JPH06282071A - Radiation-sensitive resin composition - Google Patents

Abstract

PURPOSE:To form a thick-film pattern having high light transmittance, soluble in solvent and excellent in heat resistance by incorporating a polymer having a specified repeating unit and a radiation-sensitive polymerization initiator into the composition. CONSTITUTION:This composition contains a polymer having a repeating unit shown by the formula and a radiation-sensitive polymerization initiator. In the formula, R1 is a bivalent org. group. the two R2s are the same or different and are hydrogen atom or a group having a radiation-polymerizable carbon- carbon double bond, at least one of the two R2s is a group having a radiation- polymerizable carbon-carbon double bond, the two Zs are the same or different and are oxygen atom or -NH-, and (n) is 0 or 1. A bivalent org. group contg. bivalent aromatic group, aliphatic group and a siloxane bond is exemplified as the bivalent org. group R1. Michler's ketone, benzoin, etc., are singly or jointly used as the radiation-sensitive polymerization initiator.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-sensitive resin composition having high light transmittance and solubility in a solvent, and capable of forming a thick film pattern having excellent heat resistance.

[0002]

2. Description of the Related Art Conventionally, heat-resistant polymers typified by polyimide are excellent in heat resistance, electrical and mechanical properties, and therefore, forming insulating films and passivation films used for solid-state elements in the semiconductor industry. It is widely used as a material, a resist material for forming a pattern of a circuit on a substrate in the field of printed wiring boards, an interlayer insulating material, and the like.

In recent years, in the semiconductor industry, an inorganic material has been used as an interlayer insulating material, but recently, an organic material having excellent heat resistance such as a polyimide resin is used by taking advantage of its characteristics. Has been done.

On the other hand, in the field of printed wiring boards,
Pattern formation of circuits on the substrate is a complicated and diversified process, such as film formation of resist material on the substrate surface, exposure to predetermined locations, removal of unnecessary portions by development, etching, cleaning of the substrate surface, etc. Therefore, there is a demand for the development of a heat-resistant photosensitive material in which the resist material in the necessary portion can be left as it is and used as an insulating material even after the pattern formation.

As such a heat-resistant photosensitive material, a polyimide-based photosensitive material is particularly noted because of its excellent heat resistance, and various proposals have been made. (For example, Japanese Patent Publication Sho-49-173
74, JP-B-55-30207, JP-A-54-10.
9828, JP-A-56-24343, JP-A-60-
(See No. 100143 etc.)

The polyimide-based photosensitive material is composed of a polyimide precursor and a compound having a photosensitive group. After the polyimide precursor is formed on the surface of a substrate, the polyimide precursor is subjected to heat treatment subsequent to exposure and development at a predetermined location. The body changes to a polyimide resin, and a resist pattern using this polyimide resin as a base polymer is formed.

An aromatic type is used as the polyimide precursor in order to improve the heat resistance of the polyimide resin. Due to the aromatic ring, the light transmittance of the photosensitive material in the ultraviolet region is increased. Low.

In addition, most of the drying step of dissolving a photosensitive material composed of an aromatic polyimide precursor and a compound having a photosensitive group in a solvent to prepare a coating solution and forming a coating film from this coating solution Since the solvent volatilizes, the coating film after drying is composed of the aromatic polyimide precursor and the compound having a photosensitive group. Since the compound having this photosensitive group is generally a poor solvent for the aromatic polyimide precursor, a whitening phenomenon occurs in the coating film, and even when the whitened coating film is exposed, light is scattered and as a result. This will result in a decrease in light transmittance in the ultraviolet region. Therefore, it is difficult to form a thick resist pattern with a photosensitive material using an aromatic polyimide precursor having a low light transmittance in the ultraviolet region.

However, when a polyimide-based photosensitive material is used as an insulating material, it is preferable that the film thickness be equal to or larger than the unevenness in order to cancel the unevenness of the underlying circuit and flatten the circuit, and further lower the dielectric constant. It is preferable that a thick film resist pattern can be formed in order to improve the insulating property, and improvement of the polyimide-based photosensitive material is required.

[0010]

The object of the present invention is to form a thick film pattern that functions as both a resist material and an insulating material, has high light transmittance and solubility in a solvent, and is excellent in heat resistance. Another object of the present invention is to provide a radiation-sensitive resin composition capable of

[0011]

The above object of the present invention is to provide the following formula (1):

[0012]

[Chemical 2]

(In the formula (1), R ₁ represents a divalent organic group, two R ₂ are the same or different, and have a hydrogen atom or a radiation-polymerizable carbon-carbon double bond (hereinafter,
It is called a "group having a polymerizable double bond". (Wherein at least one of the two R ₂ is a group having a radiation-polymerizable carbon-carbon double bond), and two Z are
The same or different, each represents an oxygen atom or -NH-,
Radiation-sensitive resin characterized by containing a polymer (A) having a repeating unit represented by the formula (n is 0 or 1) and a radiation-sensitive polymerization initiator (hereinafter referred to as "polymerization initiator"). Achieved by the composition.

