TWI392962B - Photosensitive resin composition and method for producing the same - Google Patents

Description

Photosensitive resin composition and method of producing the same

The present invention relates to a photoresist composition suitable for use as a positive photoresist having a photosensitive function developed by an aqueous alkali solution, a polyimide-based resin as a main component, heat resistance, chemical resistance, insulation, and flexibility. And its manufacturing method.

Conventionally, as a photosensitive polyimine-based material, a material which is a poly-proline which is a precursor of polyimine, for example, a carboxyl group of a poly-proline has been proposed to be bonded to a photosensitive group by bonding with an ester group. (Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. )Wait. However, in order to obtain the intended polyimide film, it is necessary to carry out a ruthenium imidization treatment at a high temperature of more than 300 ° C in order to obtain the high temperature, and to limit the copper oxidation of the base substrate and the wiring. The problem.

As an improvement method, there is a proposal to use a photosensitive polyimide which is a solvent-soluble resin which is yttrium imidized for the purpose of lowering the temperature of the post-stage hardening temperature (Japanese Laid-Open Patent Publication No. Hei 10-274850, In any of the above, the (meth)acrylic acid group imparts photosensitivity to the resin, and the photocuring mechanism is easily hindered by oxygen, and the residual film property is insufficient during development. For other reasons, it is difficult to improve the resolution and cannot fully satisfy the required characteristics.

On the other hand, there is also a polyimine structure which has a phenolic hydroxyl group, and a polyamine structure (Japanese Laid-Open Patent Publication No. Hei 3-209478) The positive type of the combination of the bullet and the diazonaphthoquinone. In order to ensure developability, the molecular weight of the resin is low molecular weight, and the amount of diazonaphthoquinone added as a sensitizer becomes a large amount of the resin, and it is difficult to obtain the original hardening property of the resin.

Further, the positive type of the above-mentioned resin and the diazonaphthoquinone mixed system is insufficient in residual film properties during development.

[Patent Document 1] Japanese Laid-Open Patent Publication No. SHO-54-145746 (Patent Document No. 5). Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei. Hei.

In view of the above, the present invention provides a function of both an alkali-soluble resin and a sensitizer, a polyiminoimine resin as a main component, heat resistance, chemical resistance, insulation, flexibility, and residual film property. An excellent photosensitive resin composition suitable as a positive photoresist and a method for producing the same.

As a result of the above-mentioned purpose, the inventors of the present invention have repeatedly conducted the above-mentioned purpose, and the hydrogen atom of the hydroxyl group of the polyimine having a phenolic hydroxyl group represented by the following general formula (1) is 0.02 to 0.25 per hydrogen atom. The present invention has been completed as a photosensitive resin composition obtained by using a 1,2-naphthoquinonediazidesulfonyl group-substituted polyimine resin as an alkali-soluble resin and a sensitizer.

Polyimine having a phenolic hydroxyl group represented by the following general formula (1).

Wherein X is a tetravalent organic group, Y is a divalent organic group represented by the general formula (2), Z is a divalent organic group, and W is a divalent organic group having an organic decane structure, and l is Positive number, m, n are 0 or a positive number, 0.1≦l/(l+m+n)≦1,0≦m/(l+m+n)≦0.8,0≦n/(l+m+n)≦0.8; (where A is selected from The divalent organic groups of either of them may be the same or different; B and C are each an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, which may be different or the same; a and b are 0 or 1, c An integer of 0 to 10, wherein R ¹ is an organic group selected from a phenolic hydroxyl group and substituted by a 1,2-naphthoquinonediazidesulfonyl group at a ratio of 0.02 to 0.25 mol per hydrogen atom. Base one price base)].

In the present invention, the hydrogen atom of the hydroxyl group of the polyimine resin having a phenolic hydroxyl group is substituted by a 1,2-naphthoquinonediazidesulfonyl group at a ratio of 0.02 to 0.25 mol per hydrogen atom. An amine resin as an alkali-soluble resin and a sensitizer.

