JP2009069284A - Positive photoresist composition and photosensitive film attached substrate using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photoresist composition which has high resolution, substantially avoids crack generation, and is capable of forming a photoresist pattern having good perpendicularity of a side wall, and a photosensitive film attached substrate. <P>SOLUTION: The positive photoresist composition comprises (A) an alkali-soluble novolac resin, (B) a photosensitive agent, and (C) an ester of a polyhydric alcohol having hydroxyl groups partially or entirely esterified with an organic acid. The positive photoresist composition may comprise (D) an alkali-soluble novolac resin in which part of the hydrogen atoms of all phenolic hydroxyl groups is substituted for a 1,2-naphthoquinonediazidosulfonyl group, and (C) an ester of a polyhydric alcohol having hydroxyl groups partially or entirely esterified with an organic acid. In the photosensitive film attached substrate, a photosensitive film formed using the positive photoresist composition is formed on a substrate. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a positive photoresist composition and a photosensitive film-coated substrate using the same.

  With the progress of higher integration of LSI and ASIC, multi-pin thin film mounting for mounting LSI on electronic devices is required, and attention is paid to bare chip mounting by TCP method or flip chip method. In such a multi-pin mounting, it is necessary to dispose a protruding electrode with a height of 20 μm or more, called a bump as a connection terminal, on the substrate with high accuracy, and in the future, bumps corresponding to further miniaturization of LSIs High accuracy is required.

In order to form a bump, a positive photoresist composition containing an alkali-soluble novolak resin and a quinonediazide group-containing compound that is a photosensitive agent is used.
For the bump, for example, a photoresist film having a film thickness of about 20 μm is first formed on a support, and a resist pattern is formed by exposure and development through a predetermined mask pattern. Then, it can be formed by performing a plating process using gold, copper, solder or the like and removing the surrounding resist pattern.
In this photoresist, for example, if it is a bump, the resist film does not crack at the time of plating treatment or after washing with water, and if it is TCP, the resist is similarly applied on a flexible tape substrate. It is required that the film does not crack. In addition, the verticality of the sidewalls of the photoresist pattern is good, and the photoresist composition is required to have high resolution as the pitch of bumps becomes narrower.

In order to prevent the occurrence of cracks, for example, Patent Document 1 discloses a positive photoresist composition for a thick film containing an alkali-soluble novolak resin, a quinonediazide group-containing compound, and an alkali-soluble acrylic resin as a plasticizer. Are listed.
However, when a positive photoresist composition containing a plasticizer is used, the resolution tends to decrease and the dimensional stability of the photoresist pattern tends to decrease.

Therefore, in order to prevent cracks from occurring in the photoresist pattern while suppressing a decrease in resolution and a dimensional change of the photoresist pattern after plating, further improvement of the photoresist composition is required.
JP 2002-258479 A

  The present invention solves the above-described problems, and provides a positive photoresist composition capable of forming a photoresist pattern having high resolution, being less susceptible to cracking, and having good sidewall verticality, and the positive photoresist composition. It aims at providing the board | substrate with a photosensitive film | membrane using a type photoresist composition.

  As a result of diligent research to solve the above problems, the present inventors have found that some or all of the hydroxyl groups are esterified with an organic acid as a component of a positive photoresist composition using an alkali-soluble novolak resin. The present inventors have found that the above-mentioned problems can be solved by using an ester of a polyhydric alcohol that has been formed, and have completed the present invention.

  That is, the first aspect of the present invention comprises (A) an alkali-soluble novolak resin, (B) a photosensitizer, and (C) an ester of a polyhydric alcohol in which part or all of the hydroxyl groups are esterified with an organic acid. A positive photoresist composition to be contained.

  In the second aspect of the present invention, (D) an alkali-soluble novolak resin in which a part of the hydrogen atoms of the total phenolic hydroxyl group is substituted with a 1,2-naphthoquinonediazidosulfonyl group, and (C) a part of the hydroxyl group or A positive photoresist composition containing an ester of a polyhydric alcohol, all esterified with an organic acid.

  According to a third aspect of the present invention, there is provided a photosensitive film characterized in that a photosensitive film formed using the positive photoresist composition according to the first or second aspect of the present invention is formed on a substrate. It is a substrate.

  The positive photoresist composition of the present invention is excellent in resolution. In addition, by using the positive photoresist composition of the present invention, a photoresist pattern having the above-mentioned characteristics is formed from a photoresist film that is less susceptible to cracking and has good verticality of the side wall, particularly a thick photosensitive film. can do.

  Hereinafter, embodiments of the present invention will be described in detail.

The first aspect of the present invention is a positive photoresist composition containing the component (A), the component (B), and the component (C).
[(A) component]
The component (A) is an alkali-soluble novolak resin. Although it does not specifically limit as alkali-soluble novolak resin, It obtains by making a condensation reaction in the ratio of 0.5-1.0 mol of condensing agents, for example with respect to 1 mol of phenols, in an acidic catalyst. Are preferred.

  Examples of phenols include cresols such as phenol, o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3 Xylenols such as 1,4-xylenol and 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol and p-ethylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, alkylphenols such as o-butylphenol, m-butylphenol, p-butylphenol and p-tert-butylphenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; resorcinol, catechol Polyhydric phenols such as alcohol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phlorogricinol; alkyl polyhydric phenols such as alkylresorcin, alkylcatechol, alkylkylhydroquinone (all the alkyl groups have 1 to 4 carbon atoms) And α-naphthol, β-naphthol, hydroxydiphenyl, bisphenol A and the like. These phenols can be used individually or in combination of 2 or more types.

