TWI325871B - An alkali soluble resin composition - Google Patents

Description

1325871 发明Invention Description: (―) Field of the Invention The present invention relates to an alkali-soluble resin which is suitable as a mask for semiconductor integrated circuits, thin film transistor (TFT) circuits for liquid crystal displays (LCDs), and circuit manufacturing. The photoresist required for the production or the molding material for the permanent film such as the interlayer insulating film and the protective film for the color filter. The present invention is more directed to a radiation sensitive resin composition containing the resin. (b) Prior Art In the field of the semiconductor industry, a radiation-sensitive composition is used to form a pattern to manufacture a semiconductor. With the recent miniaturization of the pattern, a radiation-sensitive resin composition having high resolution and high sensitivity is required. When manufacturing a fine pattern for forming a semiconductor, it is also required to obtain a photoresist having a high resolution of a submicron. However, for a resolution which is generally on the order of several micrometers to several tens of micrometers, it is strongly required to exhibit a high-yield high-sensitivity photoresist even when an extremely large-sized substrate is used to increase the yield. Moreover, in order to manufacture these micron-scale patterns with good productivity, various methods capable of mass processing or high-speed processing are often used in various processes. Therefore, in order to endure these processing conditions, the photoresist must have various properties. For example, in the step of engraving the base substrate, a wet etching method in which batch processing is often performed is performed. Therefore, in the photoresist for pattern formation, it is necessary to have adhesion to the substrate and chemical resistance which is not eroded by the etchant. . Further, in the case where an ion implantation step or the like is added, heat resistance which can withstand high temperature heating is required. As such a photoresist, a positive-type radiation-sensitive resin composition containing a novolac resin and a lanthanum 1325871 diazide compound has been known, and it is often used in the production of an integrated circuit. However, 'the radiation sensitive resin composition of this type is excellent in dry etching resistance required in the resolution and reactive ion etching (RIE) method, but the chemical resistance which can be endured in the above wet etching is insufficient, and further Sensitivity, adhesion to the substrate, and heat resistance are also insufficient. A liquid crystal display (LCD) that has been rapidly developed in recent years, especially an active matrix liquid crystal display (AM-LCD) with a thin film transistor (TFT) per pixel, is expected to be a replacement for CRT due to its fast response speed. The next generation of the (Brown tube) display device, and seeking to increase the 'display screen. A radiation sensitive linear composition (photoresist) capable of obtaining a resolution of about several micrometers is generally used to form a TFT circuit of an AM-LCD. In order to increase the screen area of the liquid crystal display as described above, in the same manner as in the case of mass production of semiconductors, the photoresist is required to have high resolution, excellent sensitivity, adhesion to a substrate, heat resistance, and the like. Further, in the manufacture of a liquid crystal display, in addition to the above-described AM-LCD circuit, attempts have been made to form an interlayer insulating film formed using a conventional thermosetting resin, a protective film for a color filter, or the like using a radiation sensitive resin composition. Permanent film. In the permanent film on which the interlayer insulating film, the protective film, or the like of the liquid crystal display is formed, the radiation sensitive resin composition is required to have excellent heat resistance, chemical resistance, and transparency. However, even if a conventional positive-type radiation-sensitive resin composition containing the above-described novolac resin and quinonediazide compound is used, the adhesion between the chemical resistance of the substrate and the substrate, heat resistance, transparency, and the like are not sufficient. In order to solve the shortcomings of the phenolic enamel resin, a radiation-sensitive resin composition having an iridium skeleton 1325871 has been proposed. For example, the use of a structure having a bisphenol oxime is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A heat-resistant alkali-soluble liquid resin obtained by reacting an epoxy acrylate with a polyvalent carboxylic acid or an anhydride thereof. Further, a (meth)acrylic epoxy ester having a bisphenolphthalein structure and an acid anhydride and an anhydride dianhydride are simultaneously disclosed in JP-A-H05-339356, JP-A-6- 938, and JP-A-7-3122. In the reaction, a polymerizable alkali-soluble resin having a carboxyl group is introduced. However, these alkali-soluble radiation-sensitive resins having an anthracene skeleton are only described as being used as a negative photoresist. In the processes of semiconductor and liquid crystal displays in recent years, as described above, positive-type photoresists are generally used. The resolution of the negative photoresist, the speed of photospeed, the complexity of processing, and the stability are worse than those of the positive photoresist, which cannot fully satisfy the high performance required for the photoresist. Therefore, it is possible to become positive with the above-mentioned excellent properties. A resin which is a main component of the radiation sensitive linear resin composition and a radiation sensitive resin composition containing the resin are required. (3) SUMMARY OF THE INVENTION In order to solve the above-mentioned conventional problems, the object of the present invention is to provide a radiation-sensitive resin composition, in particular, a resin having alkali-soluble properties, which can be used as a positive feeling. The main component of the radiation-linear resin composition, and a radiation-sensitive resin composition containing the resin. Another object of the present invention is to provide a radiation-sensitive resin composition which is positively associated with a conventional phenolic enamel resin. The radiation-sensitive linear resin composition is compared with the film of 1, 148,587, which is excellent in chemical resistance, adhesion to a substrate, heat resistance, and transparency, and can produce a micron-sized semiconductor integrated circuit with high productivity. An AM-LCD screen or the like is also suitable as a permanent film forming material for an interlayer insulating film, a protective film, or the like. In order to solve the above problems, the inventors of the present invention have devoted themselves to the review, and have succeeded in developing an alkali-soluble resin having a bisphenol fluorene skeleton and a radiation-sensitive resin composition containing the resin, and finally completed the present. invention. The alkali-soluble resin of the present invention is obtained by reacting an epoxy ester compound with at least one polyvalent carboxylic acid or an anhydride thereof, and the epoxy ester compound is an epoxy compound represented by the following general formula (1) and an alicyclic or aromatic group. a group of monocarboxylic acids,

Wherein R is each independently a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a phenyl group or a halogen atom. In a preferred embodiment, the above resin is obtained by reacting the above epoxy ester compound with a polybasic carboxylic acid or an anhydride thereof. In a preferred embodiment, the resin is obtained by reacting the above epoxy ester compound with a mixture of a dicarboxylic anhydride and a tetracarboxylic dianhydride. In a preferred embodiment, the resin is obtained by reacting the above epoxy ester compound 1325871 with tetracarboxylic dianhydride, and then reacting the obtained reaction product with dicarboxylic anhydride. The radiation sensitive resin composition of the present invention contains the above alkali-soluble resin. In a preferred embodiment, the composition is a positive radiation sensitive resin composition containing the above-described cerium-soluble resin and quinonediazide compound. In a preferred embodiment, the positive radiation sensitive resin composition further contains a crosslinking agent which is a compound having a functional group capable of forming a crosslinking between the alkali-soluble resins. (4) Embodiments The management form of the invention The contents of the present invention will be described in detail below. In the present specification, "radiation" means at least one of visible light, ultraviolet light, electron beam, X-ray, alpha ray, beta ray, gamma ray, synchrotron radiation, and proton beam radiation. The alkali-soluble resin used in the composition of the present invention is obtained by reacting an epoxy ester compound with at least one polycarboxylic acid or an anhydride thereof, and the epoxy ester compound is an epoxy represented by the following formula (1). a compound (hereinafter sometimes referred to as "epoxy compound (1)") and an alicyclic or aromatic monocarboxylic acid,

-9- 1325871 wherein R is each independently a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a phenyl group or a halogen atom. A representative of the epoxy ester compound (1) and the epoxy ester compound formed of the alicyclic or aromatic monocarboxylic acid is a bisphenol oxime epoxy ester compound represented by the following formula (2) (hereinafter sometimes It is called a bisphenol oxime type epoxy ester compound (2), an epoxy ester compound (2), etc.). Alternatively, one of the two epoxy groups of the above epoxy compound (1) may be esterified, and the other compound may remain as it is.

