JPH08176301A - New polyamide-imide copolymer, its production, film-forming material containing the same and method for pattern formation - Google Patents

Abstract

PURPOSE: To obtain under mild conditions a new polyamideimide copolymer as a highly reliable polymeric material excellent in heat resistance, adhesiveness, electrical properties, solvent solubility and moldability, having each specific intrinsic viscosity and structure. CONSTITUTION: This polyamide-imide block copolymer has an intrinsic viscosity of 0.1-3.0dl/g and is expressed by formula I [Ar<1> and Ar<2> are each (substituted) aromatic group; (x) is 0-150; (y) is 1-30]. The other version of this copolymer is a random copolymer having an intrinsic viscosity of 0.1-3.0dL/g and having such structure that 1-99mol% of structural unit of formula II and 99-1mol% of structural unit of formula III are mutually bound irregularly. This copolymer is obtained by the following process: an aromatic diamine of formula IV and an aromatic tetracarboxylic dianhydride of formula V are subjected to polycondensation to synthesize a polyamic acid with carboxylic anhydride groups on both terminals, which is then further put to polycondensation, in the presence of a phosphorous ester and pyridine (derivative), with a 7, 12-dimethyloctadecane compound with amino groups on both ends prepared by condensation between a 7, 12-dimethyloctadecane compound with carboxylic acid groups on both ends and an aromatic diamine followed by conducting an imide cyclization reaction.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polyamideimide copolymer, a method for producing the same, a film forming material, and a resist pattern forming method, and more specifically, a novel 7,12-dimethyloctadecane-modified polyamideimide block. And a random copolymer, a manufacturing method thereof, a film forming material, and a resist pattern forming method.

[0002]

2. Description of the Related Art In recent years, with the miniaturization and multi-functionalization of semiconductor products, the shape of LSI packages has tended to become thinner and have more pins despite the larger chips. Along with this, development of a polymer material excellent in heat resistance, adhesiveness, moldability, and electric characteristics is desired, and various proposals have been made. Polyimide resins, polyamide resins, etc. are widely known as heat-resistant polymer materials, and in addition to heat resistance, they are excellent in impact resistance, mechanical properties, solvent resistance, It has attracted attention as a material. However, since these resins have drawbacks in moldability, adhesiveness, hygroscopicity, dielectric property, etc., it has been studied to combine them with an elastomer such as polysiloxane having low hygroscopicity and low dielectricity.

[0003]

However, the conventionally proposed polyimide resins and polyamide resins have low compatibility with elastomers and are difficult to form into composites, and also have solubility of resins synthesized with a desired composition. It deteriorated, and there was a difficulty in using it as a film. Therefore, when used as a polymer electronic material, it is desired to realize a polymer material having excellent properties in all respects, such as solvent solubility and moldability, in addition to heat resistance, adhesiveness, and electrical properties. Therefore, an object of the present invention is to provide a novel polyamide-imide copolymer which satisfies the above-mentioned characteristics and is useful as a polymer material showing high reliability. Another object of the present invention is to provide a method for producing the above novel polyamide-imide copolymer, which can be easily produced under mild production conditions. Still another object of the present invention is to provide a film forming material and a resist pattern forming method using the novel polyamideimide copolymer.

[0004]

The inventors of the present invention have conducted research to solve the above-mentioned problems in the prior art, and as a result, 7,12-dimethyloctadecane, aromatic diamines and aromatic tetracarboxylic acids have been obtained. We have found that a polyamide-imide copolymer produced using dianhydride as a starting material can achieve the above-mentioned object, and have completed the present invention.

One of the polyamide-imide copolymers of the present invention has an intrinsic viscosity of 0.1 to 3.0 dl / g, preferably 0.1.
It is a polyamide-imide block copolymer of 2 to 2.0 dl / g and characterized by being represented by the following general formula (1).

[Chemical 6] (In the formula, Ar ¹ and Ar ² each represent an aromatic group which may have a substituent, x represents an integer of 0 to 150, preferably 20 to 80, and y represents 1 to 30, preferably 1
It represents an integer of 0 to 20. )

Another one of the polyamideimide copolymers of the present invention is a polyamideimide random copolymer having an intrinsic viscosity of 0.1 to 3.0 dl / g, preferably 0.2 to 2.0 dl / g. And 1 to 99 mol% of the repeating structural unit represented by the following general formula (2-1), preferably 5 to 60 mol%, and 99 to 1 mol% of the repeating structural unit represented by the following general formula (2-2). , Preferably 95 to 40 mol% are irregularly bonded.

[Chemical 7] (In the formula, Ar ¹ and Ar ² each represent an aromatic group which may have a substituent.)

One of the methods for producing the polyamide-imide block copolymer represented by the above general formula (1) of the present invention is represented by the aromatic diamine represented by the following general formula (3) and the following general formula (4). Polycondensation with an aromatic tetracarboxylic dianhydride to synthesize a polyamic acid having carboxylic acid anhydride groups at both ends,

Embedded image (In the formula, Ar ¹ and Ar ² each represent an aromatic group which may have a substituent.), 7,12-dimethyloctadecane having a carboxyl group at both ends and an aromatic diamine. 7,12 having amino groups at both ends, obtained by condensation with
-Polymerization is carried out in the presence of a dimethyloctadecane compound, a phosphite and pyridine or a derivative thereof, and then an imide ring closure reaction is carried out.

