JP2003287889A - High heat resistant photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high-performance photosensitive resin composition having excellent lithography properties and a relief pattern after heat curing having extremely high heat resistance and chemical resistance. SOLUTION: (A) a polyamide having a photopolymerizable unsaturated double bond, (B) a monomer having a photopolymerizable unsaturated double bond, (C) a photopolymerization initiator, and (D) a thermal crosslinking agent. A photosensitive resin composition containing is prepared.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photosensitive resin composition used for forming a heat resistant relief pattern such as an insulating material for electronic parts or a passivation film, a buffer coat film, an interlayer insulating film in a semiconductor device.

[0002]

2. Description of the Related Art Conventionally, a polyimide resin having excellent heat resistance, electrical characteristics and mechanical characteristics has been used as an insulating material for electronic parts, a passivation film for a semiconductor device, a surface protective film, an interlayer insulating film and the like. . Among these polyimide resins, in the case of those provided in the form of a photosensitive polyimide precursor composition, this is applied, exposed, developed, and subjected to thermal imidization treatment to form a heat-resistant relief pattern film. It can be easily formed. Such a photosensitive polyimide precursor composition has a feature that the process can be significantly shortened as compared with the case of using a conventional non-photosensitive polyimide.

However, when the above-mentioned photosensitive polyimide precursor composition is used, it is necessary to use a large amount of an organic solvent such as pyrrolidones or ketones as a developing solution in the developing step thereof, which is safe and has a recent environment. Due to growing concern about the problem, measures against organic solvents have been required. In response to this, recently, in the above material field,
Similar to photoresists, various proposals have been made for heat-resistant photosensitive resin materials that can be developed with a dilute alkaline aqueous solution.

In particular, a method using a hydroxypolyamide soluble in an alkaline aqueous solution, for example, a polybenzoxazole precursor, has been attracting attention in recent years. As such a material, for example, a method of mixing the resin with a photoactive component such as quinonediazide and using it as a positive photosensitive material (Japanese Patent Publication No. 1-46862, JP-A-63-96).
162), or a compound having a photopolymerizable unsaturated double bond introduced into a part of the phenolic hydroxyl group of the resin, and having a photopolymerizable unsaturated double bond,
A method of mixing a photopolymerization initiator or the like and using it as a negative photosensitive material (Japanese Patent Laid-Open No. 2002-12665) is known.

According to such a method, the pattern formation after development is easy, the storage stability of the composition is good, and the polybenzoxazole film obtained by heating and curing the precursor is equivalent to polyimide. Due to its thermosetting properties, it has been attracting attention as a promising alternative material for organic solvent developable polyimide precursors. On the other hand, the transition of packaging methods for semiconductor devices using the above materials has been remarkable. In recent years, from the viewpoints of improvement in integration and functions and reduction in chip size, there is a marked tendency to make the package multi-layer wiring, and the conditions under which the polyimide or polybenzoxazole film is exposed in the process of forming the structure are more diverse than before. The chemical resistance to strong acids and strong bases is required.

For the same reason, the mounting method of the semiconductor device on the printed wiring board is a BGA (ball grid array) capable of higher density mounting than the conventional mounting method using metal pins and lead-tin eutectic solder. , CSP (chip size packaging) and the like, polyimide and polybenzoxazole films are changing to a structure in which they directly contact the solder bumps. The solder used is also being replaced with a lead-free solder having a high melting point for the purpose of reducing the environmental load, and the bump solder is generally one having a higher melting point than that for mounting on a substrate. That is, the polyimide or polybenzoxazole film is exposed to a higher temperature than ever before, while being in contact with the flux in the solder bump reflow process, etc., so that further heat resistance and high temperature flux resistance are required. It's coming.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for forming a relief pattern having extremely high heat resistance and chemical resistance on a substrate after heat curing and a high-performance photosensitivity used therefor. It is to provide a resin composition. Another object of the present invention is to provide a method for producing a semiconductor device using the method or the photosensitive resin composition.

[0008]

Means for Solving the Problems The inventors of the present invention have made extensive studies in order to solve the above-mentioned problems, and as a result, have found that a thermal cross-linking agent, that is, a polyamide film after pattern formation is heated at 200 ° C. or higher to obtain polyimide, or At the time of conversion into a polybenzoxazole skeleton structure, at the same time, a compound capable of undergoing intermolecular crosslinking or forming a crosslinked network by itself is added to the specific photosensitive resin composition used in the present invention. As a result, they have found that the aforementioned problems can be solved at a high level, and have completed the present invention.

That is, the present application provides the following inventions. (I) (A) Polyamide having photopolymerizable unsaturated bond: 100 parts by mass, (B) Monomer having photopolymerizable unsaturated double bond: 1
To 50 parts by mass, (C) photopolymerization initiator: 1 to 20 parts by mass, (D) thermal crosslinking agent: 5 to 30 parts by mass, and a photosensitive resin composition. (II) The polyamide having a photopolymerizable unsaturated double bond (A) is a polybenzoxazole precursor having a structural unit represented by the following formula (1), and the above (I The photosensitive resin composition as described in 1) above.

[0010]

[Chemical 11] (In the formula, X₁Is a divalent aromatic group, Y₁Is a tetravalent aromatic
And n is an integer of 2 to 150. R₁, R₂
Are each independently represented by a hydrogen atom or the following formula (2).
Monovalent Organic Group Having a Photopolymerizable Unsaturated Double Bond
And (R₁+ R ₂) = 100 mol%,
(R₁+ R₂), 10 mol% or more, 50 mol% or less
Below is a photopolymerizable unsaturated doublet represented by the following formula (2).
It is a monovalent organic group having a bond.

[0011]

[Chemical 12] However, R ₃ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10. is there. )

(III) (A) A polyamide having a photopolymerizable unsaturated double bond is a polyimide precursor having a structural unit represented by the following formula (3). The photosensitive resin composition according to I).

[Chemical 13] (In the formula, X ₂ is a tetravalent aromatic group, and —COOR ₆
The a group and -COOR ₇ radical -CONH- group in the ortho position to each other. Y ₂ is a divalent aromatic group, and p is 2
Is an integer from 150 to 150. R ₆ and R ₇ are each independently a hydrogen atom, a monovalent organic group having a photopolymerizable unsaturated double bond represented by the following formula (4), or a carbon number of 1
~ 4 aliphatic groups, but not all are hydrogen atoms.

[0013]

[Chemical 14] However, R ₈ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ₉ and R ₁₀ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and q is an integer of 2 to 10. is there. )

(IV) As the thermal cross-linking agent (D), an amino resin and a derivative thereof whose basic unit structure is represented by the following formulas (5) to (9) are used alone or in combination. The above (I) to (I
The photosensitive resin composition according to any one of II).

[Chemical 15]

[0015]

[Chemical 16]

[0016]

[Chemical 17]

[0017]

[Chemical 18]

[0018]

[Chemical 19] (In the formula, R _{11 to} R ₃₀ are each independently a hydrogen atom or a monovalent organic group represented by the following formula (10).

[0019]

[Chemical 20] However, in each formula, R _{11 to} R ₃₀ are not all hydrogen atoms. Z is a hydrogen atom or has 1 carbon atom.
~ 4 aliphatic groups, but not all are hydrogen atoms. )

In the above (IV), it is a preferred embodiment of the present invention that the amino resin and its derivative are melamine resin and its derivative. In addition, the above (I
In V), the degree of polymerization of the amino resin and its derivative is 1.0 or more and 2.2 or less is a preferred embodiment of the present invention. (V) (D) The thermal crosslinking agent is a melamine resin having a degree of polymerization of 1.0 or more and 2.2 or less and a derivative thereof, and the above (I) to (I).
The photosensitive resin composition according to any one of II). (VI)
(D) The thermal crosslinking agent is hexamethoxymethylated melamine, The photosensitive resin composition according to any one of (I) to (III) above.