In the formula, R is the same as in the formula (1), and R each independently contains a group having an alicyclic moiety or an aromatic moiety derived from the above alicyclic or aromatic monocarboxylic acid. The alicyclic or aromatic monocarboxylic acid used in the preparation of the above epoxy ester compound is, for example, the following compound 'but without limitation: cyclopropanecarboxylic acid, 2,2,3,3-tetramethyl-1-cyclopropanecarboxylate Acid, cyclopentanecarboxylic acid, 2-cyclopentenecarboxylic acid, 2-furancarboxylic acid, 2-tetrahydrofurancarboxylic acid 'cyclohexanecarboxylic acid, 4-propylcyclohexanecarboxylic acid, 4-butylcyclohexane Alkanecarboxylic acid, 4-pentylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid, 4-heptylcyclohexanecarboxylic acid, 4-cyanocyclohexane-1-carboxy-10- 1325871 Alkali soluble resin. (i) a first alkali-soluble resin: a resin obtained by reacting the above epoxy ester compound with one type of polyvalent carboxylic acid or an anhydride thereof; (Π) a second alkali-soluble resin: an epoxy ester compound and a dicarboxylic anhydride a resin obtained by reacting a mixture of tetracarboxylic dianhydride; (Hi) a third alkali-soluble resin: a resin obtained by reacting a reaction product obtained by reacting an epoxy ester compound with tetracarboxylic dianhydride with a dicarboxylic anhydride . These resins having different configurations can be utilized depending on the intended use. The carboxylic acid having a plurality of carboxyl groups such as a polyvalent carboxylic acid, a dicarboxylic acid or a tetracarboxylic acid used in the present invention, and the polycarboxylic acid or anhydride thereof may be, for example, the following compounds: maleic acid 'succinic acid, itaconic acid, Dicarboxylic acid such as citric acid, tetrahydrofurfuric acid, hexahydrofurfuric acid, methyl hexahydrophthalic acid, methyl endomethylene tetrahydrophthalic acid, chloric acid, methyltetrahydrofurfuric acid or glutaric acid And its anhydride; trimellitic acid and its anhydride, pyromellitic acid, diphenyl ketone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid and other tetracarboxylic acids and anhydride dianhydride Wait. The above-mentioned first alkali-soluble resin is obtained, for example, by reacting an epoxy ester compound (2) with a single type of polycarboxylic acid or an anhydride thereof. Specific examples thereof are produced by a heating reaction using a cellosolve solvent such as ethyl cellosolve acetate or butyl cellosolve acetate. The above-mentioned "one type of polycarboxylic acid or its anhydride" means "at least one of a specific polycarboxylic acid and its corresponding anhydride", for example, when the polyvalent carboxylic acid is citric acid, it means citric acid and phthalic anhydride. At least one of the second alkali-soluble resins is obtained, for example, by reacting an epoxy ester compound (2) • 12-1325871 with a mixture of a dicarboxylic anhydride and a tetracarboxylic dianhydride. Specific examples thereof are produced by a heating reaction using a cellosolve solvent such as ethyl cellosolve acetate or butyl cellosolve acetate. A representative of the second alkali-soluble resin is represented by the following formula (3).

-0—X:—0—C 0—Y—c 0- COOH ' ""Οβ*Χ'·*^〇—C 〇——Z~"C 0 - A B _ COOH . (3) Wherein X is a group represented by the formula (4):

(wherein R and 1 are the same as in the formula (2)); Y is a residue derived from the acid anhydride represented by the formula (5); and the Z is derived from the acid dianhydride represented by the formula (6). Residue: C0 <> CS) C0 C0 〇〆\〇(6) m and k are not different degrees of polymerization, m/k molar is preferably 1/99~90/10 'better 5/95~ 80/20. -13- In the present specification, "reaction with a mixture of a dicarboxylic anhydride and a tetracarboxylic dianhydride J means that the reaction is carried out in the presence of a dicarboxylic anhydride and a tetracarboxylic dianhydride. The third alkali-soluble resin, for example, first By reacting the epoxy ester compound (2) with a tetracarboxylic dianhydride, the reaction product is reacted with a dicarboxylic anhydride, and the reaction can be carried out by using ethyl cellosolve acetate and butyl cellosolve. The cellosolve such as acetate is heated in a solvent. The representative of the third alkali-soluble resin of the present invention is represented by the following formula (7).

HOOC-Y-CO-I

COOH •X — 0—CO—Z—~CO*~0· I COOH

OC-O-CO — Y — COOH (7)