Another method of producing the polyamide-imide block copolymer represented by the general formula (1) of the present invention is another method for producing the aromatic diamine represented by the general formula (3) and the general formula (4). Polycondensation of an aromatic tetracarboxylic dianhydride represented by to synthesize a polyamic acid having a carboxylic acid anhydride group at both ends, and then polyimide having an amino group at both ends by imide ring closure reaction And the polyimide having a carboxyl group at both ends 7,1
It is characterized in that polycondensation is carried out in the presence of 2-dimethyloctadecane, a phosphite and pyridine or a derivative thereof.

The method for producing a polyamideimide random copolymer comprising the repeating structural unit represented by the general formula (2-1) and the repeating structural unit represented by the general formula (2-2) of the present invention is as described above. An aromatic diamine represented by the general formula (3) and a carboxyl group at both ends 7,12
-Dimethyloctadecane is condensed in the presence of a phosphite and pyridine or a derivative thereof to synthesize 7,12-dimethyloctadecane having amino groups at both ends, and 7,12-having an amino group at both ends. Dimethyl octadecane and the aromatic diamine represented by the general formula (3) are polycondensed with the aromatic tetracarboxylic dianhydride represented by the general formula (4) to synthesize a polyamic acid.
Further, it is characterized in that an imide ring closure reaction is carried out.

The film-forming material of the present invention is characterized by containing the above-mentioned polyamide-imide block or random copolymer as a main component. Further, the resist pattern forming method of the present invention comprises forming a pattern by etching a pattern forming material provided with a coating film containing a polyamide imide block or a random copolymer as a main component with a basic etching solution. Is characterized by.

The present invention will be described in detail below. In the aromatic diamine represented by the general formula (3), which is one of the starting materials used in the production of the polyamideimide block or the random copolymer of the present invention, Ar ¹
Represents an aromatic group which may have a substituent, and specifically, a phenylene group, a naphthylene group, a xylylene group, a biphenylene group, or -O-, -S-, -SO-, -SO.
_2- , -NH-, tetramethyldisiloxy group, -CO
_{-, - CH 2 -, -} C (CH 3) 2 -, - C (CF 3)
_{2 -, - O-C 6} H 4 -O -, - O-C 6 H 4 -SO 2
_{-C 6 H 4 -O -, -} O-C 6 H 4 -CO-C 6 H 4 -
_{O -, - O-C 6} H 4 -C (CF 3) 2 -C 6 H 4 -O
A divalent group in which two benzene rings are linked to each other by-, etc., and these benzene rings may further have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a hydroxy group, Examples thereof include perfluoroalkyl groups.

Specific examples of the aromatic diamines represented by the above general formula (3) which can be used in the present invention include, for example, m-phenylenediamine, p-phenylenediamine, m-tolylenediamine, 4, 4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4 '
-Diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylthioether,
3,3'-dimethyl-4,4'-diaminodiphenylthioether, 3,3'-diethoxy-4,4'-diaminodiphenyl ether, 1,4-naphthalenediamine,
1,5-naphthalenediamine, 2,6-naphthalenediamine, benzidine, 3,3'-dimethylbenzidine,
3,3'-dimethoxybenzidine, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, m-xylylenediamine, p-xylylenediamine, 1,3-bis (m -Aminophenyl)-
1,1,3,3-tetramethyldisiloxane, 4,4 '
-Diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfone, 4,4'-bis (3-aminophenoxy) diphenyl sulfone, 4,4'-bis (4-
Aminophenoxy) diphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 1,3-bis (4-aminophenoxy) benzene, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobenzophenone , 3,3'-diaminobenzophenone, 4,
4'-bis (4-aminophenoxy) benzophenone,
4,4'-bis (3-aminophenoxy) benzophenone, 4,4'-bis (4-aminophenoxymercapto) benzophenone, 2,2-bis (3-aminophenyl) propane, 2,2-bis (4- Aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-
Bis (4-hydroxy-3-aminophenyl) hexafluoropropane, 2,2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- ( 2-trifluoromethyl-5-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-trifluoromethyl-4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4 -(3-Trifluoromethyl-5-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-trifluoromethyl-5-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (2-nonafluorobutyl-5-aminophenoxy) phenyl] hexafluoropropane, , 2-bis [4- (4-nonafluorobutyl-5-aminophenoxy) phenyl] hexafluoropropane, 4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylmethane, 3, 3'-diaminodiphenylmethane,
4,4'-methylenedi-2,6-xylidine, 4,4 '
-Methylenedi-2,6-diethylaniline, 4,4'-
Examples thereof include methylenedi-2-methyl-6-ethylaniline, but are not limited thereto.
These may be used alone or in combination of two or more.

Among the aromatic diamines represented by the above general formula (3), it is preferable to use the compounds represented by the following general formula (3-1), in which case the processability is improved.

[Chemical 9] (In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² represents an alkyl group having 1 to 4 carbon atoms.)

