10 to 100,000.

In addition to the structural unit represented by the general formula (1) or (2), another structural unit may be present. Examples of the other structural unit include, for example, a skeleton structure in which two cyclic structures are bonded to a quaternary carbon atom constituting a cyclic structure, a siloxane structure, and the like. In this case, the structural unit represented by the general formula (1) or (2) is preferably the main structural unit. Herein, the main constituent unit refers to having 50 mol% or more of the structural unit represented by the general formula (1) or (2) in the total structural unit number, more preferably 70 mol% or more.

Further, the component (A) preferably contains a group selected from an alkylene group and an alkylene ether group. These groups may contain an aliphatic ring. As the group selected from the alkylene group and the alkylene ether group, a group represented by the following general formula (3) is particularly preferable.

In the general formula (3), R ⁵ to R ⁸ each independently represent an alkylene group having 1 to 6 carbon atoms. R ⁹ to R ¹⁶ each independently represent hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms. However, the structures shown in parentheses are different from each other. x, y and z each independently represent an integer of 0 to 35;

 By having the component (A) have a group selected from an alkylene group and an alkylene ether group, high curability can be imparted to the cured film obtained by curing the resin composition containing the component (A). Further, flexibility can be exhibited in the resin, and an increase in stress that may occur when the imide precursor structure or the benzoxazole precursor structure is ring closed can be suppressed. Therefore, it is possible to suppress an increase in stress on the substrate wafer accompanying the ring closure of the precursor structure. Further, since the alkylene group and the alkylene ether group are low in ultraviolet ray absorbing property, the introduction of the alkylene group and the alkylene ether group improves the i-line transmittance and realizes high sensitivity.

The weight average molecular weight of the alkylene group and the alkylene ether group is preferably 600 or more, and more preferably 900 or more, from the viewpoint of achieving high-diffusibility in the cured film. Further, it is preferably 2,000 or less, more preferably 1,800 or less, and even more preferably 1,500 or less, from the standpoint of maintaining solubility in an alkali solution.

In the present invention, the weight average molecular weight (Mw) can be confirmed by GPC (gel permeation chromatography). For example, the developing solvent may be measured as N-methyl-2-pyrrolidone (hereinafter, sometimes abbreviated as NMP) and converted into polystyrene.

In the general formula (1), V- (R ¹ ) _p and (OH) _r -X- (COOR ³ ) _t in the general formula (2) represent an acid residue. V is an organic group having 4 to 10 carbon atoms, and among them, an organic group having 4 to 40 carbon atoms and containing an aromatic ring or a cyclic aliphatic group is preferable. X is a divalent to octavalent organic group having two or more carbon atoms, and among them, an organic group having 4 to 40 carbon atoms and containing an aromatic ring or an aliphatic group is preferable.

Examples of the acid component include dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, Dicarboxylic acid and the like; Examples of the tricarboxylic acid include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyltricarboxylic acid and the like; Examples of the tetracarboxylic acid include pyromellitic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, 2,2 ' 3,3'-biphenyltetracarboxylic acid, 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid, 3,3', 4,4'-benzophenonetetracarboxylic acid, 2,2 (3,4-dicarboxyphenyl) propane, 2,2-bis (2,3-dicarboxyphenyl) propane, 1,1- Bis (2,3-dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2,3- Methane, bis (3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 9,9-bis (3,4-dicarboxyphenyl) fluorene, 9,9- Naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,4- 5,6-pyridine tetracarboxylic acid, 3,4,9,10-perylene tetracarboxylic acid, 2,2- Switch (3, 4-dicarboxyphenyl) an aromatic tetracarboxylic acid of the structure shown in propane and to hexafluoro acid; Butanetetracarboxylic acid, cyclobutanetetracarboxylic acid, and 1,2,3,4-cyclopentanetetracarboxylic acid, and the like, but the present invention is not limited thereto. Two or more of these may be used.

In the formula, R ²⁰ represents an oxygen atom, C (CF ₃ ) ₂ or C (CH ₃ ) ₂ . R ²¹ and R ²² represent a hydrogen atom or a hydroxyl group.

These acids can be used as such or as acid anhydrides, halides and active esters.

W- (R ² ) _{q in} the general formula (1) and (OH) _s -Y- (COOR ⁴ ) _u in the general formula (2) represent a residue of a diamine. W and Y are organic groups having 2 to 8 carbon atoms, and among them, an organic group having 4 to 40 carbon atoms and containing an aromatic ring or a cyclic aliphatic group is preferable.

Specific examples of the diamine constituting the residue of the diamine include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-dia (4-aminophenoxy) benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis -Aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2'- Minibiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl- Diaminobiphenyl, 2,2 ', 3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3', 4,4'-tetramethyl-4,4'-diamino Biphenyl, 2,2'-di (trifluoromethyl) -4,4'-diaminobiphenyl, 9,9-bis (4-aminophenyl) fluorene, or at least a part of the hydrogen atoms of these aromatic rings, Or a compound substituted with a halogen atom Or the like can be given a structure shown in the aliphatic cyclohexyl diamine, methylene bis cyclohexylamine and to the diamine. Two or more of these may be used.

In the formulas, R ²³ represents an oxygen atom, C (CF ₃ ) ₂ or C (CH ₃ ) ₂ . Each of R ²⁴ to R ²⁷ independently represents a hydrogen atom or a hydroxyl group.

These diamines can be used as diamines or as corresponding diisocyanate compounds, trimethylsilylated diamines.

The component (A) preferably contains a group selected from the above-mentioned alkylene group and alkylene ether group in W in the general formula (1) or Y in the general formula (2). As a result, the resin composition can have high sensitivity and low stress in the cured film of the resin composition and high sensitivity of the resin composition. Further, when W in the general formula (1) or Y in the general formula (2) has a group represented by the general formula (3), the adhesion with the substrate metal (for example, copper) . Concretely, because the interaction between the ether group contained in the general formula (2) and the metal such as coordination bond is obtained, high adhesion with the substrate metal can be obtained.

Specific examples of the diamine containing a group selected from alkylene group and alkylene ether group include ethylene diamine, 1,3-diaminopropane, 2-methyl-1,3-propanediamine, 1,4-diaminobutane, -Diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8- diaminooctane, 1,9- 1,10-diaminodecane, 1,11-diamino undecane, 1,12-diaminododecane, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4- Bis (aminomethyl) cyclohexane, 4,4'-methylenebis (cyclohexylamine), 4-bis (aminomethyl) cyclohexane, , 4'-methylenebis (2-methylcyclohexylamine), KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D- , TH-100, THF-140, THF-170, RE-600, RE-900, RE-2000, RP-405, RP-409, RP- -1100, HT-1700 (trade name, manufactured by HUNTSMAN CO., LTD.) And the like. In addition, in these diamines, -S-, -SO-, -SO ₂ -, -NH-, -NCH ₃ -, -N (CH ₂ CH ₃ ) -, -N (CH ₂ CH ₂ CH ₃ ) may include a bond such as, -COO-, -CONH-, -OCONH-, -NHCONH- - -N (CH (CH 3) 2). Of these, diamines containing a group represented by the general formula (3) are preferred. Examples thereof include KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR- RP-409, RP-2005, RP-2009, RT-1000, D-2000, THF-100, THF-140, THF-170, RE-600, RE-900 , HE-1000, HT-1100 and HT-1700 (trade names, manufactured by HUNTSMAN CO., LTD.).

The diamine residue containing a group selected from an alkylene group and an alkylene ether group is preferably contained in an amount of 5 to 40 mol%, more preferably 10 to 30 mol%, of the total diamine residues. By including the residues in this range, it is possible to improve the developability in the alkali developing solution and to improve the elongation of the resulting cured film.

Further, diamine residues having an aliphatic polysiloxane structure may be copolymerized within a range not lowering the heat resistance, and adhesion with the substrate can be improved. Specifically, as the diamine component, 1 to 15 mol% of bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylheptasiloxane are copolymerized. Copolymerization in this range is preferable from the viewpoints of improvement in adhesion with a substrate such as a silicon wafer and from the viewpoint of not lowering the solubility in an alkali solution.

Further, a resin having an acidic group at the main chain terminal can be obtained by sealing the terminal of the component (A) with a monoamine, acid anhydride, acid chloride or monocarboxylic acid having an acidic group.

Preferable examples of the monoamine include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, Aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy- Aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, Aminophenol, 4-aminophenol, 2-aminophenol, 2-aminophenol, 2-aminophenol, 2-aminophenol, - aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like. Two or more of these may be used.

Preferred examples of acid anhydrides, acid chlorides and monocarboxylic acids include acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic acid anhydride and 3-hydroxyphthalic anhydride; Carboxyphenol, 4-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy- Monocarboxylic acids such as naphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene and 1-mercapto-5-carboxynaphthalene; And monoacid chloride compounds in which the carboxyl groups of these monocarboxylic acids are acid chloridized; Dicarboxylic acids such as terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxy naphthalene, 1,6-dicarboxy naphthalene, 1,7-dicarboxy naphthalene and 2,6- Monoacid chloride compounds in which only one carboxyl group of an acid is acid chloridated; And an active ester compound obtained by reacting a monoacid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboxyimide. Two or more of these may be used.

The content of the end sealant such as monoamine, acid anhydride, acid chloride, or monocarboxylic acid is preferably 2 to 25 mol% based on the total amount of 100 mol% of the acid component and the amine component constituting the component (A) .

The end sealant introduced into the component (A) can be easily detected by the following method. For example, by dissolving a resin into which an end sealant is introduced in an acidic solution, decomposing it into an amine component and an acid component which are constituent units of the resin, and measuring the resultant by gas chromatography (GC) or NMR, Can be detected. Apart from this, it is possible to detect the resin into which the end sealant is introduced directly by pyrolysis gas chromatography (PGC), infrared spectroscopy and ¹³ C-NMR spectrum measurement.

The component (A) preferably has a weight average molecular weight of 10,000 or more and 50,000 or less. If the weight average molecular weight is 10,000 or more, the mechanical properties of the cured film after curing can be improved. More preferably, the weight average molecular weight is 20,000 or more. On the other hand, if the weight average molecular weight is 50,000 or less, the developability due to the alkali solution can be improved.

When two or more kinds of resins are contained as the component (A), the weight average molecular weight of at least one kind may be within the above range.

The component (A) can be produced by a known method.

In the case of a polyimide precursor such as a polyamide acid or a polyamide acid ester, for example, a method in which a tetracarboxylic acid dianhydride and a diamine compound are reacted at a low temperature, a tetracarboxylic acid dianhydride and an alcohol to obtain a diester , Followed by a reaction in the presence of an amine and a condensing agent, a method in which a diester is obtained from a tetracarboxylic acid dianhydride and an alcohol, and then the remaining dicarboxylic acid is acid chloridized and reacted with an amine .

In the case of a polybenzoxazole precursor such as a polyhydroxyamide, a production method can be obtained by condensation reaction of a bisaminophenol compound and a dicarboxylic acid. Specifically, a method of reacting an acid with a dehydrating condensing agent such as dicyclohexylcarbodiimide (DCC), adding a bisaminophenol compound thereto, or a method of adding a tertiary amine-containing bisaminophenol compound And a solution of dicarboxylic acid dichloride is added dropwise.

In the case of polyimide, for example, polyimide precursor obtained by the above-mentioned method can be obtained by heating or dehydration ring closure by chemical treatment such as acid or base.

In the case of polybenzoxazole, for example, polybenzoxazole precursor obtained by the above-mentioned method can be obtained by heating or dehydrating and ring closure by chemical treatment such as acid or base.

In addition to the component (A), the resin composition may contain other alkali-soluble resin. Specific examples of the other alkali-soluble resin include a phenol resin, a polymer containing a radically polymerizable monomer unit having an alkali-soluble group, a siloxane polymer, a cyclic olefin polymer, and a cardboard resin. These resins may be used alone, or a plurality of resins may be used in combination. In that case, when the total amount of the component (A) and the other alkali-soluble resin is 100 parts by mass, the content of the other alkali-soluble resin is preferably 1 to 50 parts by mass.

Examples of the phenol resin include novolak resins and resol resins. The phenol resin is obtained by polycondensation of various phenols alone or a mixture thereof with aldehydes such as formalin.

Examples of the phenol that constitutes the phenol resin include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5- , 6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4 , 2-methylresorcin, 4-methylresorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2-methylphenol, 3-dichlorophenol, m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, Diethylphenol, p-isopropylphenol,? -Naphthol,? -Naphthol, and the like. They may be used alone or as a mixture thereof.

Examples of the aldehydes used for polycondensation with phenols include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde and the like. They may be used alone or as a mixture thereof.

The phenol resin is a resin obtained by substituting a part of hydrogen atoms added to an aromatic ring with an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group, a hydroxyl group, an alkoxyl group, an alkoxymethyl group, a methylol group, a carboxyl group, An oxygen atom, an oxygen atom, an oxygen atom, an oxygen atom, an oxygen atom, an oxygen atom, an oxygen atom, an oxygen atom, an oxygen atom or an oxygen atom.

The weight average molecular weight of the phenol resin is preferably in the range of 2,000 to 50,000, more preferably in the range of 3,000 to 30,000 in terms of polystyrene using gel permeation chromatography (GPC). When the molecular weight is 2,000 or more, the pattern shape, resolution, developability and heat resistance are excellent. When the molecular weight is 50,000 or less, the sensitivity is excellent.

