JP5381491B2 - Resin and positive photosensitive resin composition - Google Patents

Description

  The present invention relates to a resin having a specific structure as a main component. More specifically, the present invention relates to a resin suitable for a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, and a positive photosensitive resin composition using the same.

  Since polyimide resin has excellent heat resistance and electrical insulation, it is widely used for surface protection films of semiconductor elements such as LSI (Large Scale Integration), interlayer insulation films, and insulation layers of organic electroluminescence elements. Since many polyimide resins have low solubility in organic solvents, a method is generally used in which a polyimide film is obtained by applying a polyamic acid solution as a precursor and then dehydrating and ring-closing by high-temperature heating. Yes. Therefore, the solubility of the polyimide precursor in the organic solvent is an important characteristic in processing the polyimide material. Further, with the recent miniaturization of semiconductor elements, high sensitivity is required in pattern processing of photosensitive resin compositions using polyimide resins.

  As a photosensitive resin composition satisfying such requirements, a positive photosensitive fluorine-containing polyimide precursor composition containing a polyimide precursor having fluorine in a tetracarboxylic acid residue or a diamine residue has been proposed so far. (For example, see Patent Documents 1 and 2). Although these compositions are excellent in solubility and sensitivity in organic solvents, there is a problem that adhesion of a cured film obtained from the composition is low. In addition, a polyimide resin having a tetracarboxylic acid residue with a specific ratio of a hexafluoropropyl group and an ether group, a carbonyl group, a fluorenyl group, and a sulfonyl group has been proposed (for example, see Patent Document 3). However, the photosensitive resin composition obtained using such a resin also has a problem that the adhesiveness of the cured film is low.

  Furthermore, a positive photosensitive resin composition containing (a) a novolak resin, a polyimide resin precursor having a specific structure, a naphthoquinone diazide compound having a specific structure, an alkoxymethyl group-containing compound and a solvent has been proposed (for example, a patent The composition containing the polyimide-type resin precursor which has a diamine residue represented by Formula (5) mentioned later and literature (5) is illustrated. While such a composition has high sensitivity, there is a problem that adhesion of a cured film and solubility in an organic solvent are low.

JP 2002-37885 A International Publication No. 2005/121895 Pamphlet JP 2007-91828 A JP 2008-257210 A

  The present invention has been made in view of the above-described problems of the prior art, and has an object to provide a resin having excellent solubility in an organic solvent and adhesiveness of a cured film and high sensitivity when used in a positive photosensitive resin composition. And

  As a result of intensive studies to solve the above problems, the present invention has been found. That is, this invention is resin which has as a main component the structure represented by following General formula (1).

In the general formula (1), R ¹ represents a tetravalent organic group having 2 or more carbon atoms, and R ² represents a divalent organic group having 2 or more carbon atoms. However, the group represented by R ^1- (COOR ³ ) ₂ has 5 to 40 mol% of the group represented by the following formula (2), and further has 60 to 95 groups represented by the following formula (4). Has mol%. R ² is a group represented by the following general formula (3) 50 to 100 mol%. R ³ represents hydrogen or an organic group having 1 to 20 carbon atoms. n shows the range of 5-100,000.

  In the general formula (3), p and q each represents 0 or 1.

  According to the present invention, a resin excellent in solubility in an organic solvent and adhesion of a cured film can be obtained. Furthermore, by using the resin of the present invention, a positive photosensitive resin composition having excellent solubility in an organic solvent, high sensitivity, and excellent cured film adhesion can be obtained.

  The resin of the present invention has a structure represented by the following general formula (1) as a main component. The resin whose main component is the structure represented by the general formula (1) is a polyimide precursor that is ring-closed by heating and becomes a polyimide having excellent heat resistance and solvent resistance. Here, the main component means that the n structural units in the general formula (1) have 50 mol% or more in the structural unit of the resin.

In the general formula (1), R ¹ represents a tetravalent organic group having 2 or more carbon atoms, and R ² represents a divalent organic group having 2 or more carbon atoms. However, the group represented by R ^1- (COOR ³ ) ₂ has 5 to 40 mol% of the group represented by the following formula (2), and further has 60 to 95 groups represented by the following formula (4). Has mol%. R ² is a group represented by the following general formula (3) 50 to 100 mol%. In the following general formula (3), p and q each represents 0 or 1.

When the group represented by R ^1- (COOR ³ ) ₂ has 5 mol% or more of the group represented by the above formula (2), the solubility of the resulting resin in an organic solvent is improved. Moreover, the sensitivity of the positive photosensitive resin composition containing the resin obtained can be improved. Preferably it is 10 mol% or more. On the other hand, if the group represented by the above formula (2) exceeds 40 mol%, the adhesiveness of the cured film is lowered, so that it is necessary to be 40 mol% or less. In order to further improve the adhesion of the cured film, 30 mol% or less is preferable.

Further, by R ² has more than 50 mol% of the groups represented by the general formula (3), to improve the adhesion of the cured film and solubility in organic solvents. If the group represented by the general formula (3) is less than 50 mol%, sufficient solubility in an organic solvent cannot be obtained. In order to further improve the solubility in an organic solvent and the adhesion of a cured film, 60 mol% or more is preferable. On the other hand, the upper limit is 100 mol%, preferably 90 mol% or less.