Examples of the aromatic diamine represented by the above general formula (3-1) include 4,4'-methylenedi-2-
Methylaniline, 4,4'-methylenedi-2-ethylaniline, 4,4'-methylenedi-2-propylaniline, 4,4'-methylenedi-2-butylaniline, 4,
4'-methylenedi-2,6-xylidine, 4,4'-methylenedi-2,6-diethylaniline, 4,4'-methylenedi-2,6-dipropylaniline, 4,4'-methylenedi-2,6 -Dibutylaniline, 4,4'-methylenedi-3-methylaniline, 4,4'-methylenedi-3
-Ethylaniline, 4,4'-methylenedi-3-propylaniline, 4,4'-methylenedi-3-butylaniline, 4,4'-methylenedi-3,5-xylidine, 4,
4'-methylenedi-3,5-diethylaniline, 4,
4'-methylenedi-3,5-dipropylaniline, 4,
4'-methylenedi-3,5-dibutylaniline, 4,
4'-methylenedi-2,3-xylidine, 4,4'-methylenedi-2,3-diethylaniline, 4,4'-methylenedi-2,3-dipropylaniline, 4,4'-methylenedi-2,3 -Dibutylaniline, 4,4'-methylenedi-2,5-xylidine, 4,4'-methylenedi-
2,5-diethylaniline, 4,4'-methylenedi-
2,5-dipropylaniline, 4,4'-methylenedi-
2,5-dibutylaniline, 4,4'-methylenedi-2
-Methyl-6-ethylaniline, 4,4'-methylenedi-3-methyl-5-ethylaniline, 4,4'-methylenedi-2-methyl-3-ethylaniline, 4,4'-methylenedi-2-ethyl -3-methylaniline, 4,4 '
-Methylenedi-2-methyl-5-ethylaniline, 4,
Examples thereof include 4'-methylenedi-2-ethyl-5-methylaniline, but not limited thereto. In addition, these may be used alone or in combination of two or more.

Examples of the aromatic tetracarboxylic dianhydride represented by the above general formula (4) which is one of the starting materials used in the present invention include, for example, pyromellitic dianhydride, 2,3,6. , 7-Naphthalenetetracarboxylic dianhydride, 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,3,2 ′, 3′-biphenyltetracarboxylic dianhydride, bis (3 , 4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,3 4-
Dicarboxyphenyl) propane dianhydride, 3,4
Examples thereof include 3 ', 4'-benzophenone tetracarboxylic acid dianhydride and butane tetracarboxylic acid dianhydride, but are not limited thereto. In addition, these may be used alone or in combination of two or more.

Among the aromatic tetracarboxylic dianhydrides represented by the above general formula (4), the following general formula (4-1)
Compounds represented by are preferred. When these are used, the processability of the polyamide-imide copolymer is improved.

[Chemical 10] (In the formula, Z represents a ketone group or a direct bond.)

Examples of the compound represented by the above general formula (4-1) include 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride and 2,3,2', 3'-biphenyltetra. Carboxylic dianhydride, 3,4,3 ', 4'-benzophenone tetracarboxylic dianhydride, 2,3,2',
Examples thereof include 3'-benzophenone tetracarboxylic acid dianhydride.

In the first method for producing the polyamideimide block copolymer represented by the general formula (1) of the present invention, first, the aromatic diamine represented by the general formula (3) and the general formula (4) are used. (4) is polycondensed with an aromatic tetracarboxylic acid dianhydride to produce a reaction solution containing a polyamic acid having carboxylic acid anhydride groups at both ends. The polyamic acid obtained has a degree of polymerization x of 0 to 150, preferably 20 to 80, and an average molecular weight of 500 to 60,000, particularly 1,000 to 50,000.
The range is preferably. On the other hand, 7,12-dimethyloctadecane having a carboxyl group at both ends is reacted with an aromatic diamine represented by the general formula (3) in the presence of a catalyst composed of phosphite ester and pyridine or a derivative thereof. , Having amino groups at both ends 7,12-
A reaction liquid containing dimethyl octadecane is obtained. The obtained reaction solution is directly mixed with the reaction solution containing the above polyamic acid,
After the reaction and polycondensation, the imide ring closure reaction is further performed.

In the second method for producing the polyamide-imide block copolymer represented by the general formula (1) of the present invention, the aromatic diamine represented by the general formula (3) and the above-mentioned general formula are used in the same manner as above. After polycondensation with the aromatic tetracarboxylic acid dianhydride represented by the formula (4), the obtained polyamic acid having amino groups at both ends is heated to perform an imide ring closure reaction. Even in this case, the polyamic acid is
The degree of polymerization x is in the range of 0 to 150, preferably in the range of 20 to 80, and the average molecular weight is 500 to 60,000.
It is preferably 0, particularly in the range of 1,000 to 50,000. Then, in the reaction solution obtained by the above imide ring closure reaction, 7,12 having a carboxyl group at both ends
-A catalyst comprising dimethyl octadecane, phosphite esters and pyridine or its derivative is added, and polyamidation is performed by a polycondensation reaction.

The polyamideimide random copolymer comprising the repeating structural unit represented by the general formula (2-1) and the repeating structural unit represented by the general formula (2-2) of the present invention is prepared by using an aromatic diamine and an aromatic diamine. 7,12-dimethyloctadecane having a carboxyl group at both ends is reacted with phosphite ester and pyridine or a derivative thereof to form 7,12-dimethyloctadecane having an amino group at both ends, and Aromatic tetracarboxylic acid dianhydride is added to a reaction solution containing 7,12-dimethyloctadecane having an amino group at both ends and an aromatic diamine, and 7,12-having an amino group at both ends is added.
An amic acid synthesis reaction is performed between dimethyl octadecane and an aromatic diamine and an aromatic tetracarboxylic acid dianhydride to produce a polyamic acid, and further an imide ring closure reaction is performed. The degree of polymerization of the obtained random copolymer is 10 to 25.
It is preferably in the range of 0, particularly in the range of 30 to 200.

