TW200912532A - Positive photoresist composition and substrate with photo-sensitive film using the same - Google Patents

Abstract

The present invention discloses a positive photoresist composition which has a high resolution and is capable of forming a photoresist pattern which is hard to generate cracks and has a sidewall with excellent verticality, and a substrate with a photo-sensitive film using the same. The positive photoresist composition of the invention includes the following: (A) alkali soluble phenolic varnish resin; (B) a photo sensitive agent; (C) ester of polyhydric alcohols obtained from esterified partial or whole hydroxyl by organic acid. Further, the positive photoresist composition of the present invention includes the following: (D) alkali soluble phenolic varnish resin with partial hydrogen atoms of all phenolic hydroxyl replaced by 1,2-diazido-sulfamyl; ester of polyhydric alcohols obtained from esterified partial or whole hydroxyl group by organic acid. The invention also includes a substrate with a photo-sensitive film obtained from forming a photo-sensitive film formed by using the aforementioned positive photoresist composition on a substrate.

Description

200912532 IX. Description of the Invention: 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, large-scale integration, and ASIC (application-specific integrated circuit), the industry has installed LSI on multiple pins of electronic devices. Thin film packages, bare chip packages of the TCP (Tape Carrier Package) type, etc. are attracting attention. The terminal for connection of such a multi-lead package, that is, the height of the bump is called 2 0 // m electrode It is placed on the substrate with high precision. In the future, the precision of the bumps is required in the industry in response to miniaturization of the steps. In order to form bumps, a quinonediazide-containing compound containing an alkali-soluble novolac as a sensitizer is used. The positive-type light bump can be formed, for example, by forming a photoresist film having a film thickness of about 20 /zm, forming a photoresist pattern through a specific mask light, and developing it, and then using gold or The copper plating treatment removes the photoresist pattern around it. The photoresist composition has, for example, the following requirements: if it is to be washed during or after the plating treatment, the photoresist film is not otherwise, 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. When the pattern is formed on the carrier, the bumps are exposed, soldering, etc., and cracks are generated. On the substrate, the vertical pattern of the photoresist pattern sidewall 5 200912532 is good, and the photoresist is formed in the narrow pitching process of the bump arrangement. The object has high resolution and the like. 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 tree-forming diazide-based compound, and a test-resolved 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 in the resist pattern after the plating treatment, and to prevent cracking of the photoresist pattern, it is necessary to further improve the photoresist group. [Patent Document 1] Japanese Patent Laid-Open No. 2 0 0 2 - 2 5 8 4 7 9 [Disclosure] The object of the present invention is to solve the above problems and to provide a figurative property. A positive-type photoresist composition which is hard to generate cracks and has a good vertical pattern of the side walls, and a substrate in which the photosensitive film is formed using the positive-type photoresist is formed. [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 type of composition can solve the above problems, and the completion of the present invention also requires that a grease, a dilute acid-containing condition, a photoresist pattern size added to the photoresist, and a multi-light Block the group. 6 200912532 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 part or all of the hydroxyl groups are obtained by organic acidification) The second aspect of the present invention is a positive-type photoresist composition containing an alkali-soluble phenolic resin in which a part of hydrogen atoms of all phenolic hydroxyl groups are replaced by 1,2-naphthoquinonediazidesulfonium. a varnish resin, and (C) an ester of a polyol obtained by organically esterifying a part or all of a hydroxyl group. The third aspect of the present invention is a substrate with a photosensitive film, which is to be used as the present invention. The photosensitive film formed of the positive photoresist of the first or second aspect is formed on the substrate. [Effects of the Invention] The positive resist composition of the present invention is excellent in resolution. In the positive resist composition of the 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, a photoresist pattern having the above characteristics can be formed by using a film having a thick film thickness. Ways] The first aspect of the present invention includes (A) component, (B) component, and (component positive photoresist composition. [(A) component] (A) component is solubility test. 5〜1. 0摩尔的优选的酸酸。 Having a varnish resin, as a solvent-soluble lacquer resin, is not particularly limited, preferably with respect to a phenolic 1 molar condensing agent such as an aldehyde is 0. 