A polyimine resin substituted with a 1,2-naphthoquinonediazidesulfonyl group by using a hydrogen atom of a hydroxyl group of a phenolic hydroxyl group-containing polyimine resin of the present invention in a wide wavelength range Under the light exposure, the residual film property at the time of development is good, and it is not inhibited by oxygen, and a film can be formed easily. In addition, it is possible to form a pattern having excellent resolution, and further, the film obtained from the composition is excellent in adhesion to a substrate, heat resistance, and insulation, and is applicable to a protective film such as an electric or electronic member or a semiconductor element.

Hereinafter, the present invention will be described in more detail. The polyimine which is a precursor of the present invention has a repeating unit represented by the following general formula (1).

In the above formula, X in the general formula (1) is a tetravalent organic group, and specifically includes at least one group represented by the following formula.

Y in the general formula (1) is a divalent organic group represented by the following general formula (2).

Wherein A, a, b, c, and R ¹ are as defined above, and B and C are each an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, which may be the same or different, specifically, for example, methyl, ethyl or propyl. The base and the butyl group are preferable in that the methyl group and the hydrogen atom are easily obtained from the raw material.

Specifically, Y is, for example, the following structure.

Further, Z in the general formula (1) is a divalent organic group represented by the following general formula (3).

In the above formula, D is selected from The divalent organic groups of either one may be the same or different, and e, f and g are 0 or 1.

Specifically, Z is, for example, the following structure.

Further, W in the general formula (1) is a divalent organic group represented by the following general formula (4).

In the general formula (4), R ² is a monovalent hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different. Specifically, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; an aromatic group such as a phenyl group; a benzyl group or a phenyl group; An alkenyl group such as an aralkyl group such as a arylalkyl group, a vinyl group, an allyl group, a propenyl group, an isopropenyl group or a butenyl group; an acryl group; a methacryl group; A point which is easy to obtain from a raw material is preferably a methyl group, an ethyl group, a phenyl group or a vinyl group. Further, h is a positive number from 1 to 80, preferably from 3 to 70, more preferably from 5 to 50.

Moreover, l, m, and n in the general formula (1) are positive numbers of 2≦l≦2000, 0≦m≦2000, 0≦n≦2000, respectively, satisfying 0.1≦l/(l+m+n)≦1, 0≦m /(l+m+n) ≦ 0.8, 0≦n/(l+m+n) 正 0.8 positive number.

The molecular weight of the polyimine represented by the general formula (1) of the present invention may be usually from 2,000 to 800,000, more preferably from 5,000 to 500,000. When the molecular weight is 5,000 or less, the obtained polyimide pigment has a low film strength, which is not preferable, and 5,000,000 or more is not preferable because it lacks compatibility with a solvent.

In the present invention, a part of a hydrogen atom of a hydroxyl group of a polyimine resin having such a phenolic hydroxyl group is substituted with 1,2-naphthoquinonediazidesulfonyl group, and a photosensitive composition of interest can be obtained as 1, The partial esterification of the 2-indolyl compound can be carried out by a general method of partial esterification.

The polyimine having a phenolic hydroxyl group can be a diamine having a phenolic hydroxyl group and a dianhydride, and if necessary, reacting with a phenol group-free diamine and/or a diamino fluorenone to obtain a polyamine acid. It is obtained by a ring closure reaction.

As a dianhydride for the polymerization of polylysine, for example, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride , 2,3',3,4'-biphenyltetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1, 2-Dicarboxylic anhydride, 4-(2,5-dioxotetrahydrofuran-3-indenyl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 1,2,3,4 - butyl tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-hexafluorodiisopropylidene dicarboxylic acid dianhydride, 2,2-dual ( Phenyltrimethanol phenyl)propane, 1,3-tetramethyldioxane dicarboxylic acid dianhydride, 4,4-oxadic acid dianhydride.

Further, as a diamine having a phenolic hydroxyl group or a carboxyl group, for example, 3,3'-diamino-4,4'-dihydroxybiphenyl, 2,2'-diamino-4,4'-dihydroxyl linkage Benzene, 2,2-bis(4-amino-3-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 9,9'-bis(3-amine 4-hydroxyphenyl)indole, 2,2'-methylenebis[6-(4-amino-3,5-dimethylbenzyl)-4-methyl]phenol, 3,3 A diamine having a phenol group such as -diamino-4,4'-dihydroxyphenyl ether or 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

Also as a phenol-free diamine, such as 4,4'-diaminobenzidine (4,4'-diaminobenzanilide), 4,4'-diaminophenyl ether, 3,4'-diamine Phenylphenyl ether, 4,4'-diaminodiphenyl hydrazine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-(p-phenylene diisopropylene Diphenylamine, 4,4'-(m-phenylene diisopropylidene)diphenylamine, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-amino Phenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-dual 4-(4-Aminophenoxy)phenyl]hexafluoropropane, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)benzene碸, 4,4'-bis(4-aminophenoxy)biphenyl, 9,9-bis(4-aminophenyl)anthracene, and the like.

