KR20090065586A - Positive photosensitive polyimides and the composition thereof - Google Patents

Abstract

A positive-type photosensitive polyimide resin composition containing polyimide resin is provided to show excellent electrical insulation, solubility in an alkali aqueous solution as well as physical properties and low shrinkage. A polyimide resin has a repeat unit represented by the formula 1. The number-average molecular weight of the polyimide resin is 2,000-800,000. In the formula 1, l and m are independently integers of 0 to 200; n is an integer of 10 to 200; W is tetravalent organic group having tetracarboxylic acid and its derivative; X is divalent organic group insoluble in an aqueous solution comprising diamine; Y is divalent organic group containing carboxylic acid soluble in the aqueous solution comprising diamine; and Z is o-nitrobenzyl derivative represented by the formula 2.

Description

Positive photosensitive polyimide resin and composition thereof

   The present invention relates to a positive photosensitive polyimide resin and a method for preparing the same, and a positive photosensitive polyimide resin composition obtained therefrom, which has a solubility in an aqueous alkali solution due to light irradiation, thereby forming a pattern, and specifically, a nitrobenzyl derivative It relates to a polyimide resin comprising a photosensitive group consisting of, a method for producing the same, and a composition using the same. This photosensitive polyimide resin composition is suitable for forming surface protection films, interlayer insulating films, passivation films, electrode protective layers, positive photoresists and protective films of electrical and electronic devices, in particular, semiconductor devices and display devices.

   In recent years, miniaturization and compactness of various electronic components have been required, and along with this, the development of various technologies for forming patterns and the demand for materials thereof have become more advanced, and the soldering heat resistance, There is a need for a heat-resistant insulating material capable of forming a pattern having excellent performances such as electroless gold plating resistance, substrate adhesion, chemical resistance, and the like, and various specific proposals have been made to solve this problem. Among them, many proposals have been made for the invention of the photosensitive polyimide used for forming the protective film. For example, as a conventional photosensitive polyimide-based material, a photosensitive group is introduced by ester bonding to a material using a polyamic acid, which is a precursor of polyimide, for example, a carboxyl group of a polyamic acid (Japanese Patent Laid-Open No. 49-115541) And a material containing an amine compound having a polyamic acid and a photosensitive group (Japanese Patent Laid-Open No. 54-145794) and the like have been proposed. These proposals, however, do not lead to the improvement of products in recent years in terms of strong sensitivity, developability, and flexibility. Particularly, in the case of the above-described techniques, the negative photosensitive polyimide can be manufactured because it is based on the crosslinking reaction by ultraviolet irradiation. However, in the electronic industry, the photosensitive polyimide having a solubility in the light irradiation part as a method for minimizing the defect rate. It requires technology. As a technique of such a photosensitive polyimide, proposals such as (Japanese Patent Publication No. 64-60630 and U.S. Patent No. 4,395,482) are known, but since a resin of a polyamic acid state, which is a precursor, is used, heat is reduced after pattern formation. There has been a problem of volumetric shrinkage resulting from changes in molecular structure and removal of some leaving groups through the process of midmization. This volume shrinkage also remains a residual stress of the film, and ultimately the degradation of interfacial adhesion is a problem. Moreover, in these inventions, after forming a patterned film, the imidation process at high temperature exceeding 300 degreeC is essential in order to obtain the target polyimide film, and a base base material is restrict | limited in order to withstand this high temperature, Had a problem of oxidizing copper. In order to avoid this problem, photosensitive polyimides using already imidized solvent soluble resins have also been proposed (M. Ueda and T. Nakayama, Macromolecules, 29, 6427, 1996). For this reason, it is difficult to improve the resolution, and it has not been a material that satisfies all the required properties.

Accordingly, the present invention proposes a method of synthesizing polyimide resin having a positive photosensitive property, having solubility in a solvent, easy to synthesize, and easy to adjust the substitution rate of the photoreceptor, and thus excellent in developability, residual film ratio, resolution, and the like. It is going to develop the photosensitive polyimide resin composition which has the performance which can fully satisfy | fill in terms of adhesiveness, heat resistance, insulation, flexibility, etc. of a finally formed film.

   The present invention is to solve the problems of the prior art as described above, at least one repeating unit containing no soluble in the aqueous solution represented by the formula (1), and carboxylic acid soluble in the aqueous solution, By preparing a photosensitive polyimide resin composition comprising a photosensitive polyimide resin simultaneously containing at least one repeating unit introduced with a photosensitive group including a nitrobenzene derivative group, by first preparing a photosensitive polyimide resin composition to improve the existing complex synthesis step by a simple synthesis method And secondly, to prepare a photosensitive polyimide resin having a low film reduction rate, and finally to provide a polyimide resin composition having good patterning appearance and excellent color transparency.

   By using the positive photosensitive polyimide resin composition according to the present invention, it is excellent in resolution, insulation, thermal shock resistance, adhesiveness, etc., and sufficient residual film during development proposed in the problem to be solved, It also solved the problem of fairness at high temperature. In particular, the film shrinkage phenomenon that occurs during the high temperature imidization reaction, which was a problem in the development of photosensitive polyimide using the existing polyamic acid has been significantly improved.