In the formula, χ, γ, and z are the same as the above formula (3), and η is an integer of 1 or more. The 値 of η is preferably an integer of 1 to 20. In the reaction of the above epoxy ester compound with a polyvalent carboxylic acid or an anhydride thereof, in the case of any of the above first to third types of resins, it is desirable to form a hydroxyl group with a polyvalent carboxylic acid or an anhydride thereof and an epoxy compound. Perform a quantitative reaction. When the epoxy ester compound is reacted with a polyvalent carboxylic acid or an anhydride thereof, the reaction temperature is preferably from 50 to 130 ° C, more preferably from 70 to 120 ° C. When the reaction temperature exceeds 130 ° C, a part of the carboxylic acid and the hydroxyl group are condensed, and the molecular weight is sharply increased. On the other hand, if it is less than 50 °C, the reaction will not proceed smoothly, and the unreacted polycarboxylic acid or its anhydride will remain. When the above bisphenolphthalein type epoxy ester compound (2) and a polyvalent carboxylic acid or an anhydride thereof are used as a synthetic alkali-soluble resin, the polycarboxylic acid or its anhydride is based on the epoxy ester compound of -14- 1325871 (2) In terms of 1 equivalent of the hydroxyl group, the acid anhydride group is supplied to the reaction in terms of 〇. 4 to 1 equivalent, preferably 0.75 to 1 equivalent. The acid anhydride group conversion here means the amount when the polycarboxylic acid to be used and the carboxyl group and the acid anhydride group contained in the anhydride are all converted into an acid anhydride group. When the polyvalent carboxylic acid and the anhydride thereof are less than 0.4 equivalent in terms of an acid anhydride group, the molecular weight of the obtained alkali-soluble resin cannot be increased. Therefore, when the radiation-sensitive resin composition containing the resin is used for exposure and development, the heat resistance of the obtained film is insufficient, and the film remains on the substrate. When the polyvalent carboxylic acid and the anhydride thereof exceed 1 equivalent in terms of an acid anhydride group, the unreacted anhydride or acid anhydride remains, and the molecular weight of the obtained alkali-soluble resin becomes low, so that the radiation-sensitive resin composition containing the resin is obtained. The imaging performance is deteriorated. In the production of the above second and third alkali-soluble resins, the ratio of the dicarboxylic anhydride to the tetracarboxylic dianhydride is preferably from 1/99 to 90/10, more preferably from 5/95 to 8 in terms of molar ratio. 0/20. When the ratio of the dicarboxylic anhydride is less than 1 mol% of the total acid anhydride, the resin viscosity is high and the workability is lowered. Further, since the molecular weight of the obtained resin becomes excessively large, when a film is formed on the substrate using the radiation sensitive resin composition containing the resin, it tends to be difficult to obtain a target pattern. When the ratio of the dicarboxylic anhydride exceeds 90 mol% of the total acid anhydride, the molecular weight of the obtained resin becomes too small, and when the coating film is formed on the substrate using the composition containing the resin, the prebaking coating is applied. There is also a problem of contamination remaining on the membrane. The alkali-soluble resin of the present invention thus obtained is suitably used as a main component of a radiation-sensitive linear resin composition. -15· 1325871 Hereinafter, a radiation-sensitive resin composition containing an alkali-soluble resin will be described. The radiation sensitive resin composition of the present invention contains the above-obtained alkali-soluble resin (hereinafter sometimes referred to as an alkali-soluble resin (A)). More specifically, the bismuth soluble resin (A) and the radiation-reactive compound are contained. When the composition is a positive-type radiation-sensitive resin composition, the radiation-reactive compound is, for example, a quinonediazide compound (hereinafter sometimes referred to as a quinonediazide compound (B)), and is composed of a negative-type radiation-sensitive resin. In the case of a substance, the radiation-reactive compound is, for example, an acrylate or the like. The radiation sensitive resin composition of the present invention will be described below by way of an example of a positive-type radiation-sensitive resin composition. The positive radiation sensitive resin composition of the present invention contains the alkali-soluble resin (A) and the quinonediazide compound (B) obtained as described above. Alternatively, the composition further contains a crosslinking agent (hereinafter sometimes referred to as a crosslinking agent). The crosslinking agent (C) is a compound having a functional group capable of forming a crosslinking between the alkali-soluble resin (A). In either case, the composition may further contain (i) a sensitizer, a (Π) surfactant, (iii) an adhesion aid, (W) an additive, (v) a solvent, or the like, as needed. The alkali-soluble resin (A) contained in the positive-type radiation-sensitive resin composition of the present invention may be any one of the above-mentioned first, second, and third resins, which may be a monomer resin or may be two kinds. The above mixture. The quinonediazide compound (B) contained in the positive radiation sensitive resin composition of the present invention has a property that the diazo moiety in the compound becomes a carboxylic acid when irradiated with radiation, and is alkali-soluble. Therefore, since the compound is contained, the composition as a whole has a function as a positive-type radiation-sensitive resin composition -16-1325871. The brewed diazide compound (B) may be a compound in which all or a part of the polyvalent fluorene radical is esterified with 1,2-quinonediazidesulfonic acid. Specifically, it is a compound in which 20 to 100% of the hydroxyl group of the polyvalent phenol is esterified with 1,2-quinonediazidesulfonic acid. Further, a quinonediazide compound other than the above may also be used. The quinonediazide compound (B) may, for example, be an ester compound of the following: (bl) an esterified product of a tris-benzophenone with 1,2-naphthoquinonediazidesulfonic acid, (b.2) four An esterified product of benzophenone with 1,2-naphthoquinonediazidesulfonic acid, (b.3) an esterified product of pentahydroxybenzophenone with 1,2-naphthoquinonediazidesulfonic acid, (b) .4) esterification of hexahydroxybenzophenone with 1,2-naphthoquinonediazidesulfonic acid, (b.5) bis(2,4'-diphenyl)methane and 1,2-naphthoquinone An esterified product of diazidosulfonic acid, (b.6) bis(p-phenyl)methane and acetate of I,2-naphthoquinonediazidesulfonic acid, (b. 7)tris(p-phenylbenzene) Esterified product of methane with 1,2-naphthoquinonediazidesulfonic acid, esterified product of (b.8)l,l,l-tris(p-hydroxyphenyl)ethane and naphthoquinonediazidesulfonic acid , (b_9) ester of bis(2,3,4-trihydroxyphenyl)methane with 1,2-naphthoquinonediazidesulfonic acid, (bl〇) 2,2-bis (2,3,4- Esterified product of trihydroxyphenyl)propane with 1,2-naphthoquinonediazidesulfonic acid, (lKll) 丨, i, 3- cis (2,5-dimethyl-4-hydroxyphenyl)-3- Esterified product of phenylpropane and 1,2-naphthoquinonediazidesulfonic acid (b.l2) 4,4'-[l-[4-[l-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 1,2-naphthoquinone An esterified product of diazidosulfonic acid, an esterified product of (b.丨3)bis(2,5-dimethyl-cardohydroxyphenyl)_2-hydroxyphenylmethane and 12-naphthoquinonediazidesulfonic acid, (b.l4)3,3,3,,3'_Tetramethyl-1,1'-spiro-5,6,7,5',6',7'-hexanol and I,2-naphthalene An esterified product of quinonediazidesulfonic acid, (b.15) 2,2,4-trimethyl-7,2',4,-trihydroxyflavan and 1,2-naphthoquinonediazide An esterified product, and (b. 16) a quinonediazide compound other than the 1325871 compound esterified with 1,2-naphthoquinonediazidesulfonic acid. Among them, the esterified product of (bl) trihydroxybenzophenone and 1,2-naphthoquinonediazidesulfonic acid can be, for example, the following compound: 2,3,4-trihydroxybenzophenone-1, 2-naphthoquinonediazide-4-sulfonate, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,4,6-three Hydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate Wait. The esterified product of (b.2) tetrahydroxybenzophenone and 1,2-naphthoquinonediazidesulfonic acid may, for example, be the following compound: 2,2',4,4'-tetrahydroxybenzophenone- 1,2-naphthoquinonediazide-4-sulfonate, 2,2',4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2 ,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4,3'-tetrahydroxybenzophenone-1,2 -naphthoquinonediazide-5-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4 , 4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1 , 2-naphthoquinonediazide-4-sulfonate, 2,3,4,2'-tetrahydroxy-4'-methylbenzhydryl-1,2-naphthoquinonediazide-5-sulfonate Acid ester, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4,4' - Tetrahydroxy-3'-methoxybenzhydryl-1,2-naphthoquinonediazide-5-sulfonate, and the like. The esterified product of (b.3) pentahydroxybenzophenone and 1,2-naphthoquinonediazidesulfonic acid can be, for example, 2,3,4,2',6'-pentahydroxybenzophenone- 1,2-naphthoquinonediazide-4-sulfonate, 2,3,4,2',6'-pentahydroxybenzophenone-l,2-naphthoquinonediazide-5-sulfonate Wait. The esterification of (b.4) hexahydroxybenzophenone with 1,2-naphthoquinonediazidesulfonic acid can be, for example, 2,4,6,3',4',5'-hexahydroxyl Benzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,4,6,3',4',5'-hexahydroxybenzophenone-1,2-naphthoquinone Azide-5-sulfonate, 3,4,5,3',4',5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 3,4 , 5,3',4',5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, and the like. The esterified product of (b.5) bis(2,4'-dihydroxyphenyl)methane with naphthoquinonediazidesulfonic acid may be, for example, bis(2,4'-dihydroxyphenyl)methane-1. 