5~1. The catalyst is obtained by the downward condensation reaction of the catalyst. D) The group of the group is C) and the amount of the phenol is, for example, phenol, o-nonylphenol, m-nonylphenol, p-nonylphenol, etc. Indole phenols; 2, 3-dioxanol, 2,4-diphenylphenol, 2,5-diindol, 2,6-diindol, 3,4-xylene, 3, 5- Dimethyl phenol such as phenol; ethyl phenol such as o-ethyl phenol, m-ethyl phenol or p-ethyl phenol, 2-isopropyl phenol, 3-isopropyl phenol, 4-isopropyl phenol, ortho An alkanol such as butyl phenol, m-butyl phenol, p-butyl phenol or p-tert-butyl phenol; a trimethyl phenol such as 2, 3, 5 -tridecyl phenol or 3, 4, 5-tridecyl phenol Benzene , catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglucinol and other polyphenols; alkyl resorcinol, alkyl catechol, alkyl pair An alkyl polyphenol such as a benzenediol (any of the above alkyl groups is an alkyl group having 1 to 4 carbon atoms); α-naphthol, /3-naphthol, hydroxybiphenyl, bisphenol oxime or 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-cresol and p-cresol are more preferably used in combination. By adjusting the ratio of the two, it is possible to adjust various characteristics such as sensitivity and heat resistance of the photoresist composition. The ratio of the indomethacin to the indophenol is not particularly limited, and it is preferably m-cresol/p-cresol = 3 / 7 to 8 / 2 (mass ratio). When the ratio of m-cresol is less than the above lower limit, the sensitivity may be lowered, and if it is larger than the above upper limit, the heat resistance may be lowered. The condensing agent may, for example, be an aldehyde or a ketone, preferably an aldehyde, and more preferably formaldehyde or trioxane. The acidic catalyst is not particularly limited, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; and organic acids such as capric acid, oxalic acid, acetic acid, diethyl sulfuric acid, and p-sulfonic acid; Gold 8 such as zinc acetate 200912532 is a salt. These acidic catalysts may be used singly or in combination of two. In terms of developability, resolution, and resistance of the photoresist composition, the mass average molecular weight of the polystyrene conversion by gel permeation chromatography (GPC) is preferably 1 〇. 〇〇~5 0 0 0 0. The component (A) is preferably a fractionated resin having a low basis weight of 80% by mass or less, more preferably a lower fractionated resin. Here, the low-nuclear body is a phenol-based monomer as described above, a dimer obtained from two molecules of the phenol-based monomer, and a terpolymer obtained from the phenol-based monomer. By using such a classifying resin, the cross-sectional shape of the photoresist pattern is further improved, and it is difficult to generate residue on the substrate after development (floating: the resolution of the composition is improved. and the small classification treatment excellent in heat resistance can be known by the known The classification treatment method is carried out by the following fractionation treatment. First, the above phenol compound is subjected to a dehydration condensation reaction with a condensing agent, and then the combined product (novolac resin) is dissolved in a polar solvent, and water and gargane are added. Since the solubility of the low-nuclear body is relatively high, the solubility of the low-nuclear body is relatively high, so that the precipitated product is filtered to obtain a low-reduced classification resin. For example, methanol may be used, and the above combination may cause the content of the (A) adult of the plating liquid to be reduced by 50% by mass to the compound, and the perpendicularity of the three-part shape, and the photoresist is oriented. And better. For example, the resulting polycondensation can be carried out in the solution. At this time, the content of the poor nucleate is explained as an alcohol such as ethanol, 9 200912532 a ketone such as acetone or mercaptoethyl ketone, a glycol ether ester such as ethylene glycol monoethyl ether acetate, or a cyclic ether 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 G P C map, and the content of the low core body can be calculated by measuring the intensity ratio of the peak corresponding to the dissolution 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, the elution solution, the flow rate, the temperature, the detector, the sample concentration, the injection amount, the measuring device, and the like. 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 m g was dissolved in 10 mmol of tetrahydrofuran (T H F ) to prepare a sample solution.

(2) The sample solution of (1) of 10#1 was injected into the following GPC measuring apparatus, and allowed to flow for 28 minutes, and measured at a wavelength of UV (u 1 tra ν i ο 1 e ΐ, ultraviolet ray λ = The dissolution time of the sample detected near 2 80 nm.

(measurement device) using a protective column (product name "KF-G"; manufactured by Shodex Co., Ltd.) and three separation columns (a styrene-diethylene copolymer having a particle diameter of 6 lm) as a filler. The column size is 8 Am (diameter) x 300 mm (length); the product name is "KF-801"; manufactured by Shodex), and the temperature of the separation column is GPC 10 200912532 which is set to 40 °C using an oven. (Product name "GPC SYSTEM 1 1"; manufactured by Shod ex Co., Ltd.), and the measurement was carried out under the conditions of a liquid feeding rate of tetrahydrofuran (THF) eluent of 1.0 ml/min. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。. When Mw/Mn is more than 3.0, the upper portion of the gap pattern (resist pattern) becomes wider, the resolution is lowered, and the perpendicularity of the cross-sectional shape of the resist pattern tends to decrease. This tilting is particularly noticeable when the focus of the light at the time of exposure is shifted to the positive side (when the focus is shifted toward the bottom side of the photoresist film), resulting in a decrease in the depth of focus characteristic. [Component (B)] The component (B) is a sensitizer. As the component (B), a naphthoquinonediazide compound can be mentioned. The naphthoquinonediazide compound is not particularly limited as long as it is used as a sensitizer in a positive-type resist composition, and one or two or more types may be used arbitrarily. For example, a phenol compound represented by the following chemical formula (1) and an esterified product with a naphthoquinonediazidesulfonic acid compound can be used. [Chemical 1]

