TWI379159B - - Google Patents

Description

1379159

[Technical Field] The present invention relates to a positive resist composition and a substrate for a photosensitive film. [Prior Art] With the development of LSI (large-scale integration, high integration of λ i and ASIC (application specific circuit), the industry has introduced LSI in multi-lead films for electronic devices. Packages, bare chip packages such as TCP (Tape Carrier Package) are attracting attention. The terminal for connection in such a multi-lead package, that is, the height of the bump is 20 / zm, high precision In the future, in order to miniaturize the steps, the industry requires high precision of the bumps. In order to form bumps, positive light containing a quinonediazide-based compound containing an alkali-soluble novolac as a sensitizer is used. The bump can be formed, for example, by first forming a photoresist film having a film thickness of about 20 Å, passing through a specific mask light, and developing to form a photoresist pattern, followed by gold or copper. Electroplating treatment is performed to remove the photoresist pattern around the photoresist composition. For the above-mentioned photoresist composition, for example, when it is required to be washed during or after the plating treatment, the photoresist film is not added, and if it is TCP, It is required that cracks and the like are not caused even in the flexible film of the tape. In addition, light is required to be attached to it! Integrated circuits are required to be used. In the use or overlay, it is necessary to use The above protrusion LS I is a resin and a resist composition. If a pattern is formed on the carrier for exposure, soldering, etc., cracks are generated; on the substrate, the photoresist pattern sidewall 1379159

The perpendicularity is good, and the photoresist composition has high resolution and the like in the process of narrow pitching of the bump arrangement. In order to prevent the occurrence of cracks, for example, Patent Document 1 discloses a positive-type resist composition for a thick film, which contains an alkali-soluble novolak, a compound of a diazide group, and an alkali-soluble propylene resin as a plasticizer. . However, when a positive type resist composition formulated with a plasticizer is used, there is a tendency that the resolution of the photoresist composition is lowered or the dimensional stability of the film is lowered. Therefore, in order to suppress the decrease in resolution or the change of the resist pattern after the plating treatment, and to prevent cracking of the photoresist pattern, it is necessary to improve the photoresist group. [Patent Document 1] Japanese Patent Laid-Open No. 2 02-25847 No. 9 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] An object of the present invention is to solve the above problems and to provide a formability, which is difficult to produce cracks. And a positive-type photoresist composition having a good vertical pattern of sidewalls, and a substrate using the positive-type photoresist to form a photosensitive film. [Means for Solving the Problem] The present inventors have intensively studied to solve the above problems, and found that the use of an alkali-soluble novolak resin by using an ester of a certain or all of the hydroxyl groups by organic esterification of the alcohol is used. One of the components of the composition can solve the above problems, and the completion of the present invention also requires that a grease, an olefinic acid-containing photoresist pattern size is added to the photoresist, and the resulting light is blocked. Block the group. 1379159 That is, the first aspect of the present invention is a positive photoresist composition comprising (A) an alkali-soluble novolak resin, (B) a sensitizer, and (C) vi a part or all of a hydroxyl group via an organic acid ester. The resulting ester of the polyol. A second aspect of the present invention is a positive-type photoresist composition comprising (D) an alkali-soluble novolak resin in which a part of hydrogen atoms of all phenolic hydroxyl groups are substituted by 1,2-naphthoquinonediazidesulfonyl group, And (C) an ester of a polyol obtained by organically esterifying a part or all of a hydroxyl group.

A third aspect of the present invention is a substrate with a photosensitive film, characterized in that a photosensitive film formed using a positive resist composition such as the first or second aspect of the present invention is formed on a substrate. on. [Effect of the Invention] The positive resist composition of the present invention is excellent in resolution. Further, by using the positive-type photoresist composition of the present invention, it is possible to form a photoresist pattern which is less likely to cause cracks and has good verticality of the side walls, and in particular, it can be formed by using a photosensitive film having a large thickness. Resistive pattern. [Embodiment]

Hereinafter, embodiments of the present invention will be described in detail. The first aspect of the present invention is a positive resist composition comprising the component (A), the component (B), and the component (C). [(A) component] The component (A) is an alkali-soluble novolak resin. The condensing under an acidic catalyst is preferably 0. 5~1. 0 molar ratio, condensed under acidic catalyst, with respect to the phenolic phenolic resin. The winner of the reaction. i S] 7 1379159

Examples of the phenols include cresols such as phenol, o-cresol, and m-cresol cresol; 2,3-diphenylbenzene, 2,4-dimethylphenol, 2,5-phenol, and 2, 6-diphenyl phenol, 3, 4-diphenyl benzoate; tricycle, 3, 5-xylenol methyl phenol; o-ethyl phenol, m-ethyl phenol, p-ethyl phenol and other phenols, 2- Isopropylphenol, 3-isopropylphenol, 4-isopropylphenyl-butylphenol, m-butyl phenol, p-butyl phenol, p-tert-butyl phenol, etc.; 2, 3, 5 - phenols such as trimethylbenzene base, 3, 4, 5-trimethylphenol; m-diphenol, catechol, hydroquinone, hydroquinone monomethyl pyrogallol, meta-benzene Polyphenols such as phenol; alkyl polyphenols such as alkyl resorcinol, alkyl diphenol, alkyl hydroquinone (all alkyl groups having an alkyl group of 1 to 4); α - Naphthol, 5-naphthol, hydroxybiphenolphthalein, and the like. These phenols may be used singly or in combination of two or more. Among these phenols, m-cresol and p-cresol are preferred, and m-nonylphenol and p-nonylphenol are preferably used in combination. By adjusting the blending ratio of the two, it can be used as various properties such as sensitivity and heat resistance of the photoresist composition. The blending ratio of m-cresol is not particularly limited, and it is preferably m-cresol/pair = 3/7 to 8/2 (mass ratio). If the ratio of m-cresol is less than the above lower limit, there is a case where the sensitivity is lowered, and if it is larger than the above upper limit, the heat retaining property is lowered. The condensing agent may, for example, be an aldehyde or a ketone, and more preferably a formaldehyde or a trimeraldehyde. The acidic catalyst is not particularly limited, and examples thereof include inorganic acids such as acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; organic acids such as citric acid, oxalic acid 'diethylsulfate, and p-dosylsulfonic acid; and zinc acetate. , for dioxane, etc., diethyl phenate, phenol tridentate ether, orthobenzene is carbon stupid. It is to adjust the phenol and cresol values, in the resistance class, : hydrochloric acid, etc. Gold 8 1379159 is a salt. These acidic catalysts may be used alone or in combination of two or more. From the viewpoints of developability, resolution, and plating resistance of the photoresist composition, gel permeation chromatography (GPC, gel) is used. Permeati〇n chromatography) The mass average molecular weight of the component (a) obtained by polystyrene conversion is preferably from 1,000 to 50,000.