  P and q in General formula (3) show 0 or 1, and may be p + q = 0. From the viewpoint of alkali developability and photosensitivity of the positive photosensitive resin composition containing the obtained resin, it is preferable that p + q> 0.

  In addition, you may have 2 or more types of groups represented by General formula (3), and the total amount should just be 50-100 mol%.

The group represented by R ^1- (COOR ³ ) ₂ in the general formula (1) has 5 to 40 mol% of the group represented by the formula (2), and is further represented by the following formula (4). 60 to 95 mol% of the group. By having 60 mol% or more of the group represented by the following formula (4), solubility in an organic solvent and adhesion of a cured film are further improved. From the viewpoint of the adhesion of the cured film, 70 mol% or more and 90 mol% or less is more preferable.

R ¹ in the general formula (1) may have a group other than these. For example, it is preferable to have 1 to 10 mol% of a tetracarboxylic acid residue having a siloxane structure, and the adhesion of the cured film can be further improved.

R ² in the general formula (1) may be a divalent organic group having 2 or more carbon atoms having 50 to 100 mol% of the group represented by the general formula (3), and other than the general formula (3) Although the group of is not specifically limited, It is preferable to have 5-50 mol% of groups represented by following formula (5). By having 5 mol% or more of the group represented by the following formula (5), the sensitivity of the positive photosensitive resin composition containing the resulting resin can be improved. 10 mol% or more is preferable. In addition, from the viewpoint of solubility in an organic solvent by the group represented by the general formula (3) and adhesiveness of the cured film, the group represented by the following formula (5) is 50 mol% or less in R ² , and 40 Mole% or less is preferable.

R ² in the general formula (1) may have a group other than these. For example, it is preferable to have 1 to 10 mol% of an aliphatic diamine residue having a siloxane structure such as bis (3-aminopropyl) tetramethyldisiloxane or bis (p-amino-phenyl) octamethylpentasiloxane. The adhesion of the film can be further improved.

In general formula (1), R ³ represents hydrogen or an organic group having 1 to 20 carbon atoms. The organic group is preferably a hydrocarbon group. From the viewpoint of the stability of the positive photosensitive resin composition containing the obtained resin and the solubility in an alkaline developer, R ³ contains at least one hydrocarbon group having 1 to 16 carbon atoms, and the other is hydrogen. Preferably there is.

  In general formula (1), n represents the repeating number of the resin, and indicates a range of 5 to 100,000. From the viewpoint of improving the elongation of the obtained resin, n is preferably 15 or more. On the other hand, n is 100,000 or less, preferably 1,000 or less, more preferably 100 or less, from the viewpoint of solubility in an organic solvent and solubility in an alkaline developer of a photosensitive resin composition containing the resulting resin. preferable. The number of repetitions n in the present invention can be easily calculated by measuring the weight average molecular weight (Mw) by gel permeation chromatography (GPC) measurement in terms of polystyrene. When the molecular weight of the repeating unit is M and the weight average molecular weight of the resin is Mw, n = Mw / M.

  The resin of the present invention may contain other structural units as long as the main component is the structural unit represented by the general formula (1). For example, you may have 5-50 mol% of structural units which carried out the imide ring closure of the structural unit represented by the said General formula (1).

  Moreover, the terminal of the resin whose main component is the structure represented by the general formula (1) may be capped with a terminal capping agent such as monoamine, acid anhydride, acid chloride, or monocarboxylic acid. By sealing the terminal of the resin with a terminal sealing agent having a hydroxyl group, carboxyl group, sulfonic acid group, thiol group, vinyl group, ethynyl group or allyl group, the dissolution rate of the resin in an alkaline aqueous solution can be easily within a preferred range. Can be adjusted. The terminal blocking agent is preferably used in an amount of 0.1 to 60 mol%, more preferably 5 to 50 mol%, based on the total amine component of the resin.

Resin which has as a main component the structure represented by General formula (1) can be manufactured according to the manufacturing method of a well-known polyimide. For example, (1) a diamine compound having a tetracarboxylic acid dianhydride and R ² groups having R ¹ group, the monoamino compound is terminal blocking agent, a method of reacting under low temperature conditions, the (2) R ¹ group give the diester by and an alcohol tetracarboxylic dianhydride having followed the diamine compound having the R ² groups, a method of reacting in the presence of a monoamino compound and the condensing agent is a terminal blocking agent, the (3) R ¹ group Examples include a method in which a diester is obtained from a tetracarboxylic dianhydride having an alcohol and an alcohol, and then the remaining two carboxyl groups are acid chlorideed and reacted with a diamine compound having an R ² group and a monoamino compound as a terminal blocking agent. be able to. The resin polymerized by the above method is preferably put into a large amount of water or a methanol / water mixture, precipitated, filtered, dried and isolated. By this precipitation operation, unreacted monomers and oligomer components such as dimers and trimers are removed, and film properties after thermosetting are improved.

Hereinafter, as a preferred example, an example of a method for producing a polyimide precursor will be described. First, a diamine compound having an R ² group is dissolved in a polymerization solvent. To this solution, a tetracarboxylic dianhydride having an R ¹ group in a substantially equimolar amount with the diamine compound is gradually added. Using a mechanical stirrer, the mixture is stirred at -20 to 100 ° C, preferably 10 to 50 ° C for 0.5 to 100 hours, more preferably 2 to 24 hours. When using an end-capping agent, after adding tetracarboxylic dianhydride, after stirring at the required temperature and the required time, the end-capping agent may be added gradually or added all at once to react. You may let them.