[wherein, each independently represents a hydrogen atom, a halogen atom, a carbon 11 200912532 an alkyl group having 1 to 6 atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms; R12 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 and the carbon number is 1 to 6 An alkyl group or a residue represented by the following chemical formula (2) [Chemical 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 3 carbon atoms; ～6 cycloalkyl; c represents an integer of 1 to 3.), when Q1 is bonded to the end of R11, Q1 and R11, and the carbon atom between Q1 and R11 together represent a carbon number of 3~ a cycloalkyl group; 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 extension of the base. Among them, a phenol compound represented by the following chemical formula (3) is preferred. [化3] 12 200912532

Further, in addition to the phenol compound of the chemical formula (3), examples of the phenol compound according to the chemical formula (1) include tris(4-hydroxyphenyl)decane and bis(4-hydroxy-3-methylphenyl). 2-hydroxyphenylnonane, bis(4-hydroxy-2,3,5-tridecylphenyl)-2-hydroxybenzene, bis(4-hydroxy-3,5-dimethylphenyl) 4-hydroxyphenyl decane, bis(4-hydroxy-3, 5-dimethylphenyl)-3-hydroxybenzone, bis(4-hydroxy-3, 5-dimercapto)-2 -hydroxyphenyl decane, bis(4-hydroxy-2,5-diamidinophenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-didecylphenyl)-3-hydroxy stupid Methane, bis(4-hydroxy-2, 5-dimercapto)-2-hydroxybenzene, bis(4-hydroxy-3, 5-dimethylphenyl)-3,4-dihydroxybenzene Methane, bis(4-hydroxy-2,5-dimercaptophenyl)-3,4-dihydroxybenzocane, bis(4-hydroxy-2,5-dimercaptophenyl)-2,4- Dihydroxyphenyl decane, bis(4-hydroxyphenyl)-3-decyloxy-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-indolylphenyl)-4-hydroxybenzene Decane, bis(5-cyclohexyl-4-hydroxy-2-indolyl)-3-hydroxybenzoquinone, Bis(5-cyclohexyl-4-yl-2-ylidenephenyl)-2-carbylbenzoate, bis(5-cyclohexyl-4-hydroxy-2-indolylphenyl)-3,4 a trisphenol type compound such as dihydroxybenzene decane; 2,4-bis(3,5-dimethyl-4-hydroxybenzyl)-5-hydroxyphenol, 2,6-bis(2,5-diindole) Linear 4-nucleoside phenolic compound such as 4-hydroxybenzyl)-4-nonylphenol; 13 200912532 1, bis[3-(2-hydroxy-5-methylbenzyl)-4-hydroxy-5- Cyclohexyl]isopropane, bis[2,5-dimercapto-3-(4-hydroxy-5-fluorenylbenzylhydroxyphenyl]decane, bis[2,5-dimercapto-3-(4) -hydroxybenzyl)-4-phenyl]methane, bis[3-(3,5-dimercapto-4-hydroxybenzyl)-4-hydroxybenzylphenyl]methane, bis[3-(3 ,5-dimercapto-4-hydroxybenzyl)-4--5-ethylphenyl]methane, bis[3-(3,5-diethyl-4-hydroxybenzylhydroxy-5-methyl Phenyl]methane, bis[3-(3,5-diethyl-4-hydroxyfyl)-4-hydroxy-5-ethylphenyl]methane, bis[2-hydroxy-3-(3, 5 -di-4-hydroxybenzyl)-5-nonylphenyl]decane, bis[2-hydroxy-3-(2--5-mercaptobenzyl)-5-nonylphenyl]decane, Bis[4-hydroxy-3-(2--5-methylbenzyl)-5-nonylphenyl a linear tetranuclear phenol such as methane, bis[2,5-dimercapto-3 hydroxy-5-mercaptobenzyl)-4-hydroxyphenyl]methane; 2,4-bis[2-hydroxy-3 -(4-hydroxybenzyl)-5-fluorenyl]ylhexylphenol, 2,4-bis[4-hydroxy-3-(4-hydroxybenzyl)-5-methyl]-6-cyclohexyl Linear pentanucleoside phenol such as benzophenone, 2,6-bis[2,5-dimercapto-3-(2-carbyl-i-benzyl)-4-hydroxybenzyl]-4-methylphenol Isobaric polyphenolic compound; bis(2,3,-trihydroxyphenyl)decane, bis(2,4-dihydroxybenzene J, 2,3,4-trisyl-based 4'- Aristotle, 2-(2,3,4-triphenyl)-2-(2',3',4'-trihydroxyphenyl)propane, 2-(2,4-dihydroxy)-2 -(2',4'-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-phenylphenyl)propane, 2-(3-fluoro-4-ylphenyl)- 2-(3'-fail-4' stupyl)propane, 2-(2,4-di-phenyl)-2-(4'-phenylphenyl)benzene)-4-hydroxy-5 -hydroxy)-4-ylbenzylmethylhydroxyl-(2-(6-cyclobenzyl-5- decyl) k) hydroxyphenylbenzene (4'-hydroxyl-alkane, 14 200912532 2 -(2, 3, 4-trisylphenyl) -2-(4'-Phenylphenyl)propane, 2-(2,trihydroxyphenyl)-2-(4'-hydroxy-3',5'-dimethylphenyl)propane ; [1-(4-hydroxyphenyl)isopropyl]-4-[1,b-bis(4-hydroxy-ethyl)benzene, 1-[1_(3-methyl-4-phenylphenyl) a polynuclear branched compound such as isopropyl]-4-[1,(3-methyl-4-hydroxyphenyl)ethyl]benzene; a condensation type such as bis(4-hydroxyphenyl)cyclohexane These may be used alone or in combination of two or more. All of the phenolic hydroxyl groups of the compound represented by the above chemical formula (1) can be used for the purpose of the present invention, and can be carried out by a conventional method. For example, a method of condensing naphthoquinonediazidesulfonium with a chemical represented by the above chemical formula (1). For example, it can be prepared by dissolving a specific amount of the compound represented by the above formula (1) with naphthalene-1,2-diazido-4 (or 5: helium gas dissolved in dioxane). , N-mercapto group, in an organic solvent such as pirone, diamine, tetrahydrofuran, etc., in which triethylamine, an alcoholamine, a specific bite, a metal carbonate, an alkali metal hydrogencarbonate, etc. are added. The esterification rate of the compound represented by the above chemical formula (1) in the naphthoquinone diazide is not particularly limited, and it is preferred to carry out the reaction. 2 0 to 8 0 %, more preferably 3 0 to 7 0%. If the esterification rate is less than 20%, the resolution is lowered, and if it is more than 80%, the sensitivity is lowered. The composition, in addition to the above-mentioned preferred naphthoquinone bismuth 3,4 ~ bismuth fluorenyl) or the chemistry of the phytochemical, the lyophilized ethylene ester, the esterification of the ester nitrogen ester 15 200912532 Other naphthoquinone diazide esters may also be used, for example polyhydroxybenzophenone or gallate may also be used. Vinegar alkyl phenol compound with naphthoquinonediazide acetic acid compound of the performance of the reaction product of nitrogen. In view of the effect of the present invention, the amount of the other naphthalene diazide ester compound used is preferably 80% by mass or less, particularly preferably 50% by mass or less, based on the component (B). 