Examples of the polymer containing a radically polymerizable monomer unit having an alkali-soluble group include a polymer containing a radically polymerizable monomer unit having a phenolic hydroxyl group or a carboxyl group. hydroxystyrene, p-hydroxystyrene, and their monomer units selected from the group consisting of alkyl, alkoxy, alkoxymethyl, and methylol substituents are selected from the group consisting of the sensitivity at the time of patterning, And is preferably used from the viewpoints of the film rate, heat resistance, storage stability of the solution, and the like. These may be used alone or in combination of two or more.

Further, the above-mentioned monomers and other monomers having no alkali-soluble group may be copolymerized. Preferred examples of other radically polymerizable monomers include alkyl, alkoxy, alkoxymethyl, methylol, halogen, haloalkyl substituents at the a-, o-, m- and p-positions of styrene and styrene; Butadiene, isoprene; Methyl, ethyl, n-propyl, N-butyl, glycidyl and tricyclo [5.2.1.0 ^2,6 ] decan-8-yl of methacrylic acid or acrylic acid. From the viewpoint of sensitivity at the time of patterning, residual film ratio after resolution development, heat resistance, solvent resistance, adhesiveness to the base, storage stability of the solution, and the like. These may be used alone or in combination of two or more.

When a copolymer of a radically polymerizable monomer having a phenolic hydroxyl group and another radically polymerizable monomer is used as the component (A), the proportion of the other radically polymerizable monomer is not particularly limited so long as the ratio of the radically polymerizable monomer having the phenolic hydroxyl group and the other Is preferably 5% by mass or more based on the total amount of the radical polymerizable monomer. Further, it is preferably 30 mass% or less, more preferably 20 mass% or less. When the proportion of the other radical polymerizable monomer is 5 mass% or more, heat resistance and chemical resistance are improved, which is preferable. When the content is 30% by mass or less, it is preferable because alkali developability is facilitated. When a copolymer of a radically polymerizable monomer having a carboxyl group and another radically polymerizable monomer as the component (A) is used, the preferable ratio of the other radically polymerizable monomer is a ratio of a radically polymerizable monomer having a carboxyl group and other radically polymerizable monomers It is preferably 10% by mass or more based on the total amount of the monomers. Further, it is preferably 90 mass% or less, more preferably 80 mass% or less. When the proportion of the other radical polymerizable monomer is 10 mass% or more, heat resistance and chemical resistance are improved, which is preferable. When it is 90% by mass or less, it is preferable because alkali developability is facilitated.

The weight average molecular weight of the polymer containing a radically polymerizable monomer having an alkali-soluble group is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, particularly preferably 5,000 to 100,000, in terms of polystyrene using gel permeation chromatography. 30,000. When the weight average molecular weight is 2,000 or more, the pattern shape, resolution, developability and heat resistance are improved. When the weight average molecular weight is 100,000 or less, developability and sensitivity are improved.

These polymers containing radically polymerizable monomers having alkali-soluble groups may be used singly or in combination of two or more. Alternatively, an alkali-soluble resin may be synthesized by a method of introducing a protecting group into a carboxyl group or a phenolic hydroxyl group before polymerization and deprotecting it after polymerization to give alkali solubility. In addition, transparency and softening point in visible light may be changed by hydrogenation treatment or the like.

The siloxane polymer is a siloxane polymer obtained by hydrolysis and condensation of an organosilane. For example, a method of adding a solvent, water and a catalyst, if necessary, to the organosilane and heating and stirring the mixture at 50 to 150 ° C for 0.5 to 100 hours may, for example, be mentioned. During the stirring, hydrolysis by-products (alcohol such as methanol) and condensation by-products (water) may be distilled off by distillation if necessary.

Specific examples of the organosilane include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane and tetraphenoxysilane; Trifunctional silanes such as methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane phenyltrimethoxysilane, phenyltriethoxysilane, and p-hydroxyphenyltrimethoxysilane; Dimethyldimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, Bifunctional silanes such as methyldiethoxysilane, di (1-naphthyl) dimethoxysilane and di (1-naphthyl) diethoxysilane; Monofunctional silanes such as trimethylmethoxysilane, tri-n-butylethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane and (3-glycidoxypropyl) dimethylethoxysilane; M silicate 51, Silicate 40, Silicate 45, Methyl silicate 51, Methyl silicate 53A, Ethyl silicate 40 and the like manufactured by FUJISAGA Kogaku Kogyo K.K. . Two or more of these organosilanes may be used.

The weight-average molecular weight of the siloxane polymer is not particularly limited, but it is preferably 1,000 or more in terms of polystyrene measured by GPC (gel permeation chromatography) because the film property is improved. On the other hand, from the viewpoint of solubility in a developing solution, the weight average molecular weight is preferably 100,000 or less, more preferably 50,000 or less.

The cyclic olefin polymer is a homopolymer or copolymer of a cyclic olefin monomer having a cyclic structure (alicyclic or aromatic ring) and a carbon-carbon double bond. The cyclic olefin polymer may have a monomer other than the cyclic olefin monomer.

Examples of the monomer for constituting the cyclic olefin polymer include cyclic olefin monomers having a protonic polar group, cyclic olefin monomers having a polar group other than the protonic ones, cyclic olefin monomers having no polar group, and monomers other than cyclic olefins.

Specific examples of the cyclic olefin monomers having a protonic polar group include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-hydroxycarbonylbicyclo [2.2.1] 2-ene, 8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene; 2.2.1] hept-2-ene, 5-methyl-5- (4-hydroxyphenyl) bicyclo [2.2.1] (4-hydroxyphenyl) tetracyclo [4.4.0.1 ^2,5 .1 ^{7, 10],} and the like hydroxyl group-containing cyclic olefin such as dodeca-3-ene.

Specific examples of cyclic olefin monomers having a polar group other than the protonic group include 5-acetoxybicyclo [2.2.1] hepto-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hept- Cyclic olefins having an ester group such as 8-acetoxytetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene; Cyclic olefins having an N-substituted imide group such as N-phenyl- (5-norbornene-2,3-dicarboxyimide); 8-cyano-tetracyclo [4.4.0.1 ^2,5 .1 ^{7, 10]} dodeca-3-ene, 8-methyl-8-cyano-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane Cyclic olefins having cyano groups such as carboxy-3-ene, 5-cyanobicyclo [2.2.1] hept-2-ene; 8-chloro-tetracyclo [4.4.0.1 ^2,5 .1 ^{7, 10]} dodeca-3-ene, 8-methyl-8-chloro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca- And cyclic olefins having halogen atoms such as 3-ene.

Specific examples of the cyclic olefin monomer having no polar group, bicyclo [2.2.1] hept-2-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, tricyclo [4.3.0.1 ^2,5 ] Deca-3, 7-diene, and the like. Specific examples of the monomers other than cyclic olefins include chain olefins such as? -Olefins having 2 to 20 carbon atoms such as ethylene, propylene and 1-butene, and nonconjugated dienes having 2 to 20 carbon atoms such as 1,4-hexadiene have.

These monomers may be used alone or in combination of two or more.

As a method for polymerizing the cyclic olefin polymer using the monomer, a general method can be used. Examples thereof include ring-opening polymerization and addition polymerization. As the polymerization catalyst, metal complexes such as molybdenum, ruthenium, and osmium are suitably used. These polymerization catalysts may be used alone or in combination of two or more.

The cardo resin is a cardo structure, that is, a resin having a skeleton structure in which two cyclic structures are bonded to a quaternary carbon atom constituting a cyclic structure. The general structure of the cardo structure is a benzene ring bonded to a fluorene ring. Specific examples thereof include a fluorene skeleton, a bisphenol fluorene skeleton, a bisaminophenyl fluorene skeleton, a fluorene skeleton having an epoxy group, and a fluorene skeleton having an acryl group. The cardo resin is formed by polymerization by a reaction in a functional period in which a skeleton having this cardo structure is bonded thereto. The cardo resin has a structure (cardo structure) in which a main chain and a bulky side chain are linked by one element, and has a cyclic structure in a substantially vertical direction with respect to the main chain.

Specific examples of monomers having a cardo structure include bis (glycidyloxyphenyl) fluorene type epoxy resins, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4- 9,9-bis (cyanoalkyl) fluorenes such as 9,9-bis (cyanomethyl) fluorene and 9,9-bis (3-methylphenyl) fluorene, Aminopropyl) fluorene, and other 9,9-bis (aminoalkyl) fluorenes. Or may be a copolymer with other copolymerizable monomers.

As the polymerization method of the monomer, a general method can be used, and examples thereof include a ring-opening polymerization method and an addition polymerization method.

The resin composition of the present invention may contain (B) a photosensitizer (hereinafter sometimes referred to as component (B)). By containing the component (B), photosensitivity can be imparted to the resin composition.

The component (B) is a compound which changes its chemical structure in response to ultraviolet rays, and examples thereof include a photo-acid generator, a photobase generator, and a photopolymerization initiator. When a photoacid generator is used as the component (B), an acid is generated in the light irradiation portion of the resin composition and the solubility of the light irradiation portion in the alkali developer is increased, so that a positive pattern in which the light irradiation portion is dissolved can be obtained. When a photo-base generator is used as the component (B), a base is generated in the light irradiation portion of the resin composition and the solubility of the light irradiation portion in the alkali developer is lowered. have. When a photopolymerization initiator is used as the component (B), radicals are generated in the light irradiated portion of the resin composition, and the radical polymerization proceeds, and insoluble in the alkali developer, whereby a negative pattern can be formed. Further, the UV curing at the time of exposure is promoted, and the sensitivity can be improved.

Among the above-mentioned components (B), a photoacid generator is preferable in that a pattern with high sensitivity and high resolution can be obtained. Examples of the photoacid generator include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. In addition, sensitizers and the like may be included if necessary.

As the quinone diazide compound, a compound in which a sulfonic acid of naphthoquinone diazide is bonded to a compound having a phenolic hydroxyl group is preferable. Examples of the compound having a phenolic hydroxyl group usable herein include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP- DLC-MBP, DML-OCHP, DML-Bis-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris- DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, DML-PZP, DML-PC, DML-PTBP, DML-34X, DML- TML-BP, TML-BP, TML-BP-BP, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., BIP-A (trade name, Asahi Yukihaishi Kogyo Co., Ltd. (trade name, manufactured by Asahi Kasei Kogyo Co., Ltd. ), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzo Bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, Honshu Chemical Industries Co., Ltd. ) Can be exemplified as preferable ones, but other compounds may also be used. [0043] The term " anhydride "

It is also preferable that at least 50 mol% of the entire functional groups of the compound having a phenolic hydroxyl group are substituted with quinone diazide. By using a quinone diazide compound substituted by 50 mol% or more, the affinity of the quinone diazide compound to an aqueous alkali solution is lowered, and the solubility of the resin composition in the unexposed portion in an alkali aqueous solution is greatly lowered, The quinone diazide sulfonyl group is changed to indenecarboxylic acid, whereby a large dissolution rate of the resin composition having photosensitivity to the exposed portion in the aqueous alkaline solution can be obtained. As a result, the dissolution rate ratio of the exposed and unexposed portions of the composition is increased Thus, a pattern can be obtained with a high resolution. By using such a quinone diazide compound, it is possible to obtain a resin composition having positive photosensitivity that is sensitive to i-line (365 nm), h-line (405 nm), g-line (436 nm) and broadband light including general mercury lamps. The component (B) may be used alone or in combination of two or more, and a resin composition having high photosensitivity may be obtained.

As the quinone diazide, a 5-naphthoquinone diazide sulfonyl group and a 4-naphthoquinone diazide sulfonyl group are all preferably used. The 5-naphthoquinone diazidesulfonyl ester compound increases absorption up to the g line area of a mercury lamp, and is suitable for g-line exposure and full wavelength exposure. The 4-naphthoquinone diazidesulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. It is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound by the wavelength to be exposed. In addition, a naphthoquinone diazide sulfonyl ester compound containing a 4-naphthoquinone diazidesulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule can be obtained. A 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound may be used in combination.

The quinone diazide compound can be synthesized by a known method by an esterification reaction between a compound having a phenolic hydroxyl group and a quinonediazide sulfonic acid compound. The use of a quinone diazide compound improves resolution, sensitivity, and residual film ratio.

The molecular weight of the component (B) is preferably 300 or more, more preferably 350 or more, preferably 3,000 or less, and still more preferably 1,500 or less, from the viewpoints of heat resistance, mechanical properties and adhesiveness of the film obtained by the heat treatment .

Among the components (B), the sulfonium salt, the phosphonium salt and the diazonium salt are preferable because they appropriately stabilize the acid component generated by exposure. Among them, sulfonium salts are preferable.

The content of the component (B) is preferably 0.1 part by mass or more and 100 parts by mass or less based on 100 parts by mass of the component (A). When the content of the component (B) is 0.1 part by mass or more and 100 parts by mass or less, photosensitivity can be imparted while maintaining the heat resistance, chemical resistance and mechanical properties of the film after heat treatment.