  Among the phenols, m-cresol and p-cresol are preferable, and it is more preferable to use m-cresol and p-cresol in combination. By adjusting the blending ratio of the two, various characteristics such as sensitivity and heat resistance as a photoresist can be adjusted. The blending ratio of m-cresol and p-cresol is not particularly limited, but m-cresol / p-cresol = 3/7 to 8/2 (mass ratio) is preferable. When the ratio of m-cresol is less than the above lower limit, the sensitivity may decrease, and when the ratio exceeds the upper limit, the heat resistance may decrease.

  Examples of the condensing agent include aldehydes and ketones, and aldehydes, particularly formaldehyde and paraformaldehyde are preferable.

  Examples of the acidic catalyst include, but are not limited to, for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid, organic acids such as formic acid, oxalic acid, acetic acid, diethylsulfuric acid, and paratoluenesulfonic acid, acetic acid Examples thereof include metal salts such as zinc. These acidic catalysts can be used alone or in combination of two or more.

  The mass average molecular weight of the component (A) in terms of polystyrene as measured by gel permeation chromatography (GPC) is preferably 1000 to 50000 from the viewpoints of developability, resolution, and plating solution resistance of the photoresist composition.

The component (A) is preferably a fractionation resin in which the content of the low nuclei is reduced to 80% by mass or less, more preferably 50% by mass or less before the fractionation by the fractionation process.
Here, the low nuclear body means a phenol compound as described above, that is, a phenol monomer, a dimer obtained from two molecules of the phenol monomer, a trimer obtained from three molecules of the phenol monomer, and the like.
By using such a fractionation resin, the perpendicularity of the cross-sectional shape of the photoresist pattern is further improved, a residue (scum) is hardly generated on the substrate after development, and the resolution is improved. Moreover, there exists a tendency which is excellent in heat resistance, and it is preferable.

  The fractionation treatment can be performed by a known fractionation treatment method, for example, by the following fractional precipitation treatment. First, as described above, after a dehydration condensation reaction between a phenol compound and a condensing agent, the obtained polycondensation product (novolak resin) is dissolved in a polar solvent, and water, heptane, hexane is added to this solution. Add a poor solvent such as pentane or cyclohexane. At this time, since the low nuclei have a relatively high solubility, they remain dissolved in the poor solvent, and thus a fractionated resin with a reduced content of the low nuclei can be obtained by filtering the precipitate. .

  Examples of the polar solvent include alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, glycol ether esters such as ethylene glycol monoethyl ether acetate, and cyclic ethers such as tetrahydrofuran.

  (A) Content of the low nucleus in a component can be confirmed from the result of GPC measurement. That is, from the GPC chart, the molecular weight distribution of the synthesized phenol novolak resin can be confirmed, and the content can be calculated by measuring the intensity ratio of the peak corresponding to the elution time of the low-nuclear body. . In addition, since the elution time of a low nuclear body changes with measuring means, identification of a column, an eluent, a flow rate, temperature, a detector, a sample concentration, an injection amount, a measuring device, etc. is important. In the present invention, by using the following measuring means, the elution time of the phenolic monomer is around 23 to 25 minutes, the elution time of the dimer is around 22 minutes, and the elution time of the trimer is around 21 minutes, respectively. Can be attributed.

[Measuring means of GPC in the present invention]
(1) A sample solution is prepared by dissolving 20 mg of a sample in 10 ml of tetrahydrofuran (THF).
(2) Inject 10 μl of the sample solution of (1) into the following GPC measurement apparatus, flow for 28 minutes, and measure the elution time of the sample detected in the vicinity of the UV wavelength λ = 280 nm.
(Measurement device) Guard column (product name “KF-G”; manufactured by Shodex) and three separation columns (column size 8 μm (diameter) × 300 mm using a 6 μm particle size styrene-divinylbenzene copolymer as a filler) (Length), product name “KF-801”; manufactured by Shodex), and the separation column temperature was set to 40 ° C. using an oven (product name “GPC SYSTEM 11”; manufactured by Shodex) ) And the feed rate of the eluent of tetrahydrofuran (THF) is 1.0 ml / min.

  Further, the dispersity [Mw / number average molecular weight (Mn)] of the fractional resin is preferably 3.0 or less, and particularly preferably 2.2 to 2.8. When Mw / Mn exceeds 3.0, the upper portion of the space pattern (photoresist pattern) spreads, the resolution is lowered, and the perpendicularity of the cross-sectional shape of the photoresist pattern tends to be lowered. This tendency is particularly noticeable when the focus of light at the time of exposure is shifted to the plus side (when the focus is shifted to the bottom side of the photoresist film), and as a result, the depth-of-focus characteristic is deteriorated.

[Component (B)]
The component (B) is a photosensitizer. (B) A naphthoquinone diazide esterified product can be mentioned as a component. The naphthoquinone diazide esterified product is not particularly limited as long as it is generally used as a photosensitizer in a positive photoresist composition, and one or more can be arbitrarily selected and used.
For example, an esterified product of a phenol compound represented by the following chemical formula (1) and a naphthoquinone diazide sulfonic acid compound can be used.

[Wherein R ^{1 to} R ¹⁰ are each independently 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 cycloalkyl group having 3 to 6 carbon atoms. R ^{12 to} R ¹⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and when R ¹¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Q ¹ is hydrogen. An atom, an alkyl group having 1 to 6 carbon atoms, or a residue represented by the following chemical formula (2)

Wherein R ¹⁶ and R ¹⁷ are each independently 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 cycloalkyl group having 3 to 6 carbon atoms. the expressed; and c is an integer of 1 to 3), ^{if Q 1} is bonded with the terminal of ^{R 11} is, ^{Q 1} together with the carbon atoms between ^{R 11,} and ^{Q 1} and ^{R 11,} carbon A represents a cycloalkyl group having 3 to 6 atoms; a and b represent an integer of 1 to 3; d and e represent an integer of 0 to 3; x and y represent an integer of 0 to 3 and x + y = 0-3. ]

Incidentally, ^{Q 1, R 11,} and together with the carbon atoms between ^{Q 1, R 11,} when forming a cycloalkyl group having 3 to 6 carbon atoms is, ^{Q 1, R 11} are bonded, carbon An alkylene group having 2 to 5 atoms is formed.