The component (A) is preferably a fractionated resin which is reduced to 80% by mass or less, more preferably 50% by mass or less, before the classification treatment by the classification treatment. Wherein the term "low-nuclear body" means a compound as described above, that is, a monomer, a dimer obtained from two molecules of the phenolic monomer, and a terpolymer obtained from three molecules of the phenolic monomer. Wait. By using such a classifying resin, the perpendicularity of the cross-sectional shape of the photoresist pattern is further improved, and it is difficult to generate residue (scum) on the substrate after the filming, and the resolution of the photoresist composition is improved. Further, it tends to be excellent in heat resistance.

The classification treatment can be carried out by a known classification treatment method, for example, by subjecting the following compound to a dehydration product (novolac resin) to dissolve water, Heptane, hexane, and pentane are reduced in classification by the solubility of the low nucleus relative to the state in the agent. The condensation reaction is then condensed into a polar solvent, and in the solution, a poor solvent such as cyclohexanol is high at this time, so that it remains dissolved in the poor precipitate, and a low nucleus content can be obtained. Examples of the polar solvent include alcohols such as decyl alcohol and ethanol, ketones such as m 9 1379159 propylene and decyl ethyl ketone, glycol ether esters such as ethylene glycol monoethyl ether acetate, and cyclic ethers such as tetrahydrofuran. The content of the low nucleus in the component (A) can be confirmed based on the results of GPC measurement. Namely, the molecular weight distribution of the synthesized phenolic novolac resin can be confirmed based on the GPC chart, and the content of the low core body can be calculated by measuring the intensity ratio of the peak corresponding to the elution time of the low core body. Further, since the dissolution time of the low-nuclear body differs depending on the measurement method, it is important to define the column 'solution, flow rate' temperature, detector, sample concentration, injection amount, and measuring device. Further, in the present invention, by using the following measurement method, the elution time of the phenolic monomer can be respectively assigned to the vicinity of 23 to 25 minutes, and the dissolution time of the dimer is attributed to the vicinity of 22 minutes. The dissolution time of the trimer was attributed to around 21 minutes. [Method for Measuring GPC of the Present Invention] (1) A sample of 20 mg was dissolved in 10 mmol of tetrahydrofuran (THF) to prepare a sample solution.

(2) The sample solution of (1) of 1 0 1 was injected into the following GPC measuring apparatus, and allowed to flow for 28 minutes, and measured at a wavelength of UV (u 11 ravi ο 1 et, UV) A = 2 80 nm The dissolution time of the sample detected nearby.

(measurement device) using a protective column (product name "KF-G"; manufactured by Shodex Co., Ltd.) and three separation columns (a styrene-divinylbenzene copolymer having a particle diameter of 6 m) as a filler, a column The size is 8 μπι (diameter) x 300 mm (length); the product name is "KF-801j; manufactured by Shodex", and the temperature of the separation column is GPC 10 1379159 which is set to 40 °C using an oven. The number of atoms is 1 to 6 An alkyl group, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms; and R" to R15 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; When R11 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Q1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a residue represented by the following chemical formula (2) [Chemical 2]

r11C^r17 (2) (〇H)c

(wherein R16 and R17 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkane having 3 to 6 carbon atoms; The base; c represents an integer of 1 to 3. In the case where Q1 is bonded to the end of R11, Q1 and R11, and the carbon atom between Q1 and R11 together represent a cycloalkyl group having 3 to 6 carbon atoms. ; a, b represents an integer of 1 to 3; d, e represents an integer of 0 to 3; x, y represents an integer of 0 to 3, and x + y = 0 to 3. Further, when Q1 and R11, and the carbon atom between Q1 and Rn together form a cycloalkyl group having 3 to 6 carbon atoms, Q1 and R11 are bonded to each other to form a carbon number of 2 to 5. The alkyl group. Among them, a phenol compound represented by the following chemical formula (3) is preferred. [chemical 3] i S] 12 (3) 1379159

Further, in addition to the phenol compound of the chemical formula (3), examples of the compound conforming to the chemical formula (1) include, for example:

Tris(4-hydroxyphenyl)decane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,3,5-trimethylphenyl)- 2-hydroxyphenyl decane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dianonylphenyl)-3-hydroxyl Cumoxane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxybenzylmethane, Bis(4-hydroxy-2, 5-dimercaptophenyl)-3-hydroxyphenylnonane, bis(4-hydroxy-2, 5-dimercapto)-2-hydroxyphenylmethane, bis (4 -hydroxy-3,5-dimercapto)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxymethane, double (4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxybenzone, bis(4-hydroxyphenyl)-3-methoxy-4-hydroxyphenyl decane, bis ( 5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylnonane, double (5-cyclohexyl-4-hydroxy-2-indolyl)-2-hydroxy benzyl, bis(5-cyclohexyl-4-hydroxy-2-indolylphenyl)-3,4- a trisphenol type compound such as hydroxybenzocane; 2,4-bis(3,5-dimethyl-4-hydroxybenzyl)-5-hydroxyphenol, 2,6-bis(2,5-dimethyl- Linear trinuclear phenolic compound such as 4-hydroxybenzyl)-4-mercaptophenol; • I S3 13 1379159