The present invention will be described in detail below, but other objects, configurations and advantages of the present invention will be apparent.

First, the polymer (A) will be described. The divalent organic group represented by R ₁ in the above formula (1) is 2
Examples thereof include a divalent aromatic group, a divalent aliphatic group, a divalent alicyclic group, and a divalent organic group containing a siloxane bond.

The following can be preferably exemplified as such a divalent organic group.

Aromatic group: the following formula (2)

[0018]

[Chemical 3]

Aliphatic or alicyclic group: the following formula (3)

[0020]

[Chemical 4]

(In the formula (3), i and j are integers of 1 to 10, A represents cycloalkylene having 3 to 8 carbon atoms, and X ₃ , X ₄ and Y are the same as those in the formula (2). Is the same)

Divalent organic group containing a siloxane bond:
Formula (4) below

[0023]

[Chemical 5]

(In the formula (4), R ₃ represents an alkylene group having 1 to 6 carbon atoms, R ₄ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ₅ represents a hydrogen atom or 1 carbon atom. Represents an alkyl group of 6 and p and q represent an integer of 1 or more)

The group having a polymerizable double bond represented by R ₂ in the above formula (1) is represented by the following formula (5)

[0026]

[Chemical 6]

The group represented by can be exemplified.

In the formula (5), R ₆ , R ₇ and R ₈ are the same or different and each represents a hydrogen atom, a methyl group, a phenyl group, a styryl group, a nitrile group or a furyl group, and R ₉ is 2
Represents a valent hydrocarbon group. Here, 2 represented by R ₉
As the valent hydrocarbon group, an alkylene group having 2 to 20 carbon atoms is preferable, and a linear alkylene group having 2 to 10 carbon atoms is particularly preferable.

Further, when Z in the formula (1) represents an oxygen atom, examples of the group having a polymerizable double bond represented by R ₂ include groups represented by the following formulas (6) to (9). You can

[0030]

[Chemical 7]

In the above formulas (6) to (9), R ₆ , R ₇ and R ₈
And R ₉ are the same as in the case of the above formula (5) including the preferable embodiment. R ₁₀ and R _{11 in} formula (7) are the same or different and each represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. R _{12 in the} formula (8) represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. In the formula (9), r and s represent integers of 1 to 3 and r + s = 4.

The group R ₂ represented by the above formulas (7) to (9)
Is a cation and is bound to the carboxylate present in formula (1) via an ionic bond.

The polymerizable double bond in R ₂ of the formula (1) is a carbon-carbon double bond which is polymerizable by irradiation with radiation including dimerization.

The polymer (A) of the present invention contains a repeating unit represented by the formula (1) as a main component. However, in the composition of the present invention, the following formula (10) is used as long as the solubility and the light transmittance of the polymerizable unsaturated monomer used as necessary are not impaired.

[0035]

[Chemical 8]

The unit represented by the formula (A) can be contained in the polymer (A) in an amount of usually 70 mol% or less, preferably 50 mol% or less.

Examples of the aromatic tetracarboxylic dianhydride of the formula (11) include pyromellitic dianhydride, 3,
3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3, 4,9,10-perylene tetracarboxylic dianhydride, 4,4′-sulfonyldiphthalic dianhydride and the like can be mentioned.

The polymer (A) preferably contains the repeating unit represented by the formula (1) in an amount of 10 mol% or more, particularly 40 mol% or more. When the content of the repeating unit represented by the formula (1) is less than 10 mol%, the light transmittance of the polymer (A) is lowered and the solubility in a solvent is lowered.

The polymer (A) having a repeating unit represented by the above formula (1) is first prepared by the formula (12).

[0040]

[Chemical 9]

By polyadding the compound represented by the formula (wherein n is 0 or 1) and the diamine,
3)

[0042]

[Chemical 10]

A polymer having a repeating unit represented by the formula (wherein R ₁ and n are synonymous with the formula (1)) (hereinafter referred to as “precursor”) is synthesized, and then the precursor is polymerized. It can be obtained by reacting a compound containing a double bond and a group which easily reacts with a carboxyl group.

When the unit represented by the formula (10) is contained in the polymer (A), when the acid anhydride represented by the formula (12) and the diamine are polyadded, the above-mentioned formula (1)
The aromatic tetracarboxylic dianhydride of 1) may be used in combination.

The diamine is represented by the formula (14)

[0046]

[Chemical 11]

(Wherein R ₁ is the same as in the case of the formula (1)) can be used, and specific examples of R ₁ are the above formulas (2), (3) and (4). The same as those shown in can be mentioned.