2-naphthoquinonediazide-4-sulfonate, bis(2,4'-dihydroxyphenyl)methane-1,2-naphthoquinonediazide-5-sulfonate, and the like. The esterified product of (b.6) bis(p-hydroxyphenyl)methane and 1,2-naphthoquinonediazidesulfonic acid may be, for example, bis(p-hydroxyphenyl)methane-I,2-naphthoquinone quinone A sulfonate, bis(p-hydroxyphenyl)methane-I,2-naphthoquinonediazide-5-sulfonate, and the like. The esterified product of (b·7) tris(p-hydroxyphenyl)methane and 1,2-naphthoquinonediazidesulfonic acid may be, for example, tris(p-hydroxyphenyl)methane-I,2-naphthoquinone quinone Nitro-4-sulfonate, tris(p-hydroxyphenyl)methane-I,2-naphthoquinonediazide-5-sulfonate (b.8) tris(p-hydroxyphenyl)ethane with 1, The esterified product of 2-naphthoquinonediazidesulfonic acid can be, for example, 1,1,1-tris(p-hydroxyphenyl)ethane-1,2-naphthoquinonediazide-4-sulfonate, 1, 1,1-tris(p-hydroxyphenyl)ethane-1,2-naphthoquinonediazide-5-sulfonate, and the like. The esterified product of (b.9) bis(2,3,4-trihydroxyphenyl)methane and 1,2-naphthoquinonediazidesulfonic acid may be, for example, bis(2,3,4-trihydroxybenzene) Methane-1,2-naphthalene roll diazide-4-sulfonate, bis(2,3,4-trihydroxyphenyl)methane-1,2-naphthoquinone-19- 1325871 diazide-5 - sulfonate and the like. The esterified product of (b_10) 2,2-bis(2,3,4-trihydroxyphenyl)propane and 1,2-naphthoquinonediazidesulfonic acid can be, for example, 2,2-bis (2,3) ,4-trihydroxyphenyl)propane-I,2-naphthoquinonediazide_4_sulfonate, 2,2-bis(2,3,4-trihydroxyphenyl)propane-1,2-naphthalene醌Diazide-5-sulfonate and the like. (b. 11) 1, an esterified product of 1, 3-paran (2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane and 1,2-naphthoquinonediazidesulfonic acid, for example Can be: 1,1,3-glycol (2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonate, 1, 1,3-Shen (2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonate. (b.12) 4,4'-[1-[4.[1-[4-Hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 1,2-naphthalene The esterified product of quinonediazidesulfonic acid can be, for example, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene] Phenol 4,2-naphthoquinonediazide-4-sulfonate, 4,4'-[1·[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl] Ethyl]bisphenol-1,2-naphthoquinonediazide-5-sulfonate. The esterified product of (b. 13) bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane with naphthoquinonediazidesulfonic acid can be, for example, bis(2,5- Dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid vinegar, bis(2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonate. (15.14) 3,3,3',3'-tetramethyl-1,1'-spiro-5,6,7,5',6',7'-hexanol and 1,2-naphthoquinone The esterified product of diazidosulfonic acid can be, for example, 3,3,3',3'-tetramethyl-1,1'-spiro-5,6,7,5',6',7'- Alcohol-1,2-naphthoquinonediazide-4-sulfo 1325871 acid ester, 3,3,3',3'-tetramethylspiro-5,6,7,5',6',7'- Hexanol-1,2-naphthoquinonediazide-4-sulfonate and the like. The esterified product of (13_15) 2,2,4-trimethyl-7,2,,4'-trihydroxyflavan and 1,2-naphthoquinonediazidesulfonic acid can be, for example, 2, 2, 4-trimethyl-7,2',4'-trihydroxyflavan-I,2-naphthoquinonediazide-4-sulfonate, 2,2,4-trimethyl-7,2', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonate and the like. (b. 16) The quinonediazide compound other than the compound esterified with 1,2-naphthoquinonediazidesulfonic acid may be, for example, o-benzoquinonediazide, o-naphthoquinonediazide, ortho-quinone Bismuth azide or o-naphthoquinone diazide sulfonate, and a nuclear replacement derivative thereof; a reaction product of o-naphthoquinone sulfonium chloride with a compound having a hydroxyl group or an amine group. The above compound having a hydroxyl group or an amine group may be, for example, a phenol, a p-methoxyphenol, a dimethylphenol, a hydroquinone, a bisphenol A, a naphthol, a methanol, a pyrocatechol, a pyrogallol, a pyrogallol mono Ether, pyrogallol-I, 3-dimethyl ether, gallic acid, partially esterified or etherified gallic acid, aniline, p-aminodiphenylamine, and the like. In addition, J. Kosar, published by John Willey & Son, New York, can also use the "Photosensitive System" on pages 339 to 3 52 (1 965) and WS De Forse from McGraw-Hill, New York. The quinonediazide compound described in page 50 (1 975) and the like. In the above, the quinonediazide compound (B) is preferably the following compound: 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2, 3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,4,-tetrahydroxybenzophenone-1,2-naphthoquinone Azide-4-sulfonate, 2,3,4,4,-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 1,1,3-parade (2 ,5-Dimethyl-4--21 · 1325871-based 4-phenyl 3 )-methyl-~ benzene, 5 yl (2, hydroxy propyl hydroxy hydroxy phthalate naphthalene 0, 2--4--1 nitrogen Alkylpropanediyl ii-i naphthalene-3 - S 2,yl-1 phenylalkyl • 4 rL I tl rL - 4 4 , Sqi acid sulfoethylmethyl-1-phenyl hydroxy hydroxy azide Sulfonium I 4 -azidedipinenaphthalene 2-, phenolic bis-diyl-phenylene bis- 1J-based ethylidene phenyl yl yl yl yl yl 11 - U phenyl hydroxy 2 yl -7 methyl 11 -1 A 4 3 2m - 2 4 2 2' ester, acid ester sulfonate 4--5I nitrogen-5 stack 醌 2-dinaphthyl-1, 醌2-院^-1黄1.2-,^基1黄Hydroxytrihydroxy, triterpenoid, azaphthoquinonediazide-5-sulfonate, l,i,i-tris(p-hydroxyphenyl)ethane-1 , 2-naphthoquinonediazide·4-sulfonate, 1,1,1-tris(p-hydroxyphenyl)ethane-I,2-naphthoquinonediazide-5-sulfonate, etc. Or a combination of two or more kinds of quinonediazide compounds (Β). Among the quinone gas compounds (Β), a particularly preferred 1,2-quinonediazide sulfonate is, for example, 1,2-anthracene. The halide of the diazide sulfonic acid is obtained by reacting with a corresponding polyvalent phenol (polyvalent hydroxy compound) in the presence of a base catalyst to be esterified. More specifically, for example, by 2, 3, 4, 4 Condensation of '-tetrahydroxybenzophenone with 1,2-quinonediazide-5-sulfonic acid chloride to give 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthalene醌Diazide-5-sulfonate. In the esterification reaction, 1.0 to 1.2 equivalents of 1,2-quinonediazide is usually used in terms of 1 equivalent of the hydroxyl group of the above polyvalent hydroxy compound. The above-mentioned quinonediazide compound (Β) is preferably used in an amount of 5 to 100 parts by weight, more preferably 10 to 50 parts by weight per 1 part by weight of the alkali-soluble resin (Α). Parts by weight. If the amount of the quinonediazide compound (Β) is less than 5 parts by weight, then Exposed portion of the coating composition formed by (partly irradiated with radiation) -22-1325871 unexposed portion (a portion not irradiated with radiation) of the solubility becomes small, the patterning difficult. On the other hand, when the amount of the quinonediazide compound (B) exceeds 100 parts by weight, the quinonediazide compound in the coating film is not sufficiently dissolved under a short period of radiation irradiation, and as a result, the sensitivity is lowered. The cross-linking agent (C) may be contained in the composition of the present invention in order to form a film on the substrate using the composition, and after exposure and development, the alkali-soluble resin (A) is cross-linked by heating. And strengthen the film after development. The crosslinking agent (C) is, for example, a melamine, a glycoluril or a compound having at least two epoxy groups in the molecule. The above melamines may, for example, be hexamethylol melamine, hexahydroxybutyl melamine, partially methylolated melamine and its alkoxyalkylate, tetramethylolbenzoguanamine, partial hydroxymethyl Benzobenzoguanamine and its alkylate and the like. Among them, alkoxyalkylated melamines, especially alkoxymethylated melamines, are preferred. Representative examples thereof are N, N, N', N', N", N"-(hexa-oxymethyl) melamine represented by the following formula (8):