1, bis[3-(2-hydroxy-5-mercaptobenzyl)-4-hydroxy-5-cyclohexyl]isopropane, bis[2,5-dimercapto-3-(4-hydroxyl) -5-decylbenzyl)-4-hydroxyphenyl]methane, bis[2,5-dimethyl-3-(4-hydroxybenzyl)-4-hydroxyphenyl]methane, bis[3-( 3,5-diamidino-4-hydroxybenzyl)-4-hydroxy-5-nonylphenyl]methane, bis[3-(3,5-dimercapto-4-hydroxybenzyl)-4- Hydroxy-5-ethylphenyl]methane, bis[3-(3,5-diethyl-4-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane, bis[3-(3 , 5-diethyl-4-hydroxybenzyl)-4-hydroxy-5-ethylphenyl]methane, bis[2-hydroxy-3-(3,5-didecyl-4-hydroxybenzyl) _5 - fluorenyl] decane, bis[2-hydroxy-3-(2-hydroxy-5-fluorenylbenzyl)-5-methylphenyl]methane, bis[4-hydroxy-3-(2) -hydroxy-5-mercaptobenzyl)-5-nonylphenyl]decane, bis[2,5-dimercapto-3-(2-hydroxy-5-methylbenzyl)-4-hydroxy Base] methane and other linear tetranucleotide phenolic compounds;

2,4-bis[2-hydroxy-3-(4-hydroxybenzyl)-5-methylbenzyl]-6-cyclohexylphenol, 2,4-bis[4-hydroxy-3-(4-hydroxyl) Benzyl)-5-methylbenzyl]-6-cyclohexylbenzene, 2,6-bis[2,5-dimercapto-3-(2-propionyl-5-fluorenylbenzyl)-4 Linear polyphenolic compound such as a linear pentanucleoside phenol compound such as -hydroxybenzyl]-4-methylphenol; bis(2,3,-trihydroxyphenyl)decane, bis(2,4-dihydroxyphenyl) Methane, 2, 3, 4-trihydroxyindolyl-4'-hydroxybenzone' 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxy Phenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-di-phenyl)propyl, 2-(4-yl-phenyl)-2-() 4'-P-Phenylphenyl) Propane, 2-(3-Ga-4-pyrimidinyl)-2-(3fluoro-4'-pyridylphenyl)propane, 2-(2,4-di Hydroxyphenyl)-2-(4-hydroxyphenyl)propane, [S3 14 1379159

2-(2,3,4-trihydroxyphenyl)-2-(4-hydroxyphenyl)propane, 2-(2,trihydroxyphenyl)-2-(4'-hydroxy-3',5'- a compound of the formula of dipropenyl) propane; [1-(4-hydroxyphenyl)isopropyl]-4-[1, b-bis(4-hydroxy$ethyl)benzene, 1-[b (3 -Mercapto-4-hydroxyphenyl)isopropyl]-4-[1,(3-methyl-4-hydroxyphenyl)ethyl] phenyl and other polynuclear branched compounds; 1,1-double (4 A condensed phenol compound such as a hydroxyphenyl group or a cyclohexane may be used alone or in combination of two or more. The entire phenolic hydroxyl group of the compound represented by the above chemical formula (1) may be esterified and used. The esterification is carried out by a usual method, for example, a method of condensing naphthoquinonediazidesulfonium with a chemical represented by the above formula (1). For example, it can be produced by using a specific amount of the above formula (1) The compound represented by naphthoquinone-1,2-diazido-4 (or 5: the brewing gas is dissolved in two. Dioxane, N-methyl 0 ratio, ketone, diamine, In an organic solvent such as tetrahydrofuran, triethylamine, an alcohol amine, a pyridine, an alkali metal carbon are added thereto. One or more kinds of basic ones such as a salt and an alkali metal hydrogencarbonate are reacted, and the obtained product is washed with water to prepare an ester of the compound represented by the above chemical formula (1) in naphthoquinonediazide. The rate of conversion is not particularly limited, and is preferably from 20 to 80%, more preferably from 30 to 70%. If the esterification ratio is less than 20%, the resolution is lowered, and if it is more than 80%, it is present. The case where the sensitivity is lowered. As the component (B), in addition to the above-exemplified preferred naphthoquinone bismuth 3,4-bisphenol [yl] 1-dual and anthracene or exemplified chemical 丨-renewing B-B The catalyst may be dried and esterified with a good nitrogen ester ί S3 15 1379159. Other naphthoquinone diazide ester compounds may also be used. For example, polyhydroxy bicinchone or gallic acid alkyl _ Xue may also be used. The esterification reaction product of the phenol compound and the naphthoquinonediazidesulfonic acid compound, etc. The use amount of the other naphthoquinone diazide esters in the component (B) is 80% by mass in terms of the effect of the invention of the invention. Hereinafter, it is especially preferable when it is 50 mass % or less.

As the component (B), an alkali-soluble novolac resin in which all of the phenolic hydroxyl groups are partially substituted with a 1,2-naphthoquinonediazidesulfonyl group can obtain high resolution and good perpendicularity of the photoresist pattern. Especially good. Such a (β) component can be esterified with an alkali-soluble novolak resin and a 1,2-naphthoquinonediazidesulfonic acid compound, for example, according to the method described in Japanese Patent Laid-Open Publication No. Hei No. Hei 07-96076. Chemical reaction to manufacture. The alkali-soluble novolac resin used herein may, for example, be the above-mentioned solvent-soluble varnish resin or the like which is used as the component (A).

Examples of the 1,2-naphthoquinonediazidesulfonic acid compound include 1,2-naphthoquinonediazide-4-sulfonic acid gas and 1,2-naphthoquinonediazide-5-sulfonic acid gas. A toothing of an azide compound. The ratio of the hydrogen atom of all the phenolic hydroxyl groups in the above alkali-soluble novolac resin to the 1,2-naphthoquinonediazidesulfonyl group, that is, the reaction rate of the esterification reaction, is preferably 2 to 10 moles. %, better is 3 to 7 mol%, and more preferably 3 to 5 mol%. When the reaction rate is less than 2 mol%, there is a case where the film-reduction tendency of the unexposed portion is increased. For example, when the gap pattern is formed, the upper portion of the gap pattern is widened. When the reaction rate is more than 10 mol%, the transmittance of the ghi line is lowered, the m 16 1379159 is lowered under the sensitivity, the upper portion of the gap pattern is widened, and the perpendicularity of the cross-sectional shape is lowered. The amount of the component (B) in the positive resist composition varies depending on the kind of the sensitizer. In the case of the conventional sensitizer, it is preferably from 5 to 40% by mass, more preferably from 10 to 20% by mass, based on the component (A).