   The positive photosensitive polyimide resin according to the present invention, a manufacturing method thereof, and a positive photosensitive polyimide resin composition obtained therefrom will be described in detail as follows.

(A) The present invention relates to one or more repeating units having no solubility in an aqueous solution represented by the formula (1), at least one repeating unit containing a carboxylic acid soluble in an aqueous solution, and a photosensitive group including a nitrobenzene derivative group. The present invention relates to a polyimide resin having photosensitivity including at least one repeating unit.

In the formula, the repeating units l and m are each an integer of 0 or more and 200 or less, n is an integer of 10 or more and 200 or less, W represents a tetravalent organic group constituting tetracarboxylic acid and its derivatives, and X is a diamine. Is a divalent organic group that is not soluble in the aqueous solution constituting the compound, Y is a divalent organic group containing carboxylic acid soluble in the aqueous solution constituting the diamine, Z is an ortho-nitrobenzyl derivative represented by the formula (2) .)

(In the formula, R1 and R2 are each selected from an alkyl group having 1 to 12 carbon atoms or hydrogen, and R3 and R4 are each represented by hydrogen or an alkyl group having 0 to 4 carbon atoms, or an alkoxy group or a halogen group.)

(B) The present invention also comprises at least one repeating unit having no solubility in an aqueous solution represented by the following formula (3) and a carboxylic acid soluble in an aqueous solution in order to produce the photosensitive polyimide resin represented by the formula (1) After preparing a soluble polyimide resin containing at least one repeating unit simultaneously, 10 to 100 mol% of the carboxylic acid groups present in the resin is reacted with a compound having an ortho-nitrobenzyl group represented by the following formula (4) It relates to a method for producing a polyimide resin comprising the step of replacing at least some of the hydrogen atoms of the carboxyl groups with ester groups of ortho-nitrobenzyl derivatives.

(Wherein repeating unit l is an integer of 0 or more and 200 or less, m is an integer of 10 or more and 400 or less, W represents a tetravalent organic group constituting tetracarboxylic acid and its derivatives, and X constitutes diamine). It is a divalent organic group which is not soluble in aqueous solution, and Y is a divalent organic group containing carboxylic acid which is soluble in the aqueous solution which comprises a diamine.)

(Wherein R1 and R2 are each selected from an alkyl group having 1 to 12 carbon atoms or hydrogen, and R3 and R4 are each hydrogen or an alkyl group having 0 to 4 carbon atoms or an alkoxy or halogen group, and Q is a halogen group, a hydroxyl group or a carboxy) Is a functional group capable of reacting with a group to form an ester group.)

(C) The present invention also relates to a positive photosensitive polyimide resin composition prepared by dissolving a photosensitive polyimide resin represented by the formula (1) in an organic solvent and other additives for controlling physical properties of the resin solution.

The present invention is described in more detail below.

In the present invention, the repeating units l and m of the components constituting the general formula (1) are each an integer of 0 or more and 200 or less, n is an integer of 10 or more and 200 or less, W is a tetravalent constituting tetracarboxylic acid and its derivatives. An organic group, X is a divalent organic group having no solubility in the aqueous solution constituting the diamine, Y is a divalent organic group containing a carboxylic acid soluble in the aqueous solution constituting the diamine, Z is represented by the formula (2) The ortho-nitrobenzyl derivative is not particularly limited.