f^-O-CH/ 'CH2-0-R2 (8)

F^-O-CH,, N R2 -0-CH2' /CHj-O-R2 N ^CH^O-R2 (wherein the six R 2 groups are each independently an alkyl group, preferably having a carbon number of 1 ~4 alkyl). -23- 1325871 The above-mentioned glycolurils are preferably alkoxymethylated glycolurils. This compound is, for example, 1^,1^',:^',;^''-(tetraalkoxymethyl)glycolide represented by the following formula (9):

(wherein the four R3 groups are each independently an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms). The melamine and glycoluril are commercially available compounds, such as the three-chemical chemical NISKAKU MW30LM, MW100LM, MX-750, MX-290, MX-280, M-2702, etc., and Mitsui Saudi Library. Company-made PL-U74, CYMEL 3 00, etc. Among the above melamines and glycolurils, alkoxyalkylated melamines are preferred, and alkoxymethylated melamines are particularly preferred. In the case where the above crosslinking agent (C) is a melamine or a glycoluril, the content of the crosslinking agent is preferably from 1 to 100% by weight based on 100 parts by weight of the alkali-soluble resin (A). Good 5~50 parts by weight. When the crosslinking agent (C) is less than 1 part by weight relative to 100 parts by weight of the alkali-soluble resin (A), the composition is used to form a film on the substrate, and heat treatment is performed even after exposure and development. Also, sufficient cross-linking cannot be obtained, so that the heat resistance of the resulting film is insufficient. When the content exceeds 1 part by weight, the solubility of the entire composition in the alkali becomes high, so that the residual film ratio at the time of development is lowered, and it is not suitable. -24 - 1325871 In the above crosslinking agent (C) The compound having at least two epoxy groups in the molecule is, for example, an aliphatic diglycidyl ether type epoxy resin, a phenol-phenolic enamel type epoxy resin, a cresol-phenolic enamel type epoxy resin, and a bisphenol A type ring. Oxygen resin 'bisphenol F type epoxy resin, bisphenol S type epoxy resin, trisphenol type epoxy resin, biphenyl type epoxy resin, alicyclic type epoxy resin, etc. epoxy resin: and triple shrinkage A relatively low molecular weight epoxy compound having at least two epoxy groups, such as glyceryl isocyanurate or diglycidyl isocyanurate. The compound having at least two epoxy groups may be used alone or in combination of two or more. The content of the epoxy group-containing compound in the composition is from 1 to 50 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). The sensitizer of the above (i) is contained in the composition of the present invention in order to improve the sensitivity of the quinonediazide compound (B) to radiation. The sensitizer is, for example, 2H-pyrido-(3,2-b)-l,4-oxo-3(4H)-one, 10H-pyrido-(3,2-b)-l,4 - Benzothiazide, urinazole, carbendazim, barbituric acid, glycine anhydride, 1-hydroxybenzotriazole, urushi acid, maleimide, and the like. A combination of them can also be used. The sensitizer is usually 100 parts by weight or less, preferably 4 to 60 parts by weight, per 100 parts by weight of the quinonediazide compound (B). The surfactant of the above (ii) is, for example, for preventing streaking (coating) when coating a solvent-containing radiation sensitive resin composition of the present invention on a substrate, thereby improving coating properties, or for providing coating. The imaging properties of the film. The surfactant is, for example, the following compound or commercial product: polyethylene oxide alkyl ether such as polyethylene oxide 25- 1325871 lauryl ether 'polyethylene oxide stearyl ether' polyethylene oxide oleyl ether Polyethylene oxide aryl ethers such as polyethylene oxide octyl phenyl ether, epoxy phenyl phenyl ether; polyethylene oxide dilaurate, polyethylene oxide Non-ionic surfactants such as polyoxyethylene dialkyl esters such as fatty acid esters; Evertep EF 301, Evertep 303, Evertep 3352 (manufactured by New Akita Chemicals Co., Ltd.); Mecab bitter 171, mecab bitter F172, mecab bitter F173 (Greater Japan Ink Chemicals (stock) system); Vero Wright FC-43 0, Vero Wright FC-431 (Sumitomo 3M (shares) )): Asha Picard AG710, Seflon S-3 82, Seflon SC-101, Seflon SC-1〇2, Seflon SC-103, Seflon SC-104, Seflon A commercially available fluorine-based surfactant such as SC-105 or Seflon SC-106 (Asahi Glass Co., Ltd.); organic siloxane polymer - KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); Acrylic Copolymer Polyphron No. 57, No. 95 (manufactured by Kyoeisha Oil Chemical Industry Co., Ltd.), etc., may be used singly or in combination of two or more. The content of the surfactant is 2% by weight or less, preferably 1% by weight or less based on the total of the radiation sensitive resin composition. The adhesive agent of the above (iii) is for improving the adhesion between the liquid composition containing the solution and the substrate. Sex. The adhesion aid is, for example, a functional decane coupling agent or the like. The additive of the above (iv) is, for example, an antistatic property, a storage stabilizer, a defoaming agent, a pigment, a dye or the like. The solvent of the above (v) is for uniformly coating the components in the composition, for example, for easy coating on a substrate. The solvent does not react with the components of -26-1325871 in the composition, but is an organic solvent capable of dissolving or dispersing them, and is not particularly limited. The solvent is, for example, the following compounds: alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ether, ethylene glycol monoethyl ether, and the like. 'Ethylene glycol alkyl ether acetates such as alcohol ethers, methyl cellosolve acetate, ethyl cellosolve acetate, etc., diethylene glycol monomethyl ether, diethylene glycol diethyl ether, two Diethylene glycol such as ethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether or diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, etc. Propylene glycol ethane ether acetate, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, methyl amino ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone And ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, methyl ethoxyacetate, ethyl hydroxyacetate, 2 Methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethyl 3-ethoxypropionate Ester, ethyl acetate, butyl acetate, methyl lactate, An ester such as ethyl lactate. Among them, glycol ethers, alkylene glycol alkyl ether acetates, diethylene glycol dialkyl ethers, and diethylene glycols are preferred. Particularly preferred is ethyl 3-ethoxypropionate, ethyl lactate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, methyl amino ketone, and diethylene glycol ethyl methyl ether. These solvents may be used singly or in combination of two or more. The film is formed on the substrate by using the radiation-sensitive resin composition containing the alkali-soluble resin (A) of the present invention, and after radiation irradiation, a film having a predetermined pattern can be formed by development. For example, in the case of a positive type composition, the alkali-soluble resin (A) is dissolved in a solvent, and a quinonediazide compound (B) which is a radiation-reactive compound is mixed in the solution at a predetermined ratio. The various components such as the above-mentioned crosslinking agent (C), sensitizer, and surfactant are optionally used, and a liquid material containing each component of the radiation sensitive resin composition is obtained. For example, it is preferably filtered through a micropore filter having a pore diameter of 〜5 to 1.0 μm to form a uniform liquid. The components of the radiation sensitive resin composition are usually mixed shortly before use, and the mixed solution has excellent long-term storage stability. The liquid positive-type radiation-sensitive resin composition thus obtained is applied onto the surface of the substrate, and the solvent is removed by means of heating or the like to form a film. The method of applying the radiation sensitive resin composition to the surface of the substrate is not particularly limited, and for example, various methods such as a spray coating method, a roll coating method, and a spin coating method can be employed. Then, the coating film is usually heated (prebaked). The heating conditions vary depending on the type and mixing ratio of each component, but usually 70 to 120 ° C, for a predetermined time, for example, 1 to 10 minutes on a hot plate, and heated in an oven for 10 to 30 minutes. The film can be obtained by the treatment. However, the pre-baked coating film is irradiated with radiation, for example, ultraviolet rays, through a designated pattern mask. Therefore, the radiation-reactive compound changes. For example, in the case of a positive composition containing a quinonediazide compound, the diazo moiety of the compound is changed to a carboxylic acid to become alkali-soluble. Therefore, the solubility of the entire composition in the alkali is higher than that before the irradiation due to the irradiation of the radiation. In the case of a negative type composition containing an acrylate compound, the acrylate is polymerized due to irradiation of radiation. Therefore, the solubility of the entire composition of 28- 1325871 in the alkali is lower than before the irradiation. Therefore, it can be visualized, for example, by using a developing solution containing an alkali at an appropriate concentration. Then, the unnecessary portion is removed by a suitable developing solution to form a film of a