In the case where a photosensitive component is added to a non-photosensitive compound, the amount of the component (B) is different depending on the addition ratio of the photosensitive component. For example, in the case of an alkali-soluble novolac resin in which a part of all phenolic hydroxyl groups of the present invention is substituted with a 1,2-naphthoquinonediazidesulfonyl group, the amount of the component (B) is relative to (A) The component is preferably from 100 to 10,000% by mass, more preferably from 500 to 2,000% by mass. When the amount of the component (B) is less than the above lower limit, the film-reducing tendency of the unexposed portion may increase. When the amount is larger than the upper limit, the transmittance of the ghi line may be lowered and the sensitivity may be lowered. [(C) ingredient]

The component (C) is an ester of a polyhydric alcohol obtained by organically acidifying a part or all of a hydroxyl group. By using the component (C) in the positive resist composition, the photoresist pattern can be imparted while maintaining excellent resolution of the positive photoresist composition and maintaining good perpendicularity of the sidewall of the photoresist pattern. Softness prevents cracking of the photoresist pattern. This effect can also be exhibited particularly in a resist pattern having a thick thickness formed by using the positive resist composition. Therefore, cracks can be effectively prevented from occurring in the manufacturing and processing steps of bumps and the like, for example. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-propanediol '1,4-butanediol, and 1,2-butanediol '1,3-butanediol '2-methyl-1. , 3-propanediol, 2,4_diethyl_1,5-pentanediol, 3_mercapto-1,5-pentanediol, m 17 1379159

1,6-hexanediol, 3-mercapto-1,6-hexanediol, 4-mercapto-1,7-heptanediol' 1,9-nonanediol, diethylene glycol, triethylene glycol An aliphatic diol such as alcohol, tetraethylene glycol, polyethylene glycol, dipropylene glycol or polypropylene glycol; hydroquinone, 1,5-dihydroxynaphthalene, 4,4'-dihydroxyl stupid, double (pair) An aromatic diol such as hydroxyphenyl) decane or bis(p-hydroxyphenyl)-2,2-propane; 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,3- An alicyclic alcohol such as cyclohexane dimethanol or tricyclodecandiol; a trihydric or higher alcohol such as glycerin, trihydroxydecylethane, trihydroxydecyl propane, pentaerythritol, dipentaerythritol, xylitol or inositol Wait. Preferred among these are polybasic aliphatic alcohols, of which glycerin, ethylene glycol and propylene glycol are more preferred. The polyols may be used singly or in combination of two or more. The organic acid may, for example, be a carboxylic acid or a sulfonic acid, and is preferably a carboxylic acid.

The carboxylic acid may, for example, be a mono-, di-, or polycarboxylic acid. These are, for example, long-chain or branched aliphatic, aromatic or alicyclic saturated or unsaturated hydrocarbon acids. One or more hydrogen atoms of the hydrocarbon portion of the above carboxylic acid may be substituted by a halogen, a nitro group or the like. Alternatively, an acid anhydride corresponding to the acids may be used to produce vinegar. Examples of the carboxylic acid include aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, 2-ethylbutyric acid, n-pentanoic acid, valerianic acid, caproic acid, and heptanoic acid. Saturated monocarboxylic acid such as caprylic acid, citric acid, citric acid, lauric acid, myristic acid, palmitic acid, stearic acid, acrylic acid, methacrylic acid, crotonic acid, myristic acid, palmitic acid, oleic acid , linoleicaci, linolenic acid, and other unsaturated monocarboxylic acids, oxalic acid, malonic acid, succinic acid, fumaric acid, i S] 18 1379159

Maleic acid, citraconic acid, itaconic acid 'glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decane dicarboxylic acid, dodecane dicarboxylic acid, etc. a carboxylic acid, a tribasic acid, a tetracarboxylic acid, a polycarboxylic acid such as 1,2,3,4-butanetetracarboxylic acid; an aromatic carboxylic acid such as benzoic acid, o-didecanoic acid or m-benzoquinone; Acid, terephthalic acid, stupid tricarboxylic acid, polymellitic acid, phthalic acid, acetoacetic acid, diphenylacetic acid, phenylpropionic acid, etc.; alicyclic carboxylic acid, for example 1, 3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2 , 5-norbornane dicarboxylic acid, etc.; various naphthalene dicarboxylic acids; carboxylic acids having a substituent such as salicylic acid, gallic acid, tartaric acid, trifluoroacetic acid, fluoro 6 acid, gaseous acetic acid, α-aluminum Acid, methoxyacetic acid, cold-ethoxypropionic acid, p-chlorobenzoic acid, 2,4-dioxaoxyacetic acid, and the like; and anhydrides of such carboxylic acids. Among these, acetic acid, propionic acid, butyric acid and valeric acid are more preferred.

Examples of the sulfonic acid include aliphatic sulfonic acids such as sulfonic acid and dodecyl sulfonic acid; aromatic sulfonic acids such as sulfonic acid; and aliphatic aromatic sulfonic acids such as dodecylbenzenesulfonic acid. The polyol must have some or all of the hydroxyl groups organically esterified. The ester of the polyhydric alcohol is preferably an ester of the above preferred polyol with an organic acid, preferably glycerol monoacetate, diacetin and triacetin, particularly preferably Triacetin. The compounding amount of the component (C) in the positive resist composition is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass, based on the component (A). When the amount of the component (C) is less than the above-mentioned lower limit, the flexibility is lowered, and [S3 19 1379159 is likely to be cracked. If it is larger than the upper limit, the coating property is deteriorated and development is caused. The film thickness is reduced, and the photoresist is poorly adhered. The second aspect of the present invention is a positive resist composition comprising the component (D) and the component (C). [(D) component]

The component (D) is an alkali-soluble novolac resin in which a part of hydrogen atoms of all phenolic hydroxyl groups are substituted with 1,2-naphthoquinonediazidesulfonyl group, and is described as particularly excellent in the description of [(B) component]. Compound of the agent. This component (D) functions as both the component (A) and the component (B). In the case of the positive resist composition comprising the component (D) and the component (C), the compounding amount of the component (C) is preferably from 1 to 50% by mass based on the component (D), more preferably 5 to 30% by mass. When the amount of the component (C) is less than the above lower limit, the flexibility is lowered and cracking tends to occur. When the amount is more than the upper limit, the coating property is deteriorated and the film is reduced during development. The case where the photoresist is poorly sealed.