In addition, the tetravalent organic group W which comprises the repeating unit tetracarboxylic acid and its derivative in the said diamine, the divalent organic group X which is not soluble with respect to the aqueous solution which comprises a diamine, and the carboxylic acid which is soluble in the aqueous solution which comprises a diamine. The diamine components, such as divalent organic group Y containing these, may be individual or multiple pieces, respectively. As a specific example, the diamine of the divalent organic group Y containing the carboxylic acid which is soluble in an aqueous solution, for example, 1,3-diamino-4-carboxybenzene, 1,3-diamino-5-carboxybenzene, 1 , 3-diamino-4,6-dicarboxybenzene, 1,4-diamino-2-carboxybenzene, 1,4-diamino-2,5-dicarboxybenzene, bis (4-amino-3-carboxy Phenyl) ether, bis (4-amino-3,5-dicarboxyphenyl) ether, bis (4-amino-3-carboxyphenyl) sulfone, bis (4-amino-3,5-dicarboxyphenyl) sulfone, 4 , 4'-diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethylbiphenyl, 4,4'-diamino- 3,3'-dicarboxy-5,5'-dimethoxybiphenyl, 1,4-bis (4-amino-3-carboxyphenoxy) benzene, 1,3-bis (4-amino-3-carboxyphenoxy Benzene, bis [4- (4-amino-3-carboxyphenoxy) phenyl] sulfone, bis [4- (4-amino-3-carboxyphenoxy) phenyl] propane, 2,2-bis [4- (4-amino Diamine which has carboxyl groups, such as 3-carboxyphenoxy) phenyl] hexafluoro propane, is mentioned. The diamine represented by the divalent organic group X which is insoluble in an aqueous solution is 1,3-diamino-4-hydroxybenzene, 1,3-diamino-5-hydroxybenzene, 1,3-diamino- 4,6-dihydroxybenzene, 1,4-diamino-2-hydroxybenzene, 1,4-diamino-2,5-dihydroxybenzene, bis (3-amino-4-hydroxyphenyl) Ether, bis (4-amino-3-hydroxyphenyl) ether, bis (4-amino-3,5-dihydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) methane, bis (4 -Amino-3-hydroxyphenyl) methane, bis (4-amino-3,5-dihydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3- Hydroxyphenyl) sulfone, bis (4-amino-3,5-dihydroxyphenyl) sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis ( 4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3,5-dihydroxyphenyl) hexafluoropropane, 4,4'-diamino-3,3 '-D Hydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-5, 5'-dimethoxybiphenyl, 1,4-bis (3-amino-4-hydroxyphenoxy) benzene, 1,3-bis (3-amino-4-hydroxyphenoxy) benzene, 1,4- Bis (4-amino-3-hydroxyphenoxy) benzene, 1,3-bis (4-amino-3-hydroxyphenoxy) benzene, bis [4- (3-amino-4-hydroxyphenoxy) Phenyl] sulfone, bis [4- (3-amino-4-hydroxyphenoxy) phenyl] propane, 2,2-bis [4- (3-amino-4-hydroxyphenoxy) phenyl] hexafluoropropane Diamines having phenolic hydroxyl groups such as 1,3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene, bis ( Diamine and 1,3-diaminobenzene-4-sulfonic acid having a thiophenol group such as 4-amino-3-mercaptophenyl) ether 2,2-bis (3-amino-4-mercaptophenyl) hexafluoropropane , 1,3-diaminobenzene-5-sulfonic acid, 1,4-dia Nobenzene-2-sulfonic acid, bis (4-aminobenzene-3-sulfonic acid) ether, 4,4'-diaminobiphenyl) 3,3'-disulfonic acid, 4,4'-diamino-3,3 ' Diamines having sulfonic acid groups such as -dimethylbiphenyl-6,6'-disulfonic acid, bis (4-amino-3-carboxy-5-hydroxyphenyl) ethers having a plurality of these groups, and bis (4-amino-3 -Carboxy-5-hydroxyphenyl) methane, bis (4-amino-3-carboxy-5-hydroxyphenyl) sulfone, 2,2-bis (4-amino-3-carboxy-5-hydroxyphenyl) propane , 2,2-bis (4-amino-3-carboxy-5-hydroxyphenyl) hexafluoropropane and the like, 4,4-methylene-bis (2,6-ethylaniline), 4,4'-methylene -Bis (2-isopropyl-6-methylaniline), 4,4'-methylene-bis (2,6-diisopropylaniline), bis [4- (3-aminophenoxy) phenyl] sulfone, 2, 2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 4,4'-diamino-3,3 '-Dimethyldicyclohexyl Tan, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) Benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy ) Phenyl] hexafluoropropane etc. are mentioned. Alternatively, a siloxane-containing diamine component such as Formula 5 may be used for adhesion to the substrate.

(Wherein p represents an integer of 1 to 10)

In addition, although the tetracarboxylic acid and its derivative which comprise W in General formula (1) are not specifically limited, For example, 1,2,4,5-benzene tetracarboxylic acid, 3,3 ', 4, 4'-biphenyltetracarboxylic acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 2,2-bis (3,4-di Aromatic tetracarboxylic acids, such as carboxyphenyl) hexafluoro propane and bis (3, 4- dicarboxyphenyl) sulfone, these dianhydrides, and these dicarboxylic acid diacid halides, etc. are mentioned. From the viewpoint of solubility, 3,3'4,4'-biphenyltetracarboxylic acid, 3,3'4,4'-benzophenonetetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexa Tetracarboxylic acids such as fluoropropane and bis (3,4-dicarboxyphenyl) sulfone and their dianhydrides and their dicarboxylic acid diacid halides are preferred.

Furthermore, cyclobutane-1,2,3,4-tetracarboxylic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid, 2,3,5-tricarboxycyclo Alicyclic such as pentyl acetic acid, bicyclo (2,2,2) octo-7-ene-2,3,5,6-tetracarboxylic acid, tetrahydrofuran-2,3,4,5-tetracarboxylic acid Tetracarboxylic acid, these dianhydrides, and these dicarboxylic acid diacid halides; and the like. In addition, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid, dianhydrides thereof, and dicarboxylic acid diacid halides thereof may also be mentioned. Among these, cyclobutane-1,2,3,4-tetracarboxylic acid, its dianhydride, its dicarboxylic acid diacid halide and the like are used to obtain sufficient sensitivity as the photosensitive polyimide and obtain a highly transparent polyimide resin. This is preferred.

