TWI447782B - Pattern forming method and composition for the same - Google Patents

Description

Pattern forming method and photosensitive resin composition therefor

This invention relates to photoresist compositions. In particular, the present invention relates to a photoresist composition suitable for coating by slit coating.

Conventionally, a photoresist for forming a pattern for a driving circuit for a liquid crystal display is generally produced by pre-baking and drying a photosensitive resin composition after being discharged from a central portion of a glass and being spin-coated. However, as the size of the substrate increases and the amount of photoresist decreases, the coating method also changes, and after the slit coating, a method of rotating and re-baking is also used. Then, as the size of the substrate is increased, the rotation is difficult, and the production method of drying under reduced pressure and pre-baking after the slit coating cannot be used.

The rotary rotation performed after the slit coating is performed by evaporating a part of the solvent contained in the coating film while uniformizing the coating film. Therefore, in the method of performing the rotary rotation after the slit coating, the coating uniformity is maintained by the rotary rotation. However, in the method of drying under reduced pressure after the slit coating, since it is impossible to homogenize the coating film by the rotation, the coating film after the slit coating must be uniform. However, according to the study by the inventors of the present invention, it is difficult to directly use the photosensitive resin composition used in the prior art to make the coating film after the slit coating sufficiently uniform. Further, in the vacuum drying which is performed later, the problem that the traces such as the chuck or the needle for the substrate after the fixed coating are likely to remain on the film surface is likely to occur.

Further, the conditions for drying under reduced pressure after the slit coating are various In many cases, a method of vigorously decompressing from atmospheric pressure of about 101 kPa to about 20 Pa and about 30 seconds at room temperature is basically used. In order to apply such a relatively strict vacuum drying condition, it is necessary to adjust the degree of drying of the coating film. When the degree of drying of the coating film is unsuitable, there is a big problem with the pattern shape or the coating property, which is a cause of various problems.

For the solvent of the photosensitive resin composition used, since the vapor pressure system of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) generally used is about 500 Pa at 20 ° C / l air pressure, It is very easy to evaporate when pressed and dried. As a result, PGMEA rapidly evaporates from the surface of the coated film after coating, and forms a dry coating film near the surface, which impairs the evaporation of PGMEA inside the coating film. When such a photoresist film is used to form a pattern, since the vicinity of the surface of the photoresist film is not easily imaged, the inside becomes easy to develop, so that the pattern shape becomes an inverted tapered shape (also referred to as a T-top), and is post-baked. When the corner portion of the pattern is left in the baking, the peeling failure is caused, and the drying inside the photoresist pattern is insufficient, so that the etching resistance is also insufficient, and the metal wiring formed by the photoresist pattern is used. The reason for becoming uneven.

Further, in the pattern formation using the positive type resist, when developing the exposed photoresist film, it is generally known that when the unexposed portion is in contact with the developing liquid, the sensitizer forms an azo bond with the resin, so that the alkali is revealed. The solubility of the liquid is lowered, and a contrast between the exposed portion and the unexposed portion can be formed. In the method of drying under reduced pressure after the slit coating, the surface of the unexposed portion is relatively difficult to dissolve in the alkali developing solution due to the drying of the photosensitive composition after the application of the coating. The apparent contrast has become too strong. For understanding To solve such problems, for example, a sensitizer called a contrast enhancer is not added as a highly reactive molecular weight resin component, or the amount of the sensitizer is reduced. However, in these methods, although the pattern shape is considered to have a certain improvement effect, at the same time, the pattern width is not uniform due to the insufficient amount of the sensitizer, and the actual contrast is lowered due to the absence of the contrast reinforcing agent. problem.

Further, in order to suppress coating unevenness when the photosensitive resin composition is applied to form a photoresist film, it is studied to mix a plurality of kinds of solvents. For example, Patent Document 1 discloses a photosensitive resin composition using diethylene glycol dialkyl ether, ethyl 3-ethoxypropionate, alkyl acetate, and alkyl lactate as a solvent. The photosensitive resin composition described in the above-mentioned document 1 is intended to improve the unevenness of the horizontal line in the slit coating, the unevenness of the longitudinal line, and the unevenness of the entire substrate. Then, although the solvent combination considers the evaporation rate, the evaporation rate is the evaporation rate at the time of coating, and the evaporation rate such as drying under reduced pressure is not considered. Therefore, there is still room for improvement in solving the problems at the time of drying under reduced pressure as described above by the inventors and the like.