For the positive resist composition containing the component (D) and the component (C), the sensitizer of the component (B) may be used as needed. [Other Components] In the positive resist composition of the present invention, in addition to the components (A) to (D) used in the first aspect and the second aspect of the present invention, the sensitivity can be further adjusted as needed. A sensitizer, a adhesion improver for improving the adhesion between the photoresist composition and the substrate, a high-boiling organic solvent, and various additives conventionally used in the art. • Sensitivity improver 20 1379159

The sensitivity improving agent is not particularly limited, and a public sensitivity improving agent can be used, and examples thereof include bis(4-hydroxytrimethylphenyl)-2-hydroxyphenylmethane and 1,4-bis[1-(3). ,5-dihydroxyphenyl)isopropyl] stupid, 2,4-bis(3,5-dimethyl-4-hydroxy)-6-mercaptophenol, bis(4-hydroxy-3,5 - dimethylphenyl)-2 decane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyindole hydroxy-3, 5-dimercapto)-3, 4-dihydroxybenzylmethane, [1-phenyl)isopropyl]-4-[l,l-bis(4-hydroxyphenyl)ethyl]benzene, 1 methyl-4-hydroxyphenyl) Propyl]-4-[1,1-bis(3-indol-4-yl)ethyl]benzene, 2,6-bis[1-(2,4-dihydroxyphenyl)isopropyl] Phenol, 4,6-bis[1-(4-hydroxyphenyl)isopropyl]resorcinol, (3,5-dimethoxy-4-hydroxyphenylmethyl)pyrogallol, 4 ,6-dimercapto-4-hydroxyindolyl) pyrogallol, 2,6-bis(2,5·4-hydroxyphenylmethyl)-4-methylphenol, 2,6- Bis(3-indolyl-4-ylphenylmethyl)-4-nonylphenol, 2,6-bis(2,3,4-trihydroxy)-4-nonylphenol, 1,1-double ( 4-hydroxy stupid ) Cyclohexane Qin • adhesion improving agent

Examples of the adhesion improving agent include the adhesion improving agent described in the Japanese Patent Application Laid-Open No. Hei. No. 2 2 3 3 3 3, and the like. :6-Methyl-8 #,6-Ethyl-8 - 啥基啥琳, 5-曱-yl-8- 啥基啥琳, 8 #,8-乙乙氧啥琳, 4 -经基喋Bite, 2,4-di-dihydroquinone hydroxy acridine-2-sulfonic acid, 2-ethyl-4-hydroxyacridine, 2-methyl-4-pyridine, 1,10-morpholine, 5, 6-di Mercapto-1,10-morpholine, 3,8-dimethyl I-known β-2, 3, 5-methyl-4-.phenylindole-hydroxybenzene, bis(4-(4-hydroxyl[ 1-(3-Hydroxybenzene 4-methyl 4,6-bis-bis(3, 5--dimethyl, 6-dihydroxyphenyl-methyl). Special opening: Gazette, etc. - hydroxyquino-hydroxyquino: Acridine, 4-hydroxyindole: -!, !0- I S3 21 1379159 morpholine, 3, 8-dihydroxy-1,10-morpholine, 5-carboxy-1,10-morpholine, 5,6- Dihydroxy-1,10-morpholine, 1,10-morpholine-5-sulfonic acid, 4,4'-dimercapto-2,2, _.bipyridyl, 2,2,-linked. , 2, 2,.-聨. than bite a 5-carboxylic acid, 5,5,-dichloro-2, 2'-biacidine, 3,3'-dihydroxy-2, 2'-bipyridine, 3 ,3'-dimercapto-2, 2'- In addition, in particular, an aromatic having at least one of the bonds represented by the following chemical formulas (4) and (5) and at least one of the bonds represented by the following chemical formula (6) is added to the ring. The heterocyclic compound can significantly improve the adhesion of the positive photoresist composition to the substrate. (4) (5) —N: 5 R18

I -N - Chinese

For the number of primary carbons or sub-hydrogens, the hydrogenation of the 8 R-alkyl groups (6)

The base of the original carbon is substituted or the base is shown in Table 9 R

Straight or branched alkyl group of Ti S 22 1379159~5. )

Examples of the above-mentioned heterocyclic compound include an oxime compound and a porphyrin system described in pp. 362-401 of "Organic Compound Structural Formula Index" (published on December 20, 1977, Maruzen Co., Ltd.). a heterocyclic compound having a five-membered ring skeleton of a nitrogen atom, such as a compound or a phthalocyanine compound; a pyridine compound, an anthraquinone compound, a hydrazine-based compound, a heterologous compound, a bite-based compound, a benzoquinacridine compound, a heterocyclic compound having a six-membered ring skeleton of a nitrogen atom, such as a naphthene compound or a phenanthroline compound; a heterocyclic compound having two nitrogen-membered five-membered ring skeletons, such as a stimulating compound, a miso-salt compound, a benzoic-based compound, or a benzimidazole-based compound; a heterocyclic compound having a six-membered ring skeleton of two nitrogen atoms, such as a diazine compound, a hydrogenation ratio biting compound, a benzodiazepine compound, or a dibenzodiazine compound; a triazole compound, stupid a heterocyclic compound having a three-membered ring skeleton of three nitrogen atoms such as a triazole-based compound; a heterocyclic compound having three nitrogen-membered six-membered ring skeletons; a tetrazole, pentylenetetrazole or the like having four nitrogen atoms; a heterocyclic compound of a five-membered ring skeleton;

a heterocyclic compound having a six-membered ring skeleton of four nitrogen atoms, such as 1, 2, 4, 5-tetrazine; in addition to this, an anthraquinone compound, a biting compound, a B-azine (alloxazine) compound, 2H -0 is better than 嘻. In addition, it is preferable that the compound represented by the following chemical formula (7) is preferable in terms of a positive-type resist composition which can suppress the generation of scum and is excellent in adhesion to a substrate, and particularly preferably 2-( 2-hydroxyethyl)pyridine. [化7] ί S3 23 1379159