For preparing the photosensitive polyimide resin of Chemical Formula 1, the following method may be used. That is, a soluble polyimide resin simultaneously containing at least one repeating unit X having no solubility in an aqueous solution represented by the formula (3) and at least one repeating unit Y containing a carboxylic acid having solubility in an aqueous solution is used in a known method. 10 to 100 mol% of the carboxylic acid groups present in the resin after the reaction is reacted with a compound having an ortho-nitrobenzyl group represented by Formula 4 to at least a part of the hydrogen atoms of the carboxyl group of the polyimide to form an ortho-nitrobenzyl derivative. A photosensitive polyimide resin represented by Chemical Formula 1 is prepared by a method of substituting with an ester group of. A method for producing a soluble polyimide resin simultaneously comprising at least one repeating unit X having no solubility in an aqueous solution represented by the formula (3) and at least one repeating unit Y containing a carboxylic acid having solubility in an aqueous solution is as follows. Although the same example is mentioned, this does not limit the method of manufacturing the polyimide resin which is soluble in the aqueous solution represented by General formula (3). For example, the method of synthesize | combining a polyimide precursor by reaction of tetracarboxylic dianhydride and diamine, and dehydrating ring closure is mentioned. The reaction temperature of tetracarboxylic dianhydride and diamine can select arbitrary temperature of -20 degreeC-150 degreeC, Preferably -5 degreeC-100 degreeC. At this time, as a solvent, N, N-dimethylformamide (hereinafter referred to as DMF), N, N-dimethylacetoamide (hereinafter referred to as DMAC), N, N-dimethylmethoxyacetoamide, and N-methyl-2-pyrrolidone ( NMP), 1,3-dimethyl-2-imidazolinone, caprolactam, N-methylcaprolactam, dimethyl sulfoxide, dimethyl sulfone, sulfolane, tetramethyl urea, hexamethylphosphoramide, phenol, cresol, Xylenol, chlorophenol, ethylene glycol, diethylene glycol, triethylene glycol, glyme, diglyme, triglyme, and the like, but among these, polar solvents such as N-methylpyrrolidone and dimethylacetamide Use is preferred. In order to convert the polyimide precursor into a polyimide, the polyimide precursor may be heated in a solution state at 150 ° C. to 250 ° C., and azeotropic dehydration is performed by adding toluene, xylene, or the like in order to remove water generated by the dehydration ring closure. It is also possible to. In addition, catalyst imidization is a simpler method of converting polyimide precursors into polyimides. In this case, tertiary amines, such as acetic anhydride, triethylamine, pyridine, isoquinoline, and imidazole, are added to a polyimide precursor solution, and chemical imidation can be performed at arbitrary temperature of 0 degreeC-250 degreeC.

The polyimide resin soluble in the aqueous solution represented by the formula (3) prepared in this way is reacted with a compound having an ortho-nitrobenzyl group represented by the formula (4) by 10 to 100 mol% of the carboxylic acid groups present in the resin A photosensitive polyimide resin represented by Chemical Formula 1 is prepared by substituting at least a portion of the hydrogen atoms of the carboxyl groups of the polyimide with ester groups of ortho-nitrobenzyl derivatives. As a method for reacting 10 to 100 mol% of the carboxylic acid groups present in the polyimide resin soluble in the aqueous solution represented by the formula (3) with a compound having an ortho-nitrobenzyl group represented by the formula (4) Although it depends on the kind of chemical functional group represented by Q among the compounds which have an ortho-nitrobenzyl group, the method is not limited as a case where it demonstrated by the following example. That is, when Q is halogen, the polyimide resin represented by the formula (3) and the compound having the ortho-nitrobenzyl group represented by the formula (4) are mixed to obtain a desired substitution ratio, and then the tertiary amine as the catalyst is the ortho- represented by the formula (4). 10 to 200 mol% of the compound having a nitrobenzyl group may be added, and reacted at 10 to 150 ° C. for 1 to 48 hours to prepare a photosensitive polyimide resin represented by Chemical Formula 1. At this time, the tertiary amines that can be used include tertiary amines consisting of alkyl groups having 1 to 10 carbon atoms such as trimethylamine and triethylamine, 1,8-diazabicyclo (5,4,0) unde-7-cene, and the like. The same cycloalkyl tertiary amine may be used, and may be any catalyst used for preparing ester groups between carboxyl and halogenated alkyls, but preferably triethylamine or 1,8-diazabicyclo (5,4). Tertiary amines such as (0) unde-7-cene) can be used efficiently. In addition, when Q is a hydroxyl group, the carboxyl group of the polyimide resin soluble in the aqueous solution represented by the formula (3) is represented by the formula (3) by using a thionyl chloride or phosphorus trihalide which can convert the carboxyl group into a carboxylic acid halide group. After converting to a carboxy group of a polyimide resin soluble in an aqueous solution and mixed with a compound having an ortho-nitrobenzyl group represented by the formula (4) to obtain the ratio of the desired substitution amount and reacted for 1 to 48 hours at 0 to 150 ℃ The photosensitive polyimide resin shown by 1 can be manufactured. In order to neutralize the generated halogen acid, a base such as pyridine and triethyl amine may be used in an amount of 10 to 200 mol% based on the compound having an ortho-nitrobenzyl group represented by Formula 4.