The ratio of the polyamine derivative to the diamine component of the tetracarboxylic dianhydride component is appropriately determined depending on the molecular weight of the polyimine, and the molar ratio is usually 0.95 to 1.05, more preferably 0.98 to 1.02. range. Further, in order to adjust the molecular weight of the polyimine, an acid anhydride such as phthalic anhydride or an aniline or an amine compound may be added. The amount of addition in this case is preferably 5 mol% or less to the tetracarboxylic dianhydride component or the diamine component.

The polyimine synthesis is carried out by heating the polyamic acid solution obtained above to a temperature of usually 80 to 200 ° C, preferably 140 to 180 ° C, or adding a acetic anhydride/pyridine mixed solution to polyamine. The acid solution is then heated to 50 ° C or higher, and the guanamine portion of the poly-proline is subjected to a dehydration ring-closure reaction to obtain a polyimine.

The reaction of the diamine with the dianhydride is usually carried out in a solvent. As such a solvent, it is sufficient to dissolve the polyimine. Specific examples of the solvent include ethers such as tetrahydrofuran and anisole; and ligands such as cyclohexanone, 2-butanone, methyl isobutyl ketone, 2-heptanone, 2-octanone, and acetophenone; An ester of butyl acetate, methyl benzoate or γ-butyrolactone; a cellosolve such as cellosolve butyl acetate or propylene glycol monomethyl ether acetate; N,N-dimethyl Anthracene such as formamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone, and aromatic hydrocarbons such as toluene and xylene are preferably ketones, esters and The base cellulose is particularly preferably γ-butyrolactone, propylene glycol monomethyl ether acetate, N,N-dimethylacetamide or n-methyl-2-pyrrolidone. These solvents may be used alone or in combination of two or more. Usually, the yield of each batch, considering the dissolved viscosity, the concentration of polyimine is adjusted to a range of 10 to 40% by weight.

The photosensitive composition having a 1,2-naphthoquinonediazidesulfonyl group is synthesized by adding 1,2-quinonediazidesulfonyl chloride and a basic compound to the polyimine solution obtained above. The mixture was stirred at room temperature to obtain the intended photosensitive composition.

That is, a diamine having a phenolic hydroxyl group and a dianhydride are reacted with a diamine and/or a diamine fluorenone which does not contain a phenolic hydroxyl group, if necessary, to obtain a polylysine, followed by a dehydration ring closure (ring closure) The reaction is carried out by obtaining a polyimine having a phenolic hydroxyl group represented by the general formula (5) and then reacting with a 1,2-quinonediazide compound.

[In the formula, X, Z, W, 1, m, and n are as described above, and Y' is a divalent organic group represented by the following general formula (6).

(wherein A, B, C, a, b, and c are as described above).

In this case, as an introduced 1,2-quinonediazide compound for 1,2-naphthoquinonediazidesulfonyl group, for example, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride.

At this time, the hydrogen atom of the hydroxyl group of the polyimine resin is substituted with 1,2-naphthoquinonediazidesulfonyl group at a ratio of 0.02 to 0.25 mol%. When more than 0.25 mol% is substituted, the photosensitive resin solution is in a high concentration, the holding temperature is high, and the diazide may be decomposed and decomposed, and it may be difficult to obtain adhesion for a long time. Further, when it is substituted by less than 0.02 mol%, the residual film property during development is poor, the pattern cannot be cut, and it is not possible to use it as a photosensitive resin composition.

In addition, the basic compound at this time is not particularly limited as long as it reacts with the generated hydrogen chloride to form a salt during the reaction and promotes the reaction. For example, diethylamine, triethylamine, and the like.