predetermined pattern. The developing solution is usually an aqueous solution containing an alkali such as an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate or ammonia, or a first grade such as ethylamine or n-propylamine. a secondary amine such as an amine, diethylamine or di-n-propylamine; a tertiary amine such as triethylamine or methyldiethylamine; an alcohol amine such as dimethylethanolamine or triethanolamine; a quaternary ammonium salt of ammonium, tetraethylammonium hydroxide, choline, etc., pyrrole, pyridinium, 1,8-diazabicyclo[5.4 · 0 ] - 7 -undecene, 1,5-diaza Bicyclo [4 · 3 · 0 ] - 5 - decene. Further, an aqueous solution containing an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be used in the aqueous alkali solution. The development time is usually 30 to 180 seconds, and the current method can be a full liquid method, a spray method, or a dipping method. After the image is developed, it is washed with running water for 30 to 90 seconds, and the unnecessary portion is removed, and air-dried by compressed air or compressed nitrogen to form a pattern. Then, by heating means such as a heating plate, an oven, or the like, at a predetermined temperature, for example, 150 to 250 ° C, for a predetermined time, for example, 2 to 30 minutes on a hot plate, and heat-treating in an oven for 30 to 90 minutes. A patterned hardened film is obtained. Thus, a radiation-sensitive resin composition having excellent properties is provided by combining the alkali-soluble resin of the present invention with a predetermined radiation-reactive compound. For example, a positive-type radiation-sensitive resin composition containing the alkali-soluble resin and the diazide compound is applied as a liquid composition containing a solvent, and is applied onto a substrate, and the pre-baked coating film is free from stains. Therefore, the pattern can be densely exposed by the 1325871 pattern, resulting in extremely high resolution. Further, the imaging property is good, and the residual film property at the time of development is excellent. The cured film obtained by curing the composition of the present invention has excellent heat resistance, transparency, adhesion to a substrate, acid resistance, alkali resistance, solvent resistance, surface hardness, and the like. Further, since the cured film is an organic coating film, it is a low dielectric constant. Therefore, the composition of the present invention can be utilized for many purposes. For example, a positive photoresist which is required as a semiconductor integrated circuit, a thin film transistor (TFT) circuit for liquid crystal display (LCD), a photomask for circuit fabrication, or the like is used. Further, it is applied to a material for a protective film of an electronic component (for example, a material for forming a protective film used for a liquid crystal display element including a color filter, an integrated circuit element, or a solid-state imaging element); interlayer insulation and/or planarization A material for forming a film; a solder resist used for producing a printed wiring board; or an alkali-soluble photosensitive composition for forming a columnar spacer in place of a bead spacer in a liquid crystal display device. Further, the composition of the present invention is suitable as a material for various optical components (lenses, LEDs, plastic films, substrates, optical disks, etc.): a coating agent for forming a protective film of the optical component; a binder for an optical component (adhesive for an optical fiber) Etc.); a coating agent for producing a polarizing plate; a photosensitive resin composition for hologram recording, and the like. [Examples] The present invention will be specifically described by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited by the Examples. In the following synthesis examples, examples and comparative examples, "parts" means "parts by weight". (Synthesis Example 1) Synthesis of epoxy ester compound In a 1-liter liquid-distributing flask, 200 g of a bisphenol fluorene-type epoxy compound (a compound represented by the formula (1); R = H: an epoxy equivalent of 231) was charged. 1.9 g of triethyl 1325791-benzylammonium chloride, 154.1 g of 1-adamantanecarboxylic acid and 152.6 g of diethylene glycol methyl ethyl ether, while blowing nitrogen gas at a flow rate of 25 ml/min, at 100~ The reaction was carried out at a temperature of 105 ° C for 16 hours. After completion of the reaction, 20 0 3.4 g of diethylene glycol methyl ethyl ether was added to dilute to obtain a bisphenol quinone type epoxy ester resin (the compound represented by the formula (2); R = H; R, = from King Kong The residue of the alkanecarboxylic acid was used as a pale yellow transparent resin solvent having a solid concentration of 50% by weight. (Synthesis Example 2) Synthesis of epoxy ester compound In a 1 liter liquid-distributing flask, 'injected 212 g of a bisphenol quinone type epoxy compound (a compound represented by the formula (1); R = CH3: epoxy equivalent 245), L9 g of triethylbenzylammonium chloride, 丨54·1 g of 1_Jinangyuan citric acid and 152.6 g of diethylene glycol methyl ethyl ether, while blowing nitrogen gas at a flow rate of 25 ml/min, 1 〇〇~ 1 〇 5 °c temperature reaction for 24 hours. After completion of the reaction, '215.4 g of diethylene glycol methyl ethyl ether was added to dilute' to obtain a bisphenol-elevated epoxy ester resin (a compound represented by the formula (2); R = CH3; R1 = from adamantanecarboxylic acid The residue was a pale yellow transparent resin solvent having a solid concentration of 50% by weight. (Synthesis Example 3) Synthesis of epoxy ester compound In a 1-liter liquid-distributing flask, 200 g of a bisphenol fluorene-type epoxy compound (a compound represented by the formula (1); R = H: epoxy equivalent 231) was charged. 9 g of triethylbenzylammonium chloride, 109.4 g of cyclohexanecarboxylic acid and 132-6 g of diethylene glycol methylethyl acid were heated while blowing nitrogen gas at a flow rate of 25 ml/min ' at 1 0 0~ The temperature was reacted at 1 0 5 ° C for 16 hours. After the completion of the reaction, 1 7 6 ·8 g of diethylene glycol methyl ethyl ether was added to dilute 'to obtain a bisphenol oxime epoxy ester tree-31 - 1325871 lipid (the compound represented by the formula (2); R = H; R, = residue derived from cyclohexanecarboxylic acid) A pale yellow transparent resin solvent having a solid forming concentration of 50% by weight. (Synthesis Example 4) Synthesis of epoxy ester compound In a 1-liter liquid-distributing flask, 200 g of a bisphenol quinone type epoxy compound (a compound represented by the formula (1); R = H: an epoxy equivalent 231) was charged. 9 g of triethylbenzylammonium chloride, 182.0 g of 9-fluorene carboxylic acid and 163.7 g of diethylene glycol methyl ethyl ether, while blowing nitrogen gas at a flow rate of 25 ml/min, at 10 0 The reaction was carried out at a temperature of ~105 °C for 16 hours. After completion of the reaction, 21 8.3 g of diethylene glycol methyl ethyl ether was added to dilute to obtain a bisphenol quinone type epoxy ester resin (the compound represented by the formula (2); R = H; Rl = from 9-蕗Residue of carboxylic acid) A pale yellow transparent resin solvent having a solid concentration of 50% by weight. (Example 1) Synthesis of alkali-soluble resin In a 300 ml liquid separation flask, 96.0 g of the resin solution obtained in Synthesis Example 1, 23.7 g of diethylene glycol methyl ethyl ether, and 12.8 g of benzophenone were charged. The tetracarboxylic dianhydride was reacted at 90 to 95 t for 6 hours to obtain a pale yellow transparent alkali-soluble resin. The disappearance of the acid anhydride group in the reaction liquid was confirmed by IR spectroscopy. The acid value (in terms of resin solid content) of the resin contained in the obtained solution was 98.5 mgKOH/g, and the weight average molecular weight was 4,000. (Example 2) Synthesis of alkali-soluble resin In a 300 ml liquid separation flask, 96.0 g of the resin solution obtained in Synthesis Example 2, 23.7 g of diethylene glycol methyl ethyl ether, and 12.4 g of diphenyl ketone were charged. The tetracarboxylic dianhydride was reacted at 90 to 95 ° C for 6 hours to obtain a pale yellow transparent alkali-soluble resin. The acid value (resin solid - 32 - 1325871 component) of the resin contained in the solution obtained by confirming the disappearance of the acid anhydride group in the reaction liquid by IR spectrum was 98.5 mgKOH/g, and the weight average molecular weight was 4,200. (Example 3) Synthesis of alkali-soluble resin In a 300 ml liquid separation flask, 96.0 g of the resin solution obtained in Synthesis Example 3, 23.7 g of diethylene glycol methyl ethyl ether, and 14.8 g of benzophenone were charged. The tetracarboxylic dianhydride was reacted at 90 to 95 ° C for 6 hours to obtain a pale yellow transparent alkali-soluble resin. The disappearance of the acid anhydride group in the reaction liquid was confirmed by IR spectroscopy. The acid value (in terms of resin solid content) of the resin contained in the obtained solution was 102.5 mgKOH/g, and the weight average molecular weight was 3,850. (Example 4) Synthesis of alkali-soluble resin In a 300 ml liquid separation flask, 96.0 g of the resin solution obtained in Synthesis Example 4, 23.7 g of diethylene glycol methyl ethyl ether, and 12.0 g of diphenyl acetate were charged. The ketone tetracarboxylic dianhydride was reacted at 90 to 95 ° C for 6 hours to obtain a pale yellow transparent alkali-soluble