(wherein k represents an integer of 1 to 3, and R2° represents a linear or branched alkyl group having 1 to 5 carbon atoms in the hydroxy group.) The above-mentioned (A) component, (B) component, and C) The composition or the addition amount of the photoresist group adhesion improving agent containing the component (D) and the component (C) is 0.1 to 1.0% by mass, particularly preferably 0.2 to 0.7, based on the total amount of the above components. quality%. When the amount of the modifier added is less than 0.1% by mass, there is a case where the effect of improving the adhesion of the positive substance to the substrate is insufficient, and if the amount is large, the resolution is lowered, and the substrate after development is generated. tendency. • High-boiling organic solvent In the present invention, at least one selected from the group consisting of a high-boiling organic solvent having a boiling point of 200-right can be formulated as needed. Thereby, the effect of agglomeration (bu 1 k ) can be reduced, that is, the variation of the film density, that is, the positive-type photoresist composition, can be formed vertically when the photoresist film is formed on the substrate having a high or low difference on the surface. A photoresist pattern excellent in properties is preferred. Further, it is preferable that the prebaking treatment and the conditions of the PEB (exposure bake) treatment (heating time and heating can form a good photoresist pattern), and therefore, as the above-mentioned high boiling organic solvent, for example, 1 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The quality of some scum / 3 50 ° C left photoresist film used in the case of thick film, so heat, Post method, etc.) such as benzyl acid ester, dicapric acid di m 24 1379159

Ethyl ester, dibutyl phthalate, dinonyl phthalate, 7-butyrolactone, ethyl benzoate, butyl benzoate, propyl citrate, benzyl benzoate, B Glycol monoether, ethylene glycol monohexyl ether 1, 1, 3-octanediol, diethylene glycol, diethylene glycol diacetate, diethylene glycol dibutyl ether, diethylene glycol monoethyl ether, Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, dipropylene glycol, dipropylene glycol monobutyl ether, triethylene glycol, triethylene glycol di-2 -ethyl butyrate, triethylene glycol dimethyl ether, triethylene glycol monoethyl ether, triethylene glycol monomethyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, 2-ethylhexanoic acid, octanoic acid, caproic acid , catechol, octylphenol, N-methylpyrrolidone, and the like. These may be used singly or in combination of two or more. Among them, an organic solvent having a boiling point of from 250 to 350 ° C is preferred, and a salicylic acid ester is particularly preferred.

The photoresist composition containing the component (A), the component (B) and the component (C), or the photoresist composition containing the component (D) and the component (C) is high relative to the total amount of the component The blending amount of the boiling point organic solvent is preferably from 3 to 15% by mass, particularly preferably from 6 to 12% by mass. When the amount of the high-boiling organic solvent is less than 3% by mass, the effect of suppressing the above-described phenomenon is not obtained. When the amount is more than 15% by mass, the verticality of the cross-sectional shape may be lowered due to the widening of the upper portion of the gap pattern. 0 1〜10质量百分比左右。 The composition of the composition of the composition of the present invention is about 0. 0 1~ 10% by mass, respectively, with respect to the composition of the composition of the positive resistive composition of the present invention, in order to improve the resolution, the exposure margin, and the residual film rate. Add p-toluenesulfonate (PTSC), 4, 4'-bis(diethylamino)benzophenone, 1,4-bis[1-(2-mercapto-4-hydroxy-5) - 25 1379159 Cyclohexylphenyl)isopropyl]benzene, 1,3-bis[1-(2-methyl-4-hydroxy-5-cyclohexylphenyl)isopropyl]benzene, and the like.

Further, in the positive resist composition of the present invention, it is further possible to add a compatible additive to the range which does not hinder the object of the present invention, for example, an ultraviolet absorber for preventing halation, For example, 4-dimethylamino 2',4'-di-dibenzoquinone, 5-amino-3-indolyl-1-phenyl-4-(4-hydroxyphenyl azo)pyrene Oxazole, 4-didecylamino-4'-hydroxyazobenzene, 4-diethylamino-4'-ethoxyazobenzene, 4,4'-diethylaminoazobenzene, Curcumin, etc.; or surfactants used to prevent streaks, such as Fluorad FC-430, FC431 (trade name, manufactured by Sumitomo 3M), F TopEF122A, EF122B, EF122C, EF126 (trade name, Tohchem Products) ) Manufacturing), a fluorine-based surfactant such as Megafac R-08 (manufactured by Dainippon Ink Chemicals Co., Ltd.).

The positive resist composition of the present invention preferably has the above-mentioned (A) component, (B) component, and (C) component, or (D) component and (C) component, and the above-mentioned various additive components added as needed. It is dissolved in a suitable solvent and used in the form of a solution. Examples of such a solvent include a solvent used in the conventional positive-type resist composition, and examples thereof include acetone, mercaptoethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone. Ketones; ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate or such monomethyl ether, monoethyl ether, monopropyl ether Polyols such as monobutyl ether or monophenyl ether and derivatives thereof; cyclic ethers such as di-β-alkane; and ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, pyruvic acid Ethylene 1379159 ester, methyl methoxypropionate, ethyl ethoxy propionate and other esters. These may be used singly or in combination of two or more. Particularly preferred are ketones such as acetone, mercaptoethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone; ethyl lactate, decyl acetate, ethyl acetate, butyl acetate, decyl pyruvate An ester such as ethyl acrylate, methyl methoxypropionate or ethyl ethoxypropionate. The solvent may be used singly or in combination of two or more solvents.

For example, when a spin coating method is used, and a film thickness of, for example, 3 /zm or more is to be obtained, the solvent is preferably used in such a manner that the solid concentration of the positive resist composition is in the range of 20 to 65 mass%. Inside. When the solid content concentration is less than 20% by mass, it is difficult to obtain a thick film having a film thickness of, for example, 3 or more. When the content is more than 65% by mass, the fluidity of the composition is lowered, and handling becomes difficult, which is difficult by spin coating. A situation in which a uniform photoresist film is obtained.