In the present invention, the polyimine which is introduced into the 1,2-naphthoquinonediazidesulfonyl group is used as a film-forming material resin and a sensitizer, and the additive component can be further formulated. As such an additive component, for example, in order to improve coatability, a conventional surfactant can be added. As the surfactant, it is preferred to be nonionic, such as a fluorine-based surfactant, specifically, for example, perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkyl oxide amine, fluorine-containing organic oxime An alkyl compound or the like.

These can be used as commercially available products, such as FLUORAD "FC-4430" (any one is Sumitomo 3M (share)), SAFRON "S-141" and "S-145" (any one is Asahi Glass Co., Ltd.) UNIDYNE "DS-401", "DS-4031" and "DS-451" (any one is Daikin Industries Co., Ltd.), MEGAFACE "F-8151" (Daily Ink Industry Co., Ltd.), "X-70-093" (any one is Shin-Etsu Chemical Co., Ltd.). Among them, FLUORAD "FC-4430" (Sumitomo 3M (share) system) and "X-70-093" (Shin-Etsu Chemical Industry Co., Ltd.) are preferable.

As the other additive component, a decane coupling agent such as an epoxy decane coupling agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be added as the adhesion-improving agent. Further, when the photosensitive composition of the present invention is used for a photoresist or the like, it is usually used for a photoresist or the like, and any other additive component may be added. Further, the amount of the above-mentioned additive component added is a general amount within a range that does not impair the effects of the present invention.

Further, in order to improve the residual film property, other sensitizers may be prepared as needed. A sensitizer which acts on the resin and has a dissolution preventing effect on the developer is preferable, and specifically, for example, "NT-300P" (manufactured by Toyo Seiki Co., Ltd.).

The preparation of the photocurable resin composition of the present invention can be carried out by a general method, and the above components and the above-mentioned organic solvent, additives, and the like are stirred and mixed, and then the solid component is filtered by a filter or the like as needed to prepare the photosensitive material of the present invention. Resin composition.

The photosensitive resin composition of the present invention prepared as described above is suitably used for, for example, a protective film for a semiconductor element, a protective film for a wiring, a protective film, a solder resist, and the like as a material for photoresist for fine processing.

The method of forming a pattern for forming a pattern using the above-mentioned photosensitive resin composition includes the following steps.

(i) a step of applying the above-mentioned photosensitive resin composition onto a substrate or forming a film by another method; (ii) passing through a photomask, performing an exposure step with light including a light source having a wavelength of 240 to 500 nm, and performing exposure as needed a subsequent heating (so-called PEB step) step; (iii) a step of developing with a developing solution.

After the pattern is formed by the above three steps, and then the pattern is formed by (iV), the step of heating in the subsequent stage hardening is performed to obtain a protective film of the final purpose.

In the method of forming a pattern of the present invention, first, the above-mentioned photosensitive resin composition is applied onto a substrate. Examples of the substrate include a germanium wafer, a plastic, a ceramic circuit board, and the like. Further, the solution can be thinned by another method and attached to the substrate.

As the coating method, it can be carried out by a conventional lithography technique. For example, it is applied by a method such as a dipping method, a spin coating method, or a roll coating method. The amount of coating can be appropriately selected depending on the purpose, and the film thickness is preferably 0.1 to 100 μm. Further, a film of the composition may be formed in advance, and the film may be bonded to a substrate.

At this time, in order to carry out the photodecomposition reaction efficiently, the solvent may be volatilized first by preheating as needed. The preheating system is carried out, for example, at a temperature of from 40 to 140 ° C for 1 minute to 1 hour. Then, it is exposed to light having a wavelength of 240 to 500 nm through a photomask to be decomposed. The reticle can for example dig out the desired figure. Further, the material of the photomask is preferably such that light having a wavelength of 240 to 500 nm can be shielded. For example, chromium or the like is preferably used, but it is not limited thereto.

As the light having the wavelength of 240 to 500 nm, light of various wavelengths is generated by, for example, a radiation generating device, for example, ultraviolet rays such as g-line or i-line, far ultraviolet rays (248 nm), or the like. The exposure amount is preferably, for example, 10 to 2000 mJ/cm ² . If necessary, in order to further improve the development sensitivity, heat treatment after exposure can be performed. The heat treatment after the above exposure is, for example, 0.5 to 10 minutes at 40 to 140 °C.