resin. The disappearance of the acid anhydride group in the reaction liquid was confirmed by IR spectroscopy. The acid value (in terms of resin solid content) of the resin contained in the obtained solution was 90.0 mgKOH/g, and the weight average molecular weight was 4,200. (Example 5) Synthesis of alkali-soluble resin In a 300 ml liquid separation flask, 96.0 g of the resin solution obtained in Synthesis Example 1, 23.7 g of diethylene glycol methyl ethyl ether, and 12.8 g of benzophenone were charged. The carboxylic acid dianhydride and 4.4 g of 1,2,3,6-tetrahydrophthalic anhydride were reacted at 110 to 115 ° C for 2 hours to obtain a yellow transparent alkali-soluble resin. The acid value (in terms of resin solid content) of the resin contained in the obtained solution was 105.0 mgKOH/g, and the weight average molecular weight was 3,500. (Example 6) Synthesis of alkali-soluble resin In a 300 ml-distributed flask, 96.0 g of a resin solution of -33 - 1325871 obtained in Synthesis Example 1, 23-7 g of diethylene glycol methyl ethyl ether, and 12.8 g were charged. The benzophenone tetracarboxylic dianhydride was reacted at 90 to 95 ° C for 2 hours, and after confirming the disappearance of the acid anhydride group in the reaction liquid by IR spectroscopy, 4.4 g of 1,2,3,6-tetrahydrophthalic anhydride was added. The reaction was carried out at 90 to 95 ° C for 4 hours to obtain a pale yellow transparent alkali-soluble resin. The acid value (in terms of resin solid content) of the resin contained in the obtained solution was 97.0 mgKOH/g, and the weight average molecular weight was 3,500. (Example 7) 1% by weight of the alkali-soluble resin (A) obtained in Example 1 (in terms of solid content of the resin in the solution), and 20 parts by weight of 2,3,4,4'-tetrahydrogen 1,2-naphthoquinonediazide-5-sulfonate of benzophenone (quinonediazide; corresponding to b.2 above) and 10 parts by weight of epoxy compound (crosslinking agent (C); Mitsui Chemical (stock) TECHMORE VG3101) was dissolved in propylene glycol monomethyl ether acetate to have a solid concentration of 30% by weight. It was filtered through a 0.2 μm pore size microporous filter. Using the obtained solution, a pattern was formed on the substrate in accordance with the pattern forming method shown in the following (1). The pattern forming step and the obtained pattern were tested by the items shown in the following (2). The composition of the components in the above solution used in the present example is shown in Table 1, and the evaluation results of the respective tests are shown in Table 2. Examples 8 to 14 and comparative examples described later are also shown in Tables 〖 and 2. (1) Method of Forming a Pattern The solution obtained above was applied onto a ruthenium substrate (disk shape) having a diameter of 4 Å using a spin coater, and then prebaked on a hot plate at 90 ° C for 2 minutes to form. Film thickness 2. 涂μπι coating film. The obtained coating film was exposed to a light-34·1325871 cover of a predetermined pattern, and exposed to a predetermined time by a Kano-made PLA-501F contact type exposure machine, and then 0.5% by weight of an aqueous solution of tetramethylammonium hydroxide (TMAH) was used. The image was developed at °C for 60 seconds. Next, it was rinsed with water, and a pattern was formed on the ruthenium substrate by drying. (2) Evaluation method 2.1. Sensitivity In the above, a grading plate (a negative mask having an optical density of 12 steps) was placed on the coating film in close contact with the coating film to perform exposure and development. Then, the number of segments of the grading plate remaining on the substrate was investigated. The minimum necessary exposure required to remove the coating film of the exposed portion is obtained. 2.2. Residual film ratio The film thickness (initial film thickness) after prebaking and the film thickness after development were measured. (film thickness after development / initial film thickness) x = residual film ratio, as evaluated below: ◎: residual film rate of 95% or more 残: residual film rate of 90 or more to less than 95% X: residual film rate is lower than 90% 2.3. Development The scanning electron microscope (SEM) was used to observe the surface dry spots of the line portion after the development and the presence or absence of the resin residue (scum) in the spacer portion, as evaluated below: ◎: No observation at all To the dross: part of the saw dross X: see the dross in full 2.4. Resolution -35 - 1325871 The size of the interval of the minimum spacing pattern for the best exposure time resolution is measured by a scanning electron microscope. 2.5. Adhesiveness According to the pattern forming method (1) described above, line-and-space patterns of various line widths were formed on the substrate. Observing the lack of pattern after imaging, as the following evaluation: ◎: No lack of seeing the pattern: seeing a part missing X: seeing a total lack of 2.6. Transparency using a glass substrate "Kni Niko 7059 (Kni In the same manner as the above-described pattern forming method, a pattern is formed in place of the ruthenium substrate. The glass substrate having this pattern was irradiated with ultraviolet rays of 405 nm and a light intensity of 9.5 mW at 500 mJ/cm2. Next, the transmittance of the obtained glass substrate was measured using a spectrophotometer "U-2000 (manufactured by Toray Industries, Ltd.)" at a wavelength of 400 to 700 nm, and evaluated as follows: 〇: the minimum transmittance was 95% or more X: the lowest transmission The rate is less than 95%. 2.7. Heat resistance According to the pattern forming method (1) described above, a line-and-space pattern of about ΙΟμηη is formed on the ruthenium substrate. The ruthenium substrate having this pattern was irradiated with ultraviolet rays of 405 nm and a light intensity of 9.5 mW at 500 mJ/cm 2 . Heat it at 240 °C for 60 minutes in a clean oven to observe the thermal distortion of the line pattern. The cross-sectional shape of the line pattern before and after heating was compared as follows: 1325871 ◎: No change was observed before and after heating 〇: slight change was observed before and after heating △: Some changes were seen X: Significant changes were observed 2.8. Thermal discoloration In the case of 2.7, a glass substrate "Knikogu 7059 (manufactured by Nikko Co., Ltd.)" was used instead of the ruthenium substrate, and a spectrophotometer "U-2000 (manufactured by Hitachi, Ltd.)" was used to measure the wavelength at 400 to 70 〇 nm. The transmittance of the glass substrate of the film. The change in transmittance is obtained by the following formula: Change in transmittance = [(transmittance before heating - transmittance after heating) / transmittance before heating] χ 100 (%) ◎: change in transmittance is less than 5% Δ: transmission The rate change is in the range of 5 to 10%. X: the transmittance changes by more than 10%. 2.9. Chemical resistance The coating film is formed on the ruthenium substrate in the same manner as the above-described pattern formation method (1), and is exposed in a clean oven. Heat treatment at 200 ° C for 30 minutes. The heat-treated substrate having the film was immersed in various chemical solutions described below under the following conditions: (a) Acid solution: 5 wt% 11 <:1 aqueous solution was immersed at room temperature for 24 hours (b) Alkaline solution: (b-1) 5 wt% NaOH aqueous solution immersed in room temperature for 24 hours at room temperature (b-2) 4 wt% aqueous KOH solution, immersed at 50 ° C for 10 minutes, 132857-1 (b-3) l% by weight aqueous NaOH solution at 80 ° C immersion for 5 minutes (c) Solvent: (cl) N-methylpyrrolidine (NMP) was immersed at 40 ° C for 1 minute (c-2) NMP was immersed at 80 ° C for 5 minutes to measure the film thickness before and after immersion, The film thickness change rate was determined by the following formula, and the chemical resistance was evaluated as follows: Film thickness change rate = [(film thickness before treatment - film thickness after treatment) / film thickness before treatment] x l00 (%) ◎ : (a - (c) In all the treatments, the film thickness change rate is less than 2%. 〇: (a) to (c) in all the treatments, the film thickness change rate is 2% or more and less than 5% Δ: at least one In the chemical treatment, the film thickness change rate is 2% or more and less than 10% X: In at least one of the chemical liquid treatments, the film thickness change rate is 1% or more. (Examples 8 to 14) The alkali-soluble resin (A), the quinonediazide compound (B), and the crosslinking agent (C) of the types and amounts shown in Table 1 were used, and the same procedure as in Example 7 was carried out. to evaluate. (Comparative Example) The same procedure as in Example 7 was carried out, except that the alkali-soluble resin (A) was used in the same manner as in Example 7 except that a conventional m-p-cresol novolac resin was used and a 2.38 wt% aqueous solution of TMAH was used as a developing solution. . -38- 1325871 Table 1 Alkali-soluble resin (A) Antimony diazide compound (B) Crosslinking agent (C) Example 7 Example 1 100 20 Epoxy compound" Example 8 Example 2 100 20 Epoxy compound ι 10 Example 9 Example 3 100 20 Epoxy compound Μ 10 Example 10 Example 4 100 20 Epoxy compound 10 Example 11 Example 5 100 20 Epoxide compound 10 Example 12 Example 6 100 20 Epoxy compound" Example 13 Example 6 100 20 Melamine * 2 10 Example 14 Example 6 100 20 Epoxy compound Μ 5 Melamine * 2 5 Comparative Example Novolac resin 100 20 Epoxy compound Ν 10