  Among these, a phenol compound represented by the following chemical formula (3) is preferable.

In addition to the phenol compound of the chemical formula (3), examples of the phenol compound corresponding to the chemical formula (1) include:
Tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane, Bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-3,5- Dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3-hydroxyphenylmethane, Bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyl Nylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4- Hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) ) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenyl Methane, bis (5-cyclohexyl-4-hydro Shi-2-methylphenyl) -3,4-trisphenol compounds such dihydroxyphenyl methane;

Linear type 3 such as 2,4-bis (3,5-dimethyl-4-hydroxybenzyl) -5-hydroxyphenol, 2,6-bis (2,5-dimethyl-4-hydroxybenzyl) -4-methylphenol Nuclear phenolic compounds;
1,1-bis [3- (2-hydroxy-5-methylbenzyl) -4-hydroxy-5-cyclohexylphenyl] isopropane, bis [2,5-dimethyl-3- (4-hydroxy-5-methylbenzyl) ) -4-hydroxyphenyl] methane, bis [2,5-dimethyl-3- (4-hydroxybenzyl) -4-hydroxyphenyl] methane, bis [3- (3,5-dimethyl-4-hydroxybenzyl)- 4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-dimethyl-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- Loxy-5-ethylphenyl] methane, bis [2-hydroxy-3- (3,5-dimethyl-4-hydroxybenzyl) -5-methylphenyl] methane, bis [2-hydroxy-3- (2-hydroxy-) 5-methylbenzyl) -5-methylphenyl] methane, bis [4-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane, bis [2,5-dimethyl-3- ( Linear tetranuclear phenolic compounds such as 2-hydroxy-5-methylbenzyl) -4-hydroxyphenyl] methane;

2,4-bis [2-hydroxy-3- (4-hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,4-bis [4-hydroxy-3- (4-hydroxybenzyl) -5 Linear type 5 such as -methylbenzyl] -6-cyclohexylphenol and 2,6-bis [2,5-dimethyl-3- (2-hydroxy-5-methylbenzyl) -4-hydroxybenzyl] -4-methylphenol Linear polyphenol compounds such as nuclear phenol compounds;

  Bis (2,3-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) methane, 2,3,4-trihydroxyphenyl-4′-hydroxyphenylmethane, 2- (2,3,4- Trihydroxyphenyl) -2- (2 ′, 3 ′, 4′-trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2 ′, 4′-dihydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (4′-hydroxyphenyl) propane, 2- (3-fluoro-4-hydroxyphenyl) -2- (3′-fluoro-4′-hydroxyphenyl) propane, 2- ( 2,4-dihydroxyphenyl) -2- (4′-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (4′-hydroxypheny) ) Propane, 2- (2,3,4-hydroxyphenyl) -2- (4'-hydroxy-3 ', 5'-dimethylphenyl) bisphenol compounds such as propane;

1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl]- Polynuclear branched compounds such as 4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene;
Examples thereof include condensed phenol compounds such as 1,1-bis (4-hydroxyphenyl) cyclohexane.
These can be used alone or in combination of two or more.

The phenolic hydroxyl group of the compound represented by the chemical formula (1) may be all or partly esterified, and esterification can be performed by a conventional method. For example, the method of condensing a naphthoquinone diazide sulfonyl chloride with the compound represented by the said Chemical formula (1) is mentioned.
For example, a predetermined amount of the compound represented by the chemical formula (1) and naphthoquinone-1,2-diazide-4 (or 5) -sulfonyl chloride in an organic solvent such as dioxane, n-methylpyrrolidone, dimethylacetamide, and tetrahydrofuran. It can be prepared by dissolving and reacting by adding one or more basic catalysts such as triethylamine, triethanolamine, pyridine, alkali carbonate, alkali hydrogen carbonate, and washing the resulting product with water and drying. .
Although the esterification rate in the naphthoquinone diazide esterified compound of the compound represented by the chemical formula (1) is not particularly limited, it is preferably 20 to 80%, more preferably 30 to 70%. When the esterification rate is less than 20%, the resolution may decrease, and when it exceeds 80%, the sensitivity may decrease.

As the component (B), in addition to these exemplified preferred naphthoquinone diazide esterified products, other naphthoquinone diazide esterified products can also be used. For example, phenol compounds such as polyhydroxybenzophenone and alkyl gallate and naphthoquinone diazide sulfonic acid compounds The esterification reaction product of can also be used.
The amount of these other naphthoquinone diazide esterification products is preferably 80% by mass or less, particularly 50% by mass or less in the component (B), from the viewpoint of improving the effect of the present invention.

As the component (B), an alkali-soluble novolak resin in which a part of hydrogen atoms of all phenolic hydroxyl groups is substituted with 1,2-naphthoquinonediazidesulfonyl group has high resolution and good verticality of a photoresist pattern. It is particularly preferable for obtaining.
Such component (B) is produced by an esterification reaction between an alkali-soluble novolak resin and a 1,2-naphthoquinonediazide sulfonic acid compound, for example, according to the method described in JP-A-10-97066. Can do.

Examples of the alkali-soluble novolak resin used here include the above-mentioned alkali-soluble novolak resins used as the component (A).
Examples of the 1,2-naphthoquinonediazide sulfonic acid compound include halides of quinonediazide compounds such as 1,2-naphthoquinonediazide-4-sulfonic acid chloride and 1,2-naphthoquinonediazide-5-sulfonic acid chloride.