  The polymerization solvent is not particularly limited as long as it can dissolve tetracarboxylic dianhydrides and diamines which are raw material monomers. For example, N, N-dimethylformamide, N, N-dimethylacetamide, amides of N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α -Cyclic esters such as methyl-γ-butyrolactone, carbonates such as ethylene carbonate and propylene carbonate, glycols such as triethylene glycol, phenols such as m-cresol and p-cresol, acetophenone, 1,3-dimethyl- Examples include 2-imidazolidinone, sulfolane, dimethyl sulfoxide, and the like. The polymerization solvent is preferably used in an amount of 100 to 1900 parts by weight, more preferably 150 to 950 parts by weight, with respect to 100 parts by weight of the obtained resin.

  Next, the positive photosensitive resin composition of the present invention will be described. The positive photosensitive resin composition of the present invention contains (a) a resin mainly composed of the structure represented by the general formula (1), (b) a quinonediazide compound, and (c) a solvent.

  The positive photosensitive resin composition of the present invention contains (a) the resin of the present invention described above. Two or more of these may be contained.

  The positive photosensitive resin composition of the present invention contains (b) a quinonediazide compound. The quinonediazide compound includes a polyhydroxy compound in which a sulfonic acid of quinonediazide is bonded with an ester, a polyamino compound in which a sulfonic acid of quinonediazide is bonded to a sulfonamide, a sulfonic acid of quinonediazide in an ester bond and / or sulfone Examples include amide-bonded ones. Two or more of these may be contained. Although all the functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, from the viewpoint of the contrast between the exposed part and the unexposed part, 50 mol% or more of the entire functional group is substituted with quinonediazide. Preferably it is. By using such a quinonediazide compound, it is possible to obtain a positive photosensitive resin composition that is sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp that is a general ultraviolet ray. it can.

  Polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC , DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (above, trade name, Asahi Organic Materials Co., Ltd.) Manufactured), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, Bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name) Honshu Chemical Industry like Ltd.), but is not limited thereto.

  Examples of polyamino compounds include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diamino. Examples thereof include, but are not limited to, diphenyl sulfide.

  Examples of the polyhydroxypolyamino compound include, but are not limited to, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3,3'-dihydroxybenzidine and the like.

  In the present invention, quinonediazide is preferably a 5-naphthoquinonediazidesulfonyl group or a 4-naphthoquinonediazidesulfonyl group. The 4-naphthoquinone diazide sulfonyl ester compound is suitable for i-line exposure, and the 5-naphthoquinone diazide sulfonyl ester compound is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength to be exposed. Further, it may contain a naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound. You may contain.

  The molecular weight of the quinonediazide compound is preferably 350 or more and 1600 or less.

  The content of the (b) quinonediazide compound is preferably 3 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the resin whose main component is the structure represented by (a) the general formula (1).

  (B) The quinonediazide compound can be obtained, for example, by a method of reacting 5-naphthoquinonediazidesulfonyl chloride with a phenol compound in the presence of triethylamine.

  The positive photosensitive resin composition of the present invention contains (c) a solvent. Solvents include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, etc. Ethers, acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol and other ketones, ethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxymethylpropanate, 3-ethoxyethylpropanate, ethyl acetate, ethyl lactate, and other esters And aromatic hydrocarbons such as toluene and xylene. Two or more of these may be contained. The content of the solvent (c) is preferably 100 parts by weight or more and 1500 parts by weight or less with respect to 100 parts by weight of the resin whose main component is the structure represented by (a) the general formula (1).

  The positive photosensitive resin composition of the present invention may contain components other than the above (a) to (c), and preferably contains an alkoxymethyl group-containing compound. Since an alkoxymethyl group causes a crosslinking reaction in a temperature range of 150 ° C. or higher, by containing an alkoxymethyl group-containing compound, a cured film having excellent mechanical properties can be obtained by crosslinking by heat treatment. The content of the alkoxymethyl group-containing compound is preferably 10 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the resin whose main component is the structure represented by the general formula (1).

  The positive photosensitive resin composition of the present invention can contain a silane compound. By containing the silane compound, the adhesion of the cured film is improved. Specific examples of the silane compound include N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, N-phenylaminobutyltri Methoxysilane, N-phenylaminobutyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltri Examples include methoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. The content of the silane compound is preferably 0.01 parts by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the resin whose main component is the structure represented by (a) the general formula (1).

  The positive photosensitive resin composition of this invention can contain the compound which has a phenolic hydroxyl group as needed. By containing a compound having a phenolic hydroxyl group, the resulting positive photosensitive resin composition is hardly dissolved in an alkali developer before exposure, and easily dissolved in an alkali developer upon exposure. Less film loss and easy development in a short time. For this reason, pattern workability improves. Preferred examples of the compound having a phenolic hydroxyl group include Bis-Z, TekP-4HBPA, TRisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-PC, BIR-PTBP, BIR-BIPC-F (trade name, manufactured by Asahi Organic Materials Co., Ltd.) and the like can be mentioned. The content of the compound having a phenolic hydroxyl group is preferably 3 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the resin whose main component is the structure represented by (a) the general formula (1). In addition, in this invention, even if it is a compound which has a phenolic hydroxyl group, when it has quinone diazide, it shall classify | categorize into (b) quinone diazide compound.