When the component (B) is a quinone diazide compound, the content of the component (B) is more preferably not less than 1 part by mass and more preferably not less than 3 parts by mass based on 100 parts by mass of the component (A). More preferably 100 parts by mass or less, and even more preferably 80 parts by mass or less. When the amount is 1 part by mass or more and 80 parts by mass or less, photosensitivity can be imparted while maintaining the heat resistance, chemical resistance and mechanical properties of the film after heat treatment.

When the component (B) is a sulfonium salt, a phosphonium salt or a diazonium salt, the content of the component (B) is more preferably not less than 0.1 part by mass, more preferably not less than 1 part by mass, per 100 parts by mass of the component (A) And particularly preferably 3 parts by mass or more. More preferably 100 parts by mass or less, further preferably 80 parts by mass or less, and particularly preferably 50 parts by mass or less. When the amount is 0.1 part by mass or more and 80 parts by mass or less, photosensitivity can be imparted while maintaining heat resistance, chemical resistance and mechanical properties of the film after heat treatment.

The resin composition may contain a compound having a phenolic hydroxyl group for the purpose of supplementing alkali developability. Examples of the compound having a phenolic hydroxyl group include Bis-Z, BisOC-Z, BisOP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP- BisPX-CP, BisP-PZ, BisP-IPZ, BisCRIPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (tetrakis P- TrisP-PHBA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X- BIR-PC, BIR-PCB, BIR-PCHP, BIP-PCHP, BIS-OCHP, Methylenetris-FR-CR, BisRS-26X and BisRS-OCHP (trade names, manufactured by Honshu Chemical Industry Co., (Trade name, manufactured by Asahi Yuki Kagaku Kogyo Co., Ltd.), 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1 , 6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,4- Hydroxyquinoline, 2,6-dihydroxyquinoline, 2,3-dihydroxyquinoline Anthracene-1,2,10-triol, anthracene-1,8,9-triol, 8-quinolinol, and the like.

Since the resin composition contains a compound having a phenolic hydroxyl group, the resin composition is hardly dissolved in an alkali developing solution before exposure and is easily dissolved in an alkaline developing solution upon exposure. Therefore, the reduction in film due to development is small, It becomes easy. Therefore, the sensitivity tends to be improved.

When a photo-base generator is used as the component (B), specific examples of the photo-base generator include an amide compound and an ammonium salt.

Examples of the amide compound include 2-nitrophenylmethyl-4-methacryloyloxypiperidine-1-carboxylate, 9-anthrylmethyl-N, N-dimethylcarbamate, 1- (anthraquinone- (E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] piperidine, and the like.

Examples of the ammonium salt include (Z) - {[bis (dimethylamino) methylene) guanidinium 2- (3-benzoylphenyl) propionate such as 1,2-diisopropyl- (3-fluorophenyl) borate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanide, n-butyl tri Phenyl borate and the like.

When the photo-base generator is used as the component (B), the content of the component (B) in the resin composition is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more based on 100 parts by mass of the component (A) More preferably 0.7 part by mass or more, and particularly preferably 1 part by mass or more. When the content is within the above range, the sensitivity at the time of exposure can be improved. On the other hand, the content is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, further preferably 17 parts by mass or less, and particularly preferably 15 parts by mass or less. When the content is within the above range, the resolution after development can be improved.

When a photopolymerization initiator is used as the component (B), examples of the photopolymerization initiator include benzylketal photopolymerization initiators,? -Hydroxyketone photopolymerization initiators,? -Aminoketone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, An oxime ester photopolymerization initiator, an acridine photopolymerization initiator, a benzophenone photopolymerization initiator, an acetophenone photopolymerization initiator, an aromatic ketoester photopolymerization initiator or benzoate ester photopolymerization initiator, and a titanocene photopolymerization initiator. From the viewpoint of improving the sensitivity at the time of exposure, it is preferable to use a polymerization initiator such as an? -Hydroxyketone type photopolymerization initiator, an? -Aminoketone type photopolymerization initiator, an acylphosphine oxide type photopolymerization initiator, an oxime ester type photopolymerization initiator, an acridine type photopolymerization initiator, An initiator is more preferable, and an? -Aminoketone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, and an oxime ester photopolymerization initiator are more preferable.

As the benzylketal photopolymerization initiator, 2,2-dimethoxy-1,2-diphenylethan-1-one can be mentioned, for example.

Examples of the? -hydroxyketone-based photopolymerization initiator include 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 2-hydroxy- -1-one, 1-hydroxycyclohexyl phenyl ketone, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy- - [4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl] -2-methylpropan-1-one.

Examples of the? -aminoketone photopolymerization initiator include 2-dimethylamino-2-methyl-1-phenylpropan-1-one, 2-diethylamino- 1-one, 2-dimethylamino-2-methyl-1- (4-methylphenyl) propan- Methylphenyl) -2-methylpropan-1-one, 1- (4-butylphenyl) Methylpropan-1-one, 2-dimethylamino-2-methyl-1- (4-methylthio- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-dimethylamino-2 - [(4-methylphenyl) methyl] - < / RTI & 1- [4- (4-morpholinyl) phenyl] -1-butanone.

As the acylphosphine oxide photopolymerization initiator, for example, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide or bis (2,6- Dimethoxybenzoyl) - (2,4,4-trimethylpentyl) phosphine oxide.

Examples of the oxime ester photopolymerization initiator include 1-phenylpropane-1,2-dione-2- (O-ethoxycarbonyl) oxime, 1-phenylbutane-1,2- (O-ethoxycarbonyl) oxime, 1- [4- (phenylthio) phenyl] octane-1, 2- (O-benzoyl) oxime, 1- [4- [4- (carboxyphenyl) thio] phenyl] propane- Yl] ethanone-1- (O-acetyl) oxime, 1- [9-ethyl- 6- [2-methyl- Benzoyl] -9H-carbazol-3-yl] ethanone-1- (O-acetyl) oxime or "adeka Aces "NCI-831. ≪ / RTI >

As the acridine-based photopolymerization initiator, 1,7-bis (acridine-9-yl) -n-heptane is exemplified.

Examples of the benzophenone-based photopolymerization initiator include benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, (4-hydroxybenzophenone), 4-hydroxybenzophenone, alkylated benzophenone, 3,3 ', 4,4'-tetrakis (t- butylperoxycarbonyl) benzophenone, 4-methylbenzophenone, dibenzyl ketone or fluoro Lennon.

Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, 2,3-diethoxyacetophenone, 4-t-butyldichloroacetophenone, benzalacetophenone or 4-azidobenzalacetophenone. .

As the aromatic keto ester-based photopolymerization initiator, for example, methyl 2-phenyl-2-oxyacetate may be mentioned.

Examples of the benzoic acid ester photopolymerization initiator include ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (2-ethyl) hexyl, 4-diethylaminobenzoate and methyl 2-benzoylbenzoate.

As the metallocene titanocene photopolymerization initiator, for example, bis (η ⁵ -2,4- cyclopentadiene-1-yl) -bis [2,6-difluoro) -3- (1H- pyrrol-1-yl) phenyl ] Titanium (IV) or bis (η ⁵ -3-methyl-2,4-cyclopentadien-1-yl) -bis (2,6-difluorophenyl) titanium (IV).

When a photopolymerization initiator is used as the component (B), the content of the component (B) in the resin composition is preferably at least 0.1 part by mass, more preferably at least 0.5 part by mass, based on 100 parts by mass of the component (A) More preferably 0.7 part by mass or more, and particularly preferably 1 part by mass or more. When the content is within the above range, the sensitivity at the time of exposure can be improved. On the other hand, the content is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, further preferably 17 parts by mass or less, and particularly preferably 15 parts by mass or less. When the content is within the above range, the resolution after development can be improved.

When a photopolymerization initiator is used as the component (B), it is preferable that the resin composition further contains a radically polymerizable compound.

The radical polymerizable compound means a compound having a plurality of ethylenically unsaturated double bond groups in the molecule. When the photopolymerization initiator is contained as the component (B), the radical polymerization of the radical polymerizable compound progresses due to the radicals generated from the photopolymerization initiator at the time of exposure by including the radical polymerizable compound, It is insoluble in an alkali developing solution, whereby a negative pattern can be formed. When the resin composition contains a radically polymerizable compound, the UV curing at the time of exposure is promoted, and the sensitivity at the time of exposure can be improved. In addition, the crosslinking density after thermosetting is improved, and the hardness of the cured film obtained by curing the resin composition can be improved.

As the radical polymerizing compound, a methacrylic group and / or an acrylic group (hereinafter also referred to as a (meth) acrylic group, which is likely to undergo radical polymerization) may be used. Compounds are preferred. From the viewpoint of improving the sensitivity at the time of exposure and improving the hardness of the cured film, a compound having two or more (meth) acryl groups in the molecule is more preferable. The double bond equivalent of the radically polymerizable compound is preferably 80 to 400 g / mol from the viewpoints of improving the sensitivity upon exposure and improving the hardness of the cured film.

Examples of the radical polymerizable compound include diethyleneglycol di (meth) acrylate, triethyleneglycol di (meth) acrylate, tetraethyleneglycol di (meth) acrylate, propyleneglycol di (meth) acrylate, trimethylol (Meth) acrylate, ethoxylated trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, (Meth) acrylate, 1, 3-butanediol di (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, Acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, dimethylol-Pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapenta (Meth) acrylate, pentapentaerythritol dodeca (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, trimethylolpropane trimethacrylate, (Meth) acryloxyethyl) isocyanate (meth) acrylate, 2,2-bis [4- (Meth) acryloxyethyl) isocyanuric acid, 9,9-bis [4- (2- (meth) acryloxyethoxy) phenyl] fluorene, 9,9-bis (Meth) acryloxyphenyl) fluorene or an acid-modified product thereof, an ethylene oxide modified product, or propylene oxide (hereinafter referred to as " And a seed modified product. (Meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate and the like, from the viewpoints of improving the sensitivity at the time of exposure and improving the hardness of the cured film. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol (Meth) acrylate, pentaerythritol octa (meth) acrylate, 2,2-bis [4- (3- (meth) acryloxy- (Meth) acryloxyethyl) isocyanuric acid, 9,9-bis [4- (2- (meth) acryloxyethoxy) phenyl] fluorene, Phenyl] fluorene or 9,9-bis (4- (meth) acryloxypropoxy) phenyl] Methacrylic oxyphenyl) fluorene is preferable bodies or their acid modified product, ethylene oxide modified products or in terms of propylene oxide-modified and preferably, improve the resolution after development bodies, their acid or modified product of ethylene oxide-modified. From the viewpoint of improvement of the resolution after development, it is also possible to add a compound obtained by subjecting a compound having two or more glycodoxy groups in a molecule to an unsaturated carboxylic acid having an ethylenically unsaturated double bond group to effect ring-opening addition reaction with a polybasic carboxylic acid or polybasic carboxylic acid A compound obtained by reacting a carboxylic acid anhydride is also preferable.

The content of the radical polymerizing compound is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, further preferably 25 parts by mass or more, and particularly preferably 30 parts by mass or more, per 100 parts by mass of the component (A) Do. When the content is within the above range, the sensitivity at the time of exposure can be improved. On the other hand, the content is preferably 65 parts by mass or less, more preferably 60 parts by mass or less, further preferably 55 parts by mass or less, and particularly preferably 50 parts by mass or less. When the content is within the above range, the heat resistance of the cured film can be improved.

The resin composition of the present invention comprises (E) a compound having a tertiary amide structure having a molecular weight of 60 or more and 1000 or less. (E), the component (B) or the component (D) is stabilized by interacting with the component (B) or the component (D) described later. Therefore, when the resin composition is stored at room temperature, for example, inactivation of the component (B), reaction with other components, and reaction with other components of the component (D) can be suppressed, so that the storage stability is improved . The same effect is also exhibited for the resin film obtained from the resin composition. Further, since the resin film also interacts with components such as acid generated during exposure to stabilize it, the post-exposure delay stability after application and after exposure is also improved. The sensitivity is also improved. Further, in the cured film obtained by curing the resin composition, the component (E) remains in the cured film, and in order to capture an acid or the like generated from the component (B) in the device reliability test, , Ionization and the like are suppressed to suppress peeling between the cured film and the metal material. That is, deterioration of the device characteristics after the reliability test of the device can be suppressed.

Since the component (E) has a molecular weight of 60 or more and 1000 or less, interaction with the component (B) or the component (D) is easily formed, and the stabilizing action is improved.

As the component (E), the compounds represented by the general formulas (4) to (6) are preferable.

In the general formula (4), Z represents an oxygen atom or a nitrogen atom. R ²⁸ represents an alkyl group having 1 to 10 carbon atoms, or a group in which the alkyl group is substituted by -CO-, -O-, or -OH. R ²⁹ represents an unsubstituted group when Z is an oxygen atom, an alkyl group having 1 to 10 carbon atoms when Z is a nitrogen atom, or a group in which the alkyl group is substituted by -CO-, -O-, or -OH. R ³⁰ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group in which the alkyl group is substituted by -CO-, -O-, or -OH. m represents an integer of 0 to 1, and n represents an integer of 1 to 5.

In the general formula (5), R ³¹ to R ³⁴ each independently represent an alkyl group having 1 to 6 carbon atoms.

In the general formula (6), R ³⁵ and R ³⁶ each independently represent an alkyl group having 1 to 10 carbon atoms or a group in which the alkyl group is substituted by -CO-, -O-, or -OH. R ³⁵ and R ³⁶ may form a cyclic structure. R ³⁷ represents an alkyl group having 1 to 20 carbon atoms, an aromatic group, or a group in which the alkyl group or aromatic group is substituted by -CO-, -O-, or -OH.