After the above exposure or heat treatment after exposure, development is carried out with a developer. As the developer, an organic solvent is used as a solvent, for example, dimethylacetamide, cyclohexanone or the like. The development can be carried out by a general method such as impregnation of a pattern formation or the like. Then, washing, washing, drying, and the like are carried out as needed to obtain a film having a desired pattern. Further, the pattern forming method is as described above, and when it is not necessary to form a pattern, for example, a uniform film may be formed, and the method of forming the pattern may be carried out in the same manner as the above method without using the mask.

Further, the obtained pattern is heated by using an oven or a hot plate at a temperature of 120 to 300 ° C for 10 minutes to 10 hours, and by removing the remaining volatile components, the adhesion to the substrate is excellent, heat resistance and strength are formed. A film that is also good in electrical properties.

The cured film obtained from the above-mentioned photosensitive resin composition is excellent in adhesion to a substrate, heat resistance, and electrical insulation, and can be used as a protective film for electric, electronic members, semiconductor elements, etc., and can be used for formation of fine patterns. The formed film is excellent in adhesion to the substrate, electrical properties, mechanical properties, and the like, and is suitable for use as a protective film for a semiconductor element, a protective film for wiring, a protective film, and a solder resist.

[Examples]

Hereinafter, the present invention will be specifically described by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to these examples.

[Synthesis Example 1]

Into a flask equipped with a stirrer, a thermometer, and a nitrogen substitution device, 31.0 g (0.1 mol) of 4,4'-oxydiphthalic acid dianhydride and 150 g of n-methyl-2-pyrrolidone were placed. Then, 25.8-bis (4-amino-3-hydroxyphenyl)propane 25.8 g (0.1 mol) was dissolved in a solution of 100 g of n-methyl-2-pyrrolidone while adjusting the temperature of the reaction system to not exceed 50. At ° C, it was dropped into the above flask. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Next, a reflux condenser equipped with a water receiver was placed in the flask, and 70 g of xylene was added thereto, and the temperature was raised to 150 ° C, and the temperature was maintained at this temperature for 6 hours to obtain a brown solution.

After thus resulting brown solution was cooled to room temperature (25 deg.] C), its IR spectrum analysis, no absorption was observed from the polyamide acid was observed 1780cm ^{- 1} and 1720 ^- based on the absorption of ^an imino acyl, and observed 3400cm ^{- 1} absorbed from the vicinity of the phenolic group, that is a repeating unit represented by the following formula as a resin. Further, as a result of gel permeation chromatography (GPC) analysis, the number average molecular weight (Mn) in terms of polystyrene was 52,300.

Then, 200 g of the obtained resin solution (resin solid content: 17%), 1.43 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 1.37 g of triethylamine were placed in a flask, and stirred at room temperature for 6 hours. . After completion of the reaction, the reaction solution was placed in 1 liter of methanol, and after drying, the desired polyimine was obtained. As a result of 1H-NMR analysis of the resin, the peak of 10 ppm from the phenolic hydroxyl group was reduced by 90%, whereas 5.3 ppm of the peak derived from hydrogen bonded to the carbon bonded to the diazide group was observed. The resin (A-1) having the structure of the repeating unit represented by the following formula is known. Further, as a result of gel permeation chromatography (GPC) analysis, the resin had a number average molecular weight of 59,200.

[Synthesis Example 2]

In a flask equipped with a stirrer, a thermometer, and a nitrogen substitution device, 54.3 g (0.175 mol) of 4,4'-oxydiphthalic acid dianhydride and 4,4'-hexafluoroisopropylidene dicarboxylic acid dianhydride were placed. 33.3 g (0.075 mol) and n-methyl-2-pyrrolidone 400 g. Then, 64.6 g (0.25 mol) of 2,2-bis(4-amino-3-hydroxyphenyl)propane was dissolved in a solution of 200 g of n-methyl-2-pyrrolidone while adjusting the temperature of the reaction system to not exceed 50. At ° C, it was dropped into the above flask. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Next, a reflux condenser equipped with a water receiver was placed in the flask, and 70 g of toluene was added thereto, and the temperature was raised to 150 ° C, and the temperature was maintained at this temperature for 6 hours to obtain a brown solution.