*1: TECHMORE VG3101 manufactured by Mitsui Chemicals Co., Ltd. *2: MW-100LM manufactured by Sanwa Chemical Co., Ltd. Table 2

Sensitivity (mJ/cm2) Residual film rate imaging resolution (μπι) Adhesive transparency Heat resistance Thermochromism Chemical resistance Example 7 140 "〇〇1.2 〇〇〇〇〇Example 8 140 〇〇1.2 〇〇 〇〇〇Example 9 120 〇〇 1.2 〇〇〇〇〇 Example 10 160 〇〇 1.2 〇〇〇〇〇 Example 11 120 〇〇 1.2 〇〇〇〇〇 Example 12 140 〇〇 1.2 〇〇〇〇 〇Example 13 140 〇〇 1.2 〇〇〇〇〇 Example 14 140 ◎ 〇 1.2 〇〇 ◎ 〇 ◎ Comparative Example 120 〇〇 1.2 Δ XXXX

As is apparent from Tables 1 and 2, the positive-type radiation-sensitive resin composition of the present invention is excellent in sensitivity and development, excellent residual film ratio, heat resistance, chemical resistance of -39-1325871, and adhesion to a substrate. A film (pattern) excellent in properties and transparency. In particular, the film obtained by using the positive-acting radiation-sensitive resin composition of the present invention is inferior in heat resistance and transparency, and is excellent in thermal discoloration and adhesion resistance in comparison with the resin composition of the comparative example. A film with excellent drug properties. (Examples 15 to 22) The solutions obtained by the microporous filters obtained in Examples 7 to 14 were stored at 5 ° C for 3 months. Using the solution after storage, each pattern was formed in the same manner as in the above-described Example 7, and evaluation of each item was carried out. The same results were obtained for each of Examples 7 to 14. Therefore, it is understood that the positive-type radiation-sensitive resin composition is also excellent in storage stability. EFFECTS OF THE INVENTION The present invention provides a resin having a bisphenol fluorene skeleton, an alkali-soluble property, and a radiation-sensitive resin composition containing the resin. The resin composition is excellent in heat resistance, sensitivity, and image development. A film (pattern) having excellent residual film ratio, chemical resistance, adhesion to a substrate, and transparency can be formed. Furthermore, preservation stability is also excellent. Therefore, the resin composition of the present invention can be used as a permanent film forming material for a photoresist material, an interlayer insulating film, a protective film, or the like for manufacturing a semiconductor integrated circuit or a TFT circuit for LCD.

Claims (1)

Ι3258Ή_ Announcement No. 92117910 ί8. Year 9·胥1 Revision of the “alkali-soluble resin” patent case (amended on September 11, 2009) Pick-up, patent application scope: An alkali-soluble resin, which is an epoxy ester compound And reacting with at least one selected from the group consisting of a dicarboxylic acid, a tetracarboxylic acid, a trimellitic acid, and an anhydride thereof, the epoxy ester compound being an epoxy compound represented by the following formula (1) Formed with an alicyclic monocarboxylic acid, RR (wherein R is each independently a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a phenyl group or a halogen atom); and the alicyclic monocarboxylic acid is selected from the group consisting of cyclopropanecarboxylic acid, 2, 2,3,3-tetramethyl-1-cyclopropanecarboxylic acid, cyclopentanecarboxylic acid, 2-cyclopentenecarboxylic acid, 2-furancarboxylic acid, 2-tetrahydrofurancarboxylic acid, cyclohexanecarboxylic acid, 4 -propylcyclohexanecarboxylic acid, 4-butylcyclohexanecarboxylic acid, 4-pentylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid, 4-heptylcyclohexanecarboxylic acid, 4· Cyanocyclohexane-1-carboxylic acid, 4-hydroxycyclohexanecarboxylic acid, 1,3,4,5-tetrahydroxycyclohexane-1-carboxylic acid, 1-aminocyclohexanecarboxylic acid, 4 -Aminomethylcyclohexane-1-carboxylic acid, 2-(1,2-dihydroxy-4-methylcyclohexyl)propionic acid, shikimic acid, 3-(2-sided oxy ring Hexyl)propionic acid, 3-cyclohexene-1-carboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid monoalkyl ester, cycloheptanecarboxylic acid, raw borneol carboxylic acid, tetracyclododecene At least one 1325871 type of carboxylic acid, 1-adamantanecarboxylic acid, and (4·tricyclo[5.2·1.02 6]indol-4-yl)acetic acid. 2. The alkali-soluble resin of claim 1, wherein the epoxy ester compound is reacted with a dicarboxylic acid, a tetracarboxylic acid, trimellitic acid or an anhydride thereof. 3. The alkali-soluble resin of claim 1, which is obtained by reacting the epoxy ester compound with a mixture of a dicarboxylic anhydride and a tetracarboxylic dianhydride. 4. The alkali-soluble resin according to the first aspect of the invention, which is obtained by reacting the epoxy ester compound with tetracarboxylic dianhydride, and then reacting the obtained reaction product with a dicarboxylic anhydride. A photosensitive resin composition containing the alkali-soluble resin according to any one of claims 1 to 4. A positive-type radiation-sensitive resin composition containing the alkali-soluble resin and the quinonediazide compound according to any one of claims 1 to 4, with respect to 100 parts by weight of the alkali-soluble resin, The quinonediazide compound is contained in a ratio of 5 to 100 parts by weight. 7. The positive-type radiation-sensitive resin composition of claim 6, further comprising a crosslinking agent which is a compound having a functional group which can be crosslinked between the alkali-soluble resins.