Examples of the compound represented by the general formula (4) include, but are not limited to, the following structures.

The compounds represented by the general formula (5) include, for example, the following compounds, but are not limited to the following structures.

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

As the component (E), a compound having a melting point of -70 占 폚 to 15 占 폚 and a boiling point of 100 占 폚 to 400 占 폚 is preferable. When the melting point and the boiling point of the component (E) fall within this range, the storage stability of the resin composition, the post-exposure delay stability, and the deterioration of the device characteristics after the reliability test of the device using the cured film obtained by curing the resin composition are suppressed . The melting point of the component (E) is preferably from -50 DEG C to 10 DEG C from the viewpoints of handling at the time of production, storage stability of the resin composition, and delayed post exposure delay stability. Further, by setting the boiling point of the component (E) to not less than 150 ° C and not more than 300 ° C, an appropriate amount of the component (E) remains after heat-drying or curing, thereby improving the storage stability of the resin composition and post- From the viewpoint that the degradation of the device characteristics after the reliability test of the device using the cured film obtained by curing the composition can be suppressed.

The content of the component (E) is preferably 4 parts by mass or more and 1600 parts by mass or less based on 100 parts by mass of the component (A). The content is more preferably 10 parts by mass or more. The content is more preferably 1000 parts by mass or less. When the content is 4 parts by mass or more, deterioration of the device characteristics after the reliability test of the device using the cured film obtained by curing the resin composition and the storage stability of the resin composition after the exposure and after the exposure can be suppressed. When the content is less than or equal to 1600 parts by mass, the uneven application of the resin composition is reduced, the in-plane uniformity is improved, the out gas from the cured film is reduced, and the chemical resistance is improved. The content of the component (E) is preferably 5% by mass or more and 50% by mass or less, based on 100% by mass of the total liquid component. Here, the liquid component is a component that is liquid at 25 占 폚, and corresponds to the component (E) and the component (C) described later.

It is preferable that the resin composition of the present invention is applied to a substrate so as to have a thickness of 13 탆 after drying and the content of the component (E) contained in the resin film obtained by heating and drying at 120 캜 for 3 minutes is from 0.001% by mass to 30% . When the content of the component (E) contained in the resin film is within the above range, the storage stability of the resin film and the post-exposure delay stability are improved. The content of the component (E) contained in the resin film is more preferably 0.002 mass% or more, and still more preferably 0.005 mass% or more. From the viewpoint of preventing stickiness of the resin film, the content of the component (E) is more preferably 20 mass% or less, and further preferably 10 mass% or less.

The content of the component (E) contained in the cured film obtained by curing the resin composition is preferably 0.05 ppm or more and 1000 ppm or less. By setting the content of the component (E) contained in the cured film within the above range, deterioration of the device characteristics after the reliability test of the device can be suppressed. From the viewpoint of the above effect, the content of the component (E) contained in the cured film is more preferably 0.1 ppm or more, and still more preferably 0.5 ppm or more. From the viewpoint of reducing the outgas from the cured film, the content of the component (E) contained in the cured film is more preferably 500 ppm or less, and further preferably 300 ppm or less.

The resin composition of the present invention may further contain (C) a solvent (hereinafter sometimes referred to as component (C)). By containing the component (C), the resin composition can be used as a solution.

The content of the component (C) in the resin composition is preferably such that the solid content concentration in the resin composition is 5 to 70% by mass, more preferably 10 to 60% by mass. Here, the solid content is a component which is solid at 25 占 폚 and corresponds to components (A), (B), (D) and (F). By setting the content of the component (C) within the above range, a resin composition having excellent coatability can be obtained.

As the component (C), the resin composition preferably contains (C1) at least one solvent having a boiling point of 100 占 폚 or more and 150 占 폚 or less at atmospheric pressure.

By containing the component (C1), since the component (C1) has high volatility, the solvent can be removed from the coated film of the resin composition in a short period of time. In addition, since the drying of the coating film progresses, the solubility of the developing solution in the unexposed area is lowered, so that the difference in contrast between the exposed area and the unexposed area increases, thereby improving the sensitivity.

As the component (C1), a solvent capable of dissolving the solid content is preferable. Specific examples thereof include alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether (boiling point 124 ° C), propylene glycol monomethyl ether (boiling point 120 ° C), propylene glycol monomethyl ether acetate (boiling point 146 ° C); Alkyl acetates such as propyl acetate (boiling point 102 캜), butyl acetate (boiling point 125 캜), and isobutyl acetate (boiling point 118 캜); Ketones such as methyl butyl ketone (boiling point 116 占 폚), methyl isobutyl ketone (boiling point 116 占 폚), and methyl propyl ketone (boiling point 102 占 폚); and alcohols such as n-butyl alcohol (boiling point 117 ° C) and isobutyl alcohol (boiling point 108 ° C). Two or more of these may be contained.

The content of the component (C1) is preferably 0.1% by mass or more and 40% by mass or less in 100% by mass of the total liquid component. When the content is 0.1% by mass or more, the sensitivity is improved. By setting the content to 40 mass% or less, it is possible to obtain a highly stable material having suppressed coating nonuniformity and excellent storage stability, post exposure delay stability and in-plane uniformity.

(C), in addition to the component (C1), at least one solvent selected from a solvent represented by the general formula (C2) shown by the general formula (10) may be contained.

In the general formula (10), R ⁵⁰ and R ⁵¹ each independently represent an alkyl group or an aromatic group having 1 to 10 carbon atoms. R ⁵⁰ and R ⁵¹ may form a cyclic structure.

 As the component (C2), a solvent capable of dissolving a solid content is preferable. Specific examples thereof include polar aprotic solvents such as? -Butyrolactone,? -Valerolactone and? -Valerolactone; And esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, methyl benzoate and ethyl benzoate. Two or more of these may be contained.

The content of the component (C2) is preferably 10% by mass or more and 94.9% by mass or less in 100% by mass of the total liquid component.

The resin composition of the present invention (D) contains a thermal crosslinking agent having three or more epoxy groups. The thermal crosslinking agent refers to a compound having at least two heat-reactive functional groups in its molecule. Here, the heat-reactive functional group is an alkoxymethyl group, a methylol group, an epoxy group, an oxetanyl group, or the like. The thermosetting agent can crosslink the component (A) or other added components to increase film heat resistance, chemical resistance and hardness after thermosetting. Two or more types of thermal crosslinking agents may be used in combination.

Since component (D) has three or more epoxy groups in the molecule, it can react at a low temperature. Therefore, even when curing is carried out at a low temperature, component (D) is firmly crosslinked with other additives to improve the chemical resistance of the cured film . In general, epoxy compounds having a functional group number of 3 or more tend to deteriorate storage stability and post-exposure delay stability because of high reactivity. However, the resin composition of the present invention contains the component (E) Delay stability is improved.

Specific examples of the component (D) include, but are not limited to, the following structures.

The resin composition preferably contains one or more kinds of compounds selected from trifunctional or more alkoxymethyl compounds and trifunctional or higher methylol compounds (hereinafter may be omitted as component (D2)) in addition to the component (D) . (D2), the crosslinking becomes stronger, and the chemical resistance of the cured film can be further improved. Further, by including the component (D2), the storage stability of the solution and the post-exposure delay stability are improved. Further, since the obtained cured film is densified, peeling between the cured film and the metal material in the device reliability test is suppressed. That is, deterioration of the device characteristics after the reliability test of the device can be suppressed.

Specific examples of the component (D2) include the following methylol compounds or alkoxymethyl compounds in which the hydrogen atom of the methylol group is substituted with a methyl group or an ethyl group, but the structure is not limited to the following structure.

The resin composition preferably contains, in addition to the component (D), a heat crosslinking agent containing a structural unit represented by the following general formula (7) (hereinafter sometimes referred to as a component (D3)).

In the general formula (7), R ³⁸ is a divalent organic group having an alkylene group or an alkylene ether group having 1 to 15 carbon atoms and may be any of linear, branched and cyclic. Specific examples of R ³⁸ include a combination of an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group and a heterocyclic group Etc., and may further have a substituent. R ³⁹ and R ⁴⁰ each independently represent a hydrogen atom or a methyl group.

 Since the component (D3) has a flexible alkylene group and a rigid aromatic group per se, the resulting cured film has heat resistance and can be improved in elongation and low in stress by containing the component (D3). Further, the densification of the cured film suppresses the peeling between the cured film and the metal material in the device reliability test.

As the crosslinking group contained in the component (D3), an acrylic group, a methylol group, an alkoxymethyl group, an epoxy group and the like can be exemplified, but the present invention is not limited thereto. Among these, an epoxy group is preferable in that it can react with the phenolic hydroxyl group of the component (A) to improve the heat resistance of the cured film and react without dehydration.

Specific examples of the compound containing the structural unit represented by the general formula (7) include, but are not limited to, the following structures.

Wherein j is an integer of 1 to 5, and i is 1 to 20. It is preferable that j is 1 to 2 and i is 3 to 7 in view of achieving both heat resistance and elongation improvement.

Two or more kinds of the thermal crosslinking agents may be used in combination.

The content of the heat crosslinking agent is preferably 1 part by mass or more and 200 parts by mass or less based on 100 parts by mass of the component (A). When the content of the heat crosslinking agent is 1 part by mass or more and 200 parts by mass or less, a cured film having excellent chemical resistance can be obtained while being excellent in storage stability and post-exposure delay stability of the resin composition and capable of being cured by heat treatment at a low temperature , And deterioration of the device characteristics after the reliability test of the device to which the cured film is applied can be suppressed.

The content of the component (D) is preferably 1% by mass or more and 60% by mass or less, and more preferably 5% by mass or more and 50% by mass or less, based on 100% by mass of the total of all the thermal crosslinking agents. When the content is 1% by mass or more, the chemical resistance of the cured film is improved even when cured at a low temperature. When the content is 60 mass% or less, the storage stability of the resin composition and the post-exposure delay stability can be maintained. The content of the component (D2) is preferably from 1 to 95% by mass, more preferably from 5 to 90% by mass. When the content is 1% by mass or more, the storage stability, the post-exposure delay stability and the chemical resistance are improved, and deterioration of the device characteristics after the reliability test of the device can be suppressed. When the content is 90 mass% or less, the sensitivity of the resin composition can be maintained. The content of the component (D3) is preferably from 1 to 60 mass%, more preferably from 5 to 50 mass%. Since the content is 1% by mass or more, the chemical resistance can be improved in the heat treatment at a low temperature, and the reinforcement and the low stress can be achieved. When the content is 60 mass% or less, the sensitivity of the resin composition can be maintained.

The resin composition may contain (F) an antioxidant (hereinafter sometimes referred to as component (F)), if necessary. As the component (F), there may be mentioned a compound represented by the general formula (8), but it is not limited to the following structure.

In the general formula (8), R ⁴¹ represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms and R ⁴² represents an alkylene group having 2 or more carbon atoms. R ⁴³ represents an alkylene group having at least 2 carbon atoms, a monovalent to tetravalent organic group containing at least any one of an O atom and an N atom. k represents an integer of 1 to 4; R ^{43 is preferably an} alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, -, -NHNH-, and combinations thereof, and may further have a substituent. Among them, an alkyl ether group or -NH- is preferable from the viewpoint of solubility in a developing solution and metal adhesion, and -NH- is more preferable from the viewpoint of interaction with the component (A) and metal adhesion by metal complex formation Do.

(F), it is possible to suppress the oxidation deterioration of the aliphatic group and the phenolic hydroxyl group of the component (A). Further, by the rust-preventive action against the metal material, metal oxidation by external moisture or photosensitizer, and peeling between the cured film and the metal material accompanying thereto are suppressed. That is, deterioration of the device characteristics after the reliability test of the device can be suppressed. Specific examples of the component (F) include, but are not limited to, the following.

The addition amount of the component (F) is preferably from 0.1 to 10 parts by mass, more preferably from 0.2 to 5 parts by mass, per 100 parts by mass of the component (A). The addition amount is 0.1 part by mass or more, thereby improving the adhesion to the metal material and suppressing peeling. Further, when the addition amount is 10 parts by mass or less, the sensitivity of the resin composition can be maintained.

The resin composition may contain an adhesion improver if necessary. As the adhesion improver, it is preferable to contain a compound represented by the following general formula (9).

In the general formula (9), R ⁴⁴ to R ^{46 each} represent an O atom, an S atom or an N atom, and at least one of R ⁴⁴ to R ⁴⁶ represents an S atom. d represents 0 or 1; e and f each independently represent an integer of 0 to 2; Each of R ⁴⁷ to R ⁴⁹ independently represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. Examples of R ⁴⁷ to R ⁴⁹ include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an arylether group, a carboxyl group, a carbonyl group, A combination thereof, and the like, and may further have a substituent.

By containing the compound represented by the general formula (9), adhesion between the cured film after heat curing and a metallic material, particularly copper, can be remarkably improved and peeling can be suppressed. This is due to the fact that the S atom or N atom of the compound represented by the general formula (9) is derived from the efficient interaction with the metal surface and also has a three-dimensional structure which is easy to interact with the metal surface. By these effects, a cured film excellent in adhesion to a metal material can be obtained.