  The positive photosensitive resin composition of the present invention may contain a photoacid generator other than (b) a quinonediazide compound, if necessary. As the photoacid generator that appropriately stabilizes the acid component generated by exposure, a sulfonium salt, a phosphonium salt, or a diazonium salt is preferable. Since the cured film obtained from the positive photosensitive resin composition of the present invention is used as a permanent film, it is not environmentally preferable that phosphorus and the like remain, and it is necessary to consider the color tone of the film. Of these, sulfonium salts are preferably used.

  The positive photosensitive resin composition of the present invention may contain other alkali-soluble resins in addition to the component (a). Specific examples include alkali-soluble polyimide resins, alkali-soluble polybenzoxazole resin precursors, acrylic polymers copolymerized with acrylic acid, novolak resins, and siloxane resins. Such a resin is soluble in an aqueous alkali solution such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate. By containing these alkali-soluble resins, the properties of each alkali-soluble resin can be imparted while maintaining the adhesion and excellent sensitivity of the cured film. Since the resin whose main component is the structure represented by the general formula (1) of the present invention is excellent in compatibility with other alkali-soluble resins, a positive photosensitive resin composition containing other alkali-soluble resins is used. White turbidity that is likely to occur in a developed film obtained by exposure and development can be suppressed. In addition, a positive photosensitive resin composition containing a conventionally known polyimide precursor and a novolak resin is likely to have a sea-island pattern (rough surface) at the surface of the developing film or at the interface between the exposed portion and the unexposed portion. Although there was a tendency, the positive photosensitive resin composition using a resin whose main component is the structure represented by the general formula (1) of the present invention is rough and cloudy even when it contains a novolac resin. A development film having a good appearance can be obtained.

  In addition, the photosensitive resin composition of the present invention includes surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and alcohols such as ethanol, if necessary, for the purpose of improving the wettability with the substrate. , Ketones such as cyclohexanone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane may be contained. In addition, inorganic particles such as silicon dioxide and titanium dioxide, or polyimide powder may be contained.

  Next, the manufacturing method of the positive photosensitive resin composition of this invention is illustrated. Each of the above components (a) to (c) and, if necessary, other components are placed in a glass flask or stainless steel container and stirred and dissolved with a mechanical stirrer, etc., ultrasonically dissolved, planetary stirring The method of stirring and dissolving with a defoaming apparatus is mentioned. The viscosity of the positive photosensitive resin composition is preferably 1 to 10,000 mPa · s. Moreover, you may filter with the filter of 0.1 micrometer-5 micrometers pore size in order to remove a foreign material.

  Next, a method for forming a heat-resistant resin film pattern using the positive photosensitive resin composition of the present invention will be described with examples.

  First, a positive photosensitive resin composition is applied on a substrate. As the substrate, a silicon wafer, ceramics, gallium arsenide, metal, glass, metal oxide insulating film, silicon nitride, ITO, or the like is used, but is not limited thereto. Examples of the coating method include spin coating using a spinner, spray coating, roll coating, and slit die coating. The coating film thickness varies depending on the coating method, the solid content concentration of the positive photosensitive resin composition, the viscosity, etc., but it is generally applied so that the film thickness after drying is 0.1 to 150 μm.

  Next, the substrate coated with the positive photosensitive resin composition is dried to obtain a photosensitive resin film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like in the range of 50 ° C. to 150 ° C. for 1 minute to several hours.

  Next, the photosensitive resin film is exposed to actinic radiation through a mask having a desired pattern. Examples of actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. In the present invention, i rays (365 nm), h rays (405 nm), and g rays (436 nm) of a mercury lamp are used. preferable.

  In order to form the pattern of the heat resistant resin film from the photosensitive resin film, the exposed portion may be removed using a developer after exposure. The developer is an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylamino An aqueous solution of a compound exhibiting alkalinity such as ethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable. In some cases, polar aqueous solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, isopropanol are used in these alkaline aqueous solutions. One or more kinds of alcohols such as ethyl lactate, esters such as propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added. After development, it is common to rinse with water. For the rinsing treatment, one or more alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate, propylene glycol monomethyl ether acetate, and 3-methoxymethylpropanoate may be added to water.

  After development, a temperature of 200 ° C. to 500 ° C. is applied to convert it to a heat resistant resin film. This heat treatment is preferably carried out for 5 minutes to 5 hours by selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature. As an example, a method of performing heat treatment at 130 ° C., 200 ° C., and 350 ° C. for 30 minutes each, a method of linearly raising the temperature from room temperature to 320 ° C. over 2 hours, and the like can be mentioned.

  The heat-resistant resin film formed by the positive photosensitive resin composition of the present invention includes a semiconductor passivation film, a protective film for a semiconductor element, an interlayer insulating film for a multilayer wiring for high-density mounting, an insulating layer for an organic electroluminescent element, etc. It is suitably used for applications.