By the above method, 10 to 100 mol% of the carboxylic acid groups present in the resin are reacted with a compound having an ortho-nitrobenzyl group represented by Formula 4 from a polyimide resin soluble in an aqueous solution represented by Formula 3 through the above method. The photosensitive polyimide resin represented by Formula 1 can be prepared by substituting at least a part of the hydrogen atoms of the carboxyl group of the polyimide with an ester group of an ortho-nitrobenzyl derivative, but this method is represented by Formula 1 from the soluble polyimide of Formula 3 It is not limited as a method of obtaining the photosensitive polyimide which becomes.

The present invention also relates to a positive photosensitive polyimide resin composition prepared by dissolving a photosensitive polyimide resin represented by Chemical Formula 1 in an organic solvent and additionally including an additive for controlling physical properties of a resin solution. The photosensitive resin composition is explained in more detail.

First, examples of the polar solvent that can be used in the present invention include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetonitrile, diclim, γ Butyrolactone, phenol, cyclohexanone and the like, among which N-methyl-2-pyrrolidone (NMP) and γ-butyrolactone are particularly preferred.

The photosensitive polyimide resin composition of the present invention may further contain other additives such as a sensitizer, an adhesion aid, and a leveling agent, in addition to the photosensitive polyimide resin component represented by Chemical Formula 1. Moreover, the well-known polyimide resin and polyamic acid resin which are soluble in an organic solvent can also be mixed with the photosensitive polyimide resin represented by General formula (1), and can also be used together.

The sum of the contents of the solid content in the total composition, that is, a known polyimide resin, a polyamic acid resin, and (C) other additives, which are soluble in (A) soluble polyimide and (B) an organic solvent used by mixing Depending on the thickness of the film, it is generally preferred to be from 0.1 to 60% by weight of the total photosensitive polyimide precursor composition. When the content of solids exceeds 60% by weight, there is a difficulty in processes such as spin coating due to the high viscosity.

The photosensitive polyimide resin composition of this invention is positive type, and uses aqueous alkali solution as a developing solution. It is more environmentally friendly and economical than organic solvents. Examples of the alkali developer include aqueous solutions of metal hydroxides such as sodium hydroxide, sodium carbonate, sodium hydroxide, potassium hydroxide and potassium carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like of quaternary ammonium hydroxides. Amine type aqueous solution, such as aqueous solution or ammonia, ethylamine, propylamine, diethylamine, and triethylamine, is mentioned. Among them, tetramethylammonium hydroxide (TMAH) aqueous solution is most commonly used.

By using the photosensitive resin composition of this invention, the heat resistant polyimide film patterned on the board | substrates, such as glass and a silicon wafer, can be formed easily. In this case, as a method of coating the resin composition, spin coating, bar coating, screen printing, or the like may be used.

It is preferable that the thickness of the film to be coated is about 0.1 to 200 μm, and the thicker the film, the lower the resolution. After coating, the solvent is evaporated by prebaking at 50 to 150 ° C. for 2 to 15 minutes to form a prebaked film. Next, ultraviolet rays are irradiated using a photomask on which a pattern to be processed is formed. As for the exposure amount at the time of irradiation, 20-4,000 mJ / cm <2> is preferable. By such a series of processes, the orthonitrobenzyl ester group present in the exposed portion is decomposed to generate an acid upon exposure. As a result, when developing in the above-mentioned alkali developer, the dissolution rate of the exposed portion is significantly increased compared to the non-exposed portion, It is easily removed by the developer to form a desired pattern. The pattern thus formed is washed with distilled water or alcohol and dried to leave only the polyimide pattern on the substrate. In this case, since the obtained pattern has already been imidized, no further imidation step is necessary, but if another soluble polyamic acid resin is mixed with the photosensitive polyimide resin represented by Formula 1, appropriate heat treatment It may require an imidization process such as the process. The heat treatment is carried out stepwise or continuously for 0.5 to 5 hours under vacuum or nitrogen stream, with a maximum temperature specified between 100 ° C and 450 ° C. In the heat treatment step, the substituents of the dissolution inhibitor are pyrolyzed and removed, and the polyamic acid is imidized, and at the same time, a crosslinking reaction occurs between the reactive terminal blockers at the molecular chain ends of each of the soluble polyimide and the polyamic acid. This is converted to a polyimide higher than the initial.

In general, the resolution of the photosensitive resin is expressed as an aspect ratio (d / w), which is a ratio of the thickness (d) to the line width (w) of the formed pattern, and using the photosensitive polyimide resin composition of the present invention, an aspect ratio of 3.0 Achieve high levels of resolution. That is, it can manufacture from the film thickness of 15 micrometers to the pattern of the line width of 5 micrometers.

Thereby, the film | membrane which is excellent in the adhesive force with respect to a base material, and also has favorable electrical property can be formed. The said film is used suitably for protective films and coverlay films, such as electrical and electronic components, and a semiconductor element.