The addition amount of the compound represented by the general formula (9) is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the component (A). When the addition amount is 0.1 part by mass or more, the effect of adhesion to the metal material can be sufficiently obtained. When the amount of addition is 10 parts by mass or less, it is preferable that the resin composition is a resin composition having positive photosensitivity because the sensitivity of the resin composition before curing can be suppressed by interaction with the photosensitizer.

Examples of the compound represented by the general formula (9) include, but are not limited to, the following structures.

The resin composition may contain an adhesion improver other than the compound represented by the general formula (9). Examples of other adhesion improvers include vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p- Silane coupling agents such as styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane, titanium chelating agents, aluminum chelating agents , A compound obtained by reacting an aromatic amine compound with an alkoxy group-containing silicon compound, and the like. Two or more of these may be contained. By containing these adhesion improvers, adhesion to a base substrate such as a silicon wafer, ITO, SiO ₂ , silicon nitride, or the like can be enhanced when the resin film is developed. In addition, resistance to oxygen plasma and UV ozone treatment used for cleaning can be increased.

The content of the adhesion improver in the resin composition is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the component (A). By setting this range, it is possible to provide a resin composition having high adhesion after development and excellent resistance to oxygen plasma or UV ozone treatment.

Here, the content of the other adhesion modifier is preferably 10 to 500 parts by mass relative to 100 parts by mass of the compound represented by the general formula (9). By setting the amount in this range, the effect of each of the adhesion improvers can be sufficiently manifested.

The resin composition may contain an adhesion improver. Examples of the adhesion improver include an alkoxysilane-containing aromatic amine compound, an aromatic amide compound, or an aromatic-free silane compound. Two or more of these may be contained. By containing these compounds, adhesion between the cured film obtained by curing the resin composition and the substrate can be improved.

Specific examples of the alkoxysilane-containing aromatic amine compound and the aromatic amide compound are shown below. In addition, a compound obtained by reacting an aromatic amine compound with an alkoxy group-containing silicon compound may be used. For example, a compound obtained by reacting an aromatic amine compound with an alkoxysilane compound having a group reacting with an amino group such as an epoxy group or a chloromethyl group .

Examples of the aromatic-free silane compound include vinylsilane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, and vinyltris (? -Methoxyethoxy) silane, 3-methacryloxypropyltrimethoxy Containing a carbon-carbon unsaturated bond such as silane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, Silane compounds and the like. Of these, vinyltrimethoxysilane and vinyltriethoxysilane are preferable.

The content of the adhesion improver is preferably 0.01 to 15 parts by mass based on 100 parts by mass of the component (A). By setting this range, adhesion between the cured film obtained by curing the resin composition and the substrate can be improved. Further, it may contain a compound having both functions of an adhesion improver and an adhesion improver such as vinyltrimethoxysilane, vinyltriethoxysilane and the like.

The resin composition may contain a surfactant for the purpose of improving the wettability with the substrate or improving the film thickness uniformity of the coating film as required. Specific examples of the silicone surfactant include SH series, SD series, ST series, BYK series manufactured by Dow Corning Silicone Co., Ltd., BYK series manufactured by Big Chem Japan Co., KP series manufactured by Shinsei Silicone Co., (TSF series of Toshiba Silicone Co., Ltd.), and the fluorinated surfactants include "Megapak" (registered trademark) series of Dainippon Ink and "Fluoride series" of Sumitomo 3M, (Registered trademark) series, "ASAHI GUARD " series, EF series of Shin Akita Kasei Co., and POLYXX series of OMNOBA SOLUTION, and acrylic series and / or methacrylic series Examples of the surfactant obtained from the polymer are polyfluoro series of Kyoeisha Chemical Co., Ltd., Series), and the like, but the present invention is not limited thereto.

The content of the surfactant is preferably 0.001 part by mass or more and 1 part by mass or less based on 100 parts by mass of the component (A). By setting to the above-mentioned range, the wettability of the resin composition and the substrate and the uniformity of the film thickness of the coating film can be improved without causing problems such as bubbles and pinholes.

Next, a method for producing the resin composition of the present invention will be described. For example, the respective components of (A), (B), (C), (D), (D2), (D3) The resin composition can be obtained by mixing and dissolving a compound, a radical polymerizing compound, an adhesion improver, an adhesion improver, a surfactant, and the like. Examples of the dissolution method include heating and stirring. When heating, the heating temperature is preferably set within a range that does not impair the performance of the resin composition, and is usually from room temperature to 80 ° C. In addition, the order of dissolution of each component is not particularly limited, and there is, for example, a method of sequentially dissolving a compound having a low solubility. In the case of stirring, the number of revolutions is preferably set within a range that does not impair the performance of the resin composition, and is usually 200 rpm to 2000 rpm. When stirring, it may be heated as occasion demands, and usually it is room temperature to 80 ° C. In addition, with respect to components that are likely to generate bubbles during stirring and dissolving, such as a surfactant or a part of an adhesion improver, other components may be dissolved and added last, thereby preventing defective dissolution of other components due to the generation of bubbles .

The viscosity of the resin composition is preferably from 2 to 5,000 mPa · s. It is easy to obtain a desired film thickness by adjusting the solid content concentration so that the viscosity is 2 mPa 占 퐏 or more. On the other hand, if the viscosity is 5,000 mPa · s or less, it is easy to obtain a highly uniform coating film. The resin composition having such a viscosity can be easily obtained by, for example, setting the solid content concentration to 5 to 60 mass%.

The obtained resin composition is preferably filtered using a filter to remove dust or particles. The filter hole diameter is, for example, 0.5 탆, 0.2 탆, 0.1 탆, 0.05 탆, 0.02 탆, and the like, but is not limited thereto. Examples of the material of the filter include polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE) and the like. Polyethylene and nylon are preferred.

Next, a method for producing a cured film using the resin composition of the present invention or a resin film formed from the resin composition will be described.

Here, the term "resin film" is defined as a film obtained by applying a resin composition onto the surface of a substrate and drying it. The cured film is defined as a film obtained by curing the resin film.

The cured film production method of the present invention comprises a step of coating the resin composition on a substrate and drying to form a resin film, a step of exposing the resin film to light when it has photosensitivity, a developing step of developing the exposed resin film, And a heat treatment step of heat-treating the developed resin film.

First, the resin composition of the present invention is applied to a substrate to obtain a coating film of the resin composition. As the substrate, a silicon wafer, a ceramics type, a gallium arsenide, an organic circuit substrate, an inorganic circuit substrate, and a circuit material are arranged on these substrates, but the present invention is not limited thereto. Examples of the application method include spin coating, slit coating, dip coating, spray coating, and printing. The thickness of the coating film is usually 0.1 to 150 mu m after the drying, though it varies depending on the coating method, the solid content concentration of the composition, the viscosity and the like.

Prior to application, the substrate to which the resin composition is applied may be pre-treated with the aforementioned adhesion improver. For example, the adhesion improver may be dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate or diethyl adipate in an amount of 0.5 to 20 mass% A method of treating the substrate surface by a method such as spin coating, slit die coating, bar coating, dip coating, spray coating, or steam treatment using a solution. After the substrate surface is treated, a vacuum drying treatment may be carried out if necessary. After that, the reaction between the substrate and the adhesion improver may be conducted by heat treatment at 50 to 280 ° C.

Subsequently, the coated film of the resin composition is dried to obtain a resin film. The drying is preferably performed at a temperature of 50 to 140 캜 for 1 minute to several hours using an oven, a hot plate, an infrared ray or the like.

In the exposure step, a chemical ray is irradiated onto a resin film having photosensitivity through a mask having a desired pattern. Although there are ultraviolet rays, visible rays, electron beams, X rays and the like as the actinic rays used for exposure, it is preferable to use g line (436 nm), h line (405 nm) or i line (365 nm) .

Subsequently, the exposed resin film is developed. Examples of the developing solution include organic solvents such as tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, An aqueous solution of a compound showing alkalinity such as dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable. Further, in some cases, these alkaline aqueous solutions may be mixed with an aqueous solution of N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, Polar solvent; Alcohols such as methanol, ethanol and isopropanol; Esters such as ethyl lactate and propylene glycol monomethyl ether acetate; Ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, methyl isobutyl ketone, etc. may be added alone or in combination of two or more. After development, it is common to rinse with water. Also here, rinsing may be performed by adding alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate, propylene glycol monomethyl ether acetate and the like to water.

The thus obtained resin film is heated to proceed the thermal crosslinking reaction to obtain the cured film of the present invention. The cured film is improved in heat resistance and chemical resistance by crosslinking. This heating treatment may be performed either stepwise or continuously. The heat treatment is preferably performed for 5 minutes to 5 hours. As an example, heat treatment is performed at 110 캜 for 30 minutes, followed by heat treatment at 170 캜 for 60 minutes. The heat treatment conditions are preferably 140 deg. C or higher and 280 deg. C or lower. The heat treatment conditions are preferably 140 ° C or higher, and more preferably 160 ° C or higher, in order to proceed the thermal crosslinking reaction. The present invention also aims to provide a cured film excellent in low temperature curability, and in order to suppress defective operation accompanied by thermal history of a semiconductor device to be described later and improve the yield, the heat treatment conditions are preferably 280 DEG C or lower More preferably 250 ° C or lower, and even more preferably 230 ° C or lower.

The cured film of the present invention can be used for electronic parts such as semiconductor devices. That is, the semiconductor device of the present invention is a semiconductor device having a metal wiring and an insulating film, and is a semiconductor device having the cured film of the present invention as an insulating film. A semiconductor device generally refers to a device including a semiconductor element and an integrated circuit integrated with the semiconductor element as a component. The semiconductor device according to the present invention includes not only an apparatus including a semiconductor device but also a semiconductor device component such as a wiring board. Also included in the semiconductor device of the present invention is a semiconductor package in which a semiconductor element or the like is protected by a sealing resin and has a function of electrically connecting with the outside. Specifically, the cured film of the present invention is suitably used for applications such as passivation films for semiconductors, protective films for semiconductor devices, and interlayer insulating films for multilayer wiring for high density mounting.

As a preferable example of the semiconductor device of the present invention, for example, MRAM having low heat resistance can be cited. That is, the cured film of the present invention is suitable for the surface protective film of the MRAM. In addition to MRAM, promising polymer memory (PFRAM) or Phase Change RAM (PCRAM) or Ovonic Unified Memory (OUM), which is a promising next-generation memory, There is a high possibility of using new materials. Therefore, the cured film of the present invention is also suitable for these surface protective films. In addition, a display device including a first electrode formed on a substrate and a second electrode provided opposite to the first electrode, specifically, a display device using an LCD, an ECD, an ELD, and an organic electroluminescent device Organic electroluminescence device) and the like.

Particularly, in recent semiconductor devices, semiconductor devices having copper electrodes, copper wirings, and bumps are mainstream as the electrodes of semiconductor elements and the wirings of the substrate are further miniaturized, and copper Or in contact with a large amount of chemical liquid such as flux in an etching process of a barrier metal or a pattern forming process of a resist. When the cured film of the present invention is used as a protective film for such an electrode or wiring, it is particularly preferably used since it has high resistance to the chemical liquid. Further, the copper wiring may be subjected to oxidation treatment in the manufacturing process. Even in such a case, the cured film of the present invention can be preferably used.

Next, an example in which the cured film of the present invention is applied to a semiconductor device having bumps will be described with reference to the drawings. 1 is an enlarged cross-sectional view of a pad portion of a semiconductor device having bumps. As shown in Fig. 1, an aluminum (hereinafter referred to as Al) pad 2 and a passivation film 3 for input and output are formed on a silicon wafer 1 and a via hole is formed in the passivation film 3 . An insulating film 4 containing the cured resin composition of the present invention is formed thereon and a metal film 5 is formed so as to be electrically connected to the Al pad 2. As the material of the metal film 5, Cr, Ti, or the like is preferably used. A metal wiring (6) is provided on the metal film (5). As the material of the metal wiring 6, Ag, Cu or the like is preferably used. In recent years, copper wiring is particularly preferably used as described above. The metal wiring 6 is preferably formed on the metal film 5 by a plating method. An insulating film 7 including the cured resin composition of the present invention is formed on the insulating film 4 and the metal film 5. The insulating film 7 needs to be opened by a photolithography process in a scribe line 9 and a pad portion on which the solder bumps 10 are provided. After the barrier metal 8 is formed on the pad portion, the solder bump 10 is formed. When a flexible component is introduced into the resin composition of the present invention, since warping of the wafer is small, exposure and transfer of wafers can be performed with high accuracy. In addition, since the polyimide resin or the polybenzoxazole resin has excellent mechanical properties, the stress from the sealing resin can be relieved even during mounting, and damage to the low-k layer can be prevented, and a highly reliable semiconductor device can be provided can do.