  Hereinafter, the present invention will be described with reference to examples and the like, but the present invention is not limited to these examples. In addition, evaluation of the resin and positive photosensitive resin composition in an Example was performed with the following method.

(1) Solubility Evaluation in Organic Solvent After adding polymer powder to acetone and MMP (3-methoxymethylpropanate) to a solid content concentration of 5 wt% and 10 wt% and stirring at room temperature for 1 hour, The state was observed visually. A resin in which insoluble resin was not confirmed in any of the 5% by weight concentration and the 10% by weight concentration. ◎ An insoluble resin was confirmed in the 10% by weight concentration, and no insoluble resin was observed in the 5% by weight concentration. The resin in which an insoluble resin was confirmed at 5% concentration by weight was evaluated as x.

(2) Evaluation of Adhesiveness of Cured Film A positive photosensitive resin composition (hereinafter referred to as varnish) is spin-coated on a silicon wafer, and then a 120 ° C. hot plate (Tokyo Electron Co., Ltd. coating and developing apparatus Mark) -7 use) for 3 minutes to prepare a pre-baked film having a thickness of 8 μm. This film was put into an oven and heat-treated at 170 ° C. for 30 minutes and then at 300 ° C. for 1 hour to obtain a cured film. The heat treatment was performed in nitrogen. The cured film was cut into 10 rows and 10 columns at 2 mm intervals, and a pressure cooker test of 100 hours, 200 hours, and 400 hours (hereinafter referred to as PCT, EHS-221MD manufactured by Tabai Co., Ltd.) Processed. With no PCT treatment (0 hours), 100 hours, 200 hours, and 400 hours, stripping is performed with “Selotape (registered trademark)” (manufactured by Nichiban Co., Ltd.), and it adheres according to how many squares are peeled out of 100 squares. Sexuality was evaluated. The peeling number was evaluated as good when less than 10 and 10 or more as bad. The PCT treatment was performed under a saturation condition of 121 ° C. and 0.21 MPa.

(3) Sensitivity evaluation Preparation of development film varnish was spin-coated on a 6-inch silicon wafer, and then baked on a 120 ° C hot plate (using a coating and developing apparatus Mark-7 manufactured by Tokyo Electron Ltd.) for 3 minutes. A pre-baked film having a thickness of 5 μm was produced. The membrane was exposed at 10 mJ / cm ² steps by the exposure amount of 0~500mJ / cm ² using an i-line stepper (GCA manufactured DSW-8000). After the exposure, the film was developed with a 2.38 wt% tetramethylammonium (TMAH) aqueous solution (manufactured by Mitsubishi Gas Chemical Co., Ltd., ELM-D) for 90 seconds, and then rinsed with pure water to obtain a developed film.

Method for Measuring Film Thickness Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. was used, and the film after prebaking was measured at a refractive index of 1.629.

Calculation of sensitivity After exposure and development, the exposure amount at which the exposed portion was not completely eluted (referred to as minimum exposure amount Eth) was defined as sensitivity. If Eth is 250 mJ / cm ² or less, it can be determined that the sensitivity is high. 150 mJ / cm ² or less is more preferable.

(4) Evaluation of appearance of developed film in case of containing other alkali-soluble resin Preparation of developed film 20 g of acrylic resin (e) solution obtained in Synthesis Example 5 below on 50 g of varnish, Novolac resin obtained in Synthesis Example 6 ( f) After mixing 20 g of the solution and 20 g of the polybenzoxazole precursor (g) solution obtained in Synthesis Example 7, respectively, a developing film was prepared by the same method as in (3) Sensitivity evaluation.

Appearance Evaluation of Developed Film The surface of the obtained developed film and the interface between the exposed part and the unexposed part were observed at a magnification of 4000 times using FE-SEM manufactured by Hitachi High-Technologies Corporation. Moreover, the presence or absence of cloudiness was observed visually. The case where surface roughness or white turbidity was not observed on the developed film was evaluated as ◯, the case where surface roughness was observed on the surface of the developed film or the interface was evaluated as △, and the case where white turbidity was observed visually was evaluated as ×. .

The names of the abbreviations of acid dianhydride and diamine shown in the following examples and comparative examples are as follows.
6FDA: 4,4′-hexafluoroisopropylidene diphthalic dianhydride ODPA: 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride BSAA: 2,2-bis [4- (3,4 -Dicarboxyphenoxy) phenyl] propane dianhydride BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride SiDA: 1,1,3,3-tetramethyl-1,3-bis (3 -Aminopropyl) disiloxane BAHF: 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane APBN: 1,3-bis (3-aminophenoxy) benzene DDS: 4,4'-diaminodiphenyl ether FDA : 9,9'-bis (4-aminophenyl) fluorene NMP: N-methyl-2-pyrrolidone MMP: 3-methoxymethylpro Panate KBM-403: 3-glycidoxypropyltrimethoxysilane.

Synthesis Example 1 Synthesis of hydroxyl group-containing diamine compound (a) 18.3 g (0.05 mol) of BAHF was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride in 100 mL of acetone was added dropwise thereto. After completion of dropping, the mixture was reacted at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.

  30 g of the obtained white solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated by confirming that the balloons were not deflated any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration, and concentrated with a rotary evaporator to obtain a hydroxyl group-containing diamine compound (a) represented by the following formula. The obtained solid was used for the reaction as it was.