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 component (B) can be, for example, an ester of an alkali-soluble novolak resin and a 1,2-naphthoquinonediazidesulfonic acid compound according to the method described in Japanese Patent Laid-Open Publication No. Hei No. Hei 07-96076. Chemical reaction to manufacture. The above-mentioned solvent-soluble varnish resin used as the component (A) may be mentioned. Examples of the 1,2-naphthoquinonediazidesulfonic acid compound include 1,2-naphthoquinonediazide-4-sulfonic acid gas, and 1,2-naphthoquinonediazide-5-sulfonic acid chloride. a halide of an azide compound. The ratio of the hydrogen atom of all the phenolic hydroxyl groups in the above alkali-soluble novolac resin is substituted by 1,2-naphthoquinonediazidesulfonyl group, that is, the reaction rate of the esterification reaction, 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% by mole, there is a case where the transmittance of the gh i line (gh i 1 i ne ) is lowered, the sensitivity is lowered by 16 200912532, the upper portion of the gap pattern is widened, and the verticality 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 ordinary 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 phenolic phenolic resin in which a wide part of all phenolic hydroxyl groups of the present invention are substituted with 1,2-naphthoquinonediazidesulfonyl group, the amount of the component (B) is relatively The component (A) is preferably from 1 to 10% by mass, more preferably from 50,000 to 2,000 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 gh i line may be lowered and the sensitivity may be lowered. [(C) component] The component (C) is an ester of a polyhydric alcohol obtained by organically esterifying a part or all of a hydroxyl group. By using the component (C) in the positive resist composition, it is possible to impart excellent resolution while maintaining the positive resist composition and maintaining good perpendicularity of the sidewall of the photoresist pattern. The pattern is soft and 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-propylene glycol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, and 2-mercapto-1. , 3-propanediol, 2, 4-diethyl-1,5-pentanediol, 3-mercapto-1,5-pentanediol, 17 200912532 1,6-hexanediol, 3-mercapto-1 , 6-hexanediol, 4-mercapto-1,7-heptane 1,9-nonanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol and other aliphatic a glycol; an aromatic diol such as hydroquinone, hydroxynaphthalene, 4,4'-dihydroxybiphenyl, bis(p-hydroxyphenyl)methane 'hydroxyphenyl)-2,2-propane; 4-cyclohexanedicyclohexanediethanol, 1,3-cyclohexanedimethanol, tricyclodecanediol type alcohol; glycerin, trimethylolethane, trihydroxymethylpropane, penta A divalent or higher alcohol such as dipentaerythritol, xylitol or inositol. Preferred among these are polybasic aliphatic alcohols, of which 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. Preferred examples of the carboxylic acid include mono-, di-, and polycarboxylic acids. One or more hydrogen atoms such as a long chain aliphatic, aromatic or alicyclic saturated or unsaturated hydrocarbon acid-smoothed tobacco moiety may be substituted by a halogen or a nitrate group. Further, an acid anhydride vinegar corresponding to the acids may also be used. Examples of the carboxylic acid include aliphatic carboxylic acids such as acetic acid, butyric acid, 2-ethylbutyric acid, n-pentanoic acid, valerianic acid, caproic acid, heptanoic acid, caprylic acid, and citric acid. Saturated monocarboxylic acid, methacrylic acid, crotonic acid, myristic acid, palmitoleic acid, linoleic acid (1 i η ο 1 eicaci ), lauric acid, myristic acid, palmitic acid, stearic acid, etc. Linoleic acid (1 i η ο 1 eni and other unsaturated monocarboxylic acids, oxalic acid, malonic acid, succinic acid, reverse butyl diol, diol, 1,5-di•bis (pair, 1,4- Such as alicyclic tetraol, glycerol, carboxylic acid. Chain or branch. The above base or its manufacture of propionic acid, oxalic acid, acrylic acid, c acid) diacid, 18 200912532

Maleic acid, thiconic acid, itaconic acid, glutaric acid, adipic acid, heptanedioic acid, azelaic acid, sebacic acid, decane dicarboxylic acid, dodecanedicarboxylic acid, Pyromellitic acid, pyromellitic acid, 1,2,3,4-butane tetracarboxylic acid; aromatic carboxylic acid, such as benzoic acid, o-didecanoic acid, dicarboxylic acid, p-benzoic acid Citric acid, trimellitic acid, poly me 1 litic acid, phthalic acid, phenylacetic acid, diphenylethyl phenylpropionic acid, etc.; alicyclic carboxylic acid, such as 1,3 - ring Butane didecanoic acid, cyclopentane dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedithio 1,4 -cyclohexanedicarboxylic acid, 2, 5-norbornane II Niobic acid or the like; various naphthoic acids; carboxylic acids having a substituent such as salicylic acid, gallic acid, tartar trifluoroacetic acid, fluoroacetic acid, gaseous acetic acid, α-propionic acid, methoxyacetic acid-ethoxylated Propionic acid, p-chlorobenzoic acid, 2,4-diphenoxyacetic acid, etc.; acid anhydrides of such carboxylic acids, and the like. Among these, acetic acid, propionic acid, butyric acid and valeric acid are more preferred. Examples of the sulfonic acid include an aromatic sulfonic acid such as an anthracenesulfonic acid, a dodecylsulfonic acid aliphatic sulfonic acid or a benzenesulfonic acid, and an aromatic aromatic sulfonic acid such as dodecylbenzenesulfonic acid. The polyol must have some or all of the hydroxyl groups organically esterified. As the ester of the polyhydric alcohol, preferred are the above-mentioned preferred polyols and acids. Among them, preferred are glycerin monoacetic acid S, glycerol diacetate triacetate, and particularly preferred is triacetin. Acid ester. The compounding amount of the component (C) in the positive resist composition is preferably from 1 to 50 mass% / Torr, more preferably from 5 to 30 mass%, based on the component. When the blending amount of the Bi component is less than the above lower limit, the softness is lowered, and acid, acid, and the like are stearic acid, 1,3-acid, dicapric acid, β, and the like fat organic and sweet. (C) 19 19125125 The crack is likely to occur, and if it is larger than the upper limit, the coating property may be deteriorated, the film thickness during development may be reduced, and the photoresist may be 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 novolak resin in which a part of hydrogen atoms of all the desired radicals are substituted with 1,2-naphthoquinonediazidesulfonyl group, which is described in [(B) component] A compound which is described as a particularly good sensitizer. 