Next, a detailed manufacturing method of the semiconductor device will be described with reference to Fig. The resin composition of the present invention is applied onto the silicon wafer 1 on which the Al pad 2 and the passivation film 3 are formed in the step of FIG. 2A, and the pattern is formed by using the photolithography process, And the insulating film 4 is formed by curing. Subsequently, in the step of FIG. 2B, the metal film 5 is formed by a sputtering method. 2 (c), the metal wiring 6 is formed on the metal film 5 by the plating method. 2, a resin composition of the present invention is applied, and a pattern is formed by using a photolithography process, followed by curing. As a result, as shown in Fig. 2D, An insulating film 7 is formed. At this time, the insulating film 7 is formed with an opening in the scribe line 9. (A so-called rewiring line) may be further formed on the insulating film 7. By repeating the above steps, a multilayer wiring structure in which two or more layers of wiring lines are separated by an insulating film containing the cured resin composition of the present invention can be formed. The insulating film for separating the rewiring lines is referred to as an interlayer insulating film. At this time, the formed insulating film comes into contact with various kinds of chemical liquid a plurality of times. However, since the insulating film containing the cured resin composition of the present invention has excellent adhesion and chemical resistance, a good multilayer wiring structure can be formed. There is no upper limit on the number of layers of the multilayer wiring structure, but a layer having 10 or less layers is often used.

Next, as shown in FIG. 2E and FIG. 2F, a barrier metal 8 and a solder bump 10 are formed. Then, the wafer is diced along the scribe line 9 and cut into chips. If the opening 7 is not formed in the scribe line 9 or the residue remains, cracks or the like occur during dicing, which affects the reliability of the chip. For this reason, it is preferable to provide a patterning process that is excellent in thick-film processing because it achieves high reliability of the semiconductor device.

Further, the resin composition of the present invention is suitably used also in a fan-out wafer level package (fan-out WLP) or a fan-out panel level package (fan-out PLP). The fan-out WLP is a technique for collectively manufacturing a plurality of semiconductor packages on a wafer. A fan-out PLP is a technique for collectively manufacturing a plurality of semiconductor packages on a rectangular substrate, that is, a panel, in some or all processes.

3 is a cross-sectional view of a manufacturing process of an example of a semiconductor device having a cured film of the present invention. Specifically, this is an enlarged cross-sectional view of a semiconductor package called a Chip-first fan-out WLP or a Chip-first fan-out PLP. The silicon wafer on which the Al pad 2 and the passivation film 3 are formed is diced and cut by the semiconductor chip 1 'and then sealed with the sealing resin 11. The resin composition of the present invention is applied over the encapsulating resin 11 and the semiconductor chip 1 'and an opening is formed by pattern formation using a photolithography process and then cured to form the insulating film 4 . A metal film 5 containing Cr, Ti or the like and a metal wiring 6 containing Ag, Cu or the like are formed on the insulating film 4. The metal film 5 and the metal wiring 6 are electrically connected to the Al pad 2 provided on the semiconductor chip 1 'in the opening formed in the insulating film 4. And an insulating film 7 is further formed thereon. The resin composition of the present invention is also preferably used for forming the insulating film 7. A barrier metal 8 and a solder bump 10 are formed in the opening formed in the insulating film 7. [ The barrier metal (8) and the solder bump (10) are electrically connected to the metal wiring (6).

Chip-first fan-out WLP or Chip-first fan-out PLP is a method in which an expansion part is provided by using a sealing resin such as epoxy resin around the semiconductor chip, rewiring is performed from the electrode on the semiconductor chip to the corresponding extension part, And the number of necessary terminals is secured by mounting the solder balls in the extended portion. In the chip-first fan-out WLP or Chip-first fan-out PLP, wiring is provided so as to extend across the boundary formed by the main surface of the semiconductor chip and the main surface of the sealing resin. That is, an insulating film 7 is disposed as an interlayer insulating film on a substrate made of two or more kinds of materials, a semiconductor chip and a sealing resin, and a metal wiring (rewiring) 6 is disposed on the interlayer insulating film.

In the case of Chip-first fan-out WLP or Chip-first fan-out PLP, miniaturization of re-wiring is proceeding. The cured film of the present invention is suitably used also for fine wiring because it has high metal adhesion even to a wiring having a width of 5 m or less and a distance between adjacent wiring. Here, the width of the metal wiring and the distance between adjacent wirings are 5 mu m or less, which means that the width of the metal wiring is 5 mu m or less and the distance between adjacent wirings is 5 mu m or less.

In a chip-first fan-out WLP or a chip-first fan-out PLP having such a fine structure, a plurality of re-wiring layers are laminated and a re-wiring layer It is preferable that the width of the metal wiring and the interval between adjacent wirings are the same or narrower than the width of the metal wiring of the re-wiring layer farther from the semiconductor chip and the distance between adjacent wirings. Here, the rewiring layer refers to a multilayer wiring structure in which a plurality of rewiring lines are separated by a plurality of interlayer insulating films, and includes a set of rewiring lines and an interlayer insulating film formed thereon. There is also a case where the re-wiring layer includes only one layer. The reason why the width of the metal wiring of the re-distribution layer and the interval between the adjacent wirings are equal or narrow is that the width of the metal wiring of the re-distribution layer near the semiconductor chip is smaller than the width of the metal wiring And the interval between adjacent wirings in the re-wiring layer closer to the semiconductor chip is compared with the interval between adjacent wirings in the re-wiring layer farther from the semiconductor chip And means the same or narrow.

In this structure, the thickness of the interlayer insulating film in the rewiring layer closer to the semiconductor chip among the adjacent rewiring layers is equal to or thinner than the thickness of the interlayer insulating film in the rewiring layer farther from the semiconductor chip .

That is, it is preferable that each of the re-wiring layers constituting the multilayer wiring structure is gradually pitch-wise from the side away from the semiconductor chip to the side closer to the semiconductor chip. By having such a structure, the semiconductor chip and the terminal can be smoothly connected even if the semiconductor chip is highly integrated. In order to manufacture such a structure, the in-plane uniformity of the interlayer insulating film in each re-wiring layer is important.

Further, in the fan-out WLP or the fan-out PLP, a plurality of rewiring layers including a metal wiring (rewiring line) and an interlayer insulating film are stacked on a supporting substrate on which a mounting material is disposed, There is a type of semiconductor packaging manufactured by a process called RDL (Redistribution Layer) -first, in which a semiconductor package is manufactured and then the supporting substrate and the re-wiring layer are peeled off to separate the semiconductor package. That is, the supporting substrate is used only in the manufacturing process, and is not included in the completed semiconductor package. In this step, a glass substrate or the like which is more flexible than a silicon wafer is often used as the supporting substrate, and therefore, the insulating film is preferably low in stress. Further, in this process, since a large-sized panel is used for the cost advantage of mass production, there is a problem to reduce the warp caused by film shrinkage of the interlayer insulating film and to improve the uniformity of the film thickness in the plane have.

A method of manufacturing the semiconductor device in the RDL first will be described with reference to FIG. 4A, a barrier metal such as Ti is formed on a support substrate 20 such as a glass substrate or a silicon wafer by a sputtering method, a Cu seed (seed layer) is further formed thereon by a sputtering method, And an electrode pad 21 including Cu is formed by a plating method. Subsequently, in the step of FIG. 4B, the resin composition of the present invention is applied to the entire surface of the support substrate 20 on which the electrode pads 21 are formed, a pattern is formed by using a photolithography process, An insulating film 22 is formed. Subsequently, in the step of FIG. 4C, the seed layer is formed again by the sputtering method, and the metal wiring 23 (re-wiring) containing Cu is formed by the plating method. Thereafter, the processes of FIG. 4B and FIG. 4C are repeated to form a multilayer wiring structure as shown in FIG. 4D. Subsequently, in the step of FIG. 4E, the resin composition of the present invention is applied again, a pattern is formed by using a photolithography process, and then, the insulating film 22 is formed by curing, , A Cu post (24) is formed on the metal wiring (23) by a plating method. Here, the pitch of the Cu posts 24 and the pitch of the conductive parts of the semiconductor chip 26 are made equal. That is, the pitch of the conductive portions of the semiconductor chip 26 is a pitch that is finer than the pitch of the electrode pads 21. As shown in Fig. 4E, each re-wiring layer constituting the multi- To the Cu post 24, the wiring is made multi-layered while making the pitch gradually fine. The thickness of the adjacent interlayer insulating film 22 in the multilayer wiring structure also becomes equal or thinner as it approaches the semiconductor chip. Subsequently, the semiconductor chip 26 is connected to the Cu post 24 through the solder bumps 25 in the step of FIG. Thereby, the electrode pad 21 and the semiconductor chip 26 are electrically connected through the metal wiring 23 and the solder bump 25. Thereafter, the semiconductor chip 26 is sealed with a sealing resin to form a semiconductor package, and the supporting substrate and the re-wiring layer are peeled off to separate the semiconductor package. Thus, a semiconductor device having a multilayer wiring structure using the RDL first process can be obtained.

In addition, in the semiconductor package of the type in which the semiconductor chip is embedded in the recess formed in the glass epoxy resin substrate, the wiring is provided so as to extend across the boundary line between the main surface of the semiconductor chip and the main surface of the printed board. Also in this embodiment, an interlayer insulating film is formed on a substrate made of two or more kinds of materials, and wirings (rewiring lines) are formed on the interlayer insulating film. The cured film obtained by curing the resin composition of the present invention has high adhesion to a semiconductor chip to which a metal wiring is applied and also has a high adhesion strength to a sealing resin in an epoxy resin or the like and therefore is provided on a substrate made of two or more kinds of materials Is used suitably as an interlayer insulating film.

Further, the resin composition of the present invention is suitably used also for coil parts of an inductor device. 5 is a cross-sectional view of a coil part of an inductor device showing an embodiment of the present invention. As shown in Fig. 5, an insulating film 13 is formed on the entire surface of the substrate 12, and an insulating film 14 having an opening formed thereon is formed. As the substrate 12, ferrite or the like is used. The resin composition of the present invention may be used either in the insulating film 13 or in the insulating film 14. A metal film 15 containing Cr, Ti, or the like is formed in the opening of the insulating film 14, and a metal wiring 16 containing Ag, Cu, or the like is formed thereon by a plating method. The metal wiring 16 is formed in a spiral shape. By repeating the above process a plurality of times, the insulating film 13, the insulating film 14, the metal film 15, and the metal wiring 16 are laminated to each other to have a function as a coil. The metal wiring 16 provided on the uppermost layer is connected to the electrode 18 by the metal wiring 17 including Ag or Cu and is sealed by the sealing resin 19. [

The resin composition of the present invention is suitably used also in organic EL display devices. The organic EL display device has a driving circuit, a planarizing layer, a first electrode, an insulating layer, a light emitting layer and a second electrode on a substrate, and the planarizing layer and / or insulating layer includes the cured film of the present invention. Although the organic EL light emitting material is susceptible to deterioration due to moisture and adversely affects the area of the light emitting portion such as reduction of the area ratio of the light emitting portion, the cured film of the present invention has a low water absorption rate, Loses. [0003] For example, an active matrix type organic EL display device includes a TFT and a wiring on the side of the TFT and connected to the TFT on a substrate including glass or various plastics, And a display element is provided on the planarizing layer. The display element and the wiring are connected through the contact hole formed in the planarization layer.

6 shows a cross-sectional view of an example of a TFT substrate. A TFT (thin film transistor) 27 of a bottom gate type or a top gate type is provided in a matrix form on a substrate 32 and a TFT insulating layer 29 is formed in a state of covering the TFT 27 . Further, a wiring 28 connected to the TFT 27 is provided on the TFT insulating layer 29. A flattening layer 30 is provided on the TFT insulating layer 29 in a state in which the wiring 28 is buried. In the planarization layer 30, a contact hole 33 reaching the wiring 28 is provided. A transparent electrode 31 including ITO or the like is formed on the planarization layer 30 in a state of being connected to the wiring 28 through the contact hole 33. Here, the transparent electrode 31 is an electrode of a display element (for example, an organic EL element). The insulating layer 34 is formed to cover the periphery of the transparent electrode 31. The organic EL element may be a top emission type that emits light emitted from the opposite side of the substrate 32, or may be a bottom emission type that emits light from the substrate 32 side. In this manner, an active matrix type organic EL display device in which TFTs 27 for driving the organic EL elements are connected is obtained.

The TFT insulating layer 29, the planarization layer 30, and / or the insulating layer 34 are formed by a process of forming a resin film containing the resin composition of the present invention, a process of exposing the resin film, And a step of heat-treating the developed resin film. From the manufacturing method having these steps, an organic EL display device can be obtained.

Example

Hereinafter, the present invention will be described with reference to examples and the like, but the present invention is not limited to these examples. The evaluation of the resin composition in Examples was carried out by the following methods. For the evaluation, a resin composition (hereinafter referred to as Vanishi) filtered through a 1 占 퐉 polytetrafluoroethylene filter (manufactured by Sumitomo Heavy Industries, Ltd.) was used in advance.

≪ Evaluation of non-photosensitive resin composition >

(1) In-plane uniformity

Varnish (resin composition) was prepared and coated on an 8-inch silicon wafer by a spin coating method using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Co., Ltd.) so as to have a thickness of 12.5 占 퐉 after pre-baking Prebaking was performed, and a prebaked film was produced. Or a slit coater by a slit coating method, followed by drying under reduced pressure and prebaking to prepare a prebaked film. The prebake was performed by heating at 120 DEG C for 3 minutes. Thereafter, film thicknesses of 9 points were measured at intervals of 2 cm from the center of the 8-inch wafer from the center, and the difference between the minimum value and the maximum value of the film thickness was determined as the in-plane uniformity of the film thickness. The values of 3, more than 0.35 탆 and less than 0.6 탆 were considered to be good, and those having a thickness of more than 0.6 탆 were evaluated as "1".