Synthesis Example 2 Synthesis of quinonediazide compound (b) Under a dry nitrogen stream, TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 21.22 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 26.86 g (0.10 mol), 13.43 g (0.05 mol) of 4-naphthoquinonediazide sulfonyl chloride was dissolved in 50 g of 1,4-dioxane and brought to room temperature. Here, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (b) represented by the following formula.

Synthesis Example 3 Synthesis of quinonediazide compound (c) Under a dry nitrogen stream, TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 15.31 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 40.28 g (0.15 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. A quinonediazide compound (c) represented by the following formula was obtained in the same manner as in Synthesis Example 2 using 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane.

Synthesis Example 4 Synthesis of quinonediazide compound (d) Under a dry nitrogen stream, TekP-4HBPA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 28.83 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 13.43 g (0.05 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. A quinonediazide compound (d) represented by the following formula was obtained in the same manner as in Synthesis Example 2 using 20.24 g of triethylamine mixed with 50 g of 1,4-dioxane.

Synthesis Example 5 Synthesis of acrylic resin (e) 5 g of 2,2′-azobis (isobutyronitrile), 5 g of t-dodecanethiol, and propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) in a 500 ml flask. 150 g was charged. Thereafter, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged and stirred for a while at room temperature. The mixture was stirred at 5 ° C. for 5 hours. Next, 15 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, and 0.2 g of p-methoxyphenol were added to the resulting solution, and the mixture was heated and stirred at 90 ° C. for 4 hours to obtain an alkali-soluble acrylic resin (e) solution. Obtained. The solid content concentration of the acrylic resin solution (e) was 43% by weight. Moreover, the weight average molecular weight (Mw) of the obtained acrylic resin (e) was 10600, and the acid value was 118 mgKOH / g.

Synthesis Example 6 Synthesis of Novolak Resin (f) Under a dry nitrogen stream, 70.2 g (0.65 mol) of m-cresol, 37.8 g (0.35 mol) of p-cresol, 75.5 g of 37 wt% aqueous formaldehyde solution ( 0.93 mol of formaldehyde), 0.63 g (0.005 mol) of oxalic acid dihydrate, and 264 g of methyl isobutyl ketone were immersed in an oil bath, and the polycondensation reaction was performed for 4 hours while refluxing the reaction solution. went. Thereafter, the temperature of the oil bath is raised over 3 hours, and then the pressure in the flask is reduced to 40 to 67 hPa, volatile components are removed, the dissolved resin is cooled to room temperature, and alkali-soluble. A novolac resin (f) polymer solid was obtained. From GPC, Mw was 3,500. Γ-Butyrolactone (GBL) was added to the obtained novolak resin (f) to obtain a novolak resin (f) solution having a solid content concentration of 43% by weight.

Synthesis Example 7 Synthesis of polybenzoxazole precursor (g) In a dry nitrogen stream, 18.3 g (0.05 mol) of BAHF was dissolved in 50 g of NMP and 26.4 g (0.3 mol) of glycidyl methyl ether, and the temperature of the solution was adjusted. Cooled to -15 ° C. A solution prepared by dissolving 14.7 g of diphenyl ether dicarboxylic acid dichloride (manufactured by Nippon Agricultural Chemicals Co., Ltd., 0.050 mol) in 25 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, stirring was continued for 6 hours at -15 ° C. After completion of the reaction, the solution was poured into 3 L of water containing 10% by weight of methanol to precipitate a white precipitate. This precipitate was collected by filtration, washed 3 times with water, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain an alkali-soluble polybenzoxazole precursor (g). GBL was added to the obtained polybenzoxazole precursor (g) to obtain a polybenzoxazole precursor (g) solution having a solid content concentration of 43% by weight.

Reference example 1
Under a dry nitrogen stream, 15.57 g (0.0425 mol) of BAHF and 0.62 g (0.0025 mol) of SiDA were dissolved in 120 g of NMP. To this, 15.61 g (0.03 mol) of BSAA and 8.88 g (0.02 mol) of 6FDA were added together with 10 g of NMP, and reacted at 40 ° C. for 1 hour. Thereafter, a solution obtained by diluting 13.10 g (0.11 mol) of N, N-dimethylformamide dimethylacetal with 15 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40 ° C. for 1 hour. After completion of the reaction, the solution was poured into 2 L of water, and a solid precipitate was collected by filtration. The resin solid was dried with a vacuum dryer at 50 ° C. for 72 hours to obtain a polyimide precursor resin A.

  17.5 g of the obtained resin A and 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2 were added to 50 g of GBL to obtain a varnish A of a positive photosensitive resin composition. As described above, the obtained resin A and varnish A were used to evaluate the solubility in organic solvents, the adhesion of the cured film, the sensitivity, and the appearance of the developed film in the case of containing other alkali-soluble resins. The evaluation results are shown in Table 2.

Example 1
Resin B as a polyimide precursor was obtained in the same manner as in Reference Example 1 except that 120 g of NMP was changed to 117 g of NMP and 15.61 g (0.03 mol) of BSAA was changed to 9.31 g (0.03 mol) of ODPA. Varnish B of a positive photosensitive resin composition was obtained by adding 17.5 g of the obtained resin B and 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2 to 50 g of GBL. Table 2 shows the results of evaluation in the same manner as in Reference Example 1 using the obtained resin B and varnish B.