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 improving agent 20 200912532 The sensitivity improving agent is not particularly limited, and a known one can be used. As the sensitivity improving agent, for example, bis(4-hydroxy-2,3,5-tridecylphenyl)-2-hydroxybenzocane, 1,4-bis[1-(3,5-diindole) 4- 4-hydroxyphenyl)isopropyl]benzene, 2,4-bis(3,5-dimethyl-4-hydroxyindolyl)-6-nonylphenol, bis(4-hydroxy-3) , 5 -dimercaptophenyl)-2-hydroxyphenyl decane, bis(4-hydroxy-2,5-diamidinophenyl)-2-hydroxyindole, bis(4-hydroxy-3,5 -didecylphenyl)-3,4-dihydroxyindole, 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-phenyl) Ethyl]benzene, 1-[1-(3-indolyl-4-hydroxyphenyl)isopropyl]-4-[1,b-bis(3-indenyl-4-hydroxyphenyl)ethyl] Benzene, 2,6-bis[1-(2,4-dihydroxyphenyl)isopropyl]-4-nonylphenol, 4,6-bis[1-(4-hydroxyphenyl)isopropyl] Resorcinol, 4,6-bis(3,5-dioxaoxy-4-hydroxyphenylindenyl) pyrogallol, 4,6-bis(3,5-dimercapto-4-hydroxyl Phenylmethyl)pyrogallol, 2,6-bis(2,5-dimercapto-4-hydroxyphenylindenyl)-4-nonylphenol, 2,6-bis(3-indenyl- 4,6-dihydroxyphenylindenyl)-4-nonylphenol, 2, 6- (2, 3, 4 A three-hydroxyphenyl) -4 - Yue-phenol, 1, Bu-bis (4 - hydroxyphenyl) cyclohexane are preferred. The adhesion improving agent is used as a adhesion improving agent, and it is exemplified in the Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. 6-2-2 2 2 4 3, Japanese Patent Laid-Open No. Hei 1 1 - 2 2 3 9 3 7 and the like. The adhesion improving agent described may, for example, be 6-methyl-8-hydroxyquinoline, 6-ethyl-8-carbazin, 5-methyl-8-pyridyl 01-lin, 8-基基琳, 8-ethoxylated 、, 4-hydroxy 喋 bit, 2,4-di-base bite, 4-base 嗓 bite _2-cross-acid, 2-ethyl-4- Base bite, 2·*mercapto-4-ylpyridinium, 1,10-morpholine, 5,6-dimethyl-1,10-morpholine, 3, 8-dimethyl-1,10 - 21 200912532 morpholine, 3,8-dihydroxy-1,10-morpholine, 5-carboxy-1,10-morpholine, 5,6-dihydroxy-1,1 quinone-morpholine, 1, 1 〇-morpholin-5-sulfonic acid, 4,4 '-dimethyl-2,2 '-bipyridine, 2,2 '-bipyridine, 2, 2 '-bipyridyl-5-carboxylic acid, 5, 5 '-Dichloro-2, 2 '-bipyridine, 3,3 '-dihydroxy-2,2 '-bipyridine, 3, 3,-dimercapto-2, 2'-biacidine and the like. Further, in particular, an aromatic heterocyclic compound 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 adhesion of the positive photoresist composition to the substrate can be remarkably improved. [Chemical 4] —N= (4) [Chemical 5] R18

I - N - (5) where J 6 is a number of pro carbons or a sub-nitrogen showing an alkyl group 3 rc-= (6)

The linear or branched chain of the base of the original carbon has a linear or branched alkyl group which is substituted or represented by R 22 200912532 〜5. For example, the oxime compound and the guanidine compound described in the pp of the "organic index" (published on December 20, 1987, Maruzen (share)), a heterocyclic compound having a five-membered ring skeleton of a gas atom; a compound, a guanidine compound, a hydrogenated phthalocyanine compound, an isoindole, a bite compound, a benzoxanthine compound, a naphthylline a compound having a six-membered ring skeleton of a nitrogen atom, such as a phenanthrene compound; a five-membered ring skeleton having two nitrogen atoms, such as a lanthanoid compound, a spectroscopy compound, a spectroscopy compound, and an imidazole compound. a compound having two nitrogen ring skeletons such as a diazine compound, a hydrogenation ratio biting compound, a dibenzodiazine compound, a triazole compound, a benzotriazole, etc. a heterocyclic compound having three nitrogen-membered five-membered ring skeletons; a heterocyclic compound having three nitrogen-membered six-membered ring skeletons; a heterocyclic ring having four nitrogen-membered five-membered ring skeletons such as tetrazole; , 4,5-tetrazine, etc. Six nitrogen atoms in the ring skeleton thereof; Yin-based compound except that include voice, voice-based compound fixed ° (a 11 ο X a z i n e) compound, 2 Η - ° 0 than each other. In addition, in order to provide a positive-type photoresist composition which can suppress scum generation and is excellent in adhesiveness, the compound represented by the following is preferable, and 2 - (2-hydroxyethyl) is especially preferable. 7] Structure of the compound. 362-401 Cyanide pyridine-based leaching compound, heterocyclic compound, benzene heterocyclic compound, benzodiatomic six-member compound ° Qin system, four α sit, pentylene a compound of a heterocyclic compound or a ruthenium on the substrate (7). 23 200912532 ^(N)k ^4-R20 (7) (wherein k represents an integer of 1 to 3, and R2° represents a linear or branched alkyl group having a hydroxy group having 1 to 5 carbon atoms.) The amount of the photoresist group adhesion improving agent containing the component (A), the component (B) and the component (C), or the component (D) and the component (C), and the total amount of the component 0质量%。 The amount of 0. 1~1. 0% by mass, particularly good is 0. 2~0. 7% by mass. 