For example, the positive resist composition of the present invention can be prepared by merely mixing and stirring the above components in a usual manner, and a disperser such as a dissolver, a homogenizer or a three-roll mill can be used to disperse the above components as needed. The mixture is mixed to prepare a positive photoresist composition of the present invention. Further, after mixing, it can be further filtered using a sieve, a membrane filter or the like. The positive resist composition of the present invention is suitable for forming a thick film photoresist layer of 3 to 30 /zm, more preferably 5 to 20 //m, and even more preferably 8 to 15 thick on the carrier. [Manufacturing Method of Substrate Attached to Photosensitive Film] A preferred example of the method for producing a substrate with a photosensitive film of the present invention is exemplified below. The positive photoresist composition of the present invention is used using a rotator or the like, and as needed IS] 27 1379159

The various additional components are dissolved in a suitable solvent as described above and applied to a substrate such as Si, Cu or Au, and dried to form a light layer on the substrate. [Method of Forming Photoresist Pattern] A desired pattern is placed on a photosensitive film of a substrate on which a photosensitive film is attached. Then, a light source emitting light having a wavelength of around 365 nm such as a low pressure mercury lamp, a high pressure mercury lamp, or an ultrahigh pressure mercury lamp is used for exposure through the pattern. Then, PEB (post-exposure heating treatment) is carried out, and the substrate is immersed in a developing solution, for example, an alkaline aqueous solution such as a 1 to 10% by mass aqueous solution of tetramethylammonium hydroxide (TMAH), and the exposed portion is removed. Thus, an image loyal to the mask pattern can be obtained. [Examples] Hereinafter, the present invention will be specifically described using examples. (Synthesis Example 1) [Synthesis of a promiscible acid varnish resin] A stirring device, a thermometer, and the like are provided. In a four-liter bottle of 3 L of the heat exchanger, the mixture of m-cresol and p-cresol in a ratio of 60:40 to m-(m-phenol:p-phenol) is mixed with 100 parts by mass. The phenol was added with 465 parts by mass of a 37% aqueous solution of formalin and 2 parts by mass of oxalic acid, and the reaction was carried out for 4 hours. Thereafter, the mixture was dehydrated under normal pressure until the inside reached ° C, and then dehydrated and dehydrated under a reduced pressure of 70 torr. Until the monomer reaches t, 850 parts by mass of a phenolic resin having a mass average molecular weight of 5900 is obtained. The solution is oxidized to form a photomask, and the oxidized to the ear-burning ratio is added to the 170 200 varnish [S3 28 1379159] (Synthesis Example 2) [Alkali-soluble novolac resin All 4.5 mole% of 1,2-naphthoquinone diazide-5-sulfonic mince hydroxyl group substituted with a photosensitive agent's]

50 g of the novolac type phenol resin obtained in Synthesis Example 1 and 4 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride (0.015 mol) were placed in a thermometer, a stirrer, and a dropping funnel. In a 1 L three-necked flask, 162 g of two were added thereto. After the alkane was dissolved, 3.0 g of triethylamine (0.03 mol) was added from a dropping funnel, and stirring was continued at room temperature for 1 hour. Thereafter, 1.63 g of hydrochloric acid (0.045 mol) was added, and the mixture was further stirred at room temperature for 30 minutes, and then subjected to filtration separation, whereby a reddish brown liquid was obtained. The liquid was added to a 2 L beaker containing 1 L of pure water while stirring, and a precipitate was precipitated to obtain 3.8 mol% of all phenolic hydroxyl groups substituted by 1,2-naphthoquinonediazidesulfonyl phenol. Varnish resin. (Synthesis Example 3) Synthesis of a sensitizer in which 2 moles of a hydroxyl group of a compound of the chemical formula (3) is substituted with 1,2-naphthoquinonediazide-5-continuation helium gas]

50 g of the compound of the formula (3) and 56.92 g of 1,2-naphthoquinonediazide-5-sulfonium (0.212 mol) were placed in a 1 L three-necked flask equipped with a thermometer, a stirrer, and a dropping funnel. After adding 2.7 g of alkane and dissolving it, 42.4 g of triethylamine (0.424 mol) was added dropwise from the dropping funnel while maintaining a rapid rise in temperature, and stirring was continued for 1 hour at room temperature. Thereafter, 23.2 g of hydrochloric acid (0.636 mol) was added, and after stirring at room temperature for 30 minutes, filtration was carried out, whereby a reddish brown liquid was obtained. t S3 29 1379159 The liquid was added to a 2 L beaker containing 1 L of pure water while stirring, and the precipitate was precipitated to obtain a target sensitizer. [化8]

(Synthesis Example 4) [Synthesis of alkali-soluble acrylic resin]

After replacing the flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank with nitrogen, 200 g of propylene glycol oxime ether acetate as a solvent was charged. While stirring, the temperature of the solvent was raised to 80 ° C, and 0.5 g of 2,2'-azobisisobutyronitrile, 130 g of 2-methoxyethyl acrylate, and 50. 0 g of ruthenium were placed in the dropping tank. Benzyl acrylate, 20.0 g of acrylic acid as a polymerization catalyst, stirred until the polymerization catalyst dissolved. Thereafter, the solution was uniformly dropped into the flask over 3 hours, followed by polymerization at 80 ° C for 5 hours, and then cooled to room temperature to obtain an alkali-soluble acrylic resin. [Example 1] 55 parts by mass of the following component (A), 15 parts by mass of the following component (B), 10 parts by mass of the following component (C), and 20 parts by mass of a sensitivity improving agent as other components were dissolved. The concentration of the solid component of the above I S1 30 1379159 was 45% by mass in propylene glycol monoethyl ether acetate. The resulting solution was filtered using a membrane filter to prepare a positive resist composition. (A) Component: alkali-soluble novolak resin (B) of Synthesis Example 1 Component: Sensitizer of Synthesis Example 3 (C) Component: Triacetin sensitivity improving agent: a compound represented by the following chemical formula (8) [ 9]

[Example 2]

5 parts by mass of the following component (A), 65 parts by mass of the following component (B), 10 parts by mass of the following component (C), and 20 parts by mass of a sensitivity improving agent as another component are dissolved in propylene glycol monoethyl ether acetate A positive resist composition solution was prepared in the same manner as in Example 1 except that the concentration of the solid component was changed to 45% by mass. (A) component: alkali-soluble acid varnish resin (B) component of Synthesis Example 1: Photosensitive agent (C) of Synthesis Example 2: Triacetin sensitivity improving agent: Compound represented by the above chemical formula (8) [ Example 3] 70 parts by mass of the following component (D), 10 parts by mass of the following (C) into [S] 31 1379159 minutes and 20 parts by mass of a sensitivity improving agent as another component were dissolved in propylene glycol monoethyl ether acetate In the same manner as in Example 1, a positive resist composition was prepared in such a manner that the concentration of the solid component was 45% by mass. (D) component: sensitizer (C) component of Synthesis Example 2: triacetin sensitivity improving agent: the compound represented by the above chemical formula (8) [Comparative Example 1] m 65 parts by mass of the following (Α) component 15 parts by mass of the following (Β) component and 20 parts by mass of a sensitivity improving agent as another component were dissolved in propylene glycol monoethyl ether acetate, and the concentration of the solid component was 45% by mass, which was the same as in Example 1. A positive photoresist composition was prepared in a manner. (A) component: Synthetic varnish resin of Synthesis Example 1 (B) Component: sensitizer of Synthesis Example 3 f-sensitivity improving agent: Compound represented by the above chemical formula (8) [Comparative Example 2]