  The ratio in which the hydrogen atoms of all phenolic hydroxyl groups in the alkali-soluble novolak resin are substituted with 1,2-naphthoquinonediazidosulfonyl groups, that is, the esterification reaction rate is preferably 2 to 10 mol%, more Preferably it is 3-7 mol%, More preferably, it is 3-5 mol%. When the reaction rate is less than 2 mol%, the tendency of the unexposed portion to decrease in the film may increase. For example, when forming a space pattern, the space pattern upper portion may spread. When the reaction rate exceeds 10 mol%, the transmittance for the ghi line is lowered, the sensitivity is lowered, the upper part of the space pattern is spread, and the perpendicularity of the cross-sectional shape may be lowered.

The amount of component (B) in the positive photoresist composition varies depending on the type of the photosensitizer. In the case of a normal photosensitizer, 5 to 40% by mass is preferable and 10 to 20% by mass is more preferable with respect to component (A).
In the case where a photosensitive component is added to a non-photosensitive compound, the blending amount of the component (B) varies depending on the addition ratio of the photosensitive component. For example, in the case of an alkali-soluble novolak resin in which a part of the hydrogen atoms of the total phenolic hydroxyl group of the present invention is substituted with 1,2-naphthoquinonediazidosulfonyl group, the blending amount of this component (B) is (A) 100-10000 mass% is preferable with respect to a component, and 500-2000 mass% is more preferable.
When the blending amount of component (B) is less than the above lower limit value, the tendency of the unexposed portion to decrease in the film thickness may increase. is there. .

[Component (C)]
Component (C) is an ester of a polyhydric alcohol in which part or all of the hydroxyl group is esterified with an organic acid. By using this component (C) in the positive photoresist composition, the photoresist is maintained in a state in which the excellent resolution of the positive photoresist composition is maintained and the verticality of the sidewall of the photoresist pattern is maintained. Flexibility is imparted to the pattern, and cracks can be prevented from occurring. This effect is also exhibited particularly in a thick photoresist pattern formed using this positive photoresist composition. Therefore, for example, it is effective in preventing the occurrence of cracks in the manufacturing and processing steps of bumps and the like.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, and 2-methyl-1,3-propane. Diol, 2,4-diethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,6-hexanediol, 4-methyl-1,7 -Aliphatic dihydric alcohols such as heptanediol, 1,9-nonanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol; hydroquinone, 1,5-dihydroxynaphthalene, 4, 4′-dihydroxydiphenyl, Aromatic dihydric alcohols such as bis (p-hydroxyphenyl) methane and bis (p-hydroxyphenyl) -2,2-propane; 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexane Alicyclic alcohols of dimethanol and tricyclodecane glycols; trivalent or higher alcohols such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, xylitol, inositol; and the like.
Among these, polyhydric aliphatic alcohols are preferable, and glycerin, ethylene glycol, and propylene glycol are more preferable.
A polyhydric alcohol can be used individually or in combination of 2 or more types.

Examples of the organic acid include carboxylic acid and sulfonic acid, and carboxylic acid is preferable.
Carboxylic acids include mono-, di-, and poly-carboxylic acids. These are, for example, long-chain or branched, aliphatic, aromatic or alicyclic saturated or unsaturated hydrocarbon acids. In the carboxylic acid, one or more of the hydrogen atoms in the hydrocarbon moiety may be replaced by halogen, nitro or other groups. In addition, acid anhydrides corresponding to these acids can also be used in the production of esters.

As carboxylic acids, aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, 2-ethylbutyric acid, valeric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, Saturated monocarboxylic acids such as palmitic acid and stearic acid, acrylic acid, methacrylic acid, crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid and other unsaturated monocarboxylic acids, oxalic acid, malonic acid, Dicarboxylic acids such as succinic acid, fumaric acid, maleic acid, citraconic acid, itaconic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, trimellitic acid, pyro Polycarbonate such as merit acid, 1,2,3,4-butanetetracarboxylic acid Boric acid; aromatic carboxylic acid such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, polymellitic acid, toluic acid, phenylacetic 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-norbornanedicarboxylic acid Various naphthalenedicarboxylic acids; carboxylic acids having substituents such as salicylic acid, gallic acid, tartaric acid, trifluoroacetic acid, fluoroacetic acid, chloroacetic acid, α-chloropropionic acid, methoxyacetic acid, β-ethoxypropionic acid, p- Chlorobenzoic acid, 2,4-dichlorophenoxyacetic acid, etc .; Examples thereof include acid anhydrides of these carboxylic acids.
Among these, acetic acid, propionic acid, butyric acid, and valeric acid are more preferable.

  Examples of the sulfonic acid include aliphatic sulfonic acids such as decyl sulfonic acid and dodecyl sulfonic acid; aromatic sulfonic acids such as benzene sulfonic acid, and aliphatic aromatic sulfonic acids such as dodecyl benzene sulfonic acid; and the like.

The polyhydric alcohol needs to be partially or entirely esterified with an organic acid.
The ester of the polyhydric alcohol is preferably an ester of the above-mentioned preferred polyhydric alcohol and an organic acid. Among them, glycerol monoacetate, glycerol diacetate, and glycerol triacetate are preferable, and glycerol triacetate is particularly preferable.

  1-50 mass% is preferable with respect to (A) component, and, as for the compounding quantity of (C) component in a positive type photoresist composition, 5-30 mass% is more preferable. When the blending amount of the component (C) is less than the above lower limit value, the flexibility may be reduced and cracks may easily occur. When the upper limit value is exceeded, the coating property is deteriorated, the film slips during development, It may cause poor adhesion.

The second aspect of the present invention is a positive photoresist composition containing the component (D) and the component (C).
[(D) component]
Component (D) is an alkali-soluble novolak resin in which a part of the hydrogen atoms of all phenolic hydroxyl groups are substituted with 1,2-naphthoquinonediazidesulfonyl groups, and a particularly preferred photosensitizer at [Component (B)] The compounds described as
The component (D) functions as both the component (A) and the component (B).