(VII) (1) Above (I) to (VI)
Applying the photosensitive resin composition according to any one of the
(2) This coating film is exposed to an actinic ray through a patterning mask and exposed, and (3) an unexposed portion of the coating film is dissolved and removed using a developing solution to form a relief pattern, (4) 2
A method of forming a relief pattern having heat resistance and chemical resistance by heating a coating film at a temperature of 00 ° C. or higher and carrying out transformation hardening. (VIII) A method for manufacturing a semiconductor device including the method for forming a relief pattern according to (VII). (IX) A method of manufacturing a semiconductor device, which comprises using the photosensitive resin composition according to any one of (I) to (VI).

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The photosensitive resin composition of the present invention comprises the following four components as essential components. Component A: A polyamide having a photopolymerizable unsaturated double bond group. Component B: a monomer having a photopolymerizable unsaturated double bond group. Component C: Photopolymerization initiator. Component D: Thermal crosslinking agent.

Of these, first, the component A represented by the chemical formula (1) or (2) will be described. <Component A> The resin component in the photosensitive resin composition of the present invention is a polyamide having the structural unit represented by the chemical formula (1) or (3), and is subjected to a heat cyclization treatment at 200 ° C. or higher. , Polybenzoxazole or polyimide. In particular, in the above chemical formula (1), it is useful that the hydroxyl group has a structure as shown below, in which the hydroxyl group is partially replaced with a group containing a photopolymerizable unsaturated double bond.

[0024]

[Chemical 21] (In the formula, X ₁ is a divalent aromatic group, Y ₁ is a tetravalent aromatic group. N is an integer of 2 to 150. R ₁ and R ₂ are each independently a hydrogen atom or the following chemical formula: A monovalent organic group having an unsaturated double bond represented by (2),
When (R ₁ + R ₂ ) = 100 mol%, (R ₁ + R 2
Among ₂ ), 10 mol% or more and 50 mol% or less are monovalent organic groups having a photopolymerizable unsaturated double bond, which are represented by the following formula (2).

[0025]

[Chemical formula 22] However, R ₃ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R ₄ and R ₅ are independently hydrogen or 1 to 3 carbon atoms.
3 is an organic group. m is an integer of 2 to 10. )

In the above chemical formula (1), the divalent aromatic group represented by X ₁ has the following structures, but is not limited thereto.

[Chemical formula 23]

Similarly, in the above chemical formula (1), the tetravalent aromatic group represented by Y ₁ has the following structures, but is not limited thereto.

[Chemical formula 24] The polybenzoxazole precursor represented by the above chemical formula (1) of the present invention _first comprises an aromatic dicarboxylic acid or a derivative thereof containing a divalent aromatic group X ₁ and a tetravalent aromatic group Y ₁ . By preparing an amide polycondensate (base polymer) with bis- (o-aminophenol) containing and then introducing a group having a photopolymerizable unsaturated double bond into a part of its hydroxyl group. can get.

(Preparation of Base Polymer) Examples of the dicarboxylic acid containing a divalent aromatic group X ₁ and its derivative which are preferably used in the present invention include, for example, phthalic acid, isophthalic acid, terephthalic acid and 4,4 ′. -Diphenyl ether dicarboxylic acid, 3,4'-diphenyl ether dicarboxylic acid, 3,3'-diphenyl ether dicarboxylic acid, 4,
4'-biphenyldicarboxylic acid, 3,4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid,
4,4'-benzophenone dicarboxylic acid, 3,4'-benzophenone dicarboxylic acid, 3,3'-benzophenone dicarboxylic acid, 4,4'-hexafluoroisopropylidene dibenzoic acid, 4,4'-dicarboxydiphenylamide, 1,4-phenylenediethanoic acid, 1,1-bis (4-carboxyphenyl) -1-phenyl-2,2,
2-trifluoroethane, bis (4-carboxyphenyl) sulfide, bis (4-carboxyphenyl) tetraphenyldisiloxane, bis (4-carboxyphenyl) tetramethyldisiloxane, bis (4-carboxyphenyl) sulfone, bis ( 4-carboxyphenyl)
Methane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,2-bis- (p-carboxyphenyl) propane, 4,4 '-(p- Examples thereof include, but are not limited to, phenylenedioxy) dibenzoic acid, 2,6-naphthalenedicarboxylic acid, acid chlorides thereof, and active ester with hydroxybenztriazole and the like. Also,
These may be used alone or in combination.

The bis (o-aminophenol) containing a tetravalent aromatic group Y ₁ which is preferably used in the present invention is, for example, 3,3, -dihydroxybenzidine,
3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-dihydroxy-4,4'-diaminodiphenyl sulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2,2-bis -(3-amino-4-
Hydroxyphenyl) propane, 2,2-bis- (3-
Amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (3-hydroxy-4-aminophenyl) hexafluoropropane, bis- (3-hydroxy-4-aminophenyl) methane, 2,2-bis −
(3-hydroxy-4-aminophenyl) propane,
3,3'-dihydroxy-4,4'-diaminobenzophenone, 3,3'-dihydroxy-4,4'-diaminodiphenyl ether, 4,4'-dihydroxy-3,
3'-diaminodiphenyl ether, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-diamino-4,4'-dihydroxybiphenyl, 2,5-dihydroxy-1,4-diaminobenzene Examples thereof include, but are not limited to, 4,6-diaminoresorcinol, and a mixture thereof.

For the purpose of improving the adhesion to the substrate, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, together with bis- (o-aminophenol),
It is also possible to copolymerize diaminosiloxanes such as 1,3-bis (3-aminopropyl) tetraphenyldisiloxane. When an aromatic dicarboxylic acid dichloride or an active ester of an aromatic dicarboxylic acid is used, bis- (o) in the presence of a basic compound such as pyridine in a suitable solvent.
The base polymer can be obtained by mixing with (aminophenol).

However, when an aromatic dicarboxylic acid is used, a suitable condensing agent is required. As such a condensing agent, a known dehydration condensing agent can be used, for example,
Dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,
1'-Carbonyldioxy-di-1,2,3-benzotriazole, N, N'-disuccinimidyl carbonate, phosphite ester and the like can be mentioned. Among these, when dicyclohexylcarbodiimide is used, it is preferable to share it with 1-hydroxy-1,2,3-benzotriazole.

The reaction solvent is preferably one which completely dissolves the base polymer to be produced, and examples thereof include N-methyl-2-pyrrolidone, N, N-dimethylacetamide,
Examples include N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, gamma butyrolactone and the like. Besides, ketones, esters, lactones,
As ethers, halogenated hydrocarbons, hydrocarbons, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane,
1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene and the like can be mentioned.
These may be used alone or in combination, if necessary.

When aromatic dicarboxylic acid dichloride is used as a raw material, it is preferable to dissolve it in a nonpolar solvent such as a glycol ether system among others in order to suppress the decomposition and deactivation thereof and to use it for the reaction. After completion of the reaction, the reaction solution is put into a poor solvent for the base polymer, such as water or a mixed solution of water and an aliphatic lower alcohol,
This is dispersed and precipitated, further purified by repeating reprecipitation, and dried in vacuum to isolate the base polymer. In order to further improve the degree of purification, the base polymer solution may be passed through a column in which the anion and cation ion exchange resin is swollen with an appropriate organic solvent and packed to remove the ionic impurities.

(Introduction of group having photopolymerizable unsaturated double bond) Among the component A of the present invention, the polyamide having a photopolymerizable unsaturated double bond group represented by the above chemical formula (1) is It is obtained by redissolving the base polymer obtained by the above reaction in an organic solvent or the like and reacting it with an isocyanate compound having a photopolymerizable unsaturated double bond represented by the following chemical formula (11).

[Chemical 25] (In the formula, R ₃₁ is a hydrogen atom or an aliphatic group having 1 to 3 carbon atoms, R ₃₁ and R ₃₂ are each independently a hydrogen atom or an aliphatic group having 1 to 3 carbon atoms, and r is 2 to 10 Is an integer.)

The isocyanate compound containing a photopolymerizable unsaturated double bond represented by the above chemical formula (11) is
For example, isocyanatoethyl acrylate, isocyanatopropyl acrylate, isocyanatobutyl acrylate, isocyanatopentyl acrylate, isocyanatohexyl acrylate, isocyanatooctyl acrylate, isocyanatodecyl acrylate, isocyanatooctadecyl acrylate, isocyanatoethyl methacrylate, isocyanatopropyl. Methacrylate, isocyanatobutyl methacrylate, isocyanatopentyl methacrylate, isocyanatohexyl methacrylate, isocyanatooctyl methacrylate, isocyanatodecyl methacrylate, isocyanato octadecyl methacrylate, isocyanatoethyl crotonate, isocyanatopropyl crotonate, isocyanatobutyl crotonate, Iso Anat pentyl Crotone - DOO, etc. isocyanatohexyl crotonate the like, preferably 2-isocyanatoethyl methacrylate is used.

The reaction between the base polymer and the isocyanate compound is usually 0 to 100 ° C., preferably 20 to 100 ° C.
It is carried out under a temperature condition of 70 ° C., and as a catalyst, amines such as triethylamine, pyridine, dimethylaminopyridine, quinuclidine, 1,4-diazabicyclo [2,2,2] octane, or dibutyltin dilaurate, dibutyltin diacetate, etc. When such a tin compound is used, the reaction becomes easier.

The organic solvent used in the reaction is preferably a solvent which is inert to the isocyanate group and which completely dissolves the dissolved components including the base polymer and the reaction product. For example, N-methyl-2-pyrrolidone, N, Examples thereof include N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, gamma butyrolactone and the like.
In addition, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate,
Butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene, etc. are also used. can do.
These may be used alone or as a mixture, if necessary.

This reaction product can be directly used for the photosensitive resin composition of the present invention, but if necessary,
It is also possible to use by pouring into a poor solvent for the polymer component produced, such as water or a mixed solution of water and an aliphatic lower alcohol, to disperse and precipitate, and to further purify by repeating reprecipitation, and to use after drying. It is important that the introduction rate of the photopolymerizable isocyanate compound containing an unsaturated double bond into the base polymer is 10 mol% or more and 50 mol% or less with respect to the number of moles of the hydroxyl groups of the base polymer.

When the introduction rate of the isocyanate compound is less than 10 mol% with respect to the number of moles of the hydroxyl groups of the base polymer, the crosslink density during photopolymerization is too low, resulting in low photosensitivity and swelling of the pattern. It is difficult to obtain a practical relief pattern. Similarly, the introduction rate is 5
When it exceeds 0 mol%, the concentration of the phenolic hydroxyl group in the skeleton is excessively reduced, so that the solubility of the obtained polyamide polymer in an alkaline aqueous solution developer is extremely low,
It is not practical because unexposed areas are likely to remain unmelted after development. Since the isocyanate compound has a high activity, a reaction in which the isocyanate compound itself partially dimerizes through the water dissolved in the reaction solution is unavoidable. Therefore, the amount of the isocyanate compound charged in the actual reaction needs to be slightly higher than the target introduction rate, and is preferably 10 to 80 mol% with respect to the number of moles of the hydroxyl group of the base polymer.

Further, as the component A of the present invention, a polyimide precursor having a structural unit represented by the following formula (3) is also useful.

[Chemical formula 26] (In the formula, X ₂ is a tetravalent aromatic group, and —COOR ₆
The a group and -COOR ₇ radical -CONH- group in the ortho position to each other. Y ₂ is a divalent aromatic group, and p is 2
Is an integer from 150 to 150. R ₆ and R ₇ are each independently a hydrogen atom, a monovalent organic group having a photopolymerizable unsaturated double bond represented by the following formula (4), or a carbon number of 1
~ 4 saturated aliphatic groups, but not all are hydrogen atoms.

[0041]

[Chemical 27] However, R ₈ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ₉ and R ₁₀ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and q is an integer of 2 to 10. is there. )

In the above chemical formula (3), examples of the tetravalent aromatic group represented by X ₂ include the following structures.
It is not limited to these.

[Chemical 28]

In the above chemical formula (3), examples of the divalent aromatic group represented by Y ₂ include the following structures.
It is not limited to these.

[Chemical 29]

[0044]

[Chemical 30] The polyimide precursor represented by the chemical formula (3) of the present invention first comprises an aromatic tetracarboxylic dianhydride containing a tetravalent aromatic group X ₂ and a photopolymerizable unsaturated double bond. After reacting the alcohols and / or saturated aliphatic alcohols having 1 to 4 carbon atoms to prepare a half acid / half ester compound, this is reacted with an aromatic diamine containing a divalent aromatic group Y _2. It is obtained by amide polycondensation between.

(Preparation of Half Acid / Half Ester Form) The tetracarboxylic acid dianhydride containing a tetravalent aromatic group X ₂ which is preferably used in the present invention includes, for example, pyromellitic dianhydride and diphenyl ether-3. , 3 ', 4,
4'-tetracarboxylic dianhydride, benzophenone-
3,3 ′, 4,4′-tetracarboxylic dianhydride, biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, diphenylsulfone-3,3 ′, 4,4′-tetra Carboxylic acid dianhydride, diphenylmethane-3,3 ',
4,4'-Tetracarboxylic acid dianhydride, 2,2-bis (3,4-phthalic anhydride) propane, 2,2-bis (3,4-phthalic anhydride) -1,1,1,3 , 3,3-
Hexafluoropropane etc. can be mentioned,
It is not limited to these. In addition, these may be used alone or as a mixture of two or more kinds.

Examples of alcohols having a photopolymerizable unsaturated double bond, which are preferably used in the present invention, include:
2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2
-Hydroxyethyl vinyl ketone, 2-hydroxy-3
-Methoxypropyl acrylate, 2-hydroxy-3
-Butoxypropyl acrylate, 2-hydroxy-3
-Phenoxypropyl acrylate, 2-hydroxy-
3-butoxypropyl acrylate, 2-hydroxy-
3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate,
2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3. -Butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-
Hydroxy-3-butoxypropyl methacrylate, 2
Examples thereof include -hydroxy-3-t-butoxypropyl methacrylate and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

In addition to the above alcohols, saturated aliphatic alcohols having 1 to 4 carbon atoms such as methanol, ethanol,
It is also possible to partially mix and use n-propanol, isopropanol, n-butanol, tert-butanol and the like. The aromatic dianhydride and alcohols suitable for the present invention, in the presence of a basic catalyst such as pyridine,
By stirring and dissolving in a suitable solvent and mixing, the esterification reaction of the acid anhydride proceeds, and the desired half acid /
A half ester body can be obtained. The reaction solvent is preferably one that completely dissolves the half acid / half ester compound and the polyimide precursor which is an amide polycondensation product of the half acid / half ester compound and the diamine component.
Methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, gammabutyrolactone and the like can be mentioned.

In addition, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate. , Diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane,
1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene and the like can be mentioned.
These may be used alone or as a mixture, if necessary.

(Preparation of Polyimide Precursor) To the above half acid / half ester solution, under ice cooling, a suitable dehydrating condensing agent such as dicyclohexylcarbodiimide, 1
-Ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1'-carbonyldioxy-di-1,
2,3-benzotriazole, N, N'-disuccinimidyl carbonate and the like are added and mixed to form a half acid / half ester compound as a polyanhydride, and then a divalent aroma suitably used in the present invention. A target polyimide precursor can be obtained by adding dropwise a diamine containing a group Y ₁ dissolved or dispersed in a solvent and subjecting it to amide polycondensation.

The diamines containing a divalent aromatic group Y ₁ which are preferably used in the present invention include, for example, p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether and 3,4 ′. -Diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,
4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4 '
-Diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diamino Diphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,
4-bis (4-aminophenoxy) benzene, 1,3-
Bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-
Aminophenoxy) phenyl] sulfone, bis [4-
(3-Aminophenoxy) phenyl] sulfone, 4,4
-Bis (4-aminophenoxy) biphenyl, 4,4-
Bis (3-aminophenoxy) biphenyl, bis [4-
(4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether,
1,4-bis (4-aminophenyl) benzene, 1,3
-Bis (4-aminophenyl) benzene, 9,10-bis (4-aminophenyl) anthracene, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-
Aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl) propane, 2,2-bis [4- (4-aminophenoxy) phenyl) hexafluoropropane, 1,4-bis (3-Aminopropyldimethylsilyl) benzene, ortho-tolidine sulfone, 9,9-bis (4-aminophenyl) fluorene, and some of the hydrogen atoms on these benzene rings are methyl, ethyl, or hydroxymethyl. Substituted with a group, a hydroxyethyl group, a halogen, etc., for example, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'- Dimethyl-4,4'-diaminodiphenylmethane, 2,2'-Dimethyl-4,4'-diaminodiphenylmethane, 3,3'- Mechitokishi-4,4 '-
Diaminobiphenyl, 3,3'-didichloro-4,4 '
-Diaminobiphenyl, a mixture thereof, and the like, but not limited thereto.

In order to improve the adhesion to various substrates, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (3-aminopropyl) tetraphenyldisiloxane, etc. It is also possible to copolymerize diaminosiloxanes. After completion of the reaction, the water-absorbing by-product of the dehydration-condensation agent coexisting in the reaction solution is filtered, if necessary, and then the obtained polymer such as water or an aliphatic lower alcohol, or a mixed solution thereof is obtained. The poor solvent of the component is added, the polymer component is precipitated, further redissolved, purified by repeating the reprecipitation precipitation operation, and vacuum dried,
Isolate the desired polyimide precursor component. In order to further improve the degree of purification, a solution of this polymer may be passed through a column in which an anion-cation exchange resin is swollen with an appropriate organic solvent and packed to remove ionic impurities.

Next, the monomer having a photopolymerizable unsaturated double bond group and the component B will be described. <Component B> As the monomer having a photopolymerizable unsaturated double bond group used as the component (B) of the photosensitive resin composition of the present invention, a (meth) acrylic compound polymerizable by a photopolymerization initiator is used. Are preferred, for example, polyethylene glycol diacrylate (the number of each ethylene glycol unit is 2 to 20), polyethylene glycol dimethacrylate (the number of each ethylene glycol unit is 2 to 2).
0), poly (1,2-propylene glycol) diacrylate, poly (1,2-propylene glycol) dimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, glycerol diacrylate, glycerol dimethacrylate, dipentaerythritol hexaacrylate. , Methylenebisacrylamide, N-methylolacrylamide, ethylene glycol diglycidyl ether-methacrylic acid adduct, glycerol diglycidyl ether-acrylic acid adduct, bisphenol A diglycidyl ether-acrylic acid adduct, bisphenol A diglycidyl ether-
Methacrylic acid adducts, N, N′-bis (2-methacryloyloxyethyl) urea and the like can be mentioned, but the invention is not limited thereto. In addition, when these are used, they may be used alone or as a mixture of two or more thereof, if necessary.

The amount added is based on the component A of the present invention.
It is preferably 1 to 50 parts by mass. However, when the component A of the present invention is a polybenzoxazole precursor, it is 10
To 50 parts by mass, preferably 20 to 50 parts by mass, more preferably 30 to 45 parts by mass. When the component A of the present invention is a polyimide precursor, the amount is 1 to 50 parts by mass, preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass. This is because if the amount added is less than 1 part by mass, the photosensitivity is low because the crosslinking density during photopolymerization is too low, so that the pattern after development is severely swollen and a practical relief pattern can be obtained. This is because it is difficult, and when the amount added exceeds 50 parts by mass, the crosslink density during photopolymerization becomes too high, and the influence of scattered light from the substrate surface on the unexposed area becomes large during exposure. This is because residues are likely to occur in the unexposed area after development, which is not preferable.

Next, the C component of the photopolymerization initiator will be described. <Component C> Examples of the photopolymerization initiator used as the component (C) of the photosensitive resin composition of the present invention include (a) benzophenone, methyl o-benzoylbenzoate, and 4-benzoyl-4′-methyldiphenyl. Benzophenone derivatives such as ketones, dibenzyl ketone, fluorenone,
(B) 2,2'-Diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, acetophenone derivatives such as 1-hydroxycyclohexylphenyl ketone, (c) thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethyl Thioxanthone derivatives such as thioxanthone, (d) benzyl derivatives such as benzyl, benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal, (e) benzoin derivatives such as benzoin and benzoin methyl ether, (f) 1-phenyl-1,2 -Butanedione-2
-(O-Methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime , 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, 1,3-diphenylpropanetrione-
Preferred examples include oximes such as 2- (o-ethoxycarbonyl) oxime and 1-phenyl-3-ethoxypropanetrione-2- (o-benzoyl) oxime, but the invention is not limited thereto. In addition, these may be used alone or as a mixture of two or more kinds.

Among the above-mentioned photopolymerization initiators, the oximes of (f) are more preferable in view of photosensitivity. The addition amount is 1 to 20 parts by mass with respect to the component A of the present invention,
It is preferably 2 to 10 parts by mass, more preferably 4 to 8 parts by mass. This is because when the addition amount is less than 1 part by mass, radicals sufficient for the photo-radical polymerization to be sufficiently supplied are not supplied at the time of exposure, so that the photosensitivity is low and the pattern swells sharply after development, which is not practical. This is because it is difficult to obtain a relief pattern, and conversely, if the addition amount exceeds 20 parts by mass, the absorption of exposure light near the surface of the coating film becomes too large, so that the exposure light reaches near the substrate surface. This is because photocrosslinking becomes non-uniform in the film thickness direction and it is difficult to obtain a practical relief pattern.

Next, the thermal crosslinking agent as the component D will be described. <Component D> The thermal cross-linking agent of the component D used in the present invention is a compound which can simultaneously cross-link the component A or itself can form a cross-linked network during the heat cyclization treatment of the component A. , Amino resins or derivatives thereof are preferably used. Among them, urea resin, glycol urea resin, hydroxyethylene urea resin, melamine resin, whose basic unit structure is represented by the following chemical formulas (5) to (9),
Benzoguanamine resin, and derivatives thereof are preferably used, and when these are used in the photosensitive resin composition of the present invention, the polybenzoxazole and the polyimide film after the heat curing treatment have excellent heat resistance and resistance that have not been obtained in the past. Exhibits chemical resistance and high temperature flux resistance.

[0057]

[Chemical 31]

[0058]

[Chemical 32]

[0059]

[Chemical 33]

[0060]

[Chemical 34]

[0061]

[Chemical 35] (In the formula, R _{11 to} R ₃₀ are each independently a hydrogen atom or a monovalent organic group represented by the following formula (10).

[0062]

[Chemical 36] However, in each formula, R _{11 to} R ₃₀ are not all hydrogen atoms. Z is a hydrogen atom or has 1 carbon atom.
~ 4 aliphatic groups, but not all are hydrogen atoms. )

Among the above amino resins and their derivatives, the use of melamine resins and their derivatives,
The effect of the present invention is maximized, which is more preferable. R _{11 to} R ₃₀ in the above formulas (5) to (9) each independently represent any one of a hydrogen atom, a hydroxymethyl group, and an alkoxymethyl group, all of which are hydrogen atoms, that is, urea, Glycol urea, hydroxyethylene urea, melamine, and benzoguanamine itself cannot be expected to have the “thermal crosslinking” effect of the compound in the present invention.
The "thermal crosslinking" effect can be expected when at least two or more of the sites are substituted with a hydroxymethyl group and / or an alkoxymethyl group, and the higher the degree of this substitution is, the polyamide of the present invention and The intermolecular cross-linking efficiency of the heat-modified polybenzoxazole or polyimide can be increased.

Further, comparing the one substituted with a hydroxymethyl group and the one substituted with an alkoxymethyl group, the one substituted with an alkoxymethyl group has a lower self-condensation property, and therefore, the photosensitive resin composition of the present invention. It is more preferable because the storage stability of the product can be improved. Specific examples of the alkoxymethyl group include a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an iso-propoxymethyl group, an n-butoxymethyl group, and a tert-butoxymethyl group. , But is not limited to this. Further, the alkoxymethyl group-substituted site may have a structure of only one of the above-mentioned preferred examples, or may have a structure in which a plurality of types are mixed, but stability and cross-linking efficiency are taken into consideration. Then, it is preferable that Z in the above chemical formula (10) has a lower molecular weight, and thus R _{11 to} R in the above chemical formulas (5) to (9) are preferable.
_The case where ₃₀ is a methoxymethyl group is most consistent with the object of the present invention.

The amino resin and its derivative preferably used in the present invention have the basic unit structure itself represented by the above chemical formulas (5) to (9) when the degree of polymerization is 1.0. Further, when the degree of polymerization exceeds 1.0, usually, a part of the nitrogen atoms in the chemical formulas (5) to (9) is
A polymer component composed of a plurality of dimer or more components, which is linked to a nitrogen atom of an adjacent basic unit structure through a CH ₂ — or —CH ₂ —O—CH ₂ — structure, and a basic unit structure It is obtained as a mixture with the monomer component which is itself, and the degree of polymerization thereof is usually represented by the weighted average degree of polymerization according to the peak area ratio of GPC (gel permeation chromatography).

In the present invention, those having a degree of polymerization (GPC peak area ratio weighted average degree of polymerization) of the above-mentioned amino resin which is suitably used are constituted by only a single component having the degree of polymerization. The polymerization degree (GPC peak area ratio weighted average degree of polymerization) may be 1 or a mixture of a monomer component and a plurality of dimer or higher polymer components. It is preferably 0.0 or more and 2.2 or less. This is because the higher the degree of polymerization of the amino resin, the lower the compatibility with the main component, polyamide, in the photosensitive resin composition of the present invention, so that the resin itself tends to aggregate, and at the same time the amino resin This is because self-condensation also tends to occur, and when the degree of polymerization exceeds 2.2, the amino resin component tends to precipitate, and the storage stability of the composition tends to decrease.

The amount of addition is 5 to 30 parts by mass, preferably 5 to 20 parts by mass with respect to the polyamide A component of the present invention.
Parts by mass, more preferably 8 to 15 parts by mass. This is because when the added amount is less than 5 parts by mass, the effects of the present invention, that is, the effect of improving the heat resistance and chemical resistance of the polybenzoxazole or polyimide film, becomes extremely thin, and the added amount is 30 parts by mass. If it exceeds the above, although the various effects of the present invention are sufficient, in the photosensitive resin composition, the photosensitive resin composition itself tends to agglomerate, and at the same time self-condensation between amino resins is likely to occur, so that the amino resin component may be precipitated. ,
This is because the storage stability of the composition tends to decrease significantly.

In addition to the above four components, a sensitizer for improving photosensitivity can be added to the photosensitive resin composition of the present invention, if desired. Examples of such sensitizers include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzylidene) cyclopentanone, 2,6.
-Bis (4'-diethylaminobenzylidene) cyclohexanone, 2,6-bis (4'-dimethylaminobenzylidene) -4-methylcyclohexanone, 2,6-bis (4'-diethylaminobenzylidene) -4-methylcyclohexanone, 4, 4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone,
2- (4'-dimethylaminocinnamylidene) indanone, 2- (4'-dimethylaminobenzylidene) indanone, 2- (p-4'-dimethylaminobiphenyl) benzothiazole, 1,3-bis (4-dimethyl) Aminobenzylidene) acetone, 1,3-bis (4-diethylaminobenzylidene) acetone, 3,3′-carbonyl-
Bis (7-diethylaminocoumarin), 3-acetyl-
7-Dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N -Phenyl-N-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N
-Phenylethanolamine, 4-morpholinobenzophenone, isoamyl 4-dimethylaminobenzoate, 4-
Isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto-
1,2,3,4-tetrazole, 1-cyclohexyl-
5-mercapto-1,2,3,4-tetrazole, 1-
(Tert-Butyl) -5-mercapto-1,2,3,4-
Tetrazole, 2-mercaptobenzothiazole, 2-
(P-dimethylaminostyryl) benzoxazole,
2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylaminostyryl) naphtho (1,
Examples thereof include 2-p) thiazole and 2- (p-dimethylaminobenzoyl) styrene, but are not limited thereto. In addition, when using it, 2
It may be a mixture of two or more species. The amount added is preferably 15 parts by mass or less with respect to the polyamide component, although there is a balance with the amount of other additive components.

A diluting solvent may be used to form a varnish of the photosensitive resin composition. As such a solvent component, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-
Examples thereof include, but are not limited to, pyrrolidone, dimethylsulfoxide, hexamethylphosphoramide, pyridine, gammabutyrolactone, diethylene glycol monomethyl ether, and diethylene glycol dimethyl ether. When used, it may be used alone or as a mixture of two or more kinds.

If desired, a polymerization inhibitor may be added to the photosensitive resin composition of the present invention in order to improve the viscosity of the composition solution during storage and the stability of photosensitivity. Examples of such a polymerization inhibitor include hydroquinone and N-
Nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6
-Di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N- Sulfopropylamino)
Phenol, N-nitroso-N-phenylhydroxyamine ammonium salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N-
(1-naphthyl) hydroxylamine ammonium salt,
Bis (4-hydroxy-3,5-tert-butyl) phenylmethane and the like can be used, but the present invention is not limited thereto. The addition amount thereof is preferably 5 parts by mass or less with respect to the polyamide component of the present invention. This is because if the addition amount exceeds 5 parts by mass, the photocrosslinking reaction itself, which is expected originally, may be hindered and the photosensitivity may be lowered. In addition to the above, the photosensitive resin composition of the present invention includes scattered light absorbers, coating smoothing agents, silane coupling agents, and other properties of the photosensitive resin composition of the present invention. Unless necessary, if necessary,
Various additives can be appropriately mixed.

Use examples of the photosensitive resin composition of the present invention are shown below. First, the composition is applied to a suitable substrate such as a silicon wafer, a ceramic or an aluminum substrate. As a coating method, a spin coater, a spray coater, dipping, printing, a blade coater, roll coating or the like can be used. After prebaking at 80 to 120 ° C. to dry the coating film, an actinic ray is irradiated through a desired photomask using an exposure projection device such as a contact aligner, a mirror projection, and a stepper. As actinic radiation,
X-rays, electron beams, ultraviolet rays, visible rays, etc. can be used,
In the present invention, it is preferable to use one having a wavelength of 200 to 500 nm. In terms of pattern resolution and handleability, the light source wavelength is especially UV-i rays (365 nm).
Is preferred, and a stepper is preferred as the exposure projection device. After that, for the purpose of improving the photosensitivity, any combination of temperature and time (preferably the temperature of 4
A post-exposure bake (PEB) or a pre-development bake may be applied at 0 ° C. to 120 ° C. for 10 seconds to 240 seconds.

Next, development is carried out, but it can be carried out by selecting from a method such as a dipping method, a paddle method and a rotary spray method. As the developer, when the coating film is composed of the alkali-soluble polybenzoxazole precursor composition of the present invention, sodium hydroxide, sodium carbonate, sodium silicate, inorganic alkalis such as aqueous ammonia, ethylamine, diethylamine, Aqueous solutions of organic amines such as triethylamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide, and water-soluble organic solvents such as methanol and ethanol as necessary. It is possible to use those to which an appropriate amount of a surfactant or the like is added.

When the coating film is composed of the polyimide precursor composition of the present invention, a good solvent can be used alone or a good solvent and a poor solvent can be appropriately mixed and used as a developing solution. Examples of the good solvent include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, gamma butyrolactone, α-acetyl-gamma butyrolactone and cyclopenta. Non, cyclohexanone, etc. are used as the poor solvent, such as toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and water. When a good solvent and a poor solvent are mixed and used, the mixing ratio is adjusted depending on the solubility of the polyimide precursor composition coating film used and the developing method used.

After completion of development, washing with a rinse solution is performed.
By removing the developing solution, a patterning coating film is obtained. As the rinse liquid, distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and the like can be used alone or in an appropriate mixture, or can be used in combination stepwise. The polyamide patterning coating film thus obtained is heated to 200 ° C. or higher to proceed with the dehydration cyclization reaction to be converted into a polybenzoxazole film or a polyimide film having excellent heat resistance and chemical resistance. It Such heat cyclization reaction is carried out on a hot plate,
It can be carried out using an inert oven or a temperature rising oven that can set a temperature program. Air may be used as the atmospheric gas at the time of heat cyclization, nitrogen,
You may use inert gas, such as argon. A semiconductor device can be manufactured from the photosensitive resin composition containing the above-mentioned polyamide. Moreover, a semiconductor device can be manufactured by using the above-described method for forming a relief pattern using a polybenzoxazole film or a polyimide film.

Examples of embodiments of the present invention will be described in detail below with reference to examples.

Reference Example 1 (Polybenzoxazole precursor PBO-
Synthesis of 1) In a separable flask having a volume of 2 L, N, N
-436 g of dimethylacetamide (DMAc), 13.45 g (0.17 mol) of pyridine, 2,2-bis (3
-Amino-4-hydroxyphenyl) hexafluoropropane (6FAP) 124.53 g (0.34 mol)
Were mixed and stirred at room temperature (24 ° C.) to dissolve them. to this,
Separately diethylene glycol dimethyl ether (DMD
G) 82.63 g (0.2%) of diphenyl ether-4,4'-dicarbonyl dichloride (DEDC) in 248 g.
What melt | dissolved 8 mol) was dripped from the dropping funnel. At this time, the separable flask was cooled in a water bath at 15 to 20 ° C. The time required for dropping was 20 minutes, and the reaction liquid temperature was 30 ° C. at the maximum. Stir for 1 hour from the end of dropping,
Then, the reaction solution was added dropwise to 5 L of water under high-speed stirring to disperse and precipitate the produced polymer, which was recovered and washed appropriately with water,
After dehydration, vacuum drying was performed to obtain a polybenzoxazole precursor having amino groups at both ends. Polystyrene equivalent GPC weight average molecular weight of this polymer (THF solvent)
Is 10,300, the residual solvent ratio is 13.95%, and the yield is 86.
It was 51%.

(Photosensitive Polybenzoxazole Precursor P
Synthesis of SP-1) 100 g of the dry powder of PBO-1 obtained above was put in a separable frass lasco having a volume of 1 L,
Gamma-butyrolactone (GBL) (400 g) was added and redissolved, dibutyltin dilaurate (0.85 g) was added, and the mixture was heated to 50 ° C. in an oil bath. In addition to this, GBL5
16.9 g of 2-isocyanatoethyl methacrylate
15 g of dissolved 4 g (0.109 mol, which corresponds to 35 mol% of all hydroxyl groups of PBO-1 calculated from the yield of PBO-1 and the amount used in the reaction).
It dripped over minutes. After completion of dropping, the mixture was stirred at 50 ° C. for 4 hours. After 4 hours, this reaction solution was added dropwise to 4 L of ion-exchanged water, and the polymer precipitated at that time was separated and washed at 50 ° C.
By vacuum drying for 24 hours, a photosensitive polybenzoxazole precursor PSP-1 having a photopolymerizable unsaturated double bond was obtained.

In this reaction, isocyanate reacts predominantly with the amino group at the end of the polymer, but also with the hydroxyl group in the polymer skeleton, so a urea bond is present at the polymer end and a urethane bond is present at a part of the hydroxyl group in the skeleton. The structure has a methacrylate group introduced through.
The 1H-NMR spectrum of this polymer was measured, and the sum of integrated intensities derived from hydrogen atoms on the aromatic ring of the repeating unit portion of the skeleton and the hydrogen atom at the tip of the carbon-carbon double bond of the introduced methacrylate group. The introduction rate of the methacrylate group to the entire skeleton can be calculated from the ratio with the integrated intensity derived from the two. In the case of this example, the introduction rate of methacrylate groups was 28.
It was calculated to be 6%.

[0078]

[Reference Example 2] (Photosensitive polybenzoxazole precursor P
Synthesis of SP-2) 100 g of the dry powder of PBO-1 obtained in Reference Example 1 was placed in a separable flask having a volume of 1 L,
Gamma-butyrolactone (GBL) (400 g) was added and redissolved, dibutyltin dilaurate (1.57 g) was added, and the mixture was heated to 50 ° C. in an oil bath. In addition to this, GBL9
2-isocyanatoethyl methacrylate 31.3 to 4 g
30 g of dissolved 5 g (0.202 mol, which corresponds to 65 mol% of all hydroxyl groups of PBO-1 calculated from the yield of PBO-1 and the amount used in the reaction)
It dripped over minutes. After completion of dropping, the mixture was stirred at 50 ° C. for 4 hours. After 4 hours, this reaction solution was added dropwise to 4 L of ion-exchanged water, and the polymer precipitated at that time was separated and washed at 50 ° C.
By vacuum-drying for 24 hours, a photosensitive polybenzoxazole precursor PSP-2 was obtained. The introduction rate of the methacrylate group calculated by the same method as in Reference Example 1 was 55.3% with respect to all the hydroxyl groups in the skeleton.

[0079]

[Reference Example 3] (Photosensitive polybenzoxazole precursor P
Synthesis of SP-3) 100 g of the dry powder of PBO-1 obtained in Reference Example 1 was placed in a separable flask having a volume of 1 L,
Gamma-butyrolactone (GBL) (400 g) was added and redissolved, dibutyltin dilaurate (0.24 g) was added, and the mixture was heated to 50 ° C. in an oil bath. In addition to this, GBL1
2-isocyanatoethyl methacrylate 4.81 in 5 g
g (0.031 mol, which is calculated from the yield of PBO-1 and the amount used for the reaction and corresponds to 10 mol% of all the hydroxyl groups of PBO-1) was dissolved over 10 minutes. Dropped. This reaction liquid was added dropwise to 4 L of ion-exchanged water, and the polymer precipitated at that time was separated and washed, then at 50 ° C.
By vacuum drying for 24 hours, a photosensitive polybenzoxazole precursor PSP-3 was obtained. The introduction rate of methacrylate groups calculated by the same method as in Reference Example 1 was 8.3% with respect to all the hydroxyl groups in the skeleton.

[0080]

[Reference Example 4] (Synthesis of photosensitive polyimide precursor PSP-4) In a separable flask having a capacity of 5 L, 310.22 g (1.00 mol) of diphenyl ether-3,3 ', 4,4'-tetracarboxylic acid dianhydride was prepared. ), 2-methacryloyloxyethyl alcohol 270.69 g (2.08 m
ol), pyridine 158.2 g (2.00 mol), G
BL 1000 g was added, mixed, and left to stir at room temperature for 16 hours. Dicyclohexylcarbodiimide 40
A solution prepared by dissolving 0.28 g (1.94 mol) in 400 g of GBL was added dropwise under ice cooling over about 30 minutes, and subsequently 4,4′-diaminodiphenyl ether 18 was added.
What dispersed 5.97 g (0.93 mol) in GBL650g was added over about 60 minutes. Ice cold 3
After stirring for 50 hours, 50 g of ethanol was added, the ice-cooled bath was removed, and the mixture was left stirring for 1 hour. After the solid content deposited in the above process was filtered under pressure, 40 L of the reaction solution was added.
Was dropped into ethanol, and the polymer precipitated at that time was separated, washed, and vacuum dried at 50 ° C. for 24 hours to obtain a photosensitive polyimide precursor PSP-4. The polystyrene-converted GPC weight average molecular weight (THF solvent) is 22.
It was 000.

(Preparation of photosensitive resin composition)

Example 1 Photosensitive polybenzoxazole precursor (P
SP-1) 100 parts by mass, tetraethylene glycol dimethacrylate 16 parts by mass, N, N'-bis (2-methacryloyloxyethyl) urea 16 parts by mass, 1-phenyl-1,2-propanedione-2- ( 6 parts by mass of O-benzoyl) oxime, 10 parts by mass of methoxymethylated melamine resin (manufactured by Sanwa Chemical Co., trade name Nicalac, product number MW-30HM, degree of polymerization 1.01) as amino resin, 1-phenyl-5-mercapto -1, 2, 3, 4-
2 parts by mass of tetrazole, 1 part by mass of 4,4′-bis (diethylamino) benzophenone and 0.1 part by mass of N-nitrosodiphenylamine were added and dissolved in 220 parts by mass of N-methyl-2-pyrrolidone (NMP) to form a varnish. To obtain a photosensitive resin composition.

[0082]

Example 2 Photosensitive polybenzoxazole precursor (P
SP-1) 100 parts by mass, tetraethylene glycol dimethacrylate 16 parts by mass, N, N'-bis (2-methacryloyloxyethyl) urea 16 parts by mass, 1-phenyl-1,2-propanedione-2- ( 6 parts by mass of O-benzoyl) oxime, 10 parts by mass of methoxymethylated melamine resin (manufactured by Sanwa Chemical Co., trade name Nicalac, product number MW-30HM, degree of polymerization 1.01) as amino resin, 2 parts by mass of Michler's ketone, N- 0.1 part by mass of nitrosodiphenylamine was added and dissolved in 220 parts by mass of N-methyl-2-pyrrolidone (NMP) to obtain a varnish-like photosensitive resin composition.

[Examples 3 to 10],

Comparative Examples 1 to 3 A varnish-like photosensitive resin composition was obtained in the same manner as in Example 2 except that the amino resin and its addition amount were as shown in Table 1.

[0083]

Example 11 Photosensitive Polyimide Precursor (PSP-4)
To 100 parts by mass, 4 parts by mass of tetraethylene glycol dimethacrylate, 4 parts by mass of 1,3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime,
Methoxymethylated melamine resin as an amino resin (manufactured by Sanwa Chemical Co., trade name Nicalac, product number MW-30H
M, degree of polymerization 1.01) 10 parts by mass, 1-phenyl-5-
2 parts by mass of mercapto-1,2,3,4-tetrazole,
4 parts by mass of N, N-bis (2-hydroxyethyl) aniline and 0.05 part by mass of N-nitrosodiphenylamine were added and dissolved in 150 parts by mass of N-methyl-2-pyrrolidone (NMP) to form a varnish-like photosensitive material. A resin composition was obtained.

[Examples 12 to 13],

Comparative Examples 9 to 11 Varnish-like photosensitive resin compositions were obtained in the same manner as in Example 11 except that the amino resin and the addition amount thereof were as shown in Table 1.

[0084]

[Table 1]

[0085]

[Comparative Examples 4 to 8] A photosensitive polyamide, a compound having a photopolymerizable unsaturated bond group, a photopolymerization initiator, and the addition amounts thereof, which are the components A, B and C of the present invention, are shown in the table below. In the same manner as in Example 2 except that the above is used,
A varnish-like photosensitive resin composition was obtained.

[0086]

[Table 2]

(Preparation of Polyamide Coating Film and Lithographic Evaluation) The varnish compositions obtained in Examples and Comparative Examples of the present invention were pretreated with 3-aminopropyltriethoxysilane in 5 inches. On a silicon wafer,
A spin coater (manufactured by Tokyo Electron, model name: Clean Track Mark 7) was applied and prebaked at 95 ° C. for 3 minutes to obtain a coating film having an initial film thickness of 10 μm. An i-line stepper exposure machine (manufactured by Nikon, model name NS
Through R2005i8A), the exposure amount was changed stepwise in the range of 50 to 500 mJ / cm ² through a photomask for evaluation. After 60 seconds from the end of the exposure, a post exposure bake (P
EB).

Thereafter, regarding Examples 1 to 10 and Comparative Examples 1 to 8, a 2.38% tetramethylammonium hydroxide aqueous solution (manufactured by Clariant Japan, product number AZ30
(0 MIF) is used to perform paddle development for a time that is 1.4 times the time until the unexposed portion completely dissolves and disappears, and then rinsed with pure water for 20 seconds to obtain a negative type patterned coating film. It was Further, regarding Examples 11 to 13 and Comparative Examples 9 to 11, 50/5 of gammabutyrolactone and xylene were used.
Using a 0 (v / v%) mixed solvent, spin spray development was performed for a time in which 1.4 was multiplied by the time until the unexposed portion completely dissolved and disappeared, followed by rinsing with isopropanol for 20 seconds, and negative type A patterned coating film was obtained. The obtained patterned coating film is observed under an optical microscope, and the minimum exposure amount (sensitivity) that gives a sharp pattern without swelling, the resolution of the via hole (rectangular development elution part) at the time of irradiation with the minimum exposure amount (resolution) ), And the presence or absence of coagulated deposits and residues after development were evaluated. Further, the film thickness before and after development in a pattern with an exposure dose of 150 mJ / cm ² was measured, and the rate of change (developing residual film rate) was calculated. The results are shown in Table 3.

(Evaluation of Heat Resistance) Each varnish of Examples and Comparative Examples of the present invention was applied on a 5-inch silicon wafer and prebaked in the same manner as in the above-mentioned lithographic evaluation, and then, a vertical cure furnace (Koyo Lindbergh) was used. Made, model name VF
-2000B) under a nitrogen atmosphere at 350 ° C. for 2
After heat curing for a period of time, a polybenzoxazole and polyimide film having a film thickness of 5 μm after curing was prepared. Dicing saw (made by Disco, model name DAD
-2H / 6T) was cut into a 3.0 mm width, immersed in a hydrofluoric acid aqueous solution and peeled off from the silicon wafer to obtain a strip-shaped film sample. The glass transition temperature (Tg) of this film sample was measured using a thermomechanical analyzer (manufactured by Shimadzu Corporation, model name TMA-50), and used as an index of heat resistance of the polybenzoxazole and the polyimide film. The measurement conditions are: sample length 10 mm, constant load 200 g / mm ² , measurement temperature range 25 ° C to 450 ° C,
The temperature rising rate is 10 ° C./min and the atmosphere is nitrogen. The results are shown in Table 4.

(Evaluation of Chemical Resistance) The patterned coating film obtained by the above-mentioned lithographic evaluation was set in the vertical curing furnace described above, and heat-cured at 350 ° C. for 2 hours in a nitrogen atmosphere. After curing, a patterned polybenzoxazole and polyimide film having a film thickness of 5 μm was prepared.
This was immersed in a resist stripping solution (product number 105, manufactured by Tokyo Ohka Kogyo) heated to 85 ° C. for 1 hour. After cooling this,
It was washed with water, dried, and observed with an optical microscope to evaluate the presence or absence of pattern damage, mainly cracks and wrinkles. Further, the film thickness before and after the chemical immersion was measured, and the change rate (film thickness change rate) was calculated. The results are shown in Table 4.

(Evaluation of High Temperature Flux Resistance) Polybenzoxazole and polyimide films with a pattern similar to those used for chemical resistance evaluation were prepared, and flux (manufactured by Nippon Alpha Metals, trade name: Solbond, product number R5003) was spin-coated (500). It was rotated for 20 seconds). This was subjected to a simulated solder reflow condition using a mesh belt type continuous firing furnace (manufactured by Koyo Lindbergh, model name 6841-20AMC-36) under a nitrogen atmosphere and a peak temperature of 380.
Heated to ° C. At this time, it is important to ensure the objectivity of the evaluation that the heating rate, the residence time near the peak temperature,
It is a standard of temperature profile such as cooling rate, which is a standard of the United States semiconductor industry group, IPC / JEDEC J-STD-, regarding a method of evaluating a semiconductor device.
The solder melting point was standardized on the assumption of the high temperature of 310 ° C. in conformity with the solder reflow condition described in 7.6 of 020A. The film after the above simulated reflow treatment was added to xylene.
It was immersed in 2-propanol for 10 minutes and left still to remove the flux, dried and then observed under an optical microscope to evaluate the damage of the pattern, mainly the presence or absence of cracks and wrinkles. Further, the film thickness before and after the series of treatments was measured, and the change rate (thickness change rate) = (thickness after treatment / thickness before treatment) × 100 (%) was calculated. The results are shown in Table 4.

[0092]

[Table 3]

[0093]

[Table 4]

Comparative Example 1 and Comparative Example 9 are cases in which the amino resin is not included in the requirements of the present invention, but in comparison with this, the Examples of the present invention have excellent lithographic properties and high lithographic properties. It has a very high level of both heat resistance and chemical resistance, and can be said to be a material that is sufficiently fine and can be applied to the manufacturing process of semiconductor devices that are exposed to high temperatures. In Comparative Examples 2 to 3 and Comparative Examples 10 to 11, the addition amount of the amino resin is too smaller than the preferred range of the present invention,
Or too much. Too little (Comparative Example 2,
10), the heat resistance and chemical resistance are insufficient, and conversely, too much (Comparative Examples 3 and 11), the heat resistance and chemical resistance are sufficient, but the residue after development is severe, In any case, it does not reach the embodiment of the present invention.

Comparative Examples 4 to 5 are cases in which the introduction ratio of the photopolymerizable unsaturated bond group in the polyamide which is the component A of the present invention is too small or too large as compared with the preferred range of the present invention. . Further, in Comparative Example 6, the addition amount of the monomer containing the photopolymerizable unsaturated bond, which is the component B of the present invention, was
This is the case when the amount is too much larger than the preferred range of the present invention. Furthermore, Comparative Examples 7 to 8 are cases in which the addition amount of the photopolymerization initiator which is the component C of the present invention is too small or too large as compared with the preferred range of the present invention. In either case, sufficient lithographic properties could not be ensured, which is inferior to the embodiments of the present invention.

[0096]

As described above, the photosensitive resin composition provided by the present invention has excellent lithographic properties of an alkali developing negative type, and at the same time, a coating film of this photosensitive resin composition is formed. The polybenzoxazole or polymide coating obtained by heating and curing has extremely high heat resistance and chemical resistance, and therefore can sufficiently satisfy the recent high demands in the semiconductor device manufacturing process.
Therefore, according to the present invention, it is possible to provide a method for forming a relief pattern having extremely high heat resistance and chemical resistance on a substrate after heat curing, and a high-performance photosensitive resin composition used therefor. . Further, it is possible to provide the method or a method for manufacturing a semiconductor device using the photosensitive resin composition.

Continued front page    (72) Inventor Kimiyuki Maruyama             Asahi Kasei Co., Ltd. 1 No. 2 Samejima, Fuji City, Shizuoka Prefecture             In the company F term (reference) 2H025 AA10 AA13 AB16 AB17 AC08                       AD01 BC13 BC42 BC69 BC70                       CA00 CC17 FA17                 4J027 AC02 AC03 AC04 AD02 BA17                       BA19 BA20 BA26 CC04 CC05                       CD10

Claims (9)

[Claims] 1. (A) Polyamide having photopolymerizable unsaturated bond: 100 parts by mass, (B) Monomer having photopolymerizable unsaturated double bond: 1
To 50 parts by mass, (C) photopolymerization initiator: 1 to 20 parts by mass, (D) thermal crosslinking agent: 5 to 30 parts by mass, and a photosensitive resin composition. 2. (A) having a photopolymerizable unsaturated double bond
Polyamide having a structural unit represented by the following formula (1)
Characterized by being a polybenzoxazole precursor
The photosensitive resin composition according to claim 1. [Chemical 1] (In the formula, X₁Is a divalent aromatic group, Y₁Is a tetravalent aromatic
And n is an integer of 2 to 150. R₁, R₂
Are each independently represented by a hydrogen atom or the following formula (2).
Monovalent Organic Group Having a Photopolymerizable Unsaturated Double Bond
And (R₁+ R ₂) = 100 mol%,
(R₁+ R₂), 10 mol% or more, 50 mol% or less
Below is a photopolymerizable unsaturated doublet represented by the following formula (2).
It is a monovalent organic group having a bond. [Chemical 2] However, R₃Is a hydrogen atom or an organic group having 1 to 3 carbon atoms
R_Four, R_FiveAre each independently a hydrogen atom or charcoal.
An organic group having a prime number of 1 to 3 and m is an integer of 2 to 10. ) 3. The polyamide precursor (A) having a photopolymerizable unsaturated double bond is a polyimide precursor having a structural unit represented by the following formula (3). The photosensitive resin composition according to item 1. [Chemical 3] (In the formula, X ₂ is a tetravalent aromatic group, and —COOR ₆
The a group and -COOR ₇ radical -CONH- group in the ortho position to each other. Y ₂ is a divalent aromatic group, and p is 2
Is an integer from 150 to 150. R ₆ and R ₇ are each independently a hydrogen atom, a monovalent organic group having a photopolymerizable unsaturated double bond represented by the following formula (4), or a carbon number of 1
~ 4 saturated aliphatic groups, but not all are hydrogen atoms. [Chemical 4] However, R ₈ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ₉ and R ₁₀ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and q is an integer of 2 to 10. is there. ) 4. The (D) thermal cross-linking agent is one in which the basic unit structure of the amino resin represented by the following formulas (5) to (9) and its derivative are used alone or in combination. The photosensitive resin composition according to any one of claims 1 to 3, characterized in that. [Chemical 5] [Chemical 6] [Chemical 7] [Chemical 8] [Chemical 9] (In the formula, R _{11 to} R ₃₀ are each independently a hydrogen atom or a monovalent organic group represented by the following formula (10). However, in each formula, R _{11 to} R ₃₀ are not all hydrogen atoms. Z is a hydrogen atom or has 1 carbon atom.
~ 4 aliphatic groups, but not all are hydrogen atoms. ) 5. The thermal crosslinking agent (D) is a melamine resin having a polymerization degree of 1.0 or more and 2.2 or less and a derivative thereof, according to any one of claims 1 to 3. The photosensitive resin composition of. 6. The photosensitive resin composition according to claim 1, wherein the thermal crosslinking agent (D) is hexamethoxymethylated melamine. 7. (1) The photosensitive resin composition according to any one of claims 1 to 6 is applied to a substrate, and (2) this coating film is
Irradiate and expose active light through a patterning mask,
(3) The unexposed portion of the coating film is dissolved and removed using a developing solution to form a relief pattern, and (4) the coating film is heated under a condition of 200 ° C. or higher to be metamorphosed and cured, thereby improving heat resistance,
A method of forming a chemical resistant relief pattern. 8. A method of manufacturing a semiconductor device, including the method for forming a relief pattern according to claim 7. 9. A method of manufacturing a semiconductor device, which comprises using the photosensitive resin composition according to claim 1.