In the present invention, each of the above reactions can be easily carried out using a known method. For example, when synthesizing a polyamide by a condensation polymerization reaction, a solution polymerization method using a mixed solvent containing an amide organic solvent and a pyridine organic solvent is usually employed. here,
The organic solvent used is limited in that it does not substantially react with both reaction components and amidation catalyst phosphite esters, but it is also a good solvent for both reaction components, and the reaction It is desirable that the solvent is a good solvent for the amide compound of the product, but as the polycondensation progresses, a heterogeneous system due to precipitation of the product may be formed. The reaction solvent in this polyamide synthesis is preferably a mixed solvent consisting of a pyridine-based organic solvent and an amide-based organic solvent represented by N-methyl-2-pyrrolidone. Amounts containing 5 to 30% by weight of the components are used.

In the method for producing a polyamide-imide copolymer of the present invention, the synthesis reaction of the above-mentioned polyamide is carried out using phosphite ester and pyridine or its derivative as a catalyst. ,
Triphenyl phosphite, diphenyl phosphite, tri-o-tolyl phosphite, di-o-tolyl phosphite, tri-m-tolyl phosphite, di-m-tolyl phosphite, phosphite Examples thereof include tri-p-tolyl, di-p-tolyl phosphite, di-o-chlorophenyl phosphite, tri-p-chlorophenyl phosphite, and di-p-chlorophenyl phosphite. It is not limited to. Furthermore, in the present invention, as pyridine or a derivative thereof that can be used together with phosphite, pyridine, 2-picoline, 3-picoline, 4-picoline,
2,3-lutidine, 2,4-lutidine, 2,5-lutidine, 2,6-lutidine, 3,4-lutidine, 3,5-lutidine and the like can be mentioned.

The amount of the phosphite ester to be used is generally an equimolar amount or more with respect to the carboxyl group, but 30
It is economically unwise to use more than the double molar amount. The amount of pyridine or its derivative used here is
It is preferably an equimolar amount or more with respect to the carboxyl group. Here, in order to synthesize polyamide efficiently, an alkali metal salt represented by lithium chloride or calcium chloride or an alkaline earth metal salt may be added to this reaction system.

The reaction temperature in the polyamide synthesis reaction is
Usually, the temperature is preferably in the range of 60 to 140 ° C., more preferably the temperature not higher than the boiling point of the pyridine organic solvent. The reaction time is largely influenced by the reaction temperature, but in any case it is advisable to stir the reaction system until the maximum viscosity, which means the highest degree of polymerization, is obtained, often between a few minutes and 48 hours.

The polyamic acid is synthesized by mixing the above aromatic diamine or 7,12-dimethyloctadecane having amino groups at both ends with an aromatic tetracarboxylic acid anhydride in an inert polar organic solvent at -20 to 20%. The reaction may be carried out at a temperature of 150 ° C., preferably 0 to 60 ° C. for several tens of minutes to several days, whereby a polyamic acid is obtained.

Examples of the inert polar organic solvent used include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea and pyridine. , Dimethyl sulfone, hexamethylphosphoric triamide, and the like. If necessary, a solvent other than those described above, that is, a low-polarity organic solvent having a carbon number of 1 that does not inhibit the amic acid formation reaction is used.
Add 0 or less lower hydrocarbon solvent, cyclic hydrocarbon solvent, aromatic solvent such as benzene, toluene, xylene, or ether solvent such as tetrahydrofuran, 1,4-dioxane, diglyme to the reaction system. Alternatively, polyamic acid may be generated.

The imide ring closure reaction of polyamic acid is
A method of dehydration and ring closure by heating is generally used in the presence of a dehydration catalyst, if necessary. This reaction temperature is 150-4
The temperature is 00 ° C, preferably 180 to 350 ° C, and the reaction time is 30 seconds to 10 hours, preferably 5 minutes to 5 hours. Examples of the dehydration catalyst include 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] undec-7-ene, acetic anhydride / sodium acetate and p-toluenesulfonic acid. Can be used.

In the polyamideimide random and block copolymers of the present invention, the terminal group has an aminoaryl group, a carboxyl group, and a carboxylic acid anhydride group at the terminal, depending on the amount of raw materials used. In the present invention, when the total number of moles of aromatic tetracarboxylic dianhydride and 7,12-dimethyloctadecane having carboxyl groups at both ends is equal to the number of moles of aromatic diamine under the above reaction conditions. Gives a polyamide-imide copolymer having a high degree of polymerization. Further, it is possible to obtain one having a small average degree of polymerization by using one of the components in excess. After completion of the reaction, the reaction mixture is poured into methanol to separate the produced polymer, and the product is purified by a reprecipitation method to remove by-products, inorganic salts, etc. A polymer can be obtained.

According to the method for producing a polyamide-imide block and a random copolymer of the present invention, amide acid synthesis, imide ring-closing reaction, and condensation polymerization can be carried out without isolation and purification of the amide compound formed in the intermediate as described above. The reaction can be performed under mild conditions by a series of continuous treatment steps,
It is possible to easily and conveniently synthesize the desired polyamide-imide copolymer. By this method, the polyamide-imide copolymer of the present invention has an advantage that a resin whose structure is regulated can be easily obtained without side reaction.

The polyamide-imide block and random copolymer of the present invention produced as described above have an intrinsic viscosity (meaning a measured value of a dimethylacetamide solution having a resin concentration of 0.5 g / dl at 30 ° C.). , 0.1
~ 3.0 dl / g, preferably 0.2-2.0 dl / g
Must be within the range. Intrinsic viscosity is 0.1 dl
/ G or less, a sufficient film cannot be obtained, and 3.0 dl / g
If the above is the case, the solubility in the solvent deteriorates, causing problems in use.