The brown solution thus obtained was cooled to room temperature (25 ° C) to obtain a polyimine having a phenolic hydroxyl group (resin solid content: 20.3%). Then, 300 g of the polyimine solution and 5.71 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 2.28 g of triethylamine were placed in a flask, and the mixture was stirred at room temperature for 6 hours. After completion of the reaction, the reaction solution was placed in 1 liter of methanol, and after drying, the desired polyimine was obtained. As a result of 1H-NMR analysis of the resin, the peak of 10 ppm from the phenolic hydroxyl group was reduced by 90%, whereas 5.3 ppm of the peak derived from hydrogen bonded to the carbon bonded to the diazide group was observed. The resin (A-2) having a structure of a repeating unit represented by the following formula is known. Further, as a result of gel permeation chromatography (GPC) analysis, the resin had a number average molecular weight of 63,000.

[Synthesis Example 3]

In a flask equipped with a stirrer, a thermometer, and a nitrogen substitution device, 89.6 g (0.25 m) of 3,3',4,4'-diphenyltetracarboxylic dianhydride and N,N'-dimethyl B were placed. Guanamine 500g. Then, 32.3 g (0.125 mol) of 2,2-bis(4-amino-3-hydroxyphenyl)propane and 43.6 g (0.125 mol) of 9,9-bis(4-aminophenyl)anthracene. A solution dissolved in 200 g of N,N'-dimethylacetamide was added dropwise to the flask while adjusting the temperature of the reaction system to not more than 50 °C. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Next, a reflux condenser equipped with a water receiver was placed in the flask, and 180 g of toluene was added thereto, and the temperature was raised to 150 ° C, and the temperature was maintained at this temperature for 6 hours to obtain a brown solution.

The brown solution thus obtained was cooled to room temperature (25 ° C) to obtain a polyiminoimine having a phenolic hydroxyl group (resin solid content 20.0%). Then, 300 g of the polyimine solution and 2.64 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 1.05 g of triethylamine were placed in a flask, and the mixture was stirred at room temperature for 6 hours. After completion of the reaction, the reaction solution was placed in 1 liter of methanol, and after drying, the desired polyimine was obtained. As a result of 1H-NMR analysis of the resin, the peak of 10 ppm from the phenolic hydroxyl group was reduced by 90%, whereas 5.3 ppm of the peak derived from hydrogen bonded to the carbon bonded to the diazide group was observed. The resin (A-3) having the structure of the repeating unit represented by the following formula is known. Further, as a result of gel permeation chromatography (GPC) analysis, the resin had a number average molecular weight of 56,800.

[Synthesis Example 4]

In a flask equipped with a stirrer, a thermometer, and a nitrogen substitution device, 77.6 g (0.25 mol) of 4,4'-oxydiphthalic acid dianhydride and 500 g of N,N'-dimethylacetamide were placed. Then, 51.7 g (0.2 mol) of 2,2-bis(4-amino-3-hydroxyphenyl)propane and diamine decane (but the average f of the general formula (6) is 9) 45.8 g (0.05 mol) was dissolved in a solution of 200 g of N,N'-dimethylacetamide while the temperature of the reaction system was adjusted to not exceed 50 ° C, and the mixture was dropped into the flask. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Next, a reflux condenser equipped with a water receiver was placed in the flask, and 150 g of toluene was added thereto, and the temperature was raised to 150 ° C, and the temperature was maintained at this temperature for 6 hours to obtain a brown solution.

The brown solution thus obtained was cooled to room temperature (25 ° C) to obtain a polyimine having a phenolic hydroxyl group (resin solid content: 20.5%). Then, 300 g of the polyimine solution, 3.98 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 1.59 g of triethylamine were placed in a flask, and the mixture was stirred at room temperature for 6 hours. After completion of the reaction, the reaction solution was placed in 1 liter of methanol, and after drying, the desired polyimine was obtained. As a result of 1H-NMR analysis of the resin, the peak of 10 ppm from the phenolic hydroxyl group was reduced by 90%, whereas 5.3 ppm of the peak derived from hydrogen bonded to the carbon bonded to the diazide group was observed. The resin (A-4) having the structure of the repeating unit represented by the following formula is known. Further, as a result of gel permeation chromatography (GPC) analysis, the resin had a number average molecular weight of 63,200.