Specific examples of the diamine include aromatic diamines: m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 4,4'-diaminodiphenylmethane, 4,4 '. -Diaminodiphenylethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminophenyl sulfone, diaminobenzophenone, m-xylylenediamine, p-xylylenediamine Aliphatic diamine: ethylenediamine 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, alicyclic diamine: cyclopropyldiamine, cyclobutyldiamine, cyclo Pentyldiamine, cyclohexyldiamine, cycloheptyldiamine, cyclooctyldiamine, 4,4'-bis (cyclohexylamine), 4,
4'-methylenebis (cyclohexylamine), 4,
4'-ethylenebis (cyclohexylamine), 4,
4'-propylenebis (cyclohexylamine), 4,
4'-tetramethylenebis (cyclohexylamine),
4,4'-bis (aminocyclohexyl) ether, 4,
4'-bis (aminocyclohexyl) sulfide, 4,
4'-bis (aminocyclohexyl) ketone, diamine having a siloxane bond:

[0049]

[Chemical 12]

Diamines such as the above are typical ones, and these can be used alone or in combination of two or more kinds.

The polyaddition reaction between the tetracarboxylic dianhydride of the formula (12) and the aromatic tetracarboxylic dianhydride of the formula (11) optionally used and the diamine of the formula (14) is usually carried out. In an inert organic solvent, the temperature is preferably 0 to 100 ° C, more preferably 5 to 60 ° C.

The molar ratio of tetracarboxylic dianhydride and diamine (tetracarboxylic dianhydride / diamine) is usually 0.8 / 1 to 1.2 / 1, and it is preferable to use approximately equimolar amounts.

As the inert organic solvent used in the above reaction, a polar solvent which completely dissolves the precursor having the repeating unit represented by the above formula (13) is generally preferable, and for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide,
Examples thereof include dimethyl sulfoxide, pyridine, tetramethylurea, hexamethylphosphoric triamide, γ-butyrolactone, N, N-dimethylpropyleneurea and N, N-dimethylethyleneurea. These can be used alone or in combination of two or more. The amount of these inert solvents used is 30 to 99.9 in the polyaddition reaction solution.
%, Preferably 50 to 99% by weight.

The precursor has a logarithmic viscosity (η _inh ) of preferably from 0.1 to 3 dl / g when measured at a concentration of 0.5 g / dl in N-methylpyrrolidone at 30 ° C., particularly preferably. Is 0.2 to 1.5 dl / g.

The precursor thus synthesized is reacted with a compound containing a polymerizable double bond and a group which easily reacts with a carboxyl group, for example, an isocyanate group, an epoxy group, an amino group or a pyridyl group. The polymer (A) used in the composition of the invention is obtained. The polymer (A) was 0.5 g / dl in N-methylpyrrolidone.
The logarithmic viscosity (η _inh ) when measured at the concentration of
Usually, it is 0.1 to 3 dl / g, preferably 0.2 to
It is 1.5 dl / g.

The above compound is represented by the following formula (15)

[0057]

[Chemical 13]

A compound represented by the following formula (16)
~ (18)

[0059]

[Chemical 14]

(In the formulas (16) to (18), R ₆ , R ₇ and R
₈ and R ₉ are the same as in the case of the above formula (5) including the preferred embodiment, R ₁₀ and R ₁₁ of the formula (16) are the same as those in the above formula (7), and R ₁₂ is the same as in the case of the above formula (8), and r and s in the formula (18) are the same as in the case of the formula (9)), and a compound containing a basic nitrogen can be mentioned. .

In the case where Q in the formula (15) is an isocyanate group, Z in the formula (1) is —NH—, and R ₂
A polymer (A) having a repeating unit in which is a group represented by the formula (5) is produced.

In the case of a compound in which Q in the formula (15) is an epoxy group, a polymer (A) having a repeating unit in which Z in the formula (1) is an oxygen atom and R ₂ is a group represented by the formula (6). )
Is generated.

Expression (16), Expression (17) or Expression (18)
In the case of the compound represented by the formula (1), a polymer having a repeating unit (A in which Z in the formula (1) is an oxygen atom and R ₂ is a group represented by the formula (7), the formula (8) or the formula (9) (A ) Is generated.

Specific examples of the compound in which Q in the formula (15) is an isocyanate group include, for example, isocyanate ethyl acrylate, isocyanate propyl acrylate,
Isocyanate butyl acrylate, isocyanate pentyl acrylate, isocyanate hexyl acrylate, isocyanate octyl acrylate, isocyanate decyl acrylate, isocyanate octadecyl acrylate, isocyanate ethyl methacrylate, isocyanate propyl methacrylate, isocyanate butyl methacrylate, isocyanate pentyl methacrylate, isocyanate hexyl methacrylate, isocyanate octyl methacrylate, isocyanate decyl Methacrylate, isocyanate octadecyl methacrylate, isocyanate ethyl crotonate, isocyanate propyl crotonate, isocyanate hexyl crotonate, isocyanate octyl crotonate, isocyanate Sulfonates decyl crotonate, and the like isocyanate octadecyl crotonate it is. A commercially available product is IEM (isocyanate ethyl methacrylate) manufactured by Dow Chemical Company. These compounds may be used alone or in combination of two or more.

The reaction of the above-mentioned isocyanate with the precursor having the repeating unit represented by the formula (13) is usually carried out in the inert organic solvent used for the synthesis of the precursor at 0 to 100 ° C.
It is preferably carried out at a temperature of 20 to 70 ° C. From the viewpoint of the sensitivity of the composition of the present invention and the heat resistance of the coating film, the ratio of the isocyanate compound to the precursor is usually 0.1 to 2 mol, preferably 0.1 mol, relative to 1 mol of the carboxyl group of the precursor. It is in the range of 4-1.2 mol.