7,12-in the polyamide-imide block and random copolymer synthesized by the production method of the present invention
The content of dimethyloctadecane is such that the proportion of repeating units containing 7,12-dimethyloctadecane in all repeating units is 5 mol% or more, particularly 5 to obtain elastomeric properties, low dielectric properties and adhesiveness. It is preferably 25 mol%. Further, the range of 10 to 30% by weight is preferable.

The polyamide-imide block and random copolymer of the present invention have excellent heat resistance, adhesiveness, solvent solubility, moldability, and electrical characteristics, and are useful as film-forming materials. For example, the polyamideimide block and the random copolymer may be dissolved in an organic solvent such as N, N-dimethylacetamide or tetrahydrofuran, and other resin or pigment may be added as necessary to form a coating solution. it can. By coating this coating liquid on glass or another substrate or an object to be coated, it is possible to form a coating that can be used as a heat-resistant film, heat-resistant paint, heat-resistant adhesive or the like.

The polyamide-imide block and random copolymer of the present invention can be easily etched with an alkaline aqueous solution such as NaOH or KOH, a hydrazine solution, or a basic etching solution such as an amine-based solvent. It is useful as a circuit board material used around a semiconductor chip that exhibits high accuracy and high reliability. For example, the polyamideimide block and the random copolymer are dissolved in a suitable solvent and applied on a suitable substrate such as a semiconductor to form a coating film, and then a photosensitive layer is formed with a photoresist material on the substrate and exposed. And developing to remove the unexposed portion of the photosensitive layer to expose the above coating, and then elute the exposed coating with a basic etching solution, and thereafter,
The pattern can be formed by peeling and removing the resist coating formed of the photoresist material. The formed pattern has excellent heat resistance and electrical insulation, and can be used as an insulating film used around a semiconductor chip.

[0034]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 1.587 g of 4,4'-methylenedi-2-methyl-6-ethylaniline in a 300 ml three neck round bottom flask.
(5.62 mmol) and N-methyl-2-pyrrolidone (20 ml) were added, and the mixture was dried at 5 ° C. under a dry nitrogen atmosphere at 3,4,4.
3 ', 4'-biphenyltetracarboxylic dianhydride 2.
942 g (10.0 mmol) was gradually added as a powder and reacted at 40 ° C. for 8 hours. Then, in another container, 4,4'-methylenedi-2-methyl-6-ethylaniline 2.474 g (8.76 mmol), lithium chloride 0.06 g, calcium chloride 0.18 g, N-methyl-.
2-Pyrrolidone (20 ml) and triphenyl phosphite (2.72 g) were added thereto, and 1.62 g (4.32) of 7,12-dimethyloctadecane having a carboxyl group at both ends dissolved in 20 ml of pyridine at 100 ° C. under a dry nitrogen atmosphere.
(8 mmol) was added and reacted at 100 ° C. for 3 hours, and the reaction solution was added to the above reaction solution at room temperature and reacted at 40 ° C. for 6 hours. To this reaction solution was added 10 ml of xylene, and 1
The dehydration ring closure reaction was performed at 90 ° C. for 3 hours, and the amount of azeotropic water was quantified by a simple moisture meter (a combination of a V-shaped tube and an eggplant-shaped flask). After the reaction was completed, the polymer solution was poured into 2 liters of methanol to precipitate the polymer. After filtration, unreacted monomers and inorganic metal salts were removed in hot methanol. After filtration, vacuum dry,
A polyamideimide block copolymer of the present invention having a yield of 98.6% and a 7,12-dimethyloctadecane content of 20% by weight was obtained. The intrinsic viscosity of this polyamide-imide block copolymer is N, N-dimethylacetamide,
At a polymer solution concentration of 0.5 g / dl and 30 ° C.,
It was 0.77 dl / g. Degree of polymerization x
And y were x = 20 and y = 10. Also, IR
Spectra were confirmed measured structure (KBr tablet method), the absorption of the amide carbonyl group near 1648 cm ^-1, absorption of an imide carbonyl group near 1725 cm ^-1,
Absorption based on an alkyl group derived from the raw material was observed at around 2850 cm ^-1 , and the compound was confirmed to be the target.

Example 2 A 300 ml three-necked round bottom flask was charged with 4.676 g (18.38 mmol) of 4,4'-methylenedi-2,6-xylidine and 20 ml of N-methyl-2-pyrrolidone and placed in a dry nitrogen atmosphere. 3.22 g of 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride at 5 ° C under
(10.0 mmol) was gradually added as a powder to obtain 40
The reaction was performed at 8 ° C. for 8 hours. Xylene 10m in the reaction solution
1 was added thereto, a dehydration ring closure reaction was carried out at 190 ° C. for 3 hours, and azeotropic water was quantified with a simple moisture meter (a combination of a V-shaped tube and an eggplant-shaped flask). Then 1 container
The mixture was cooled to 00 ° C., and dissolved in 10 ml of pyridine, 3.10 g (8.38 mmol) of 7,12-dimethyloctadecane having a carboxyl group at both ends, and lithium chloride of 0.20.
02 g, calcium chloride 0.06 g and triphenyl phosphite 5.20 g were added, and the temperature was 100 ° C. under a dry nitrogen atmosphere.
And reacted for 4 hours. After the reaction was completed, the polymer solution was poured into 2 liters of methanol to precipitate the polymer. After filtration, unreacted monomers and inorganic metal salts were removed in hot methanol. After filtration, vacuum drying, yield 9
A polyamideimide block copolymer of the present invention having a content of 8.7% and a content of 7,12-dimethyloctadecane of 30% by weight was obtained. The intrinsic viscosity of this polyamide-imide block copolymer is 0.85 at a polymer solution concentration of 0.5 g / dl in 30 ° C. in N, N-dimethylacetamide.
It was dl / g. Degree of polymerization x and y in this
Was x = 25 and y = 10. In addition, the IR spectrum (KBr tablet method) was measured and the structure was confirmed.
Absorption of amidocarbonyl group near 660 cm ^-1 , 173
Absorption of imidocarbonyl group near 0 cm ^-1 2900c
Absorption based on the alkyl group derived from the raw material was observed around m ⁻¹ , and it was confirmed that the compound was the target compound.