[Synthesis Example 5]

The polyimine was obtained in the same manner as in Synthesis Example 1 except that 1,2-naphthoquinonediazide-5-sulfonyl chloride was 7.72 g and triethylamine was 3.07 g. As a result of 1H-NMR analysis of the resin, the peak of 10 ppm from the phenolic hydroxyl group was reduced by 15%, whereas 5.3 ppm of the peak derived from hydrogen bonded to the carbon bonded to the diazide group was observed. A resin (A-5) having a structure of a repeating unit represented by the following formula is known. Further, as a result of gel permeation chromatography (GPC) analysis, the polymer had a number average molecular weight of 65,400.

[Synthesis Example 6]

The polyimine was obtained in the same manner as in Synthesis Example 1 except that 1,2-naphthoquinonediazide-5-sulfonyl chloride was 20.59 g and triethylamine was 8.20 g. As a result of 1H-NMR analysis of the resin, a peak of 10 ppm from the phenolic hydroxyl group was reduced by 40%, whereas 5.3 ppm of a peak derived from hydrogen bonded to the carbon bonded to the diazide group was observed. The resin (B-1) having a structure of a repeating unit represented by the following formula is known. Further, as a result of gel permeation chromatography (GPC) analysis, the polymer had a number average molecular weight of 73,000.

[Synthesis Example 7]

The polyimine was obtained in the same manner as in Synthesis Example 1 except that 1,2-naphthoquinonediazide-5-sulfonyl chloride was 0.51 g and triethylamine was 0.20 g. As a result of 1H-NMR analysis of the resin, a peak of 10 ppm from the phenolic hydroxyl group was decreased by 1%, whereas a peak of 5.3 ppm of hydrogen derived from carbon bonded to the carbon bonded to the diazide group was observed. A resin (B-2) having a structure of a repeating unit represented by the following formula is known. Further, as a result of gel permeation chromatography (GPC) analysis, the polymer had a number average molecular weight of 54,000.

[Examples]

Using the photosensitive polyimine resin synthesized in the above Synthesis Examples 1 to 6, a resin solid content of 20.0% was dissolved in a cyclohexanone solution, and the composition described in Table 1 was used to prepare a surfactant, a sensitizer, and the like. Then, the mixture was stirred, mixed, and dissolved, and then precisely filtered through a 0.2 μm filter made of polytetrafluoroethylene to obtain the photocurable resin compositions of the present invention of Examples 1 to 6. Further, for comparison, a resin represented by the formula (7) which is an intermediate of the formula (8) of Synthesis Example 1 was obtained by dissolving a resin solid component in a solution of 20.0% in cyclohexanone to prepare a resin solution C. -1.

Then, two sheets of a 6-inch wafer and six sides of a 6-inch wafer, which were subjected to primer treatment with hexamethyldiazane, were plated with a copper copper substrate having a thickness of 2 μm, and a spin coater was used. The composition of each example was applied to the film thickness described in the table. Among the prepared three wafers, one ruthenium substrate was heated and dried by a hot plate at 100 ° C for 1 minute to remove the solvent, and then passed through a quartz mask having a line width of 1 μm to 20 with a line of equal intervals. The light of the wavelength described in Table 1 was irradiated with the exposure amount. Further, here, NSR-1755i7A represents a stepper exposure apparatus manufactured by Nikon, and PLA-600FA represents a contact alignment type exposure apparatus manufactured by Canon. After the irradiation, it was heated at 80 ° C for 1 hour and then cooled.

Then, the coated substrate was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution for 3 minutes to carry out development. The line width of development at this time is shown in Table 2. Further, the film thickness after development is also described in combination. On the other hand, the composition of each of the examples described in Table 1 was applied to the remaining tantalum wafer and the copper substrate under the same conditions, preheating with removal of the solvent, and then immersing in dimethylacetamide. The film remaining after this operation was further heated in an oven at 200 ° C for 3 hours to obtain a film. The insulating properties and adhesion of the film were measured by the film, as described in Table 2.

The contents of the other additives used are as follows.