  In the case of a positive photoresist composition comprising the component (D) and the component (C), the blending amount of the component (C) is preferably 1 to 50% by mass, and 5 to 30% by mass with respect to the component (D). Is more preferable. When the blending amount of the component (C) is less than the above lower limit value, the flexibility may be reduced and cracks may easily occur. When the upper limit value is exceeded, the coating property is deteriorated, the film slips during development, It may cause poor adhesion.

  If necessary, the photosensitive agent of the component (B) can be used for the positive photoresist composition comprising the component (D) and the component (C).

[Other ingredients]
In addition to the components (A) to (D) used in the first aspect and the second aspect of the present invention, the positive photoresist composition of the present invention may further include a sensitivity improver (increase) as necessary. Sensitizers), adhesion improvers for improving adhesion to the substrate, high boiling point organic solvents, and various additives commonly used in the field may be blended.

-Sensitivity improver There is no restriction | limiting in particular as a sensitivity improver, A well-known thing can be used.
Examples of the sensitivity improver include bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane, 1,4-bis [1- (3,5-dimethyl-4-hydroxyphenyl) isopropyl. Benzene, 2,4-bis (3,5-dimethyl-4-hydroxyphenylmethyl) -6-methylphenol, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4 -Hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, 1- [1- (4-hydroxyphenyl) Isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, 1- [1- (3-methyl) 4-hydroxyphenyl) isopropyl] -4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene, 2,6-bis [1- (2,4-dihydroxyphenyl) isopropyl] -4 Methylphenol, 4,6-bis [1- (4-hydroxyphenyl) isopropyl] resorcin, 4,6-bis (3,5-dimethoxy-4-hydroxyphenylmethyl) pyrogallol, 4,6-bis (3 5-dimethyl-4-hydroxyphenylmethyl) pyrogallol, 2,6-bis (2,5-dimethyl-4-hydroxyphenylmethyl) -4-methylphenol, 2,6-bis (3-methyl-4,6- Dihydroxyphenylmethyl) -4-methylphenol, 2,6-bis (2,3,4-trihydroxyphenylmethyl) -4-methyl Phenol, 1,1-bis (4-hydroxyphenyl) cyclohexane as preferred.

-Adhesion improver Examples of the adhesion improver include adhesion improvers described in JP-A-62-262043, JP-A-11-223937, and the like. For example, 6-methyl- 8-hydroxyquinoline, 6-ethyl-8-hydroxyquinoline, 5-methyl-8-hydroxyquinoline, 8-hydroxyquinoline, 8-acetyloxyquinoline, 4-hydroxypteridine, 2,4-dihydroxypteridine, 4-hydroxypteridine -2-sulfonic acid, 2-ethyl-4-hydroxypteridine, 2-methyl-4-hydroxypteridine, 1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, 3,8-dimethyl-1, 10-phenanthroline, 3,8-dihydroxy-1,10-phenanthroline, 5- Carboxy-1,10-phenanthroline, 5,6-dihydroxy-1,10-phenanthroline, 1,10-phenanthroline-5-sulfonic acid, 4,4′-dimethyl-2,2′-bipyridyl, 2,2′- Bipyridyl, 2,2′-bipyridyl-5-carboxylic acid, 5,5′-dichloro-2,2′-bipyridyl, 3,3′-dihydroxy-2,2′-bipyridyl, 3,3′-dimercapto-2 , 2′-bipyridyl and the like.

  In particular, an aromatic heterocyclic compound having at least one bond represented by the following chemical formulas (4) and (5) and at least one bond represented by the following chemical formula (6) on the ring. By compounding, the adhesion of the positive photoresist composition to the substrate can be remarkably enhanced.

(Wherein R ¹⁸ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms)

(Wherein R ¹⁹ represents a hydroxyl group or a linear or branched alkyl group having 1 to 5 carbon atoms substituted by a hydroxyl group)

Examples of the heterocyclic compound include “Organic compound structural formula index” (issued on December 20, 1977, Maruzen Co., Ltd.), pp. Those having a 5-membered ring skeleton of 1 atom of nitrogen such as indole compounds, indoline compounds, and indigo compounds described in 362-401; pyridine compounds, quinoline compounds, hydroquinoline compounds, isoquinoline compounds, Those having a 6-membered ring skeleton of nitrogen, such as acridine compounds, benzoquinoline compounds, naphthoquinoline compounds, phenanthroline compounds; nitrogen 2 such as pyrazole compounds, imidazole compounds, imidazoline compounds, benzimidazole compounds Having a 5-membered ring skeleton of atoms; having a 6-membered ring skeleton of nitrogen such as diazine compounds, hydropyridine compounds, benzodiazine compounds, dibenzodiazine compounds; triazole compounds, benzotriazole compounds Nitrogen 3 atom 5 such as Those having a ring skeleton; those having a six-membered ring skeleton of nitrogen such as triazine compounds; those having a five-membered ring skeleton of nitrogen such as tetrazole and pentetrazole; 1,2,4,5-tetrazine Those having a 6-membered ring skeleton of nitrogen such as 4; other purine compounds, pteridine compounds, alloxazine compounds, 2H-pyrrole and the like.
Among these, the compound represented by the following chemical formula (7) is preferable in that it can suppress the generation of scum and can provide a positive photoresist composition having excellent adhesion to a substrate, and particularly 2- (2-hydroxy). Ethyl) pyridine is preferred.

(In the formula, k represents an integer of 1 to 3, and R ²⁰ represents a hydroxyl group or a linear or branched alkyl group having 1 to 5 carbon atoms substituted with a hydroxyl group.)