50 parts by mass of the following component (A), 15 parts by mass of the following component (B), 15 parts by mass of the component (C) as a component (C), and 20 parts by mass of a sensitivity improving agent as another component are dissolved in propylene glycol In the monoethyl ether acetate, a positive resist composition was prepared in the same manner as in Example 1 except that the concentration of the solid component was changed to 45 mass%. (A) component: Synthetic chain-stretching resin (B) component of Synthesis Example 1 · Photosensitive agent (C') component of Synthesis Example 3: benzyl salicylate sensitivity improving agent: represented by the above chemical formula (8) Compound m 32 1379159 [Comparative Example 3] 50 parts by mass of the following component (A), 15 parts by mass of the following component (B), and 15 parts by mass of the component (C' ') and 20 parts by mass of the component (C) A positive-type resist composition was prepared in the same manner as in Example 1 except that the sensitivity improving agent of the other component was dissolved in propylene glycol monoethyl ether acetate so that the concentration of the solid component was 45% by mass. (A) component: alkali-soluble novolac resin of Synthesis Example 1.

(B) component: sensitizer (C '') component of Synthesis Example 3: alkali-soluble acrylic resin sensitivity improving agent of Synthesis Example 4: The compound represented by the above chemical formula (8) was obtained by the following method: 3 and the physical properties of the positive resist composition obtained in Comparative Examples 1 to 3. The results are shown in Table 1. (1) Evaluation of cross-sectional shape A positive-type photoresist composition was applied onto a Cu substrate using a spinner, and dried on a hot plate at 100 ° C for 240 seconds to obtain a photoresist film having a thickness of 10.

5〜3秒之间的以罩 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 The line and gap of m are exposed to the photoresist film in a manner consistent with the size of the mask. Then, as a developing operation, a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23 ° C was applied to the substrate for 60 seconds, and then the aqueous solution was removed by rotation with a spinner. After repeating the development operation three times, it was washed with water for 30 seconds, and dried, and the shape of the pattern obtained was observed by SEM (scanning electron microscope) photograph, and the width of the bottom of the gap pattern (B) was observed. The ratio (B/T) of the width (T) of the upper portion of the gap pattern is 0.90 S (B/T). The pattern shape of S1.0 is expressed as 〇, and the pattern shape of 0.80 S (B/T) < 0.90 is obtained. Indicated as Δ, and the pattern shape of 0·8> (B/T) and 1.0 < (B/T) is represented as X. (2) Resolution evaluation

The minimum mask size (/zm) separated by the bottom of the pattern is used as the limit resolution in E0P (using an L&S mask with a mask size of 5.0 Mm, which can be exposed to the same size as the mask size). (3) Evaluation of flexibility (crack resistance) Using a rotator, a positive resist composition was applied to four substrates at intervals of 1 #m, and the film thickness was 8 /zm to 11 /zm. After heating for 4 minutes at 120 ° C on a hot plate, it was rapidly cooled on a stainless steel table adjusted to 23 ° C to observe the surface of the photoresist. As a result, a photoresist film having a film thickness of 8 and having cracks on the surface was formed.

In the case of XX, a photoresist film having a film thickness of 9 and having a crack on the surface is represented by X, and a photoresist film having a film thickness of 10 or more and having a crack on the surface is represented by Δ, and the film thickness is 11 and the surface is formed. A photoresist film having cracks was shown as ruthenium, and a photoresist film having a film thickness of 11. //m but no crack was generated was indicated as ©. [S] 34 1379159

Cross-sectional shape resolution softness Example 1 Δ 3 egg ◎ Example 2 〇· 1.5 ◎ Example 3 〇 1.5 Aim ◎ Comparative Example 1 Δ 3 /zm XX Comparative Example 2 Δ 3 Δ Comparative Example 3 X 5 β\Ά ◎ [Table 1] From the results, it is understood that the (A) component and the (B) component have a positive form of the present invention in which a part or all of the hydroxyl group of the component (C) is organically esterified with the ester of the polyol. a photoresist composition of the present invention; and a positive resist composition of the present invention having an ester of a polyhydric alcohol obtained as a part or all of a hydroxyl group as an organic acid in (D), having a cross-sectional shape and resolution It is excellent and has excellent flexibility. Even when the film thickness is 11, it does not crack. A formulation of an ester of a polyol obtained by partially or completely encapsulating a part of the present invention as a component (C) (Comparative Example 1 Replacing a component of the component (C) with benzyl salicylate (Comparative Example 2) In the case of using the acrylic resin instead of the component (C) (the comparative example does not provide a positive resist composition having a cross-sectional shape, resolution, and flexibility (crack resistance). [Simplified illustration] No [Major component symbol description] Unconfigured component 酉 化 / / // m hydroxy 丨, make and 3), both excellent [S] 35

Claims (1)

Γ 379159 第 09 7 1 34 5863⁄4 ?, Case 1〇1· 7· i〇 Amendment 10. Patent scope: 1. A positive-type photoresist composition containing (Α) alkali-soluble phenolic resin, (Β) sensitizer And (C) is at least one selected from the group consisting of glycerin monoacetate, glycolate, and triacetin. 2. The positive-type photoresist composition as described in claim 1 wherein the (Β) component is a bismuth-soluble phenol varnish resin in which a part of hydrogen atoms of all phenolic hydroxyl groups are replaced by quinonediazidesulfonyl. A positive-type photoresist composition comprising (D) an alkali-clear varnish resin in which all phenolic hydroxyl moiety hydrogen atoms are replaced by 1,2-naphthoquinonediazidesulfonyl group, and (C) is selected from the group consisting of glycerin At least one of acetate, glycerin diethylene and triacetin. a varnish oil, wherein the 1,2-naphthyl monophenolic acid ester, wherein the composition of the present invention is as described in claim 1. The above-mentioned (C) component is Triacetin. A substrate comprising a photosensitive film, wherein a photosensitive film is formed on a substrate by using a positive resist composition according to the first or third aspect of the patent. 36