Example 3 In a 300 ml three neck round bottom flask, 2,2-bis (4-
(4-Aminophenoxy) phenyl) propane 6.82
7 g (16.63 mmol) and 30 ml of N-methyl-2-pyrrolidone were added, and under a dry nitrogen atmosphere at 5 ° C.,
3.53Og (10.0mmol) of 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride was gradually heated as a powder and reacted at 40 ° C for 8 hours. 10 ml of xylene was added to this reaction solution, a dehydration ring closure reaction was carried out at 190 ° C. for 3 hours, and azeotropic water was quantified by a simple moisture meter (a combination of a G-shaped tube and an eggplant-shaped flask). Then, the container is cooled to 100 ° C. and pyridine 10 is added.
7,1 having carboxyl groups at both ends dissolved in ml
2-dimethyloctadecane 2.45 g (6.63 mmol), lithium chloride 0.02 g, calcium chloride 0.0
6 g and 4.11 g of triphenyl phosphite were added, and the mixture was reacted at 100 ° C. for 4 hours under a dry nitrogen atmosphere. After the reaction was completed, the polymer solution was poured into 2 liters of methanol to precipitate the polymer. After filtration, unreacted monomers and inorganic metal salts were removed in hot methanol. After filtration, vacuum drying was performed to obtain a polyamide-imide block copolymer of the present invention having a yield of 97.0% and a 7,12-dimethyloctadecane content of 20% by weight. The intrinsic viscosity of this polyamide-imide block copolymer is 0.5 g / dl of polymer solution in N, N-dimethylacetamide and 3
It was 0.97 dl / g at 0 degreeC. The polymerization degrees x and y in this product were x = 30 and y = 15. As a result of observation of the measured structure IR spectrum (KBr tablet method), the absorption of the amide carbonyl group near 1655 cm ^-1, absorption of an imide carbonyl group near 1725 cm ^-1, alkyl derived from a raw material in the vicinity of 2905cm ^-1 Absorption based on the group was observed, and it was confirmed that the target compound was obtained.

Example 4 4.570 g (14.72 g) of 4,4-methylenedi-2,6-diethylaniline in a 300 ml three-neck round bottom flask.
Mmol), 0.02 g of lithium chloride, 0.06 g of calcium chloride, 10 ml of N-methyl-2-pyrrolidone and 2.93 g of triphenyl phosphite, and both ends dissolved in 5 ml of pyridine at 100 ° C. under a dry nitrogen atmosphere. 1.75 g (4.72 mmol) of 7,12-dimethyloctadecane having a carboxyl group was added to 100 ° C.
And reacted for 3 hours. Then, at room temperature, 3, 4, 3 ',
4'-biphenyltetracarboxylic dianhydride 2.942
Gradually add g (10.0 mmol) as a powder, and
The reaction was carried out at 0 ° C for 8 hours. Xylene 10 was added to this reaction solution.
After adding ml, the dehydration ring closure reaction was carried out at 190 ° C. for 3 hours, and the azeotropic water was quantified with a simple moisture meter (a combination of a V-shaped tube and an eggplant-shaped flask). 2 after the reaction
The polymer solution was poured into liter of methanol to precipitate the polymer. After filtration, unreacted monomers and inorganic metal salts were removed in hot methanol. After filtration, vacuum drying was performed to obtain a polyamide-imide random copolymer of the present invention with a yield of 97.5% and a 7,12-dimethyloctadecane content of 20% by weight. The copolymerization ratio in this case is 3 when the repeating structural unit corresponding to the formula (2-1) is 3
2 mol%, the repeating structural unit corresponding to the formula (2-2) was 68 mol%, and the degree of polymerization was 120. The intrinsic viscosity of this polyamide-imide random copolymer is 0.5 g / d of polymer solution concentration in N, N-dimethylacetamide.
It was 0.98 dl / g at 30 ° C. As a result of observation of the measured structure IR spectrum (KBr tablet method), the absorption of the amide carbonyl group near 1650 cm ^-1, absorption of an imide carbonyl group near 1725 cm ^-1, alkyl derived from a raw material in the vicinity of 2905cm ^-1 Absorption based on the group was observed, and it was confirmed that the target compound was obtained.