Example 2
Example 1 except that 9.31 g (0.03 mol) of ODPA was changed to 10.86 g (0.035 mol) of ODPA and 8.88 g (0.02 mol) of 6FDA was changed to 6.66 g (0.015 mol) of 6FDA. Thus, a polyimide precursor resin C was obtained. Varnish C of a positive photosensitive resin composition was obtained by adding 17.5 g of the resin C thus obtained and 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2 to 50 g of GBL. Table 2 shows the results of evaluation in the same manner as in Reference Example 1 using the obtained resin C and varnish C.

Example 3
Example 1 except that 9.31 g (0.03 mol) of ODPA was changed to 13.96 g (0.045 mol) of ODPA and 8.88 g (0.02 mol) of 6FDA was changed to 2.22 g (0.005 mol) of 6FDA. Thus, a polyimide precursor resin D was obtained. 17.5 g of the resin D thus obtained and 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2 were added to 50 g of GBL to obtain a varnish D of a positive photosensitive resin composition. Table 2 shows the results of evaluation using the obtained resin D and varnish D in the same manner as in Reference Example 1.

Example 4
Resin E as a polyimide precursor was obtained in the same manner as in Example 2 except that 15.57 g (0.0425 mol) of BAHF was changed to 8.24 g (0.0225 mol) of BAHF and 5.85 g (0.02 mol) of APBN. It was. Varnish E of a positive photosensitive resin composition was obtained by adding 17.5 g of the obtained resin E and 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2 to 50 g of GBL. Table 2 shows the results of evaluation using the obtained resin E and varnish E in the same manner as in Reference Example 1.

Example 5
A polyimide precursor was obtained in the same manner as in Example 4 except that 5.85 g (0.02 mol) of APBN was changed to 12.09 g (0.02 mol) of the hydroxyl group-containing diamine compound (a) obtained in Synthesis Example 1. Resin F was obtained. Varnish F of a positive photosensitive resin composition was obtained by adding 17.5 g of the obtained resin F and 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2 to 50 g of GBL. Table 2 shows the results of evaluation in the same manner as in Reference Example 1 using the obtained resin F and varnish F.

Example 6
Implementation was performed except that 15.57 g (0.0425 mol) of BAHF was changed to 10.99 g (0.03 mol) of BAHF and 7.56 g (0.0125 mol) of the hydroxyl group-containing diamine compound (a) obtained in Synthesis Example 1. In the same manner as in Example 2 , a polyimide precursor resin G was obtained. Varnish G of the positive photosensitive resin composition was obtained by adding 17.5 g of the obtained resin G and 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2 to 50 g of GBL. Table 2 shows the results of evaluation in the same manner as in Reference Example 1 using the obtained resin G and varnish G.

Example 7
Except for changing 15.55 g (0.0425 mol) of BAHF to 13.75 g (0.0375 mol) of BAHF and 3.32 g (0.05 mol) of the hydroxyl group-containing diamine compound (a) obtained in Synthesis Example 1. In the same manner as in Example 2 , a polyimide precursor resin H was obtained. Varnish H of the positive photosensitive resin composition was obtained by adding 17.5 g of the obtained resin H and 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2 to 50 g of GBL. Table 2 shows the results of evaluation in the same manner as in Reference Example 1 using the obtained resin H and varnish H.

Example 8
Varnish I of the photosensitive resin composition was obtained by adding 17.5 g of resin G obtained in Example 6 and 2.3 g of the quinonediazide compound (c) obtained in Synthesis Example 3 to 50 g of GBL. As described above, the obtained varnish I was used to evaluate the adhesion of the cured film, the sensitivity, and the appearance of the developed film when it contains other alkali-soluble resins. The evaluation results are shown in Table 2.

Example 9
Varnish J of the photosensitive resin composition was obtained by adding 17.5 g of the resin G obtained in Example 6 and 2.3 g of the quinonediazide compound (d) obtained in Synthesis Example 4 to 50 g of GBL. Table 2 shows the results of evaluation in the same manner as in Example 8 using the obtained varnish J.

Comparative Example 1
Example 1 except that 9.31 g (0.03 mol) of ODPA was changed to 7.76 g (0.025 mol) of ODPA and 8.88 g (0.02 mol) of 6FDA was changed to 11.11 g (0.025 mol) of 6FDA. Thus, a positive polyimide precursor resin I was obtained. Varnish K of the photosensitive resin composition was obtained by adding 14.5 g of the obtained resin I and 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2 to 50 g of GBL. Table 2 shows the results of evaluation in the same manner as in Reference Example 1 using the obtained resin I and varnish K.

Comparative Example 2
Resin of polyimide precursor in the same manner as in Example 1 except that 9.31 g (0.03 mol) of ODPA was not used and 8.88 g (0.02 mol) of 6FDA was changed to 22.21 g (0.05 mol) of 6FDA. J was obtained. Varnish L of the positive photosensitive resin composition was obtained by adding 14.5 g of the obtained resin J and 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2 to 50 g of GBL. Table 2 shows the results of evaluation in the same manner as in Reference Example 1 using the obtained resin J and varnish L.