The reaction between the isocyanate compound and the precursor is carried out by using, for example, amines such as triethylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, 1,4-diazobicyclo [2.2.2] octane, It becomes easy to use a tin compound such as dibutyltin dilaurate or dibutyltin diacetate. These can be used usually in the range of 25% by weight or less based on the isocyanate compound.

The following can be mentioned as specific examples of the compound in which Q in the formula (15) is an epoxy group.

[0068]

[Chemical 15]

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

The reaction between the precursor and the above-mentioned epoxy compound is usually carried out in the solvent used for the synthesis of the precursor at 60 to 120 ° C.
Preferably, at a reaction temperature of 70 to 90 ° C., triethanolamine, triethylamine, N, N-dimethylaniline,
It can be carried out by reacting 0.1 to 2 mol, preferably 0.4 to 1.2 mol of an epoxy compound with 1 mol of a carboxyl group of a precursor using N, N-dimethylbenzylamine as a catalyst. . Here, the amount of the catalyst used is 25% by weight or less based on the epoxy compound.

Specific examples of the basic nitrogen-containing compounds represented by the formulas (16), (17) and (18) include the following.

[0072]

[Chemical 16]

[0073]

[Chemical 17]

The reaction between the precursor and these basic nitrogen-containing compounds is carried out at room temperature in the solvent used for the synthesis of the precursor,
Alternatively, it can be easily performed under heating at about 0 to 60 ° C. The ratio of the compound containing basic nitrogen to the precursor is usually 1 mol of the carboxyl group of the precursor,
The amount is 0.1 mol or more, preferably 0.4 to 2 mol.

As a method for producing the polymer (A) having a repeating unit represented by the formula (1) used in the present invention, in addition to the above-described method, a tetracarboxylic dianhydride represented by the formula (12) is added. Examples thereof include a method of reacting with an alcohol containing a group having a polymerizable double bond to obtain a half ester intermediate (hereinafter referred to as “half ester intermediate”), and reacting this intermediate with a diisocyanate compound. According to this method, the reaction proceeds as follows.

[0076]

[Chemical 18]

In the above, R ₁ and n are the same as in the case of the formula (1), R ₁₃ represents a group having a polymerizable double bond, and the group represented by the formula (5) is exemplified.

As the alcohol containing a group having a polymerizable double bond, 2-hydroxyethyl cinnamate, 2-
Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and the like can be mentioned, and triethylamine in an organic solvent such as N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, benzene, xylene, methyl ethyl ketone and γ-butyrolactone.
Using a basic catalyst such as N, N-dimethylbenzylamine in an amount of 20% by weight or less based on the above alcohol, 50 to 1
The half ester intermediate can be obtained by reacting with the compound represented by the formula (12) in the temperature range of 00 ° C, preferably 70 to 90 ° C.

Here, the organic solvent is 50 to 9 in the reaction solution.
It is suitable to use 9.9% by weight, preferably 70 to 99% by weight.
The reaction ratio with the compound represented by 2) is 1.6 in molar ratio.
/ 1 to 2.4 / 1, and it is preferable to use almost twice the molar amount.

Diisocyanate compound, ie OCN
Specific examples of the compound represented by —R ₁ —NCO include diphenylmethane diisocyanate, diphenyl ether diisocyanate, biphenyl diisocyanate, diphenyl sulfide diisocyanate, and the like, and the half ester intermediate described above and 50 to 100 ° C.
A polymer having a repeating unit represented by the formula (1) in the present invention is obtained by reacting under a basic catalyst such as triethylamine or N, N-dimethylbenzylamine, preferably in a temperature range of 70 to 90 ° C. be able to.

Examples of the polymerization initiator usable in the radiation-sensitive resin composition of the present invention include Michler's ketone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2 -T-Butylanthraquinone, 1,2-benzo-9,10-anthraquinone, anthraquinone, methylanthraquinone, 4,4'-bis (diethylamino)
Benzophenone, acetophenone, benzophenone, thioxanthone, 2,4-diethylthioxanthone, 2-
Isopropyl thioxanthone, 1,5-acenaphthene,
2,2-dimethoxy-2-phenylacetophenone, 1
-Hydroxycyclohexyl phenyl ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, diacetyl, dibenzoyl, benzyl dimethyl ketal, benzyl diethyl ketal, diphenyl disulfide, anthracene, 2,6-bis ( p-diethylaminobenzylidene) -4-aza-4-
Methylcyclohexanone, 2,6-bis (p-diethylaminobenzylidene) -4-oxocyclohexanone,
2,6-bis (p-diethylaminobenzylidene) -4
-Thiacyclohexanone and the like can be mentioned, and these can be used alone or in combination of two or more kinds.