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 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 A certain amount of dross 〆 3 5 (TC left photoresist film used in the case of thick film, so hot, Post method, etc.) such as benzyl acid ester, dicapric acid di 24 200912532 ethyl ester, phthalic acid Butyl ester, dinonyl phthalate, 7-butyrolactone, ethyl benzoate, butyl benzoate, propyl benzoate, benzyl benzoate, ethylene glycol monophenyl ether, ethylene Alcohol monohexyl ether, 1,3-octanediol, diethylene glycol, diethylene glycol diacetate, diethylene glycol dibutyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate Ester, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, dipropylene glycol, dipropylene glycol monobutyl ether, triethylene glycol, triethylene glycol di-2-ethylbutyric acid Ester, triethylene glycol dioxime ether, triethylene glycol monoethyl ether, triethylene glycol monomethyl ether, tripropylene glycol, tripropylene glycol monoterpene ether, 2-ethylhexanoic acid, octanoic acid, caproic acid, catechol , octylphenol, N-decylpyrrolidone, etc. These may be used singly or in combination of two or more. Among them, an organic solvent having a boiling point of from 2,500 to 3,500 ° C is preferred. Preferably, it is a benzyl salicylate. In 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), The blending amount of the high-boiling organic solvent is preferably from 3 to 15% by mass, particularly preferably from 6 to 12% by mass, based on the total amount of the above components. If the blending amount of the high-boiling organic solvent is less than 3% by mass, In the case of the above-mentioned phenomenon, 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 is lowered due to the widening of the upper portion of the gap pattern, etc. • Various additive components are added to the positive-type photoresist composition of the present invention. In order to improve resolution, exposure margin, and residual film rate, Add p-toluenesulfonyl chloride (PTSC), 4, 4'-bis(diethylamino) dioxin, 1,4-double to the composition of about 0.1 to 10% by mass. [1-(2-indolyl-4-hydroxy-5-125 200912532 cyclohexylphenyl)isopropyl]benzene, 1,3-bis[1-(2-indolyl-4-hydroxy-5-cyclohexyl) Phenyl)isopropyl]benzene, etc. 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 as needed, for example: An ultraviolet absorber for preventing halation, for example, 4-didecylamino-2',4'-dihydroxydipodone, 5-amino-3-methyl-;!-phenyl-4- (4-hydroxyphenylazo)pyrazole, 4-dimethylamino-4'-hydroxyazobenzene, 4-diethylamino-4'-ethoxybenzobenzene, 4,4 ' _Diethylamino azobenzene, curcumin, etc.; or surfactants to prevent streaks, such as Fluorad FC-4 3 0, FC431 (trade name, manufactured by Sumitomo 3M (share)), F TopEF122A, EF122B, EF122C, EF126 (trade name, manufactured by Tohchem Products) A fluorine-based surfactant such as gafacR-08 (manufactured by Dainippon Ink Chemicals Co., Ltd.). The positive resist composition of the present invention preferably contains the above-mentioned (A) component, (B) component, and (C) component, or (D) component and (C) component, and the above various additives added as needed. Dissolve in a suitable solvent and use it in the form of a solution. Examples of such a solvent include a solvent used in the conventional positive resist composition, and examples thereof include acetone, mercaptoethyl ketone, cyclohexanone, decyl 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; Alkane and other cyclic ethers; and ethyl lactate, decyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, pyruvic acid B 26 200912532 ester, methyl methoxypropionate, ethoxy propionic acid Ester such as ethyl ester. These may be used alone or in combination of two or more. Particularly preferred are ketones such as acetone, ethyl ethyl ketone, cyclohexanone, decyl isoamyl ketone, and 2-heptanone; lactate, methyl acetate, ethyl acetate, butyl acetate, decyl pyruvate, An ester such as ethyl propionate, decyl methoxypropionate or ethyl ethoxypropionate. The solvent may be used singly or in combination of two or more kinds of solvents, for example, by using a spin coating method, for example, a film thickness of 3 # m or more is to be obtained ('^ These solvents are preferably used in a positive amount of light. The concentration of the solid of the composition is in the range of 20 to 65 mass%. If the solid content concentration is less than the mass%, it is difficult to obtain a thick film having a film thickness of, for example, 3 /zm or more, if more than 65 mass %, the fluidity of the composition is lowered, and the operation is difficult, and it is difficult to obtain a uniform photoresist film by a spin coating method. For example, the above components can be mixed and stirred in a usual manner, and the positive of the present invention can be prepared. As the resist composition, a disperser such as a dissolver, a mass machine, or a three-roll mill may be used to disperse and mix the above components to prepare the positive resist composition of the present invention. The sieve may be further filtered using a sieve, a membrane filter, etc. The positive resist composition of the present invention is suitably formed on the support to form 3 to //m, more preferably 5 to 20 am, and even more preferably 8 to Thick film photoresist layer of 15 μm thick. Method for Producing Substrate of Photosensitive Film] An example of a method for producing a substrate with a photosensitive film of the present invention is exemplified below. The positive resist composition of the present invention and the fluorene ketone are used by using a rotator or the like. 20 The requirements of the film are 30. The film is applied to a substrate such as S i, Cu, Au, etc., dissolved in the appropriate solvent as described above, and dried to form a light layer on the substrate. Method for Forming Photoresist Pattern] A desired pattern is disposed on a photosensitive film of a substrate having a photosensitive film. 