Hereinafter, the present invention will be described in detail with reference to Examples, but these Examples are for explaining the present invention and should not be construed as limiting the protection scope of the present invention.

(Example 1)

As a method for preparing a soluble polyimide represented by the formula (3), 1 mmol of 1,3-diamino-4-carboxybenzene is added to a 100 ml round flask while nitrogen is filled, and N-methyl-2-pyrrolidone (hereinafter referred to as NMP) is dissolved. After the diamine was completely dissolved, 1 mmol of 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride was added and reacted in an ice bath for 24 hours to synthesize polyamic acid. The amount of the solvent is not particularly limited as long as the reaction proceeds, but it is preferable to use an amount such that the solid content concentration does not usually exceed 20% by weight. When it exceeds 20 weight%, a viscosity may become high and handling may become difficult. The reaction is usually carried out at room temperature over 20 hours, preferably 24 hours. Next, 6 mmol of pyridine and 6 mmol of acetic dianhydride were added to the polyamic acid solution, and the reaction was carried out for at least 6 hours, preferably at least 12 hours, at 60 ° C. in a water bath for chemical imidization. The solution was cooled to room temperature, reprecipitated several times with water and methanol, and the resulting precipitate was filtered, washed with methanol, and dried under vacuum for 24 hours to obtain a pale yellow polyimide solid. As a result of this IR spectral analysis, no absorption derived from the polyamic acid was observed, but absorption based on the imide group was observed at 1780 cm-1 and 1720 cm-1, and derived from the carboxy group in the 1 H-NMR spectrum analysis. A peak of 11 to 12 ppm was observed, and it was found that the resin represented by the following formula (6) as a repeating unit. Also, as a result of gel permeation chromatography (GPC) analysis, the number average molecular weight (Mn) in terms of polystyrene was 49200.

(Example 2)

Any dianhydride and a copolymer of the dianhydride may be used as long as it is not limited to Example 1 and can use a dianhydride capable of producing a soluble polyimide represented by the formula (3), but preferably 3,3 ', 4,4'- It can be synthesized under the same conditions as in Example 1 using phenyltetracarboxylic dianhydride (a) or diphenylsulfone dianhydride (b). As the diamine, as described in the formula (3), a soluble polyimide resin simultaneously containing at least one repeating unit X having no solubility in an aqueous solution and at least one repeating unit Y having a carboxylic acid having solubility in an aqueous solution is used. If it can be prepared, it can be any case, but it is preferable to use the 1,3-diamino-4-carboxybenzene and 3,3`- ortho-diphenyl diamine, and the air represented by the formulas (a) and (b) The coalescence was synthesized. Synthesis conditions were carried out in the same manner as in Example 1. The solutions (a) and (b) were cooled to room temperature, and then reprecipitated several times with water and methanol. The resulting precipitate was filtered, washed with methanol, and dried under vacuum for 24 hours to obtain a pale yellow polyimide solid. As a result of this IR spectral analysis, no absorption derived from the polyamic acid was observed, but absorption based on the imide group was observed at 1780 cm-1 and 1720 cm-1, and derived from the carboxy group in the 1 H-NMR spectrum analysis. 11 to 12 ppm of peaks were observed, and the result of calculating the integral of each peak showed that d is about 0.64, e is about 0.36, f is about 0.69, and g is about 0.31. It turned out that it is resin (a), (b) which makes following formula (7) a repeating unit. In addition, as a result of gel permeation chromatography (GPC) analysis, the number average molecular weight (Mn) of polystyrene conversion was 52400 (a) and 49500 (b), respectively.

Next, a method of reacting the soluble polyimide resin represented by the formula (3) obtained as described above with the compound having an ortho-nitrobenzene group represented by the formula (4) will be described.

(Examples 3 to 19)

After dissolving the soluble polyimide synthesized in Example 1 into a 100 ml round flask, N, N-dimethylformamide is preferably dissolved in an organic solvent as described above, and is not less than 10% by weight and not more than 20% by weight. Make a solution of concentration. After cooling the brown solution thus obtained to room temperature (25 ℃)

  (A) In the case where Q is a halogen group among the molecules shown in Formula 4, the brown solution thus obtained is mixed with the proposed molecule, the polyimide solution, and the desired substitution amount, and then used as a catalyst, in a molar amount of 200% of 200% of 1: 1 molar equivalent. Photosensitive polyimide was synthesize | combined by making it react at 60 degreeC or more for 24 hours using nitrogen (for example, 1,8-designers bicyclo (5,4,0) unde-7-cene). The solution was cooled to room temperature, reprecipitated several times with water and methanol, and the resulting precipitate was filtered, washed with methanol, and dried under vacuum for 48 hours to obtain a photosensitive polyimide solid.