(2) Evaluation of residual amount of component (E) in resin film

The varnish was coated and prebaked on a 8-inch silicon wafer by a spin coating method using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Co., Ltd.) so as to have a thickness of 13 mu m after prebaked, Respectively. Or a slit coater by a slit coating method, followed by drying under reduced pressure and prebaking to prepare a prebaked film. The prebake was performed by heating at 120 DEG C for 3 minutes. The film thickness after pre-baking was measured with a light interference film thickness measuring apparatus Lambda Ace STM-602 manufactured by Dainippon Screen Shoji Co., Ltd. with a refractive index of 1.629. 10 mg of the obtained pre-baked film was adsorbed by the purge-and-trap method. Specifically, the collected pre-baked film was heated at 250 ° C for 40 minutes using helium as a purge gas, and the desorbed components were collected in a suction tube.

The collected components were subjected to thermal desorption at 260 deg. C for 15 minutes in the first desorption condition, at -27 deg. C in the second desorption condition and at 320 deg. C for 5 minutes in the second desorption condition, and then the GC-MS apparatus 7890 / 5975C GC-MS analysis was carried out under the conditions of column temperature: 40 to 300 占 폚, carrier gas: helium (1.5 ml / min) and scan range: m / Z29 to 600 using Agilent. GC-MS analysis was performed on each component (E) under the same conditions as above to prepare a calibration curve, and the amount of gas generation was calculated.

As a result, it was evaluated as 1 when the residual amount of the component (E) was 0.001% by mass or more and 30% by mass or less, and when it was less than 0.001% by mass or above 30%

(3) Storage stability test (change in viscosity at room temperature)

The varnish was made and viscosity was measured with a viscometer. Thereafter, the varnish was stored under an environment of a temperature of 23 캜 and a humidity of 50%, and after 14 days, evaluation was carried out under the same conditions, and the amount of change in viscosity was measured. It is said that the change in viscosity is 0% or more and less than 10% is good, and 2% or more is 10% or more.

(4) Evaluation of Chemical Resistance

Varnish was prepared and applied and prebaked on an 8-inch silicon wafer by a spin coating method using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Co., Ltd.) so that the film thickness after pre-baking became 11 탆 , And prebaked films were prepared. Or a slit coater by a slit coating method, followed by drying under reduced pressure and prebaking to prepare a prebaked film. The prebake was performed by heating at 120 DEG C for 3 minutes. Thereafter, the prebaked film was heated to 170 DEG C at an oxygen concentration of 20 ppm or less and at 4.0 DEG C / min under nitrogen flow using an inner oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.) The pre-baked film was cured by heating for 1 hour to obtain a cured film. The silicon wafer was taken out at the time when the temperature became 50 DEG C or less and the obtained cured film was immersed in an organic chemical solution (dimethyl sulfoxide: 25% aqueous solution of tetramethylammonium hydroxide = 92: 2) at 65 DEG C for 30 minutes, Respectively.

As a result, it was evaluated as "good" in the case of peeling or elution, 2 in peeling, and "poor" in case of elution.

(5-1) Reliability Test (Evaluation of Residual Component (E) in Cured Film)

Varnish was prepared and applied and prebaked on an 8-inch silicon wafer by a spin coating method using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Co., Ltd.) so that the film thickness after development was 11 mu m, A prebaked film was prepared. Or a slit coater by a slit coating method, followed by drying under reduced pressure and prebaking to prepare a prebaked film. All the prebaking was carried out at 120 DEG C for 3 minutes. The obtained prebaked film was developed with a 2.38 mass% aqueous solution of tetramethylammonium (TMAH) (manufactured by Tamagagaku Kogyo Co., Ltd.) under the conditions of 25 seconds × 2 times to 60 seconds × 2 times so as to have a film thickness of 11 μm, It was then rinsed with pure water. Thereafter, using an inner oven CLH-21CD-S, the temperature was raised to 170 deg. C at an oxygen concentration of 20 ppm or less and at 4.0 deg. C / min under a nitrogen stream, and a heat treatment was performed at 170 deg. C for 1 hour to cure the prebaked film Film. When the temperature reached 50 DEG C or lower, the silicon wafer was taken out. The film thickness of the prebaked film after prebaking and after development and the film thickness of the cured film after heat treatment were measured using a light interference film thickness measuring apparatus Lambda Ace STM-602 manufactured by Dainippon Screen Shoji Co., Ltd., and the refractive index 1.629. 10 mg of the obtained cured film was adsorbed by the purge-and-trap method. Specifically, the collected cured film was heated at 250 캜 for 40 minutes using helium as a purge gas, and the desorbed components were collected in a suction tube.

The collected components were subjected to thermal desorption at 260 deg. C for 15 minutes in the first desorption condition, at -27 deg. C in the second desorption condition and at 320 deg. C for 5 minutes in the second desorption condition, and then the GC-MS apparatus 7890 / 5975C GC-MS analysis was carried out under the conditions of column temperature: 40 to 300 占 폚, carrier gas: helium (1.5 ml / min) and scan range: m / Z29 to 600 using Agilent. GC-MS analysis was performed on each component (E) under the same conditions as above to prepare a calibration curve, and the amount of gas generation was calculated.

As a result, it was evaluated as 1 when the amount of residual component (E) was less than 0.05 ppm and less than 1000 ppm, and 2 when it was less than 0.05 ppm or 1000 ppm or more.

(5-2) Reliability test (peel evaluation in copper wiring after HigH temperature storage (HTS)

In the evaluation of peeling in the copper wiring, the following evaluation substrates were prepared. Cylindrical copper wirings having a thickness of 5 占 퐉 and a diameter of 90 占 퐉 were formed at regular intervals on an 8-inch silicon wafer so that the distance between centers of the copper wirings was 150 占 퐉. This was used as an evaluation substrate.

The varnish was coated on the evaluation substrate by a spin coating method using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Limited) so as to have a thickness of 11 mu m after pre-baking for 3 minutes at 120 DEG C, To prepare a prebaked film. Or a slit coater by a slit coating method, followed by drying under reduced pressure and prebaking to prepare a prebaked film. All the prebaking was carried out at 120 DEG C for 3 minutes. Thereafter, the temperature was raised to 170 ° C at an oxygen concentration of 20 ppm or less and at 4.0 ° C / minute using an inner oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.) The prebaked film was cured to obtain a cured film. The evaluation substrate (hereinafter referred to as a sample) was taken out when the temperature reached 50 DEG C or lower.

Subsequently, the sample was placed in a thermostatic chamber at 175 ° C and treated for 200 hours. Thereafter, the sample was taken out and the sample was cut and observed at a cross section of 40,000 times using a scanning electron microscope FEI Helios 650 (manufactured by FEI) equipped with a converging ion beam processing apparatus to observe the peeling in the copper wiring . As the evaluation method, the degree of peeling of the side surface of the copper wiring was observed, and it was evaluated that the degree of peeling was 0% or more and less than 25% Respectively.

≪ Evaluation of Photosensitive Resin Composition >

(6) In-plane uniformity

(1) uniformity in the plane " described above.

(7) Evaluation of residual amount of component (E) in resin film

Was evaluated in the same manner as in "(2) Evaluation of the residual amount of the component (E) in the resin film".

(8) Storage stability test (change in storage sensitivity at room temperature)

Varnish was prepared and applied and prebaked on an 8-inch silicon wafer by a spin coating method using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Co., Ltd.) so that the film thickness after development became 11 mu m, A bake film was produced. Or a slit coater by a slit coating method, followed by drying under reduced pressure and prebaking to prepare a prebaked film. All the prebaking was carried out at 120 DEG C for 3 minutes. Pre-baked film obtained ghi ray mask aligner (Union high Ku (Ltd.), PEM-6M) each from 0 to 20mJ / cm ² in the exposure amount of 1500mJ / cm ² by using Step exposure. The line and space pattern used for exposure is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 30, 50, After the exposure, development was carried out using a 2.38% by mass aqueous solution of tetramethylammonium (TMAH) (manufactured by Tamagagaku Kogyo Co., Ltd.) under the conditions of 25 seconds × 2 times to 60 seconds × 2 times so as to have a film thickness of 11 μm, The relief pattern was obtained by rinsing with pure water. The film thickness of the prebaked film after prebaking and after development was measured using a light interference film thickness measuring apparatus Lambda Ace STM-602 manufactured by Dainippon Screen Seiko Co., Ltd. with a refractive index of 1.629.

After exposure and development, the minimum exposure amount at which a line and space (L / S) pattern of 20 mu m was formed one-to-one was defined as sensitivity. In that case, the sensitivity is not less than the as defective by said very good to 500mJ / cm ² is less than 3, 500mJ / cm ² or more and that good to 600mJ / cm ² is less than ^2, 600mJ / cm 2 was evaluated as one.

Thereafter, the varnish was stored under an environment of a temperature of 23 DEG C and a humidity of 50%, and after 14 days, the evaluation was carried out under the same conditions, and the dimension of the space in the 20 mu m line & space pattern was measured. Before and after storage, those having a variation of pattern dimension of 0 탆 or more and less than 1 탆 were evaluated as being very good, and those having a size of 3 탆 or more and less than 2 탆 were evaluated as good.

(9) Post-exposure delay stability test

The varnish was coated on an 8-inch silicon wafer by a spin coating method using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Co., Ltd.) so that the film thickness after pre-baking was 12.5 탆 and the film thickness after development was 11 탆 And prebake prebaking were carried out. A prebake film was formed or applied by slit coating using a slit coater, followed by drying under reduced pressure and prebaking to prepare a prebaked film. All the prebaking was carried out at 120 DEG C for 3 minutes. Pre-baked film obtained ghi ray mask aligner (Union high Ku (Ltd.), PEM-6M) each from 0 to 20mJ / cm ² in the exposure amount of 1500mJ / cm ² by using Step exposure. The line and space pattern used for exposure is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 30, 50, After the exposure, development was carried out using a 2.38% by mass aqueous solution of tetramethylammonium (TMAH) (manufactured by Tamagagaku Kogyo Co., Ltd.) under the conditions of 25 seconds × 2 times to 60 seconds × 2 times so as to have a film thickness of 11 μm, The relief pattern was obtained by rinsing with pure water. The film thickness of the prebaked film after prebaking and after development was measured using a light interference film thickness measuring apparatus Lambda Ace STM-602 manufactured by Dainippon Screen Seiko Co., Ltd. with a refractive index of 1.629.

After exposure and development, the minimum exposure amount at which a line and space (L / S) pattern of 20 mu m was formed one-to-one was defined as sensitivity.

A prebaked film was prepared on an 8-inch silicon wafer using the same varnish as above, and the film was stored under an environment of a temperature of 23 DEG C and a humidity of 50% for 8 hours after the prebaked film was formed or after exposure, The dimensions of the spaces in the obtained line and space patterns of 20 mu m were measured, and the amount of change in dimensions was measured before and after storage. In this case, after the pre-baked film is formed, those having a variation amount of the pattern dimension of not less than 0 탆 and less than 0.5 탆 are considered to be very good, and those having a thickness of not less than 3 탆 and less than 1 탆 are considered good, Respectively. After exposure, those having a variation of pattern dimension of 0 占 퐉 or more and less than 1 占 퐉 were evaluated as being very good, and those having a size of 3 占 퐉 or more and less than 2 占 퐉 were evaluated as good.

(10) Evaluation of Chemical Resistance

Was evaluated in the same manner as in "(4) Evaluation of Chemical Resistance".

(11-1) Reliability Test (Evaluation of Residual Component (E) in Cured Film)

Was evaluated in the same manner as in " (5-1) Reliability Test (Evaluation of Residual Amount of Component (E) in Cured Film) ".

(11-2) Reliability test (peeling evaluation in copper wiring after HigH temperature storage (HTS)

(Peeling evaluation in copper wiring after (H.2) reliability test (HigH Temperature Storage (HTS)) "above.

Synthesis Example 1 Synthesis of hydroxyl group-containing diamine compound [

(0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as BAHF, manufactured by Central Glass Co., Ltd.) was dissolved in 100 mL of acetone and 100 mL of propylene oxide (0.3 mol), and the solution was cooled to -15 占 폚. Then, a solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Kasei K.K.) in 100 mL of acetone was added dropwise. After completion of the dropwise addition, the mixture was stirred at -15 DEG C for 4 hours, and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 < 0 > C.

30 g of the obtained white solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Hydrogen was introduced thereinto as a balloon, and the reduction reaction was carried out at room temperature. Approximately two hours later, the balloon was confirmed to be no longer turned off and the reaction was terminated. After completion of the reaction, the reaction product was filtered to remove the palladium compound as a catalyst and concentrated by a rotary evaporator to obtain a hydroxyl group-containing diamine compound represented by the following formula.