From the viewpoint of the sensitivity of the radiation-sensitive resin composition of the present invention and the heat resistance of the pattern, the amount of these polymerization initiators to be used is the polymer (A) and, if necessary, the polymerizable unsaturated group described below. Based on 100 parts by weight of the total amount of monomers,
Usually, it is 0.01 to 50 parts by weight, preferably 0.1 to
30 parts by weight.

In addition to these polymerization initiators, a radiation-sensitive polymerization initiation auxiliary agent (hereinafter referred to as "polymerization initiation auxiliary agent").
It is also possible to use a small amount of the amines.

Examples of the amines include ethyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, isoamyl p-dimethylaminobenzoate, isoamyl p-diethylaminobenzoate, and 2- (dimethylamino) ethyl benzoate. p-dimethylaminobenzaldehyde, p-diethylaminobenzaldehyde, N, N-
Ethyl diethylanthranilate, p-dimethylaminobenzonitrile, p-diethylaminobenzonitrile,
N, N-dimethylaminonaphthalene, N-phenylglycine, N- (p-cyanophenyl) glycine, N- (p
Examples include -chlorophenyl) glycine and N- (p-bromophenyl) glycine. The amount of the polymerization initiation aid used is preferably equimolar or less with respect to the polymerization initiator.

In the radiation-sensitive resin composition of the present invention, a polymerizable unsaturated monomer can be blended for the purpose of supplementing the components which cause a crosslinking reaction. The polymerizable unsaturated monomer is preferably a good solvent for the polymer (A) having the repeating unit represented by the formula (1).

Examples of the polymerizable unsaturated monomer include acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, benzyl acrylate, carbitol acrylate. , Methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, dipropylene glycol diacrylate, 2,2-bis- (4-acryloxydiethoxyphenyl) propane, 2,2-bis- (4-acryloxypropoxyphenyl) propane, trimethylolpropane diacrylate, pentaerythritol diacrylate, trimethyl Propane triacrylate, pentaerythritol triacrylate, triacrylformal, tetramethylolmethane tetraacrylate, tris (2-hydroxyethyl) isocyanuric acid,

[0087]

[Chemical 19]

Methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, 2,2
-Bis (4-methacryloxydiethoxyphenyl) propane, trimethylolpropane dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol methacrylate, tetramethylolmethane tetramethacrylate,

[0089]

[Chemical 20]

And the like.

These polymerizable unsaturated monomers may be used alone or in admixture of two or more, and the compounding amount thereof is usually 0.0 based on 100 parts by weight of the polymer (A).
It is 1 to 30 parts by weight, preferably 0.1 to 10 parts by weight.

In the radiation-sensitive resin composition of the present invention, a radiation-sensitive crosslinking agent (hereinafter referred to as "crosslinking agent") can be used if necessary. Examples of the cross-linking agent include

[0093]

[Chemical 21]

[0094]

[Chemical formula 22]

[0095]

[Chemical formula 23]

And the like.

These cross-linking agents may be used alone or in admixture of two or more, and the amount thereof used is the total amount of the polymer (A) and the polymerizable unsaturated monomer used as the case requires. It is 30 parts by weight or less based on 100 parts by weight.

The radiation-sensitive resin composition of the present invention can be patterned by a usual fine processing technique. That is, the polymer (A) of the present invention, the polymerization initiator, and optionally the polymerizable unsaturated monomer, the polymerization initiation aid and the cross-linking agent are dissolved in a solvent to form a uniform solution. It is possible to form a relief pattern by the fine processing technique by lithography.

As the above solvent, those exemplified as the inert organic solvent used when the polymer (A) is produced by the polyaddition reaction are preferably used. The solvent is suitably used so as to occupy 30 to 99% by weight, particularly 50 to 95% by weight, in the solution.

The solution of the composition of the present invention is applied onto a supporting substrate such as a glass substrate, a silicon wafer, a copper clad laminate by a means such as spin coating, dipping or spray printing, and dried to form a coating film. You can

The solution is coated on a flexible substrate such as a polyester film, dried and laminated, and a cover sheet made of polyethylene or the like is optionally provided on the solution to prepare a radiation sensitive element having a sandwich structure in advance. Then
It is also possible to peel off the cover sheet of this radiation-sensitive element and press-bond it on the supporting substrate to be coated to form a coating film.

The film thickness of the coating film can be adjusted within the range of 1 to 200 μm by the application means, the solid content concentration of the solution of the radiation-sensitive resin composition of the present invention, the viscosity and the like.

A relief pattern is obtained by irradiating the coating film thus formed on the supporting substrate with radiation, and then releasing the dissolution of the unirradiated portion with a developing solution. At this time, ultraviolet rays, visible rays, electron beams, X-rays, far ultraviolet rays, etc. can be used as the radiation.