Further, in Citation 2, a photosensitive resin composition containing benzyl alcohol is described. The benzyl alcohol used therein is used by being mixed with a main solvent such as propylene glycol monomethyl ether acetate in order to improve coating unevenness. However, in this cited document, a method using a spin coating method as a coating method is described, and there is no description about the problem in the slit coating accompanying the above-described vacuum drying.

[Patent Document 1] JP-A-2006-171670

[Patent Document 2] International Patent Publication No. 2004/095142

As described above, according to the study by the inventors of the present invention, when a photosensitive resin composition contains propylene glycol monomethyl ether acetate which is generally used as a solvent, there is room for improvement in coating unevenness or coating uniformity at the time of coating, and Since the surface of the coating film is easier to dry than the inside, the pattern shape becomes an inverted cone shape, which causes peeling failure or excessive contrast. Therefore, they are seeking ways to solve their problems.

A pattern forming method according to the present invention, comprising the steps of: coating a photosensitive resin composition comprising an alkali-soluble resin, a photosensitive agent, and a mixed solvent on a substrate by a slit coating method to form a coating film, The mixed solvent comprises a propylene glycol monomethyl ether acetate and a co-solvent having a vapor pressure of 150 Pa or less at 20 ° C at 1 atm; drying the formed coating film under reduced pressure; followed by heating and drying, and evaporating to remove at least a portion Solvent; pattern exposure to the desired pattern; development to form a pattern; heating to harden the image after development.

Further, the photosensitive resin composition for slit coating according to the present invention comprises an alkali-soluble resin, a photosensitizer, and a mixed solvent, and the mixed solvent contains propylene glycol trimethyl ether acetate at 20 ° C at 1 atm. The co-solvent having a vapor pressure of 150 Pa or less is characteristic.

According to the present invention, uneven coating or uneven coating during coating is improved Further, since the shape of the formed pattern is preferably tapered, the unevenness of peeling or the unevenness of the line width can be improved. In the improved pattern shape, there is no problem that the pattern width of the method such as the sensitized dose or the contrast enhancer which is conventionally performed is not uniform.

The photosensitive resin composition used in the pattern forming method in the present invention contains an alkali-soluble resin, a photosensitizer, and a mixed solvent as essential components. In the photosensitive resin composition used in the pattern forming method of the present invention, the component of the photosensitive composition is adjusted for the pattern application or the like to be formed, and either a positive type or a negative type may be used.

Among them, the mixed solvent is composed of propylene glycol monomethyl ether acetate and a cosolvent. In the case of the co-solvent, the vapor pressure measured at 1 at 20 ° C is 150 Pa or less, preferably 100 Pa or less. Further, the lower limit of the vapor pressure of the co-solvent is not particularly limited, but the vapor pressure measured at 1 at 20 ° C is generally 5 Pa or more, preferably 10 Pa or more, more preferably 15 Pa or more. In the case where the vapor pressure of the co-solvent is lower than these ranges, on the one hand, the adjustment of the drying conditions in the vacuum drying becomes difficult, on the one hand, the drying under reduced pressure and the subsequent prebaking cannot be sufficiently dried due to the residual solvent. It must be noted in the photoresist film. The co-solvent can be appropriately selected from the types of other solid components contained in the photosensitive resin composition, the use of the photosensitive resin composition, the conditions of coating or drying, and the like.

As preferred embodiments of such cosolvents, alcohols, esters, and the like are mentioned. Ethers, glycol ethers, and the like. Specific examples of preferred co-solvents include benzyl alcohol, ethylene glycol butyl ether acetate, and more specifically ethylene glycol n-/iso-/second-/t-butyl ether acetate, propylene glycol. , propylene glycol diacetate, propylene glycol monoalkyl ether (alkyl group has 4 to 5 carbon atoms), dipropylene glycol dialkyl ether (alkyl group has 1 to 5 carbon atoms), dipropylene glycol monoalkyl ether (alkane) The carbon number of the base is 1~5), the diethylene glycol dialkyl ether (the carbon number is 2~5), the diethylene glycol monoalkyl ether (the carbon number of the alkyl group is 1~5), a group consisting of ethyl 3-ethoxypropionate, 3-methoxy-3-methylbutyl acetate, 3-methoxy-3-methylbutanol, butyl lactate and mixtures thereof Group of people.

Further, although benzyl alcohol is one of the preferred co-solvents, it can be further combined with other co-solvents, and the coating property can be improved by forming a mixed solvent of three components. As a mixed solvent of these preferable three components, a mixed solvent of PGMEA and benzyl alcohol and ethylene glycol-n-butyl ether acetate is exemplified. The mixed solvent of the two components of PGMEA and benzyl alcohol tends to be slightly inferior in coatability as compared with the above-mentioned three-component mixed solvent.

In the present invention, these co-solvents and PGMEA are mixed to form a mixed solvent. The mixing ratio of the mixed solvent is not particularly limited, but the content of the co-solvent is 5 to 70% by weight, preferably 5 to 60% by weight based on the total weight of the mixed solvent. In this case, in the case of using a co-solvent having a high volatility, that is, a high vapor pressure, it is preferred to contain a relatively large amount of the co-solvent. Although the residual portion is preferably only PGMEA, other solvents may be contained within a range not impairing the effects of the present invention, for example, a solvent having a vapor pressure of more than 150 Pa measured at 1 at 20 ° C. Also, in the present invention, a mixed solvent It is not always necessary to use a PGMEA and a co-solvent in a mixed state, and when a photosensitive resin composition is prepared, PGMEA and a co-solvent may be separately added and mixed in the composition.

In the case of using a mixed solvent of a co-solvent having a vapor pressure of more than 150 Pa and a PGMEA in a condition of combining at a pressure of 1 at 20 ° C, the coating property of the photosensitive resin composition is improved, but it is reduced. It is difficult to sufficiently suppress the drying of the film surface at the time of pressure drying. Further, since the surface of the film is dried, it is difficult to cause film abrasion at the time of development, and the residual film ratio becomes close to 100%, and the pattern shape tends to become an inverted tapered shape. On the other hand, the solvent having a vapor pressure of 150 Pa or less as a co-solvent is not easily dried by prebaking. Therefore, in the conventional spin coating method, it is found that the residual film ratio is lowered by the addition thereof. However, in this case, when the pressure is reduced under reduced pressure, the surface of the film can be prevented from drying even under intense pressure reduction. The residual film rate can be maintained.

Any of the conventionally applicable ones which can be used for the alkali-soluble resin of the pattern forming method in the present invention can be used. Specifically, there are, for example, a novolak resin, a polymer having a decazane structure, an acrylic polymer, a decyl alcohol, a polydecylamine, or the like. Among them, a phenolic novolak resin such as a phenol resin, particularly a cresol novolak resin or a xylenol varnish resin is preferable.

The phenolic novolak resin is a novolac type phenol resin obtained by condensation polymerization of at least one phenol with an aldehyde such as formalin.

Examples of the phenol used for the production of these phenolic novolac resins include cresols such as o-cresol, p-cresol and m-cresol; 3,5-xylenol and 2,5-dimethyl Dimethyl phenols such as phenol, 2,3-xylenol, 3,4-xylenol; 2,3,4- Tricresol, 2,3,5-trimethyl phenol, 2,4,5-trimethyl phenol, 3,4,5-trimethyl phenol, etc.; 2-tert-butylphenol, 3-tertiol, 4 - a third butanol such as a third butanol; 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2,3-dimethoxyphenol, 2,5-dimethoxyphenol, 3 , methoxyphenols such as 5-dimethoxyphenol; 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2,3-diethylphenol, 3,5-diethylphenol, 2,3,5 - Ethylphenol such as triethyl phenol or 3,4,5-triethyl phenol; chlorophenols such as o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, resorcinol, a catechol such as 2-methyl resorcinol, 4-methyl resorcinol or 5-methyl resorcin; a catechol such as 5-methylcatechol; Gallic phenols such as methyl gallophenol; bisphenols such as bisphenol A, B, C, D, E, F; hydroxymethylated cresols such as 2,6-dimethylol-p-cresol; Naphthols such as α-naphthol and β-naphthol. They may be used singly or in a mixture of plurals.

Further, in terms of aldehydes, in addition to fumarin, o-hydroxybenzaldehyde, trioxane, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, etc. are mentioned, which are either alone or in a mixture of plural kinds. To use.

The content of the alkali-soluble resin is not particularly limited, and is usually 5 to 25% by weight, preferably 7 to 20% by weight based on the total weight of the photosensitive resin composition. When the ratio is lower than this range, since the final photoresist film is required to have a constant film thickness, it is necessary to apply a thick composition, which tends to cause a flow inside the coating film, and uneven coating occurs. Further, when the resin content is higher than the above range, it is necessary to apply a thin composition, and the film thickness uniformity is insufficient. Therefore, care must be taken in the case where the resin content is outside the above range.

Further, although the sensitizer used in the pattern forming method of the present invention is The general use can be arbitrarily selected, but a sensitizer containing a decylamino group is preferred. Examples of such sensitizers include naphthoquinone diamine sulfonate chloride or benzodiazepine sulfonate chloride, and the like, and by having a functional group which has a condensation reaction with the acid chloride. A compound obtained by reacting a molecular weight compound or a high molecular weight compound. The functional group which can be condensed with an acid chloride is exemplified by a hydroxyl group, an amine group and the like, and particularly preferably a hydroxyl group. Examples of the compound containing a hydroxyl group which can be condensed with an acid chloride include hydroquinone, resorcin, 2,4-dihydroxydiphenyl ketone, 2,3,4-trihydroxydiphenyl ketone, and 2, 4,6-trihydroxydiphenyl ketone, 2,4,4'-trihydroxydiphenyl ketone, 2,3,4,4'-tetrahydroxydiphenyl ketone, 2,2',4,4' - hydroxydiphenyl ketones such as tetrahydroxydiphenyl ketone, 2,2',3,4,6'-pentahydroxydiphenyl ketone; bis(2,4-dihydroxyphenyl)methane, bis ( a hydroxyphenyl alkane such as 2,3,4-trihydroxyphenyl)methane or bis(2,4-dihydroxyphenyl)propane; 4,4',3",4"-tetrahydroxy-3,5 , 3',5'-tetramethyltriphenylmethane, 4,4',2",3",4"-pentahydroxy-3,5,3',5'-tetramethyltriphenylmethane, etc. The hydroxytriphenylmethane or the like may be used alone or in combination of two or more.

Further, examples of the acid chloride such as naphthoquinone diamine sulfonate chloride or benzodiazepine sulfonate chloride include 1,2-naphthyldiamine-5-sulfonyl chloride, 1, 2-naphthoquinonediamine-4-sulfonyl chloride or the like is preferred. The compounding amount of the sensitizer containing the decylamino group is usually 5 to 50 parts by weight, preferably 10 to 40 parts by weight, per 100 parts by weight of the alkali-soluble resin. When it is less, sufficient sensitivity as a photosensitive resin composition cannot be obtained, and when it is too much, it is necessary to pay attention to the problem of precipitation of components.

The photosensitive resin composition used in the pattern forming method of the present invention contains the above-mentioned mixed solvent, alkali-soluble resin, and sensitizer as essential components, but may further contain a surfactant. The surfactant is intended to maintain uniformity of the photosensitive resin composition, improve coating properties, and the like. In particular, when a photosensitive resin composition is applied to a substrate, a fish scale-like appearance (hereinafter referred to as "fish scale unevenness") is formed on the surface, and an interface is used in the photosensitive resin composition of the present invention. The active agent inhibits the scaly unevenness of the fish. In the photosensitive resin composition of the present invention, a nonionic surfactant is particularly preferably used. Examples of the nonionic surfactant include a fluorine-based surfactant, a ruthenium-based surfactant, and a hydrocarbon-based surfactant. Particularly, a fluorine-based surfactant is preferably used. The amount of the surfactant to be added is usually from 200 to 10,000 ppm based on 1 part by weight of the total of the alkali-soluble resin and the sensitizer. When the content of the surfactant is too large, care must be taken due to problems such as poor development.

The photosensitive resin composition used in the pattern forming method in the present invention may further contain an additive such as a contrast reinforcing agent, an epoxy compound, or an adhesion promoter such as a ruthenium-containing compound, if necessary. These additives are selected from any of the conventionally known ones without departing from the effects of the present invention.

The photosensitive resin composition used in the pattern forming method of the present invention may be coated by a spin coating method, a dip coating method, a slit coating method (also referred to as a slit coating method or a spin coating method). However, it is used in the slit coating method, in particular, the combination of the slit coating method and the vacuum drying pattern formation. In the method, the strong effect of the present invention was found. When the photoresist composition is applied onto the substrate by the slit coating method, the photoresist composition is generally stored in a supply container, and is applied onto the substrate through a pipe or a nozzle of a coating device or the like. According to the slit coating method of the photosensitive resin composition of the present invention, it is possible to apply a coating film excellent in coating film peeling or coating unevenness at a high speed.

The substrate on which the photoresist film is formed is applied by using the photosensitive resin composition of the present invention by slit coating, and then can be processed by the same method as in the prior art. In general, at least a portion of the solvent is removed under reduced pressure or vacuum, and further, if necessary, by baking to remove the solvent, pattern exposure, development to a desired pattern, and further curing of the photoresist film by heating. . Further, in the step of removing the solvent, it is not always necessary to completely remove the solvent from the coating film, and it may be removed to the extent that it does not hinder in the subsequent step. These treatments are arbitrarily selected for the use of the photoresist pattern to be produced, the type of the photosensitive resin composition, and the like.

The photoresist pattern produced by such a method can be used for the manufacture of various electronic parts. In the photoresist film, since the uniformity of the film surface is particularly important, the pattern forming method of the present invention is advantageous for manufacturing an electronic component excellent in performance, such as a semiconductor member. Further, it is particularly preferably used in the field of forming a photoresist film on a large substrate, such as a liquid crystal display, by slit coating or the like.

[Example]

The invention is illustrated by the following examples.

[Example 1]

25 parts by weight of 2,3,4,4'-tetrahydroxydiphenyl ketone and 1,2-naphthoquinone diamine - relative to 100 parts by weight of the novolak resin having a weight average molecular weight of 8,000 in terms of polystyrene An esterified product of 5-sulfonyl chloride as a sensitizer, adding 1000 ppm of a fluorine-based surfactant to all solid components, and Mecca Kg R-08 (a nonionic surfactant manufactured by Dainippon Ink and Chemicals Co., Ltd.) Adding a mixed solvent of propylene glycol monomethyl ether acetate and ethylene glycol n-butyl ether acetate (vapor pressure of 20 Pa at 1 atm and 20 ° C) (mixing weight ratio of 70:30) and stirring The mixture was filtered with a 0.2 μm filter to prepare the photosensitive composition of the present invention.

[Example 2]

Except that the solvent to be dissolved is a mixed solvent of propylene glycol monomethyl ether acetate and propylene glycol diacetate (vapor pressure of 60 Pa at 1 at 20 ° C) (mixing weight ratio is 60:40), Example 1 was carried out in the same manner to obtain the photosensitive composition of Example 2.

[Example 3]

The solvent to be dissolved is a mixed solvent of propylene glycol monomethyl ether acetate and 3-ethoxyethyl propionate (vapor pressure of 93 Pa at 1 at 20 ° C) (mixing weight ratio is 40:60). The photosensitive composition of Example 3 was obtained in the same manner as in Example 1 except for the above.

[Example 4]

In the same manner as in Example 1, except that the solvent to be dissolved was a mixed solvent of propylene glycol monomethyl ether acetate and benzyl alcohol (vapor pressure of 13 Pa at 1 atm at 20 ° C) (mixing weight ratio: 90:10). Going to get example 4 Photosensitive composition.

[Example 5]

The solvent to be dissolved was changed to a mixed solvent of propylene glycol monomethyl ether acetate and benzyl alcohol (vapor pressure of 13 Pa at 1 atm at 20 ° C) (mixing weight ratio: 95:5), and the same procedure as in Example 1 was carried out. The photosensitive composition of Example 5 was obtained.

[Example 6]

The solvent to be dissolved is propylene glycol monomethyl ether acetate and ethylene glycol n-butyl ether acetate (vapor pressure of 20 Pa at 1 atm, 20 ° C) and benzyl alcohol (at 1 at 20 ° C) The photosensitive composition of Example 6 was obtained in the same manner as in Example 1 except that the mixed solvent having a vapor pressure of 13 Pa) (mixing weight ratio of 80:15:5) was used.

[Comparative Example 1]

The photosensitive composition of Comparative Example 1 was obtained in the same manner as in Example 1 except that the solvent to be dissolved was changed to propylene glycol monomethyl ether acetate.

[Comparative Example 2]

The solvent to be dissolved was changed to a mixed solvent of propylene glycol monomethyl ether acetate and n-butyl acetate (vapor pressure of 1000 Pa at 1 atm of 20 ° C) (mixing weight ratio of 40:60), and Example 1 The photosensitive composition of Comparative Example 2 was obtained in the same manner.

[Comparative Example 3]

The solvent to be dissolved is a mixed solvent of propylene glycol monomethyl ether acetate and ethyl lactate (vapor pressure at 279 Pa at 1 atm and 20 ° C). The photosensitive composition of Comparative Example 3 was obtained in the same manner as in Example 1 except that the mixing weight ratio was 40:60.

[Comparative Example 4]

The solvent to be dissolved is a mixed solvent of propylene glycol monomethyl ether acetate and ethylene glycol ethyl ether acetate (vapor pressure of 160 Pa at 1 at 20 ° C) (mixing weight ratio of 60:40) The photosensitive composition of Comparative Example 4 was obtained in the same manner as in Example 1 except for the above.

[Comparative Example 5]

The solvent to be dissolved is a mixed solvent of propylene glycol monomethyl ether acetate and ethylene glycol ethyl ether acetate (vapor pressure of 160 Pa at 1 at 20 ° C) (mixing weight ratio is 40:60) The photosensitive composition of Comparative Example 5 was obtained in the same manner as in Example 1 except for the above.

[Confirmation of coating unevenness and coating uniformity]

The slit coating was performed in a state in which a small slit nozzle (width: 100 mm) using a 120 mm × 200 mm chrome-plated glass substrate was spaced apart from the chrome-plated glass substrate by a distance of 0.05 mm. The coating speed was set to 100 mm for 1 second, and after application, it was placed in a vacuum oven and vacuum dried for 40 seconds. The vacuum pressure after adjusting for 40 seconds at room temperature was about 80 Pa. Thereafter, the film was baked at 100 ° C for 90 seconds to obtain a photoresist film of 2.0 μm. The presence or absence of scaly or line unevenness of the obtained photoresist film was observed under a Na lamp to evaluate coating unevenness. The coating uniformity was evaluated by measuring the film thickness by a nanometer M6500 optical interference film thickness measuring instrument (manufactured by Nippon Co., Ltd.). They are based on the difference of 1. The difference is 2, the winner is 3, and the 3rd order is evaluated.

[Confirmation of unevenness during vacuum drying]

In the same manner as the above-described coating unevenness and coating uniformity, after application using a slit nozzle, the needle was placed in a vacuum drying oven, and a chrome-plated glass substrate was placed thereon and dried. After vacuum drying, the sheet was dried at 100 ° C for 90 seconds using a hot plate to evaluate the strength of the needle trace in the vacuum drying oven under a Na lamp. The person who sees the needle mark is 1. The one who barely recognizes the needle mark is 2, and the one who can't recognize the needle mark is 3 to perform the 3-stage evaluation.

[Measurement of pattern shape]

After a small amount of dropping on a 4-inch wafer, it was rotated at 800 and rotated for 2 seconds to obtain a slit film. Thereafter, it was placed in a vacuum oven and vacuum dried for 40 seconds. The vacuum pressure after adjusting for 40 seconds at room temperature was about 80 Pa. Thereafter, the film was baked at 100 ° C for 90 seconds to obtain a photoresist film of 2.0 μm. The photoresist film was exposed to a daylight g+h-ray splitter (FX-604F) and developed at 23 ° C for 60 seconds with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide. The exposed portion of the 4.0 μm mask size was observed by SEM, and the unexposed portion was exposed at a ratio of 1:1. Figure 1 is a cross-sectional view of the mode. For the shape, the first (a) figure which is close to the inverted cone shape is 1, the shape is slightly closer to the first (b) figure, the shape is a cone shape, and the first (c) figure is 3 to carry out a 3-stage evaluation.

The results obtained are shown in Table 1.

1‧‧‧Substrate

2‧‧‧Resistance pattern after development

Fig. 1 is a cross-sectional schematic view of a photoresist pattern after development.

Claims (6)

A positive pattern forming method comprising the steps of: coating a photosensitive resin composition containing a novolak resin, a sensitizer, and a mixed solvent on a substrate by a slit coating method to form a coating film, the mixed solvent system Containing propylene glycol monomethyl ether acetate, and selected from the group consisting of benzyl alcohol, ethylene glycol butyl ether acetate, propylene glycol, propylene glycol diacetate, propylene glycol monoalkyl ether (the carbon number of the alkyl group is 4 to 5) Dipropylene glycol dialkyl ether (alkyl group has 1 to 5 carbon atoms), dipropylene glycol monoalkyl ether (alkyl group has 1 to 5 carbon atoms), diethylene glycol monoalkyl ether (alkyl group carbon) The number is 1~5), ethyl 3-ethoxypropionate, 3-methoxy-3-methylbutyl acetate, 3-methoxy-3-methylbutanol, butyl lactate and a group consisting of a mixture of equal parts and a vapor pressure of 150 Pa or less at 1 at 20 ° C; drying the formed coating film under reduced pressure; followed by heating and drying, and evaporating to remove at least a portion of the solvent; Exposure becomes the desired pattern; development is performed to form a pattern; heating is performed to harden the developed pattern. The positive pattern forming method according to claim 1, wherein the content of the co-solvent is 5 to 70% by weight based on the total weight of the mixed solvent. The positive pattern forming method of claim 1, further comprising a surfactant. For example, in the method of forming a positive pattern of the second item of the patent application, it is incorporated into The step contains a surfactant. The positive pattern forming method according to any one of claims 1 to 4, wherein the pattern produced is a manufacturer for a liquid crystal display. A photosensitive resin composition for slit coating, comprising a novolak resin, a sensitizer, and a mixed solvent, wherein the mixed solvent comprises propylene glycol monomethyl ether acetate, and is selected from the group consisting of benzyl alcohol and ethylene glycol. Butyl ether acetate, propylene glycol, propylene glycol diacetate, propylene glycol monoalkyl ether (alkyl group has 4 to 5 carbon atoms), dipropylene glycol dialkyl ether (alkyl group has 1 to 5 carbon atoms), Dipropylene glycol monoalkyl ether (alkyl group has a carbon number of 1 to 5), diethylene glycol monoalkyl ether (alkyl group has a carbon number of 1 to 5), 3-ethoxypropionate ethyl ester, acetic acid - a group consisting of 3-methoxy-3-methylbutyl ester, 3-methoxy-3-methylbutanol, butyl lactate, and a mixture thereof, and the vapor pressure at 1 at 20 ° C is a co-solvent of 150 Pa or less; after coating, it is dried under reduced pressure.