Example 5 6.023 g (19.40) of 4,4-methylenedi-2,6-diethylaniline in a 300 ml three neck round bottom flask.
Mmol), lithium chloride 0.04 g, calcium chloride 0.12 g, N-methyl-2-pyrrolidone 15 ml and triphenyl phosphite 5.83 g, and both ends dissolved in pyridine 10 ml at 100 ° C. under a dry nitrogen atmosphere. 3.48 g (9.40 mmol) of 7,12-dimethyloctadecane having a carboxyl group was added to 100
The reaction was carried out at 0 ° C for 3 hours. Then, at room temperature, 3, 4,
3 ', 4'-biphenyltetracarboxylic dianhydride 2.
354 g (8.0 mmol) and 0.436 g (2.0 mmol) of pyromellitic dianhydride were gradually added as powder, and they were reacted at 40 ° C. for 8 hours. 10 ml of xylene was added to this reaction solution, a dehydration ring closure reaction was carried out at 190 ° C. for 3 hours, and azeotropic water was quantified with a simple moisture meter (a combination of a G-shaped tube and an eggplant-shaped flask). After the reaction was completed, the polymer solution was poured into 2 liters of methanol to precipitate the polymer. After filtration, unreacted monomers and inorganic metal salts were removed in hot methanol. After filtration, vacuum drying was performed to obtain a polyamideimide random copolymer of the present invention with a yield of 99.0% and a 7,12-dimethyloctadecane content of 30% by weight. The copolymerization ratio of this compound was such that the repeating structural unit corresponding to formula (2-1) was 48 mol%, the repeating structural unit corresponding to formula (2-2) was 52 mol%, and the degree of polymerization was 150. It was
The intrinsic viscosity of this polyamide-imide random copolymer was 0.90 dl / g at 30 ° C. at a polymer solution concentration of 0.5 g / dl in N, N-dimethylacetamide. As a result of observation of the measured structure IR spectrum (KBr tablet method), the absorption of the amide carbonyl group near 1660 cm ^-1, absorption of an imide carbonyl group near 1725 cm ^-1, alkyl derived from a raw material in the vicinity of 2900 cm ^-1 Absorption based on the group was observed, and it was confirmed that the target compound was obtained.

Example 6 3.0 g (15.0 mmol) of 3,4-diaminodiphenyl ether, 0.05 g of lithium chloride, 0.15 g of calcium chloride and N-methyl-2-pyrrolidone were placed in a 300 ml three-necked round bottom flask. 15 ml and 3.1 g of triphenyl phosphite were added, and the solution was dissolved in 10 ml of pyridine in a dry nitrogen atmosphere at 100 ° C. to obtain 1.85 g (5.05 g of 7,12-dimethyloctadecane having a carboxyl group at both ends).
(Mmol) and added, and reacted at 100 ° C. for 3 hours. Then, at room temperature, 4,4'-oxydiphthalic anhydride 3.
102 g (10.0 mmol) was gradually added as a powder and reacted at 40 ° C. for 8 hours. 10 ml of xylene was added to this reaction solution, a dehydration ring closure reaction was carried out at 190 ° C. for 3 hours, and azeotropic water was quantified with a simple moisture meter (a combination of a G-shaped tube and an eggplant-shaped flask). After the reaction was completed, the polymer solution was poured into 2 liters of methanol to precipitate the polymer. After filtration, unreacted monomers and inorganic metal salts were removed in hot methanol. After filtration, vacuum drying was performed to obtain a polyamide-imide random copolymer of the present invention with a yield of 98.5% and a 7,12-dimethyloctadecane content of 25% by weight. The copolymerization ratio of this compound was such that the repeating structural unit corresponding to formula (2-1) was 33 mol%, the repeating structural unit corresponding to formula (2-2) was 67 mol%, and the degree of polymerization was 100. It was The intrinsic viscosity of this polyamide-imide random copolymer is N,
Polymer solution concentration 0.5 in N-dimethylacetamide
It was 0.95 dl / g at 30 ° C. As a result of observation of the measured structure IR spectrum (KBr tablet method), the absorption of the amide carbonyl group near 1660 cm ^-1, absorption of an imide carbonyl group near 1730 cm ^-1, alkyl derived from a raw material in the vicinity of 2900 cm ^-1 Absorption based on the group was observed, and it was confirmed that the target compound was obtained.

Example 7 The polyamide-imide block copolymer synthesized in Example 1 and the polyamide-imide random copolymer synthesized in Example 4 were used.
An N-dimethylacetamide solution was produced. This polymer solution was cast on a glass plate and the solvent was removed by a vacuum drier, whereby a transparent film was obtained. Glass transition temperature of the polyamide-imide block copolymer of Example 1:
Tg is 300 ° C, thermal decomposition start temperature in air: Td is 3
Dielectric constant at room temperature at 50 ° C. and frequency of 100 KHz:
ε'was 2.9, and the moisture absorption rate was 0.3%. The Tg of the polyamide-imide random copolymer of Example 4 was 31.
0 ℃, Td 350 ℃, ε'2.3, moisture absorption 0.4
%Met.

Example 8 Using the polyamideimide block and the random copolymer obtained in Examples 1, 2, 4 and 5, respectively,
A varnish consisting of an N, N-dimethylacetamide solution having a polymer concentration of 15% by weight was prepared. Using the four types of varnishes thus prepared, a pattern made of a polyamideimide copolymer thin film was formed by the following patterning method. A polyamide-imide block or random copolymer varnish is applied on a semiconductor substrate on which wiring has been formed, using a spin coater, and the temperature is 150 ° C. for 1 hour and 200 ° C. for 3 hours.
Heat treatment was performed for 0 minutes to form a thin film having a thickness of 1 to 3 μm.
In addition, a cyclized rubber negative photoresist (OMR8
3, manufactured by Tokyo Ohka Kogyo Co., Ltd. using a spin coater,
It was dried at 90 ° C. for 20 minutes to form a 1 μm resist thin film. A photomask was brought into close contact with this thin film, and exposure (5 mJ / cm ² × 5 seconds) was performed through the photomask. After the exposure, the thin film was immersed in a developer (OMR developer, manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 20 ° C. for 2 minutes to elute and remove the unexposed portion of the thin film. Next, the exposed part of the polyamide-imide copolymer film not covered with the photoresist film was immersed in a mixed solution of hydrazine monohydrate and ethylenediamine (7: 3) at a temperature of 30 ° C. for 5 minutes. Etched.
After etching, the above-mentioned polyamide-imide copolymer film covered with a photoresist film is treated with a resist stripping solution (S-
502, manufactured by Tokyo Ohka Kogyo Co., Ltd.) to remove the photoresist film by peeling. After removing the photoresist coating, heat treatment was performed at 200 ° C. for about 30 minutes to obtain a pattern formed product composed of a polyamideimide block or a random copolymer thin film. The pattern formed product consisting of the obtained polyamideimide block or random copolymer thin film,
It was confirmed that all were sharp patterns with sharp edges. In addition, this pattern formed product is 250
No deformation of the pattern was observed even when heated to ℃.