  When Q is a hydroxyl group among the molecules represented by (B) or (4), first, the soluble polyimide synthesized in Synthesis Example 1 or 2 is placed in a flask, and the same mole% of thionyl chloride is used for the carboxyl groups included in the polymer. By stirring at room temperature for at least 24 hours and distilling under reduced pressure to remove unreacted thionyl chloride, thereby preparing a polyimide substituted with carboxylic acid chloride first and preferably N, N-dimethyl in the above-mentioned organic solvent. The solution was prepared by dissolving formamide in a solution having a concentration of at least 10% by weight and not exceeding 20%, and then mixing the presented molecules to a desired amount of substitution, and then catalyzing 100 mol% of the amine with respect to the molecule represented by the formula (4) by a catalyst. (For example, pyridine) is added and reacted at 60 DEG C for at least 24 hours in a nitrogen atmosphere to synthesize photosensitive polyimide. The. The solution was cooled to room temperature, reprecipitated several times with water and methanol, and the resulting precipitate was filtered, washed with methanol, and dried under vacuum for at least 24 hours to obtain a photosensitive polyimide solid.

  (C) When Q is epoxy among the molecules shown in Formula 4, N, N-dimethylformamide is preferably dissolved in an organic solvent. The photosensitive polyimide was synthesized by inducing a ring-opening reaction of epoxy using sodium carbonate as a catalyst, and then reacting for 24 hours or more under a nitrogen atmosphere at 60 ° C. The solution was cooled to room temperature, reprecipitated several times with water and methanol, and the resulting precipitate was filtered, washed with methanol, and dried under vacuum for 48 hours to obtain a photosensitive polyimide solid.

 The soluble polyimide used in Examples 3 to 19 can be used without limitation as long as it is a soluble polyimide that satisfies the formula (3). Here, the soluble polyimide prepared in Example 1 will be described. The photoreceptor was synthesized by selecting 17 of the organic compounds represented by the formula (4). Substitution amount of the photoreceptor may be 10 to 100 mol%, but in Examples 3 to 19 below, 40 to 60 mol% was selected and synthesized.

(Comparative Example 1)

9 moles of bromomethyl nitrobenzene in order to prepare a photosensitive polyimide having a particularly low content of ortho-nitrobenzene groups for the purpose of comparing with the photosensitive properties of the photosensitive polyimide resin represented by Formula 1 obtained in Examples 3 to 19 A photosensitive polyimide resin was synthesized in the same manner as in Example 3 except that% (0.027 g) was used.

Detailed synthesis conditions of the photosensitive polyimide prepared in Examples 3 to 19 and the photosensitive polyimide prepared in Comparative Example 1 are described in Table 1 below.

division Q's rescue Formula 6 (g) Formula 4 (g) Formula 4 (designation) Photosensitive Molar ratio Molecular Weight Example 3 A 0.1 0.212 Chloromethyl  Nitrobenzene 0.6 47200 Example 4 0.200 Bromomethyl  Nitrobenzene 0.52 62300 Example 5 0.230 Bromoethyl  Nitrobenzene 0.56 52000 Example 6 0.205 One- Bromomethyl -4,5- Dimethylnitrobenzene 0.47 48000 Example 7 0.236 One- Bromomethyl -4,5- Dimethoxynitrobenzene 0.48 51600 Example 8 0.264 1- (1- Bromeethyl ) -4,5- Dimethoxynitrobenzene 0.51 61000 Example 9 B 0.1 0.156 2- Nitrophenylmethanol 0.57 52000 Example 10 0.137 1- (2- Nitrophenyl )ethanol 0.46 49600 Example 11 0.142 4,5- Dimethoxynitrophenylmethanol 0.44 62000 Example 12 0.209 4,5- Dimethylnitrophenylmethanol 0.55 62400 Example 13 0.203 1- (4,5- Dimethoxynitrophenyl )ethanol 0.5 56700 Example 14 C 0.1 0.153 2- Nitrophenyloxirane 0.52 58000 Example 15 0.157 2- methyl -2- Nitrophenyloxirane 0.49 59400 Example 16 0.196 2- (4,5- Dimethylnitrophenyl ) Oxirane 0.57 42500 Example 17 0.241 2- (4,5- Diethylnitrophenyl ) Oxirane 0.61 63900 Example 18 0.181 2- (4,5- Ethylnitrophenyl )-2- Methyloxirane 0.43 59300 Example 19 0.177 2- (4,5- Dimethoxynitrophenyl ) Oxirane 0.44 51400 Comparative Example 1 A 0.1 0.027 Bromomethyl  Nitrobenzene 0.09 58000

(Examples 20-38)