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. The pattern is exposed. Then, PEB (exposure heating after exposure) is performed, 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 hydrogen tetramethylammonium (TMAH). Then, the exposed portion is removed, whereby 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 varnish resin] In four bottles of 3 L with a stirring device, a thermometer, and a heat exchanger, the amount of m-nonylphenol and p-cresol is relative to 100 parts by mass. The phenol was mixed with the obtained phenol in a ratio of 60:40, 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, further dehydrating and de-monomering under a reduced pressure of 70 torr until reaching ° C, obtaining 850 parts by mass of a phenolic age-old resin having a mass average molecular weight of 5900. The solution is oxidized to form a photomask. Burning ear ratio, added to 170 200 varnish 28 200912532 (Synthesis Example 2) [All of the hydroxyl groups of the alkali-soluble novolac resin was 4.5 mM. Synthesis of sensitizer substituted with 1,2-naphthoquinonediazide-5-sulfonyl group] 50 g of the novolac type phenol resin obtained in Synthesis Example 1, and 4 g of 1,2-naphthoquinone Azide-5-sulfonyl chloride (0.015 mol) was placed in a 1-L three-necked flask equipped with a thermometer, a stirrer, and a dropping funnel, and 162 g of dicodane was added thereto and dissolved, and then self-drip 3 g of triethylamine (0.03 mol) was added to the liquid funnel, and stirring was continued for 1 hour at room temperature. 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 phenolic hydroxyl group was 3.8 mol/°, and the precipitate was precipitated to obtain a phenolic hydroxyl group. A novolak resin substituted with 1,2-naphthoquinonediazidesulfonyl. (Synthesis Example 3) Synthesis of a sensitizer in which 2 moles of a hydroxyl group of a compound of the formula (3) is substituted with 1,2-naphthoquinonediazide-5-anthracene chloride] 50 g of a compound of the formula (3), And 56.92 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride (0.212 mol) was placed in a 1-L three-necked flask equipped with a thermometer, a scrambler, and a dropping funnel, and dioxane was added thereto. After dissolving 267 g and allowing the temperature to rise rapidly, 42.4 g of triethylamine (0 · 4 2 4 mol) was added dropwise from the dropping funnel, 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. 29 200912532 2 L-burning This liquid was added to a cup containing 1 L of pure water while stirring to precipitate a precipitate to obtain a target sensitizer. [化8]

(3) (Synthesis Example 4) [Synthesis of alkali-soluble acrylic acid resin] After replacing a flask equipped with a stirring device, a reflux device, and a thermometer with nitrogen, the mixture was charged with 200 g of propylene glycol oxime ether as a solvent. The temperature of the solvent was raised to 80 ° C, and 0.5 g of 2,2'-azobisisobutyronitrile, 130 g of 2-methyl acrylate, 50.0 g of benzyl methacrylate, and 20.0 g of acrylic acid were polymerized in the dropping tank. Stir until the polymerization catalyst dissolves. Thereafter, the solution was added to the flask over 3 hours, followed by polymerization at 80 ° C for 5 hours, and then cooled to obtain an alkali-soluble acrylic resin. [Example 1] 5 parts by mass of the following component (A) and 15 parts by mass of the following (minute, 10 parts by mass of the following component (C) and 20 parts by mass as a sensitivity improving agent, dissolved in propylene glycol In the monoethyl ether acetate, the dropping tank is acid-based. The ethoxylate B catalyst is added to the chamber B) to form a component, and the concentration of the above 30 200912532 solid component is 45 mass%. The resulting solution was filtered using a membrane filter to prepare a positive resist composition. (A) component: Synthetic varnish resin of Synthesis Example 1 (B) Component: Sensitizer of Synthesis Example 3 (C) Component: Triacetin sensitivity improving agent: Compound represented by the following chemical formula (8) [Chemistry 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 other components were dissolved in propylene glycol In a diethyl 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 mass%. (A) component: Synthetic test varnish resin (B) of Synthesis Example 1: Sensitizer of Synthesis Example 2 (C) Component: Triacetin sensitivity improving agent: Compound represented by the above chemical formula (8) [ Example 3] 70 parts by mass of the following component (D) and 10 parts by mass of the following (C) to 31 200912532 minutes and 20 parts by mass of a sensitivity improving agent as another component were dissolved in propylene glycol monoethyl ether acetate so that The positive resist composition was prepared in the same manner as in Example 1 except that the concentration of the solid component was 45% by mass. (D) component and sensitizer (C) component of Synthesis Example 2: Triacetin sensitivity improving agent: Compound represented by the above chemical formula (8) [Comparative Example 1] Γ' 65 parts by mass of the following (Α) The 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 so that the concentration of the solid component was 45 mass. /〇, a positive resist composition was prepared in the same manner as in Example 1. (A) component: the solubility test varnish resin of the synthesis example 1 (B) component: the sensitizer sensitivity improving agent of the synthesis example 3: the compound represented by the above chemical formula (8) [Comparative Example 2] 50 mass parts of the following (A) component, 15 parts by mass of the following (B), part, 15 parts by mass of the component (C'), and 20 parts by mass of a sensitivity improving agent as another component, dissolved in propylene glycol monoethyl ether In the acid ester, a positive resist composition was prepared in the same manner as in Example 1 except that the concentration of the above solid content was 45 mass%. (A) component: Synthetic acid varnish resin (B) of Synthesis Example 1 : Photosensitive agent (C ') of Synthesis Example 3: benzyl salicylate sensitivity improving agent: Compound represented by the above chemical formula (8) 32 200912532 [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) are used as 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 changed to 45 mass%. (A) component: alkali-soluble novolac resin (B) component of the synthesis example 1: the photosensitive agent of the synthesis example 3 (C component: the alkali-soluble acrylic resin sensitivity improvement agent of the synthesis example 4: it is represented by the above-mentioned chemical formula (8). The physical properties of the positive resist compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were determined by the following methods. The results are shown in Table 1. (1) Evaluation of the cross-sectional shape using a rotator The positive resist composition was coated on a Cu substrate, and dried on a hot plate at 100 ° C for 240 seconds to obtain a photoresist film having a thickness of 10 μm. The mask of the pattern was exposed to a film using a reduced projection exposure apparatus NSR-2005il0D (manufactured by Nikon, NA = 0.50) for 0.5 to 3 seconds so that the mask size was 5 ym and the gap was the same as the mask size. Exposure to the photoresist film in a uniform manner. Then, as a developing operation, an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide (TMAH) at 23 ° C was applied to the substrate for 60 seconds, and then utilized. The rotation of the rotator removes the aqueous solution. After repeating the development operation three times, the water is washed for 30 seconds. After drying, the shape of the pattern obtained was observed by a 33 200912532 SEM (scanning electron microscope) photograph, and the ratio of the width (B) of the bottom of the gap pattern to the width (T) of the upper portion of the gap pattern (B) / T ) is 0 · 9 0 S (B/T) S1.0 The pattern shape is expressed as 〇, and the pattern shape of 0.80S (B/T) < 0.90 is expressed as Δ, which is 0.8 > (B/T ) and the pattern shape of 1.0 < (B/T) is expressed as X. (2) Resolution evaluation f- E0P (using an L&S mask with a mask size of 5.0 #m, it can be exposed to light In the exposure amount in which the cover size is uniform, the minimum mask size (A m ) at the bottom of the pattern is used as the limit resolution. (3) The flexibility (crack resistance) is evaluated using a rotator at a distance of 1 # m. The photoresist composition is coated on four substrates and has a film thickness of 8 μm to 11 /zm. After heating for 4 minutes at 120 ° C on a hot plate, it is adjusted to 23 ° C. The stainless steel table was cooled rapidly and the surface of the photoresist was observed. As a result, the photoresist film k having a film thickness of 8 /zm and having cracks on the surface was expressed as XX, and the film thickness was 9 /zm and a photoresist film having a crack on the surface is represented by X, and a photoresist film having a film thickness of 10 /zm or more and having a crack on the surface is represented by Δ, the film thickness is 11 /zm, and a turtle is formed on the surface. The cracked photoresist film is represented by ruthenium, and the photoresist film having a film thickness of 11 /zm but no cracking is shown as ©. 34 200912532 [Table 1] Cross-sectional shape resolution softness Example 1 Δ 3 /zm ◎ Example 2 〇1.5 ◎ Example 3 〇1.5 /zm ◎ Comparative Example 1 Δ 3 /zm XX Comparative Example 2 Δ 3 Δ Comparative Example 3 X 5 /zm ◎ From these results, it is known that (A) component and (B) a positive-type photoresist composition of the present invention containing an ester of a polyol obtained by organically esterifying a part or all of a hydroxyl group of the component (C); and a compound (C) formulated in (D) The positive-type resist composition of the present invention in which a part or all of the hydroxyl groups of the component are organically esterified is excellent in cross-sectional shape and resolution, and excellent in flexibility, even if the film thickness is 1 1 There will be no cracks when // m. A formulation of an ester of a polyol obtained by organically esterifying a part or all of a hydroxyl group of the present invention as a component (C) (Comparative Example 1), and a formulation using benzyl salicylate instead of the component (C) (Comparative Example 2) and a formulation in which an acrylic resin was used instead of the component (C) (Comparative Example 3), and a positive resist having excellent cross-sectional shape, resolution, and flexibility (crack resistance) could not be obtained. Composition. [Simple description of the diagram] None [Key component symbol description] None 35

Claims (1)

200912532 X. Patent application scope: 1. A positive photoresist composition comprising (A) an alkali-soluble novolac resin, (B) a sensitizer, and (C) a part or 5 or all of the hydroxyl groups obtained by organic acidification An ester of a polyol. 2. The positive-type photoresist composition according to claim 1, wherein the component (B) is a base in which a part of hydrogen atoms of all phenolic hydroxyl groups are substituted by 1,2-naphthoquinonediazidesulfonyl group. Solvent novolak resin. 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 with 1,2-naphthoquinonediazidesulfonyl group, and (C) a part or The purpose of the polyol obtained by organically esterifying all of the hydroxyl groups. 4. The positive-type photoresist composition according to claim 1 or 3, wherein the polyhydric alcohol is a polyhydric aliphatic alcohol. 5. The positive resist composition according to claim 4, wherein the polyhydric aliphatic alcohol is at least one selected from the group consisting of glycerin, ethylene glycol, and propylene glycol. 6. The positive-type photoresist composition according to claim 1 or 3, wherein the organic acid is a tick. The positive-type photoresist composition according to claim 6, wherein the carboxylic acid is at least one selected from the group consisting of acetic acid, propionic acid, butyric acid, and valeric acid. 8. The positive resist composition according to claim 1, wherein the component (C) is at least one selected from the group consisting of glycerin monoacetic acid S, glycerin diacetate, and glycerol triacetate. 9. The positive resist composition according to claim 1, wherein the component (C) is triacetin. A substrate comprising a photosensitive film, characterized in that a photosensitive film formed by using a positive resist composition as described in claim 1 or 3 is formed on a substrate. 37 200912532 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None f 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None 4