Synthesis Example 2 Synthesis of polybenzoxazole precursor (A-1)

Under a dry nitrogen gas stream, 27.47 g (0.075 mol) of BAHF was dissolved in 257 g of NMP. Thereto was added 17.20 g (0.048 mol) of 1,1 '- (4,4'-oxybenzoyl) diimidazole (hereinafter referred to as PBOM) together with 20 g of NMP and reacted at 85 ° C for 3 hours. Subsequently, 20.00 g (0.020 mol) of a diamine containing propylene oxide and tetramethylene ether glycol structure (RT-1000, manufactured by HUNTSMAN CO., LTD.), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (0.044 mol) of PBOM were added together with 50 g of NMP, and the mixture was reacted at 85 DEG C for 1 hour. As a terminal sealing agent, 3.94 g (0.024 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride was added together with 10 g of NMP, and the reaction was carried out at 85 ° C for 30 minutes. After completion of the reaction, the reaction mixture was cooled to room temperature, and 52.82 g (0.50 mol) of acetic acid was added thereto together with 87 g of NMP, followed by stirring at room temperature for 1 hour. After completion of the stirring, the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a ventilation drier at 50 DEG C for 3 days to obtain a polybenzoxazole precursor (A-1) powder.

Synthesis Example 3 Synthesis of polybenzoxazole precursor (A-2)

(32.96 g, 0.090 mole), PBOM (29.38 g, 0.082 mole), RT-1000 (10.00 g, 0.010 mole), SiDA (1.49 g, 0.0060 mole), 5-norbornene (0.60 g, 0.0010 mol), ODPA (2.17 g, 0.0070 mol), acetic acid (49.22 g, 0.82 mol) and 360 g of NMP The same procedure was followed to obtain a powder of the polybenzoxazole precursor (A-2).

Synthesis Example 4 Synthesis of polyimide precursor (A-3)

57.4 g (0.095 mol) of the hydroxyl group-containing diamine obtained in Synthesis Example 1 and 1.24 g (0.005 mol) of SiDA were dissolved in 200 g of NMP under a dry nitrogen gas flow. 31.0 g (0.10 mol) of 4,4'-oxydiphthalic anhydride (hereinafter referred to as ODPA) was added thereto, followed by stirring at 40 ° C for 2 hours. Thereafter, a solution obtained by diluting 7.14 g (0.06 mol) of dimethylformamide dimethylacetal (hereinafter referred to as DFA, manufactured by Mitsubishi Rayon Co., Ltd.) with 5 g of NMP was added dropwise over 10 minutes. After the dropwise addition, stirring was continued at 40 ° C for 2 hours. After completion of the stirring, the solution was poured into 2 L of water, and the precipitate of the polymer solid was collected by filtration. Further, the mixture was washed three times with 2 L of water, and the collected polymer solid was dried in a vacuum dryer at 50 캜 for 72 hours to obtain a polyimide precursor (A-3).

Synthesis Example 5 Synthesis of polyimide precursor (A-4)

Under a dry nitrogen gas stream, 31.0 g (0.10 mol) of ODPA was dissolved in 500 g of NMP. Then, 39.30 g (0.065 mol) of the hydroxyl group-containing diamine compound obtained in Synthesis Example 1 and 1.24 g (0.005 mol) of SiDA were added together with 50 g of NMP, followed by reaction at 20 ° C for 1 hour and subsequent reaction at 40 ° C for 2 hours . Subsequently, 10.00 g (0.010 mol) of a diamine (RT-1000) containing propylene oxide and tetramethylene ether glycol structure was added together with 10 g of NMP, and the mixture was reacted at 40 ° C for 1 hour. Next, 4.36 g (0.04 mol) of 4-aminophenol was added as a terminal sealing agent together with 5 g of NMP, and the reaction was carried out at 40 DEG C for 2 hours. Thereafter, a solution obtained by diluting 7.14 g (0.06 mol) of DFA with 50 g of NMP was added dropwise over 10 minutes. After dropwise addition, the mixture was stirred at 40 占 폚 for 3 hours. After the completion of the stirring, the solution was cooled to room temperature, and then the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 DEG C for 24 hours to obtain a polyimide precursor (A-4).

Synthesis Example 6 Synthesis of polyimide (A-5)

(0.08 mole) of BAHF, 1.24 g (0.005 mole) of SiDA and 3.27 g (0.03 mole) of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) as a terminal sealing agent were dissolved in 80 g of NMP . To this was added 31.2 g (0.1 mole) of ODPA together with 20 g of NMP, reacted at 60 DEG C for 1 hour, and then stirred at 180 DEG C for 4 hours. After completion of the stirring, the solution was poured into 3 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 80 ° C for 20 hours to obtain a powder of polyimide (A-5).

Synthesis Example 7 Synthesis of polyimide (A-6)

Under a dry nitrogen gas stream, 31.0 g (0.10 mol) of ODPA was dissolved in 500 g of NMP. Then, 25.60 g (0.070 mol) of BAHF and 1.24 g (0.005 mol) of SiDA were added together with 50 g of NMP, followed by reaction at 20 ° C for 1 hour and subsequent reaction at 40 ° C for 2 hours. Subsequently, 10.00 g (0.010 mol) of a diamine (RT-1000) containing propylene oxide and tetramethylene ether glycol structure was added together with 10 g of NMP, and the mixture was reacted at 40 ° C for 1 hour. Next, 4.36 g (0.04 mol) of 4-aminophenol was added as an end-sealant together with 5 g of NMP, and the mixture was reacted at 60 DEG C for 1 hour, followed by stirring at 180 DEG C for 4 hours. After completion of the stirring, the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 DEG C for 20 hours to obtain a powder of polyimide (A-6).

The component (B), the component (C1), the component (C2), the heat crosslinking agent component, the component (E) and other components used in the examples and comparative examples are shown below.

Component (B):

(B-3): Photopolymerization initiator NCI-831

(C) Component:

(C1) Component: propylene glycol monomethyl ether (PGME) (boiling point 120 캜)

Propylene glycol monomethyl ether acetate (PGMEA) (boiling point 146 DEG C)

(C2) Component: gamma butyrolactone (GBL)

(D-1), (D-2) and (D-3) shown below,

(E) Component:

N, N-dimethylisobutylamide (DMIB): MW: 115; Melting point: -34 캜; Boiling point: 176 ° C

1,3-dimethyl-2-imidazolidinone (DMI) Molecular Weight: 114; Melting point: 8 캜; Boiling point: 222 ℃

Component (F): (F-1)

Other ingredients:

Radical polymerizable compound: dipentaerythritol hexaacrylate (DPHA).

[Examples 1 to 7, Comparative Examples 1 to 4]

The component (C), the heat-crosslinking agent, the component (E), and other components were added to 10 g of the resin (A-1) obtained in Synthesis Example 2 as mass parts shown in Table 1 to prepare varnishes. These properties were measured by the above evaluation method. The measurement results are shown in Table 2.

[Examples 8 to 40, Comparative Examples 5 to 9]

2.0 g of any one of the photosensitive agents (B-1) to (B-3), 10 g of any of the resins (A-1) to (A- , The component (E) and other components were added in the mass parts shown in Tables 3 and 4 to prepare varnishes. These properties were measured by the above evaluation method. The measurement results are shown in Tables 5 and 6.

1 Silicon wafer
1 'semiconductor chip
2 Al pad
3 passivation film
4 insulating film
5 metal film
6 metal wiring
7 insulating film
8 Barrier metal
9 scribe line
10 solder bump
11 sealing resin
12 substrate
13 insulating film
14 insulating film
15 metal film
16 metal wiring
17 metal wiring
18 electrodes
19 Sealing resin
20 support substrate
21 Electrode Pads
22 insulating film
23 metal wiring
24 Cu posts
25 solder bump
26 semiconductor chip
27 TFT
28 Wiring
29 TFT insulating layer
30 planarization layer
31 Transparent electrode
32 substrate
33 Contact hole
34 insulating layer

Claims (18)

(A) at least one resin selected from polyimides, polyimide precursors, polybenzoxazole, polybenzoxazole precursors, other polyamides and copolymers thereof, (D) a heat crosslinking agent having three or more epoxy groups, and ) A resin composition comprising a compound having a tertiary amide structure having a molecular weight of 60 or more and 1000 or less. The resin composition according to claim 1, further comprising (B) a photosensitive agent. The resin composition according to claim 1 or 2, wherein the component (A) is an alkali-soluble resin having a structural unit represented by the general formula (1) or (2)

In the general formula (1), V represents an organic group having 4 to 10 valences, and W represents an organic group having 2 to 8 valences; p and q each represent an integer within the range of 0 to 6; R ¹ represents a group selected from a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group and a thiol group, and when p is 2 or more, plural R ^{1 s} may be the same or different; R ² represents a group selected from a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group and a thiol group; when q is 2 or more, a plurality of R ^{2 s} may be the same or different;

In the general formula (2), X and Y each independently represent a 2 to 8-valent organic group having at least 2 carbon atoms; R ³ and R ⁴ each independently represent hydrogen or an organic group having 1 to 20 carbon atoms; r and s each represent an integer within the range of 0 to 4, and t and u represent an integer within the range of 0 to 2, respectively. The resin composition according to any one of claims 1 to 3, wherein the component (A) contains a group represented by the general formula (3)

In the general formula (3), R ⁵ to R ⁸ each independently represent an alkylene group having 1 to 6 carbon atoms; R ⁹ to R ¹⁶ each independently represent hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms; However, the structures shown in parentheses are different from each other; x, y and z each independently represent an integer of 0 to 35; The resin composition according to any one of claims 1 to 4, wherein the component (E) is at least one compound selected from the compounds represented by the general formulas (4) to (6)

In the general formula (4), Z represents an oxygen atom or a nitrogen atom; R ²⁸ represents an alkyl group having 1 to 10 carbon atoms, or a group in which the alkyl group is substituted by -CO-, -O-, or -OH; R ²⁹ represents an unsubstituted group when Z is an oxygen atom, an alkyl group having 1 to 10 carbon atoms when Z is a nitrogen atom, or a group in which the alkyl group is substituted by -CO-, -O-, or -OH; R ³⁰ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group in which the alkyl group is substituted by -CO-, -O-, or -OH; m represents an integer of 0 to 1, and n represents an integer of 1 to 5;

In the general formula (5), R ³¹ to R ³⁴ each independently represent an alkyl group having 1 to 6 carbon atoms;

In the general formula (6), R ³⁵ and R ³⁶ each independently represent an alkyl group having 1 to 10 carbon atoms, or a group in which the alkyl group is substituted by -CO-, -O- or -OH; Further, R ³⁵ and R ³⁶ may form a cyclic structure; R ³⁷ represents an alkyl group having 1 to 20 carbon atoms, an aromatic group, or a group in which the alkyl group or aromatic group is substituted by -CO-, -O- or -OH. The positive resist composition according to any one of claims 1 to 5, wherein the component (E) is a compound having a melting point of -70 캜 to 15 캜 and a boiling point of 100 캜 to 400 캜, Parts by mass and not more than 1600 parts by mass. The thermosetting resin composition according to any one of claims 1 to 6, wherein, in addition to the component (D), at least one compound selected from trifunctional or higher alkoxymethyl compounds and trifunctional or higher methylol compounds and / And a structural unit represented by the following formula (7):

In the general formula (7), R ³⁸ is a divalent organic group having an alkylene group or an alkylene ether group having 1 to 15 carbon atoms; R ³⁹ and R ⁴⁰ each independently represent a hydrogen atom or a methyl group. The positive resist composition according to any one of claims 1 to 7, further comprising a solvent (C), wherein the solvent (C) comprises (C1) a solvent having a boiling point of 100 占 폚 or more and 150 占 폚 or less , And the content of the component (C1) is 0.1% by mass or more and 40% by mass or less in 100% by mass of the total liquid component. The resin composition according to any one of claims 1 to 8, wherein the resin composition is applied on a substrate so as to have a thickness of 13 탆 after drying, and the resin composition obtained by heating and drying at 120 캜 for 3 minutes contains the content of the component (E) Is not less than 0.001 mass% and not more than 30 mass%. A cured film obtained by curing the resin composition according to any one of claims 1 to 9. The cured film according to claim 10, wherein the content of the component (E) contained in the cured film is 0.05 ppm or more and 1000 ppm or less. A process for producing a resin film, comprising the steps of applying the resin composition according to any one of claims 1 to 9 onto a substrate and drying to form a resin film, an exposure step for exposing the resin film, a developing step for developing the exposed resin film, And a heat treatment step of heating the film. A semiconductor device having a metal wiring and an insulating film, the semiconductor device having the cured film according to claim 10 or 11 as an insulating film. 14. The semiconductor device according to claim 13, wherein a width of the metal wiring and a distance between adjacent wirings are 5 mu m or less. The semiconductor device according to claim 13 or 14, further comprising a semiconductor chip, wherein the metal wiring is electrically connected to the semiconductor chip. The semiconductor device according to claim 15, wherein the semiconductor chip is sealed with a sealing resin, the insulating film is disposed as an interlayer insulating film on the semiconductor chip and the sealing resin, and the metal interconnection is disposed on the interlayer insulating film. 17. The semiconductor device according to claim 15 or 16, wherein a plurality of re-wiring layers including a wiring and an interlayer insulating film are laminated, and the width of the metal wiring of the re- Is equal to or narrower than the width of the metal wiring of the re-wiring layer farther from the semiconductor chip and the distance between the adjacent wirings. Laminating a plurality of re-wiring layers including a metal wiring and the cured film according to claim 10 or 11 on a supporting substrate on which an attaching material is disposed;
A step of arranging a semiconductor chip and a sealing resin thereon to manufacture a semiconductor package,
And then peeling off the support substrate and the semiconductor package.

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