The photosensitive experiment of the photosensitive polyimide resin obtained in Examples 3 to 19 was confirmed through Examples 20 to 38 as a general pattern formation experiment using the photosensitive polyimide resin. That is, 100 wt% of the photosensitive polyimide resin prepared in Examples 3 to 19 was dissolved in 400 wt% of N, N-dimethylformamide, and fine filtration was performed using a 0.2 micron filter manufactured by Teflon to be used in Examples 20 to 36. The photosensitive resin composition was obtained. In addition, the photosensitive resin composition to be used in Example 37 was obtained by using the photosensitive polyimide having a low content of photosensitive ortho-nitrobenzene group prepared in Comparative Example 1 to obtain a photosensitive functional group ortho-nitrobenzene group. The polyimide resin composition to be used in Example 38 was obtained by producing in the same manner using a mid resin. The obtained composition was coated on a soda lime glass with a bar coater on the whole surface with a film thickness of 20 microns, respectively, and the thickness thereof is shown in Table 2. After coating, the substrate was heated and dried on a hot plate at 100 ° C. for 2 minutes to remove the solvent for each substrate, and then the exposure apparatus was applied through a quartz mask installed 5 per micron each from 1 micron to 20 microns per line / space. The exposure was performed with light having a wavelength of 200 to 700 nm. The exposure amount at the time of irradiation was set to 3,000 mJ / cm <2>. After the irradiation, the coated substrate was developed by immersion for 3 minutes in a 2.38% aqueous tetramethylammonium hydroxide solution. The minimum line width resolved at this time is described in Table 2. In addition, the film thickness after image development was also described.

division Coating thickness ( um ) Thickness after development ( um ) Resolution Example 20 7.5 7.4 5 micron line Example 21 8.1 7.9 10 micron line Example 22 7.7 7.5 5 micron line Example 23 6.9 6.6 5 micron line Example 24 8 7.4 1 micron line Example 25 5.7 5.6 5 micron line Example 26 5.6 5.5 10 micron line Example 27 6.8 6.4 10 micron line Example 28 7 6.8 5 micron line Example 29 7.2 6.9 5 micron line Example 30 5.9 5.6 1 micron line Example 31 6.3 6.1 10 micron line Example 32 7.9 7.7 5 micron line Example 33 6.7 6.5 10 micron line Example 34 5.4 5.3 5 micron line Example 35 7.4 7.2 5 micron line Example 36 6.8 6.6 1 micron line Example 37 7.9 - - Example 38 8.2 - -

For reference, in Example 37, most of the residual film remained without forming a pattern, and in Example 38, most of the resin was dissolved without forming a pattern.

As can be seen from the film thickness after development in Table 2, the resin of the present invention is excellent in residual film properties. Moreover, the resolution is also high and it is preferable as a photosensitive material. In addition, the thermosetting film of the resin of the present invention has good adhesion and good electrical properties to various substrates,

It is useful as a protective film for furnaces or electronic components.

In addition, when obtaining the photosensitive polyimide resin represented by General formula (1) of this invention as a solid, it can be performed as follows, for example. For example, the photosensitive polyimide resin represented by the formula (1) can be precipitated by adding the reaction solution into an empty solvent such as water or methanol, or by adding an empty solvent such as water or methanol into the reaction solution. By filtering and washing this precipitate, it is possible to isolate the photosensitive polyimide resin represented by General formula (1).

Claims (5)

 A polyimide resin having a number average molecular weight of 2,000 to 800,000 and having a repeating unit represented by the following formula (1). <Formula 1>

In the formula, the repeating units l and m are each an integer of 0 or more and 200 or less, n is an integer of 10 or more and 200 or less, W represents a tetravalent organic group constituting tetracarboxylic acid and its derivatives, and X is a diamine. Is a divalent organic group that is not soluble in the aqueous solution constituting the compound, Y is a divalent organic group containing carboxylic acid soluble in the aqueous solution constituting the diamine, Z is an ortho-nitrobenzyl derivative represented by the formula (2) .) In order to produce the photosensitive polyimide resin represented by the formula (1), at least one repeating unit having no solubility in the aqueous solution represented by the following formula (3) and at least one repeating unit containing a carboxylic acid which is soluble in the aqueous solution at the same time After preparing a soluble polyimide resin to react 10 to 100 mol% of the carboxylic acid groups present in the resin with a compound having an ortho-nitrobenzyl group represented by the following formula (4) at least a part of the hydrogen atoms of the carboxy group of the polyimide Method for producing a polyimide resin comprising the step of substituting an ester group of an ortho-nitrobenzyl derivative [Formula 3]

(Wherein repeating unit l is an integer of 0 or more and 200 or less, m is an integer of 10 or more and 400 or less, W represents a tetravalent organic group constituting tetracarboxylic acid and its derivatives, and X constitutes diamine). It is a divalent organic group which is not soluble in aqueous solution, and Y is a divalent organic group containing carboxylic acid which is soluble in the aqueous solution which comprises a diamine.) <Formula 4>

(Wherein R1 and R2 are each one selected from an alkyl group having 1 to 12 carbon atoms or hydrogen, and R3 and R4 are each hydrogen or an alkyl group having 0 to 4 carbon atoms, or an alkoxy or halogen group). A positive photosensitive polyimide resin composition prepared by dissolving a photosensitive polyimide resin represented by Chemical Formula 1 according to claim 1 in an organic solvent and other additives for controlling physical properties of the resin solution. Hardened | cured material formed by photolyzing the photosensitive resin composition of Claim 3. (i) forming a layer containing the polyimide resin according to claim 1 or 2 or 3 on a substrate; (ii) exposing the layer to light having a wavelength of 200 to 700 nm through a photomask having a predetermined pattern formed thereon; (iii) dissolving the exposed layer with an alkaline solution to obtain a patterned film.