As the developing solution, for example, N-methyl-2-
Pyrrolidone, N-acetyl-2-pyrrolidone, N, N-
Dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide, dimethylimidazolidinone, N-benzyl-2
-Pyrrolidone, polar solvents such as N-acetyl-ε-caprolactam alone or in combination of two or more, or a poor solvent of the precursor, for example, methanol, ethanol, isopropyl alcohol, benzene, acetone, methyl ethyl ketone, cyclohexanone, cyclo Mixed solution with pentanone, toluene, xylene, methyl cellosolve, water or the like, or, for example, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, sodium carbonate, potassium carbonate,
It can be used as a mixed solution with a 0.0001 to 30% by weight, preferably 0.05 to 5% by weight, basic aqueous solution of sodium phosphate or the like. The amount of the poor solvent or basic aqueous solution used is 9 parts with respect to 100 parts by weight of the polar solvent.
It is 0 parts by weight or less.

Then, the relief formed by the development
The pattern is washed with a rinse liquid to remove the developer.
As the rinse solution, a poor solvent of a precursor having good miscibility with the developer is used, and examples thereof include methanol, ethanol, isopropyl alcohol, benzene, toluene, xylene,
Examples include methyl cellosolve and water.

The relief pattern thus obtained becomes a heat resistant resist pattern having an imide ring by heat treatment at 150 to 450 ° C.

[0107]

The present invention will be described in more detail by the following examples, but the present invention is not limited to these examples. In the examples,% is based on weight. here,
Various performances were evaluated by the following methods. (Film Thickness) The film thickness of the coating film after development and heat treatment was measured. (Heat resistance) The obtained resist pattern was subjected to thermogravimetric analysis (TGA) at a 5% weight loss temperature (100% under air).
ml / min, heating rate 10 ° C / min, sample amount 10m
g) was measured. (Light transmissive) A film that was spin-coated on a quartz glass substrate and exposed, developed, and heat-treated without using a photomask was put into a visible / ultraviolet spectrophotometer (u-3410, manufactured by Hitachi, Ltd.). Then, the light transmittance (%) at a wavelength of 365 nm was measured. The value of light transmittance is 1 for the film thickness.
It is shown in terms of 0 μm.

Example 1 A three-necked flask having an internal volume of 1000 ml was thoroughly dried in a drier at 120 ° C. for 3 hours, and then N-methyl-2-pyrrolidone (hereinafter referred to as “NMP”) was dehydrated while purging the inside of the flask with nitrogen. 250) 250
g was added. The water content of NMP was 8 ppm.
To this, 4,4-methylenebis (cyclohexylamine) (hereinafter abbreviated as "MBCHA") 21.036 g
(0.100 mol) was weighed and added to the flask,
The whole amount was dissolved by stirring with a stirring blade made of Teflon. Then tetracyclo [6.2.1.1.0 ^2,7 ] dodeca-4,
5,9,10-Tetracarboxylic acid dianhydride (hereinafter referred to as "NNT
Abbreviated as "A". ) 30.229 g (0.100 mol) was weighed and added to the flask with stirring. Then 24
After stirring for a time, a precursor was obtained. The logarithmic viscosity of this precursor (30 ° C., 0.5 g / dl in NMP) η _inh is 0.81 d
It was 1 / g.

The precursor thus obtained is designated as "PI-A". This PI-A solution was taken in an amount of 1/10 and diluted with NMP to a solution weight of 60 g, which was used as a PI-A solution. This PI-A solution was transferred to a 100 ml three-necked flask equipped with a thermometer, a nitrogen gas inlet and a stirrer, and after replacing the air with nitrogen gas with dry nitrogen gas, at room temperature under light blocking,
Isocyanate ethyl methacrylate (hereinafter "IEM")
Abbreviated. ) 1.55 g (10 mmol) was added and stirred for 24 hours to obtain a solution containing the polymer (A-1) having 95 mol% of the repeating unit represented by the following formula (19).

[0110]

[Chemical formula 24]

A solution containing this polymer (A-1) was added to 0.20 g of 2,4-diethylthioxanthone under the exclusion of light.
Ethyl N, N-diethylaminobenzoate (0.30 g) was added, and the mixture was stirred and mixed, and then filtered through a filter to obtain a radiation-sensitive resin composition. A silicon wafer was spin-coated with this solution, and the resulting coating film was dried at 60 ° C. for 30 minutes.
Next, using a photomask, an ultra-high pressure mercury lamp (8 mW / c
Irradiation (hereinafter referred to as “exposure”) was performed for 120 seconds at m ² ). Then, N, N-dimethylacetamide 1
Solution, 4 volumes of ethyl alcohol and 4 volumes of a 1% aqueous solution of tetramethylammonium hydroxide, followed by development, rinsing with water, and drying by air spraying, and a clear pattern was obtained. Film thickness is 31 μm
Met.

This pattern was formed in a nitrogen atmosphere at 300 ° C. for 5
A heat resistant film pattern was obtained by heat treatment for minutes. The 5% weight loss temperature of this film is 3
It was as high as 97 ° C. The light transmittance was 92%.

Example 2 A three-necked flask having an internal volume of 1000 ml was sufficiently dried in a dryer at 120 ° C. for 3 hours, and then the inside of the flask was dehydrated while purging with nitrogen.
50 g was added. The water content of NMP was 8 ppm. MBCHA 21.036g (0.100mo)
1) was weighed out, added to the flask, and stirred with a stirring blade made of Teflon to dissolve the whole amount. Then, 23.618 g of bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride (hereinafter abbreviated as "NTA")
(0.100 mol) was weighed and added to the flask with stirring. Then, the mixture was stirred for 24 hours to obtain a precursor. Logarithmic viscosity of this precursor (0.5 g in NMP at 30 ° C)
/ Dl) η _inh was 0.88 dl / g.