Comparative Example 3
Resin of polyimide precursor in the same manner as in Example 1 except that 9.31 g (0.03 mol) of ODPA was changed to 15.51 g (0.05 mol) of ODPA and 8.88 g (0.02 mol) of 6FDA was not used. K was obtained. Varnish M of the positive photosensitive resin composition was obtained by adding 14.5 g of the obtained resin K and 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2 to 50 g of GBL. Table 2 shows the results of evaluation in the same manner as in Reference Example 1 using the obtained resin K and varnish M.

Comparative Example 4
A polyimide precursor was obtained in the same manner as in Example 2 except that 15.57 g (0.0425 mol) of BAHF was changed to 25.69 g (0.0425 mol) of the hydroxyl group-containing diamine compound (a) obtained in Synthesis Example 1. Of resin L was obtained. Varnish Q of the positive photosensitive resin composition was obtained by adding 14.5 g of the obtained resin L and 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2 to 50 g of GBL. Table 2 shows the results of evaluation in the same manner as in Reference Example 1 using the obtained polymer L and varnish N.

Comparative Example 5
Comparison was made except that 15.57 g (0.0425 mol) of BAHF was changed to 10.99 g (0.03 mol) of BAHF and 7.56 g (0.0125 mol) of the hydroxyl group-containing diamine compound (a) obtained in Synthesis Example 1. In the same manner as in Example 3, a polyimide precursor resin M was obtained. Varnish O of the positive photosensitive resin composition was obtained by adding 14.5 g of the obtained resin M and 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2 to 50 g of GBL. Table 2 shows the results of evaluation in the same manner as in Reference Example 1 using the obtained resin M and varnish O.

Comparative Example 6
BAHF (10.99 g, 0.03 mol) was added to BAHF (6.41 g, 0.0175 mol), and hydroxyl group-containing diamine compound (a) obtained in Synthesis Example 1 (7.56 g, 0.0125 mol) was converted to a hydroxyl group-containing diamine. A polyimide precursor resin N was obtained in the same manner as in Comparative Example 5 except that the compound (a) was changed to 15.11 g (0.025 mol). Varnish P of the positive photosensitive resin composition was obtained by adding 14.5 g of the obtained resin N and 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2 to 50 g of GBL. Table 2 shows the results of evaluation in the same manner as in Reference Example 1 using the obtained resin N and varnish P.

Comparative Example 7
Resin O as a polyimide precursor was obtained in the same manner as in Example 2 except that 6.66 g (0.015 mol) of 6FDA was changed to 4.41 g (0.015 mol) of BPDA. Varnish Q of positive photosensitive resin composition was obtained by adding 14.5 g of the obtained resin O and 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2 to 50 g of GBL. The results of evaluation in the same manner as in Reference Example 1 using the obtained resin O and varnish Q are shown in Table 2.

Comparative Example 8
Resin P as a polyimide precursor was obtained in the same manner as in Example 2 except that 15.57 g (0.0425 mol) of BAHF was changed to 12.42 g (0.0425 mol) of APBN. Varnish R of positive type photosensitive resin composition was obtained by adding 14.5 g of the obtained resin P and 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2 to 50 g of GBL. Table 2 shows the results of evaluation in the same manner as in Reference Example 1 using the obtained resin P and varnish R.

Comparative Example 9
Resin Q as a polyimide precursor was obtained in the same manner as in Example 2 except that 15.57 g (0.0425 mol) of BAHF was changed to 10.55 g (0.0425 mol) of DDS. Varnish S of a positive photosensitive resin composition was obtained by adding 14.5 g of the obtained resin Q and 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2 to 50 g of GBL. Table 2 shows the results of evaluation using the obtained resin Q and varnish S in the same manner as in Reference Example 1.

Comparative Example 10
A polyimide precursor polymer R was obtained in the same manner as in Example 2 except that 15.57 g (0.0425 mol) of BAHF was changed to 14.81 g (0.0425 mol) of FDA. Varnish T of positive photosensitive resin composition was obtained by adding 14.5 g of the obtained resin R and 2.3 g of the quinonediazide compound (b) obtained in Synthesis Example 2 to 50 g of GBL. Table 2 shows the results of evaluation in the same manner as in Reference Example 1 using the obtained resin R and varnish T.

Claims (3)

A resin mainly composed of a structure represented by the following general formula (1).

(In the general formula (1), R ¹ represents a tetravalent organic group having 2 or more carbon atoms, and R ² represents a divalent organic group having 2 or more carbon atoms. However, R ^1- (COOR ³ ) the group represented by ₂ having a group represented by the following formula (2) from 5 to 40 mol%, further comprises 60 to 95 mol% of the groups represented by the following formula (4). ^{R 2} is represented by the following general (The group represented by the formula (3) has 50 to 100 mol%, R ³ represents hydrogen or an organic group having 1 to 20 carbon atoms, and n represents a range of 5 to 100,000.)

(In the general formula (3), p and q each represents 0 or 1)

Formula (1) ^{R 2} is in the further following formula (5) in claim 1, wherein the resin having 5 to 50 mol% of the groups represented.

A positive photosensitive resin composition comprising (a) the resin according to claim 1 or 2 , (b) a quinonediazide compound, and (c) a solvent.