[0042]

The polyamide-imide block and random copolymer of the present invention are 7,12-dimethyloctadecane-modified polyamide-imide, and have improved solvent solubility and compatibility with other resins, heat resistance and processing. Not only it has excellent properties, but also has low hygroscopicity, low dielectric constant, and excellent adhesiveness. Further, the polyamide-imide block and the random copolymer of the present invention have a film forming property, and the film is etchable with an alkaline aqueous solution and can be patterned, so that it is useful for producing a circuit board or the like. Therefore, it is a very useful material in the field of film forming materials and electronic components. Further, the production method of the present invention uses aromatic diamine, aromatic tetracarboxylic dianhydride, and 7,12-dimethyloctadecane having a carboxyl group at both ends as raw materials,
It has the advantage that the desired polyamide-imide block or random copolymer can be easily and conveniently synthesized under mild conditions by a series of continuous treatment steps without isolation and purification of the amide compound formed in the middle. In addition, there is an advantage that a polyamide-imide block and a random copolymer whose structure is regulated can be easily obtained without side reaction.

Claims (9)

[Claims] 1. A polyamide-imide block copolymer having an intrinsic viscosity of 0.1 to 3.0 dl / g and represented by the following general formula (1). Embedded image (In the formula, Ar ¹ and Ar ² each represent an aromatic group which may have a substituent, x represents an integer of 0 to 150, and y represents an integer of 1 to 30.) 2. A repeating structural unit of 1 to 99 mol%, which has an intrinsic viscosity of 0.1 to 3.0 dl / g and is represented by the following general formula (2-1) and the following general formula (2-2). A polyamide-imide random copolymer, characterized in that 99 to 1 mol% of the repeating structural units shown are bonded irregularly. Embedded image (In the formula, Ar ¹ and Ar ² each represent an aromatic group which may have a substituent.) 3. An aromatic diamine represented by the following general formula (3) and an aromatic tetracarboxylic acid dianhydride represented by the following general formula (4) are polycondensed to form carboxylic acid anhydride groups at both ends. A polyamic acid having (In the formula, Ar ¹ and Ar ² each represent an aromatic group which may have a substituent.) The polyamic acid is combined with a carboxyl group-containing 7,12-dimethyloctadecane and an aromatic diamine. 7,12 having amino groups at both ends obtained by condensation of
-Dimethyloctadecane compound, polycondensation in the presence of phosphite and pyridine or its derivative, and then imide ring-closing reaction is carried out.
The method for producing the polyamide-imide block copolymer according to 1. 4. An aromatic diamine represented by the above general formula (3) and an aromatic tetracarboxylic dianhydride represented by the above general formula (4) are polycondensed to form a carboxylic acid anhydride group at both ends. A polyamic acid having ## STR3 ## and then an imide ring-closure reaction to synthesize a polyimide having amino groups at both ends, the polyimide being 7,12-dimethyloctadecane having a carboxyl group at both ends and a phosphite ester. The method for producing a polyamide-imide block copolymer according to claim 1, wherein the polycondensation is carried out in the presence of pyridine or a derivative thereof. 5. An aromatic diamine represented by the above general formula (3) and 7,12-dimethyloctadecane having a carboxyl group at both ends are condensed in the presence of a phosphite ester and pyridine or a derivative thereof to obtain both. 7,12-dimethyloctadecane having an amino group at the terminal was synthesized,
Polycondensation of 7,12-dimethyloctadecane having amino groups at both ends and an aromatic diamine represented by the general formula (3) with an aromatic tetracarboxylic dianhydride represented by the general formula (4). 3. The method for producing a polyamide-imide random copolymer according to claim 2, wherein the polyamic acid is synthesized to perform an imide ring closure reaction. 6. The polyamideimide block according to claim 3, wherein the aromatic diamine represented by the general formula (3) is a compound represented by the following general formula (3-1). Method for producing random copolymer. [Chemical 4] (In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² represents an alkyl group having 1 to 4 carbon atoms.) 7. The aromatic tetracarboxylic dianhydride represented by the general formula (4) is a compound represented by the following general formula (4-1). The method for producing a polyamide-imide block or a random copolymer of. Embedded image (In the formula, Z represents a ketone group or a direct bond.) 8. A film-forming material comprising the polyamideimide block copolymer according to claim 1 or the polyamideimide random copolymer according to claim 2 as a main component. 9. A pattern forming material comprising a base material and a coating film comprising the polyamideimide block copolymer according to claim 1 or the polyamideimide random copolymer according to claim 2 as a main component, and a base. A method of forming a resist pattern, which comprises forming a pattern by performing an etching treatment with a hydrophilic etching solution.