The precursor thus obtained is designated as "PI-B". This PI-B solution was taken in an amount of 1/10 and diluted with NMP to a solution weight of 60 g, which was used as a sample. Thereafter, in the same manner as in Example 1, at room temperature with light shielded, IEM1.55 was used.
g (10 mmol) was added, and the mixture was stirred for 24 hours to obtain a solution containing the polymer (A-2) having 98 mol% of the repeating unit represented by the following formula (20).

[0115]

[Chemical 25]

Thereafter, in the same manner as in Example 1, the polymer (A
-2) The weights indicated for the components shown in Table 1 were added to the containing solution to obtain a uniform solution and form a pattern. Further, heat treatment was performed in the same manner as in Example 1 to obtain a heat resistant film pattern. The 5% weight loss temperature and light transmittance of this film were the values shown in Table 2.

(Example 3) In Example 1, MBCH
2.124 g of 4,4-bis (aminocyclohexyl) ether instead of A (hereinafter abbreviated as "BACHE")
(0.010 mol) and 3.023 g of NNTA (0.0.
(010 mol) was used and the reaction was performed under the same conditions as in Example 1 to obtain a solution containing the polymer (A-3). Thereafter, in the same manner as in Example 1, the weights indicated for the components shown in Table 1 were added to the solution containing the polymer (A-3) to obtain a uniform solution and form a pattern. Then, Example 1
A heat treatment was performed in the same manner as in 1. to obtain a heat-resistant film pattern. The 5% weight loss temperature and light transmittance of this film were the values shown in Table 2.

(Example 4) In Example 2, MBCH
BACHE 2.124g (0.010mo instead of A)
1) and NTA 2.362 g (0.010 mol) were used, and the reaction was performed under the same conditions as in Example 2 to obtain a polymer (A-4). Hereinafter, in the same manner as in Example 1, the components shown in Table 1 were added to the solution containing the polymer (A-4).
The indicated weight was added to obtain a uniform solution and a pattern was formed. Then, heat treatment was performed in the same manner as in Example 1 to obtain a heat resistant film pattern. 5% of this film
The weight reduction temperature and the light transmittance have the values shown in Table 2.

(Example 5) In the same manner as in Example 1, the polymer "PI-A" solution obtained was taken in an amount of 1/10 and NMP was added.
The mixture was diluted to 60 g with the addition of 1.42 g (10 mmol) of glycidyl methacrylate and 0.10 g of triethylamine at 75 ° C. under the exclusion of light and stirred for 8 hours to obtain a polymer (A-5). Thereafter, in the same manner as in Example 1, the weights shown for the components shown in Table 1 were added to the solution containing the polymer (A-5) to obtain a uniform solution and form a pattern. Then, heat treatment was performed in the same manner as in Example 1 to obtain a heat resistant film pattern. The 5% weight loss temperature and light transmittance of this film were the values shown in Table 2.

(Example 6) In the same manner as in Example 2, the polymer "PI-B" solution was taken in an amount of 1/10 and 60 g with NMP.
What was diluted with the above was added with 1.42 g (10 mmol) of glycidyl methacrylate and 0.10 g of triethylamine at 75 ° C. under the exclusion of light and stirred for 8 hours to obtain a polymer (A
6) was obtained. Thereafter, in the same manner as in Example 1, the polymer (A
The weight shown for the components shown in Table 1 was added to the solution containing -6) to obtain a uniform solution and form a pattern. Then, heat treatment was performed in the same manner as in Example 1 to obtain a heat resistant film pattern. The 5% weight loss temperature and light transmittance of this film were the values shown in Table 2.

Example 7 MBCHA in Example 1
MBCHA 1.998g instead of 21.036g
(9.5 mmol) and 0.124 g (0.5 mmol) of 1,3-bis (aminopropyl) tetramethyldisiloxane.
And the reaction was performed under the same conditions as in Example 1 except that 3.023 g (10 mmol) of NNTA was used to obtain a polymer (A-7). Thereafter, in the same manner as in Example 1, the weights shown for the components shown in Table 1 were added to the solution containing the polymer (A-7) to obtain a uniform solution and form a pattern. Then, heat treatment was performed in the same manner as in Example 1 to obtain a heat resistant film pattern. The 5% weight loss temperature and light transmittance of this film were the values shown in Table 2.

Example 8 MBCHA in Example 2
MBCHA 1.998g instead of 21.036g
(9.5 mmol) and 0.124 g (0.5 mmol) of 1,3-bis (aminopropyl) tetramethyldisiloxane.
And NTA 2.362 g (10 mmol) were used, and the reaction was performed under the same conditions as in Example 1 to obtain the polymer (A
-8) was obtained. Thereafter, in the same manner as in Example 1, the weights shown for the components shown in Table 1 were added to the solution containing the polymer (A-8) to obtain a uniform solution and form a pattern. Then, heat treatment was performed in the same manner as in Example 1 to obtain a heat resistant film pattern. The 5% weight loss temperature and light transmittance of this film were the values shown in Table 2.