FC-4430: Surfactant (commercial name of Sumitomo 3M (share)) KBE-403: Next auxiliary (trade name of Shin-Etsu Chemical Co., Ltd.) X-70-093: Surfactant (Shin-Etsu Chemical Industry Co., Ltd. ) product name) NT-300P: sensitizer (trade name of Toyo Synthetic Industrial Co., Ltd.)

In the above Table 2, the adhesion was evaluated in a pressure cooker saturated at 2 atm, and the substrate was allowed to stand for 24 hours, and then the number of peeling was measured by a checkerboard peeling test.

As a result of the above, the compositions of Examples 1 to 8 have a film thickness of about 1 μm, and have a good residual film property and resolution for a wide film thickness of a film thickness of more than 10 μm, and exhibit sufficient characteristics as a photosensitive material. At the same time, the cured film has good adhesion to various substrates and electrical properties having a so-called insulation withstand voltage, and can be obtained as a protective film for a circuit or an electronic member.

Claims (8)

A photosensitive resin composition comprising: a polyimine resin in which a part of a hydrogen atom of a phenolic hydroxyl group represented by the following general formula (1) is substituted with 1,2-naphthoquinonediazidesulfonyl group; And a photosensitive resin composition of the resin, Wherein X is a tetravalent organic group, Y is a divalent organic group represented by the general formula (2), Z is a divalent organic group, and W is a divalent organic group having an organic decane structure, and l is Positive number, m, n are 0 or a positive number, 0.1≦l/(l+m+n)≦1,0≦m/(l+m+n)≦0.8,0≦n/(l+m+n) ≦0.8; (where A is selected from The divalent organic groups of either of them may be the same or different; B and C are each an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, which may be different or the same; a and b are 0 or 1, c An integer of 0 to 10, wherein R ¹ is an organic group selected from a phenolic hydroxyl group and substituted by a 1,2-naphthoquinonediazidesulfonyl group at a ratio of 0.02 to 0.25 mol per hydrogen atom. In the general formula (2), R ¹ is a 1,2-quinone stack used as a hydrogen atom for introducing a 1,2-naphthoquinonediazidesulfonyl group into a phenolic hydroxyl group. A nitrogen compound which is 1,2-naphthoquinonediazide-4-sulfonyl chloride and 1,2-naphthoquinonediazide-5-sulfonyl chloride. The resin and the photosensitive resin composition of the first aspect of the invention, wherein in the general formula (1), X is at least one tetravalent organic group represented by the following formula The photosensitive resin composition of claim 1, which comprises a polyimine resin and a resin, and in the general formula (1), Z is a divalent organic group represented by the following general formula (3) (In the above formula, D is selected from The divalent organic groups of either one may be the same or different, and e, f and g are 0 or 1). The photosensitive resin composition of the first to second aspects of the patent application, which comprises a polyimine resin and a resin, wherein in the general formula (1), Z is a divalent product represented by the following general formula (4) Organic based helium oxide resin, (wherein R ² is a monovalent hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, and h is a positive number from 1 to 80). The photosensitive resin composition according to any one of claims 1 to 3, which contains a decyl alkane resin, and n in the general formula (1) is 3 ≦ n ≦ 400. A method for producing a photosensitive resin, which comprises reacting a diamine having a phenolic hydroxyl group and a dianhydride, and if necessary, reacting a diamine having no phenolic hydroxyl group and/or a diamine fluorenone to obtain a polylysine Thereafter, a polyimine having a phenolic hydroxyl group represented by the general formula (5) is obtained by a ring closure reaction, and then reacted with a 1,2-quinonediazide compound. Wherein X, Z, W, l, m, and n are as defined above, and Y' is a divalent organic group represented by the following general formula (6). (wherein A, B, C, a, b, and c are as described above). A method for forming a pattern, comprising: the following three steps: (i) a step of forming a photosensitive resin and a composition thereof according to any one of claims 1 to 5 on a substrate; Ii) passing through the photomask, performing an exposure step using light having a light source having a wavelength of 240 to 500 nm, and performing a heating step after exposure as necessary; and (iii) performing a developing step on the alkali developing solution. A film for protection characterized in that a film formed by a method as in the method of claim 6 is subjected to post-stage hardening at a temperature in the range of 120 ° C to 300 ° C.