  In the photoresist composition comprising the (A) component, the (B) component, and the (C) component, or the (D) component and the (C) component photoresist composition, 0.1-1.0 mass% is preferable with respect to the total amount of a component, and 0.2-0.7 mass% is especially preferable. When the addition amount of the adhesion improver is less than 0.1% by mass, the effect of improving the adhesion of the positive photoresist composition to the substrate may not be sufficient, and when it exceeds 1.0% by mass, the resolution is improved. And there is a tendency to generate a slight scum on the substrate after development.

-High-boiling organic solvent In the present invention, the bulk effect of the photoresist film, that is, the unevenness of the film density is reduced by blending at least one selected from high-boiling organic solvents having a boiling point of about 200 to 350 ° C if desired. Even when a thick photoresist film is formed on a substrate having a step on the surface using a positive photoresist composition, a photoresist pattern having excellent perpendicularity can be formed. Further, it is preferable because a favorable photoresist pattern can be formed regardless of the conditions (heating time, heating means, etc.) of the pre-bake process and PEB (post-exposure heating) process.

Examples of the high boiling point organic solvent include benzyl acetate, isoamyl salicylate, methyl salicylate, benzyl salicylate, diethyl phthalate, dibutyl phthalate, dimethyl phthalate, γ-butyrolactone, ethyl benzoate, butyl benzoate, propyl benzoate, and benzoate. Benzyl acid, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, 1,3-octylene glycol, 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 Butyl ether acetate, dipropylene glycol, dipropy Glycol monobutyl ether, triethylene glycol, triethylene glycol di-2-ethylbutyrate, triethylene glycol dimethyl ether, triethylene glycol monoethyl ether, triethylene glycol monomethyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, 2- Examples thereof include ethylhexanoic acid, caprylic acid, caproic acid, catechol, octylphenol, N-methylpyrrolidone and the like. These may be used alone or in combination of two or more. Of these, those having a boiling point of 250 to 350 ° C. are preferred, and benzyl salicylate is particularly preferred.
The blending amount of the high-boiling organic solvent is the above-described photoresist composition comprising the component (A), the component (B), and the component (C), or the photoresist composition comprising the component (D) and the component (C). 3-15 mass% is preferable with respect to the total amount of a component, and 6-12 mass% is especially preferable. If the blending amount of the high-boiling organic solvent is less than 3% by mass, the effect of suppressing the above phenomenon is poor, and if it exceeds 15% by mass, the verticality of the cross-sectional shape may be deteriorated due to the space pattern upper part spreading. is there.

Various Additive Components The positive photoresist composition of the present invention contains p-toluenesulfonic acid chloride (PTSC), 4,4′-bis (diethylamino) for the purpose of improving resolution, exposure margin and remaining film ratio. ) Benzophenone, 1,4-bis [1- (2-methyl-4-hydroxy-5-cyclohexylphenyl) isopropyl] benzene, 1,3-bis [1- (2-methyl-4-hydroxy-5-cyclohexylphenyl) ) Isopropyl] benzene or the like may be added within a range of about 0.01 to 10% by mass with respect to the composition.

  Further, the positive photoresist composition of the present invention may further include a compatible additive, for example, an ultraviolet absorber for preventing halation, such as 4-dimethylamino-2 ′, 4′-dihydroxybenzophenone, if necessary. 5-Amino-3-methyl-1-phenyl-4- (4-hydroxyphenylazo) pyrazole, 4-dimethylamino-4′-hydroxyazobenzene, 4-diethylamino-4′-ethoxyazobenzene, 4,4′-diethylamino Azobenzene, curcumin, and the like, and surfactants for preventing striation, such as Florad FC-430, FC431 (trade name, manufactured by Sumitomo 3M Co., Ltd.), Ftop EF122A, EF122B, EF122C, EF126 (trade name, Tochem) Products Co., Ltd.), Megafuck R-08 (Dainichi) An ink Kagaku Kogyo Co.) fluorinated surfactants such as such may contain additives in a range not interfering with the purposes of the present invention.

  The positive photoresist composition of the present invention comprises the component (A), the component (B), and the component (C), or the component (D), and the component (C). The additive component is preferably used in the form of a solution by dissolving in an appropriate solvent.

Examples of such solvents include those used in conventional positive photoresist compositions, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone; ethylene glycol, propylene glycol , Diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, or polyhydric alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether, and derivatives thereof; Cyclic ethers such as: ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methoxypropio Include methyl acid, esters such as ethyl ethoxypropionate. These may be used alone or in combination of two or more. Especially ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone; ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, etc. Esters are preferred.
Solvents may be used alone, or two or more solvents may be used in combination.

  The amount of these solvents used is, for example, in the range of 20% to 65% by weight of the solid content in the positive photoresist composition in order to obtain a film thickness of, for example, 3 μm or more by using a spin coating method. Is preferred. When the solid content concentration is less than 20% by mass, for example, it may be difficult to obtain a thick film having a thickness of 3 μm or more. When the solid content concentration exceeds 65% by mass, the fluidity of the composition is lowered and handling becomes difficult. Thus, in the spin coating method, it may be difficult to obtain a uniform photoresist film.

  The positive photoresist composition of the present invention can be prepared by, for example, mixing and stirring each of the above components by a usual method, and dispersing and mixing them using a disperser such as a dissolver, a homogenizer, or a three roll mill as necessary. May be. Moreover, after mixing, you may further filter using a mesh, a membrane filter, etc.

  The positive photoresist composition of the present invention is suitable for forming a thick photoresist layer having a thickness of 3 to 30 μm, more preferably 5 to 20 μm, and still more preferably 8 to 15 μm on a support.

[Method for producing substrate with photosensitive film]
The suitable example of the manufacturing method of the board | substrate with the photosensitive film | membrane of this invention is shown.
On a substrate such as Si, Cu, Au, etc., a positive photoresist composition of the present invention and, if necessary, a solution prepared by dissolving various additive components in an appropriate solvent as described above is applied with a spinner or the like and dried. A photosensitive layer is formed on the substrate.

[Method of forming resist pattern]
A desired mask pattern is arranged on the photosensitive film of the photosensitive film-coated substrate. Then, exposure is performed through this mask pattern using a light source that emits light having a wavelength of around 365 nm, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, or an ultrahigh-pressure mercury lamp. Next, if necessary, a PEB (post-exposure heating) treatment is performed, and this is immersed in a developer, for example, an alkaline aqueous solution such as an aqueous solution of 1 to 10% by mass of tetramethylammonium hydroxide (TMAH). By dissolving and removing, an image faithful to the mask pattern can be obtained.

  Hereinafter, the present invention will be specifically described by way of examples.

(Synthesis Example 1)
[Synthesis of alkali-soluble novolak resin]
Phenols prepared by mixing m-cresol and p-cresol in a molar ratio (m-cresol: p-cresol) 60:40 in a 3 L four-necked flask equipped with a stirrer, a thermometer, and a heat exchanger With respect to 1000 parts by mass, 465 parts by mass of a 37% formalin aqueous solution and 2 parts by mass of oxalic acid were charged and reacted for 4 hours by refluxing. Thereafter, dehydration was performed under normal pressure up to 170 ° C. inside, and dehydration / demonomerization was performed up to 200 ° C. under reduced pressure of 70 torr to obtain 850 parts by mass of a novolak type phenol resin having a mass average molecular weight of 5900.

(Synthesis Example 2)
[Synthesis of photosensitizer in which 4.5 mol% of all hydroxyl groups of alkali-soluble novolak resin are substituted with 1,2-naphthoquinonediazide-5-sulfonyl group]
50 g of the novolak-type phenolic resin obtained in Synthesis Example 1 and 4 g (0.015 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride were added to one liter of 3 with a thermometer, stirrer and dropping funnel. The mixture was placed in a two-necked flask and 162 g of dioxane was added and dissolved, and then 3.0 g (0.030 mol) of triethylamine was added from the dropping funnel, and stirring was continued at room temperature for 1 hour.
Thereafter, 1.63 g (0.045 mol) of hydrochloric acid was added, and stirring was further continued at room temperature for 30 minutes, followed by filtration to obtain a reddish brown liquid.
The liquid is added to a 2 liter beaker containing 1 liter of pure water with stirring to precipitate a precipitate, and 3.8 mol% of all phenolic hydroxyl groups are replaced with 1,2-naphthoquinonediazide sulfonyl groups. A novolak resin was obtained.

(Synthesis Example 3)
[Synthesis of Photosensitizer in which 2 Mole of Hydroxyl of Compound of Formula (3) is Replaced with 1,2-Naphthoquinonediazide-5-sulfonic Acid Chloride]
50 g of the compound of the chemical formula (3) and 56.92 g (0.212 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride were added to a 1 liter three-neck equipped with a thermometer, a stirrer and a dropping funnel. Into a flask, 267 g of dioxane was added and dissolved, and then 42.4 g (0.424 mol) of triethylamine was dropped from the dropping funnel while paying attention to a rapid rise in temperature, followed by stirring at room temperature for 1 hour. Continued.
Thereafter, 23.2 g (0.636 mol) of hydrochloric acid was added, and the mixture was further stirred at room temperature for 30 minutes, followed by filtration to obtain a reddish brown liquid.
The liquid was added to a 2 liter beaker containing 1 liter of pure water with stirring to precipitate a precipitate, thereby obtaining the intended photosensitizer.

(Synthesis Example 4)
[Synthesis of alkali-soluble acrylic resin]
A flask equipped with a stirrer, a reflux device, a thermometer, and a dropping tank was purged with nitrogen, and then 200 g of propylene glycol methyl ether acetate was charged as a solvent. While stirring, the temperature of the solvent is raised to 80 ° C., and 0.5 g of 2,2′-azobisisobutyronitrile, 130 g of 2-methoxyethyl acrylate, 50.0 g of benzyl methacrylate, acrylic as a polymerization catalyst in the dropping tank. 20.0 g of acid was charged and stirred until the polymerization catalyst was dissolved. Thereafter, this solution was uniformly dropped into the flask for 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 the sensitivity improver, the solid content concentration is 45% by mass. Was dissolved in propylene glycol monoethyl ether acetate. This was filtered using a membrane filter to prepare a positive photoresist composition.
(A) Component: Alkali-soluble novolak resin of Synthesis Example 1 (B) Component: Photosensitizer (C) of Synthesis Example 3 Component: Glycerin triacetate sensitivity improver: Compound represented by the following chemical formula (8)

[Example 2]
5 mass parts of the following (A) component, 65 mass parts of the following (B) component, 10 mass parts of the following (C) component, and 20 mass parts of the sensitivity improver as other components, the solid content concentration is 45 mass%. In the same manner as in Example 1, a positive photoresist composition solution was prepared by dissolving in propylene glycol monoethyl ether acetate.
(A) Component: Alkali-soluble novolak resin of Synthesis Example 1 (B) Component: Photosensitizer (C) of Synthesis Example 2 Component: Glycerin triacetate sensitivity improver: Compound represented by the above chemical formula (8)

[Example 3]
70 parts by mass of the following (D) component, 10 parts by mass of the following (C) component, and 20 parts by mass of the sensitivity improver as the other components, propylene glycol monoethyl ether acetate so that the solid content concentration is 45% by mass. And a positive photoresist composition was prepared in the same manner as in Example 1.
(D) Component: Photosensitizer of Synthesis Example 2 (C) Component: Glycerin triacetate sensitivity improver: Compound represented by the above chemical formula (8)

[Comparative Example 1]
65 parts by mass of the following (A) component, 15 parts by mass of the following (B) component, and 20 parts by mass of the sensitivity improver as other components, propylene glycol monoethyl ether acetate so that the solid content concentration is 45% by mass. And a positive photoresist composition was prepared in the same manner as in Example 1.
(A) Component: Alkali-soluble novolak resin of Synthesis Example 1 (B) Component: Photosensitizer sensitivity improver of Synthesis Example 3: 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 ′) instead of the component (C), and 20 parts by mass of the sensitivity improver as the other components, A positive photoresist composition was prepared in the same manner as in Example 1 by dissolving in propylene glycol monoethyl ether acetate so that the partial concentration was 45% by mass.
(A) Component: Alkali-soluble novolak resin of Synthesis Example 1 (B) Component: Photosensitizer (C ′) of Synthesis Example 3 Component: Benzyl salicylate sensitivity improver: Compound represented by the above chemical formula (8)

[Comparative Example 3]
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 ″) instead of the component (C), and 20 parts by mass of the sensitivity improver as other components, A positive photoresist composition was prepared in the same manner as in Example 1 by dissolving in propylene glycol monoethyl ether acetate so that the solid content concentration was 45% by mass.
(A) Component: Alkali-soluble novolak resin (B) of Synthesis Example 1 Component: Photosensitizer (C ″) of Synthesis Example 3 Component: Alkali-soluble acrylic resin sensitivity improver of Synthesis Example 4: represented by the above chemical formula (8) Compound

  Various physical properties of the positive photoresist 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 cross-sectional shape A positive 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 μm.
Next, a reduced projection exposure apparatus NSR-2005i10D (manufactured by Nikon Corporation, NA = 0.50) is used through a mask in which a predetermined light-shielding pattern is drawn on this film, and lines and spaces having a mask dimension of 5 μm are in accordance with the mask dimensions. Next, as a developing operation, an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution at 23 ° C. was applied on the substrate and held for 60 seconds. Shake off by rotation.
This development operation was repeated three times, then washed with water for 30 seconds, dried, and the obtained pattern shape was observed with a SEM (scanning electron microscope) photograph, and the pattern bottom portion relative to the width (T) of the space pattern upper portion. The width (B) ratio (B / T) is 0.90 ≦ (B / T) ≦ 1.0, ○, 0.80 ≦ (B / T) <0.90 is Δ, 0 .8> (B / T) and 1.0 <(B / T) are shown as x.

(2) Evaluation of resolution In EOP (exposure amount finished in accordance with the mask size using an L & S mask having a mask size of 5.0 μm), the minimum mask size (μm) separated from the bottom of the pattern was defined as the limit resolution.
(3) Evaluation of flexibility (anti-cracking property) Four positive photoresist compositions were applied on a substrate at a 1 μm interval from 8 μm to 11 μm on a substrate using a spinner. These were heated on a hot plate at 120 ° C. for 4 minutes, then rapidly cooled on a stainless steel table adjusted to 23 ° C., and the photoresist surface was observed.
As a result, when the film thickness is 8 μm, XX is cracked on the surface, XX is cracked at 9 μm, △ is cracked at 10 μm or more, ◯ is cracked at 11 μm, and crack is observed even at 11 μm. Items that did not enter were marked as ◎.

From these results, the positive type of the present invention in which the (A) component and the (B) component are blended with the polyhydric alcohol ester in which part or all of the hydroxyl groups are esterified with an organic acid as the (C) component. The positive photoresist composition of the present invention, in which a polyhydric alcohol ester in which a part or all of the hydroxyl groups are esterified with an organic acid is blended with the photoresist composition and the component (D) as the component (C), It can be seen that the cross-sectional shape and the resolution are excellent, the flexibility is excellent, and no crack occurs even at a film thickness of 11 μm.
As the component (C), one that does not use an ester of a polyhydric alcohol in which a part or all of the hydroxyl group is esterified with an organic acid (Comparative Example 1), and benzyl salicylate instead of the component (C). The cross-sectional shape, resolution, and flexibility (crack resistance) are both superior from the one used (Comparative Example 2) and the one using an acrylic resin instead of the component (C) (Comparative Example 3). I could not get it.

Claims (10)

  A positive photoresist composition comprising (A) an alkali-soluble novolak resin, (B) a photosensitizer, and (C) an ester of a polyhydric alcohol in which part or all of the hydroxyl groups are esterified with an organic acid.   2. The positive photoresist composition according to claim 1, wherein the component (B) is an alkali-soluble novolak resin in which a part of hydrogen atoms of all phenolic hydroxyl groups are substituted with 1,2-naphthoquinonediazidosulfonyl groups.   (D) an alkali-soluble novolak resin in which part of the hydrogen atoms of the total phenolic hydroxyl group is substituted with a 1,2-naphthoquinonediazidesulfonyl group, and (C) part or all of the hydroxyl group is esterified with an organic acid. A positive photoresist composition containing an ester of a polyhydric alcohol.   4. The positive photoresist composition according to claim 1, wherein the polyhydric alcohol is a polyhydric aliphatic alcohol.   The positive photoresist composition according to claim 4, wherein the polyhydric aliphatic alcohol is at least one selected from glycerin, ethylene glycol, and propylene glycol.   The positive photoresist composition according to claim 1 or 3, wherein the organic acid is a carboxylic acid.   The positive photoresist composition according to claim 6, wherein the carboxylic acid is at least one selected from acetic acid, propionic acid, butyric acid (butanoic acid), and valeric acid (pentanoic acid).   The positive photoresist composition according to claim 1, wherein the component (C) is at least one selected from glycerin monoacetate, glycerin diacetate, and glycerin triacetate.   2. The positive photoresist composition according to claim 1, wherein the component (C) is glycerin triacetate.   A photosensitive film-coated substrate, wherein a photosensitive film formed using the positive photoresist composition according to any one of claims 1 to 9 is formed on a substrate.