[0123]

[Table 1]

[0124]

[Table 2]

Example 9 A flask having an internal volume of 200 ml was dried, and then 50 g of dehydrated NMP was added while purging the inside of the flask with nitrogen. Water content of NMP is 8p
It was pm. MBCHA 4.207g (0.0
20 mol) was added to the flask and stirred to dissolve the whole amount. Next, 6.046g of NNTA (0.020mo
l) was added into the flask with stirring. Then 25
The precursor was obtained by stirring at 24 ° C. for 24 hours. The logarithmic viscosity (0.5 g / dl in NMP at 30 ° C.) η _inh of this precursor is
It was 0.81 dl / g.

The precursor thus obtained is designated as "PI-C". This PI-C solution was diluted with NMP to make the solution weight 85 g. The weight indicated for each component shown in Table 3 was further added to this PI-C diluted solution to obtain a uniform solution. This solution contains a polymer (A-9) having a repeating unit represented by the following formula (21).

[0127]

[Chemical formula 26]

This solution was filtered with a filter and then spin-coated on a silicon wafer. The coating film obtained is 6
It was dried at 0 ° C. for 5 minutes and then exposed to an ultrahigh pressure mercury lamp (8 mW / cm ² ) for 120 seconds using a photomask. After that, development was carried out with a mixed solution consisting of 1 volume of N, N-dimethylacetamide, 4 volumes of ethyl alcohol, and 4 volumes of a 1% by weight aqueous solution of tetramethylammonium hydroxide, followed by rinsing with water and drying. A relief pattern was obtained.

This pattern was formed in a nitrogen atmosphere at 300 ° C. for 5
A heat resistant film pattern was obtained by heat treatment for minutes.

(Example 10) In Example 9, the NNT
The reaction was performed under the same conditions as in Example 9 except that NTA 4.724 g (0.020 mol) was used instead of A,
A precursor was obtained. Logarithmic viscosity of this precursor (30 ° C, NMP
Medium 0.5 g / dl) η _inh was 0.88 dl / g.

The precursor thus obtained is designated as "PI-D". This PI-D solution was diluted with NMP to a solution weight of 85 g, and the weights shown below for the components shown in Table 3 were added in the same manner as in Example 9 to give a uniform polymer (A-10). A containing solution was obtained, dried, exposed and developed to form a relief pattern, and further heat-treated to obtain a heat resistant pattern.

(Embodiment 11) In Embodiment 9, MBC
BACHE 4.248g (0.020mo instead of HA
A reaction was performed under the same conditions as in Example 9 except that 1) was used to obtain a precursor. Logarithmic viscosity of this precursor (30 ° C, N
0.5 g / dl) η _{inh in} MP was 0.89 dl / g. The obtained precursor is designated as "PI-E". This PI
The solution E was diluted with NMP to a solution weight of 85 g, and the weights shown below for the components shown in Table 3 were added in the same manner as in Example 9 to obtain a solution containing a homogeneous polymer (A-11). Was obtained, dried, exposed and developed to form a relief pattern, and further heat-treated to obtain a heat resistant pattern.

(Embodiment 12) In Embodiment 10, MB
BACHE in place of CHA 4.248g (0.020m
ol) was used and the reaction was performed under the same conditions as in Example 9 to obtain a precursor. Logarithmic viscosity of this precursor (30 ° C,
The value of 0.5 g / dl) η _{inh in} NMP was 0.93 dl / g. The obtained precursor is designated as "PI-F". This P
The IF solution was diluted with NMP to a solution weight of 85 g,
Then, in the same manner as in Example 9, the weights shown for the components shown in Table 3 were added to obtain a uniform solution containing the polymer (A), which was dried, exposed and developed to form a relief pattern. Further, heat treatment was performed to obtain a heat resistant pattern. The results of Examples 9 to 12 are summarized in Table 3 below.

[0134]

[Table 3]

[0135]

The radiation-sensitive resin composition of the present invention has high light transmittance and solubility in a solvent, and at the same time, a thick film pattern having excellent heat resistance can be obtained. Therefore, the composition of the present invention can be used as both a resist material and an insulating material.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location H01L 21/027 21/312 B 7352-4M H05K 3/28 D 7511-4E

Claims (1)

[Claims] 1. The following formula (1): (In the formula (1), R ₁ represents a divalent organic group, and two R ₂
Are the same or different and represent a hydrogen atom or a group having a radiation-polymerizable carbon-carbon double bond (provided that at least one of two R ₂ is a group having a radiation-polymerizable carbon-carbon double bond). Two Z are the same or different and represent an oxygen atom or —NH—, and n is 0 or 1), and the polymer (A) and the radiation-sensitive polymerization initiator having a repeating unit represented by A radiation-sensitive resin composition comprising: