JP2003050460A - Chemical amplification type positive working resist composition for liquid crystal device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a chemical amplification type positive working resist composition for a liquid crystal device which is low-cost, is excellent in resolution and sensitivity and has such excellent characteristics as a small reduction in film thickness and to provide a resist pattern using the resist composition. SOLUTION: The chemical amplification type positive working resist composition is obtained by dissolving (A) an alkali-soluble resin comprising a novolak resin having 375-1,000 Å/sec alkali solubility in 2.38 wt.% aqueous solution of tetramethylammonium hydroxide, (B) a compound which generates an acid when irradiated with radiation and (C) a crosslinkable polyvinyl ether compound in an organic solvent. The resist pattern for a liquid crystal device is obtained by disposing a coating on a glass square substrate using the resist composition, exposing the coating through a mask pattern after drying and carrying out post-exposure heating and alkali development.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has excellent characteristics such as high resolution, high sensitivity and little film loss, and is a chemical amplification type used for manufacturing a liquid crystal device such as a thin film transistor (THIN FILM TRANSISTOR). The present invention relates to a positive type liquid crystal element resist composition and a liquid crystal element resist pattern using the same.

[0002]

2. Description of the Related Art In recent years,
Displays using liquid crystals have been installed in various electronic devices and are becoming widespread, and the reason for this is the low price of liquid crystal displays. Naturally, with such price reduction,
There is also a demand for cost reduction of various materials such as resists used in the manufacturing. From such a background, it is an industrially important requirement that the resist for producing liquid crystal devices today is first of all inexpensive. Further, as a resist for a substrate provided with a low-temperature polysilicon film or a continuous grain boundary crystal film, a demand for higher resolution has been increasing in recent years. Further, if the resist film thickness after development of the unexposed portion becomes smaller than the resist film thickness before development, that is, if the so-called film reduction becomes large, the selectivity with respect to the underlying substrate at the time of dry etching in the subsequent step becomes small, causing a problem. Therefore, reduction of film loss is also required for the resist for manufacturing liquid crystal elements. further,
The resist for liquid crystal device manufacturing is incomparable to silicon wafers, and the latest substrate is 680 mm in length x 88 in width.
0 mm, 600 mm x 720 mm, 550 mm x 670
mm, and since it is applied to a super-large glass substrate of 360 mm × 460 mm even in the old generation, it is necessary to increase the exposure amount. Therefore, it is necessary to increase the sensitivity in order to achieve a high through top. Furthermore, since it is applied to a very large glass substrate, it must meet the following requirements, which are completely different from those of resists for semiconductor device production.

(Improvement of Pre-bake Margin) In a resist for manufacturing a liquid crystal element, it is necessary to obtain a resist pattern of a uniform size over the large substrate as described above. In recent years, it has become necessary to obtain as many liquid crystal display devices as possible from one glass substrate in order to reduce the cost. Therefore, the size of the glass substrate is rapidly increased, and the uniformity of the resist pattern size is required. Came to be. However, the conventional resist is easily affected by the prebaking temperature, and the obtained resist pattern size varies.

(Improvement of development margin) A curtain flow type development system has been adopted as a substrate becomes larger. In this developing method, the developing solution is dropped from a slit from the lateral edge of the substrate to the lateral edge of the substrate. In such a developing method, a time difference of about 5 seconds occurs between the start of development and the end of development. This time difference causes a problem that the resist pattern size at the start of development and the resist pattern size at the end of development are displaced. Therefore, it is required to minimize the influence of this time difference and make the resist pattern size uniform.

(Improvement of peelability) In the liquid crystal element manufacturing process,
After forming the resist pattern, using the resist pattern as a mask, various processes such as wet etching, dry etching, or ion plantation are performed under different conditions depending on the manufacturing process of each user. When such various treatments are applied, the resist pattern deteriorates,
It changes to something that is difficult to remove with a resist remover. Therefore, it is necessary to improve the releasability even if it is changed to one that is difficult to peel.

However, in the conventional naphthoquinone diazito type non-chemically amplified positive resist, there is a trade-off relationship that the film loss is increased when the sensitivity is increased, and it is difficult to satisfy both of them. Further, as described above, although the problem of increasing the size of the substrate has been recognized, a means for solving these has not been found.

The conventional resist for manufacturing liquid crystal elements is
A naphthoquinonediazide-based non-chemically amplified resist has been used from the viewpoints of long reliability and high reliability as a g-line or i-line positive resist for manufacturing semiconductor devices and cost reduction. On the other hand, with regard to the resist for manufacturing a semiconductor element, in response to the recent demand for ultra-miniaturization and high sensitivity of the semiconductor element, a chemically amplified resist is adopted in some processes of 0.35 μm or less, and a finer resist in the future will be used. Chemically amplified resists are becoming mainstream in the process. From the flow of such a resist for manufacturing a semiconductor element, it is not unthinkable to adopt a chemically amplified resist as a resist for manufacturing a liquid crystal element.

However, even if high resolution and high sensitivity can be achieved, it cannot be said to be sufficient as a resist for producing a liquid crystal element, and the conventional chemically amplified resist is extremely expensive. It was not considered much because it had problems.

In the present invention, even if an attempt is made to apply a conventional chemically amplified resist to a resist for producing a liquid crystal element,
The above problems that have not been achieved, that is, low price,
An object of the present invention is to provide a resist composition for a chemically amplified positive type liquid crystal device, which has excellent properties such as excellent resolution and sensitivity and small film loss, and a resist pattern using the same.

[0010]

Means for Solving the Problems As a result of intensive studies aimed at achieving the above object, the inventors of the present invention have selected a novolak resin having a specific alkali solubility, a compound capable of generating an acid upon irradiation with radiation, and a crosslinkable polyvinyl ether. The chemical amplification type positive type liquid crystal device resist composition dissolved in an organic solvent has been found to have excellent properties such as low price, excellent resolution and sensitivity, and small film loss. Completed the invention.

That is, the present invention provides the following components (A) to
(C), (A) 2.38 wt% tetramethylammonium hydroxide (TMAH) alkali-soluble resin consisting of novolac resin having an alkali solubility in the range of 375 to 1000 Å / second, (B) irradiation The present invention provides a resist composition for a chemically amplified positive type liquid crystal element, which is obtained by dissolving an acid-generating compound and (C) a crosslinkable polyvinyl ether compound in an organic solvent. The present invention also provides a coating film on a square glass substrate using the resist composition for a chemically amplified positive type liquid crystal element according to any one of claims 1 to 5, and after drying, through a mask pattern. The present invention provides a resist pattern for a liquid crystal element, which is obtained by the steps of exposure, heat treatment after exposure, and then alkali development.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Since resists for producing liquid crystal elements tend to be large in size and the exposure amount needs to be increased as the substrate becomes larger, there is a demand for higher sensitivity in order to achieve a high through top. Was expensive. However, since there is a trade-off relationship between high sensitivity and film loss, a resist composition excellent in both these characteristics and the three characteristics of high resolution has not been known so far. The present invention using a specific novolac resin that has not been used in the conventional chemical amplification type has provided a resist composition for a liquid crystal element excellent in the above three properties for the first time.

Component (A) Component (A) comprises a novolak resin having an alkali solubility in a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution at 23 ° C. in the range of 375 to 1000 Å / sec. It is necessary to use an alkali-soluble resin. The preferable range is 500 to 750.
Å / second. If it exceeds 1000 Å, the film loss in the unexposed area after development becomes large, and if it is less than 375 Å, scum easily occurs and image formation becomes difficult. This value is the time required for the film thickness of the alkali-soluble resin to become 0 when the alkali-soluble resin is provided on the substrate with a predetermined film thickness and immersed in a 2.38 wt% TMAH aqueous solution. Alkali solubility per unit time.

The alkali-soluble resin is not particularly limited as long as it has the above-defined alkali-solubility. For example, what is conventionally used as a film-forming substance in a positive photoresist composition, for example, an aromatic hydroxy compound such as phenol, cresol, xylenol or trimethylphenol and an aldehyde such as formaldehyde in the presence of an acidic catalyst. A condensed product or the like is used. Specifically, m-cresol form novolac resin obtained by condensing 100% of m-cresol having a weight average molecular weight of 5,000 to 14,000 with formaldehydes under an acid catalyst, m-cresol 30 to 80 mol%, preferably 30 ~
Weight average molecular weight 2 obtained by condensing 50 mol% and p-cresol 70 to 20 mol%, preferably 70 to 50 mol% of mixed cresol with formaldehyde in the presence of an acid catalyst.
500-10,000 cresol form novolac resin and the like can be mentioned. Examples of the acid catalyst include oxalic acid, p-toluenesulfonic acid, acetic acid, and the like, and it is preferable to use oxalic acid because it is inexpensive and easily available. Examples of formaldehydes include formaldehyde, formalin in which formaldehyde is dissolved in water, trioxane and the like, and formalin is usually used.

Regarding the component (B), the component (A) and the component (C) are crosslinked by heat during prebaking to form an alkali-insolubilized resist layer on the entire surface of the substrate. Is generated, the crosslink is decomposed by the acid, and the insolubilized resist layer is changed into alkali-soluble. Compounds that generate an acid upon irradiation with radiation having such a function are so-called acid generators used in chemically amplified resists, and many compounds have been proposed so far, and any of these can be arbitrarily selected. And use it. Since ultraviolet rays in which g-rays, h-rays, and i-rays coexist are used in the resist for producing a liquid crystal element, of these, compounds that are irradiated with such ultraviolet rays and have high acid generation efficiency are preferable. Examples of such a compound include the following compounds.

[0016]

[Chemical 2]

[0017]

[Chemical 3]

(Where m is 0 or 1, X is 1 or 2, R is
₁Is 1 or more C₁-C₁₂Alkyl group is substituted
Phenyl group, CN, etc., R₁'Is C₂-C₁₂Archi
Rene group, R₂Is R₁Synonymous with R₃Is C₁-C₁₈Alkyl
Base, R₃’R₃Synonymous with R _Four, R_FiveAre independently hydrogen atoms
Etc., A represents S, O, etc. ) Compound represented by (USP
6004724). Specifically, for example

[0019]

[Chemical 4]

Included are thiolene-containing oxime sulfonates such as:

[0021]

[Chemical 5]

(In the formula, R ⁶ and R ⁷ are each a carbon number of 1 to 1.
3 represents an alkyl group. ) And a bis (trichloromethyl) triazine compound represented by

[0023]

[Chemical 6]

(Wherein Z represents a 4-alkoxyphenyl group or the like) in combination with a bis (trichloromethyl) triazine compound (JP-A-6-289).
No. 614, Japanese Patent Laid-Open No. 7-34412). Specifically, for example, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl)-
1,3,5-triazine, 2- [2- (3-methoxy-
4-Ethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2
-(3-Methoxy-4-propoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5
-Triazine, 2- [2- (3-ethoxy-4-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4
-Diethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2
-(3-Ethoxy-4-propoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5
-Triazine, 2- [2- (3-propoxy-4-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3-
Propoxy-4-ethoxyphenyl) ethenyl] -4,
6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4-dipropoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3
Examples thereof include 5-triazine. These triazine compounds may be used alone or in combination of two or more kinds.

On the other hand, the triazine compound (IV)
Examples of the triazine compound (V) used in combination as desired include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5
-Triazine, 2- (4-ethoxyphenyl) -4,6
-Bis (trichloromethyl) -1,3,5-triazine, 2- (4-propoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2-
(4-Butoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl)-
1,3,5-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5
-Triazine, 2- (4-propoxynaphthyl) -4,
6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-butoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4
-Methoxy-6-carboxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2-
(4-Methoxy-6-hydroxynaphthyl) -4,6-
Bis (trichloromethyl) -1,3,5-triazine,
2- [2- (2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2-
[2- (5-methyl-2-furyl) ethenyl] -4,6
-Bis (trichloromethyl) -1,3,5-triazine, 2- [2- (5-ethyl-2-furyl) ethenyl]
-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (5-propyl-2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,
3,5-triazine, 2- [2- (3,5-dimethoxyphenyl) ethenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3-methoxy- 5-Ethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2
-[2- (3-Methoxy-5-propoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,
3,5-triazine, 2- [2- (3-ethoxy-5-
Methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2-
(3,5-Diethoxyphenyl) ethenyl] -4,6-
Bis (trichloromethyl) -1,3,5-triazine,
2- [2- (3-ethoxy-5-propoxyphenyl)
Ethenyl] -4,6-bis (trichloromethyl) -1,
3,5-triazine, 2- [2- (3-propoxy-5
-Methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2-
(3-Propoxy-5-ethoxyphenyl) ethenyl]
-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,5-dipropoxyphenyl) ethenyl] -4,6-bis (trichloromethyl)-
1,3,5-triazine, 2- (3,4-methylenedioxyphenyl) -4,6-bis (trichloromethyl)-
1,3,5-triazine, 2- [2- (3,4-methylenedioxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine and the like can be mentioned. These triazine compounds may be used alone or in combination of two or more.

Component (C) The crosslinkable polyvinyl ether compound of component (C) is
Both the component (A) and the component (A) are crosslinked by heating during prebaking to form an alkali-insolubilized resist layer on the entire surface of the substrate. Then, by the action of the acid generated from the component (B), the crosslinks are decomposed, the exposed area changes to alkali-soluble, and the unexposed area remains alkali-insoluble. Therefore, (A)
There is no particular limitation on the type of component as long as it is a component (C) having a function of crosslinking by heating during prebaking to form an alkali-insolubilized resist layer on the entire surface of the substrate. Such a polyvinyl ether compound is disclosed in JP-A-6-148.
No. 889 and Japanese Unexamined Patent Publication No. 6-230574 are listed, and any of them can be selected and used. Particularly, a resist profile shape resulting from thermal crosslinkability and acid decomposability. , And considering the characteristics of the contrast between the exposed and unexposed areas, the alcohol represented by the following general formula

[0027]

[Chemical 7]

(Wherein R is a group obtained by removing n hydrogen atoms from an alkane of a linear group, a branched group or a cyclic group, and n is an integer of 2, 3 and 4). A compound in which a part or the whole is etherified with a vinyl group is preferable. Specifically, engineering ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,3-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylolethane trivinyl ether, Hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, cyclohexane dimethanol divinyl ether and the like can be mentioned. Among these, a crosslinkable divinyl ether compound is more preferable, and cyclohexanedimethanol divinyl ether is particularly preferable.

The blending amounts of the components (B) and (C) are
Component (B) is 1 to 30 parts by weight relative to component (A) 100 parts by weight.
The amount of the component (C) is preferably 0.1 to 25 parts by weight, particularly preferably 1 to 15 parts by weight.

Regarding the component (D), amines are added to the resist composition for a chemically amplified positive type liquid crystal device of the present invention from the viewpoint of preventing excessive diffusion of acid from the exposed area and stability of the resist pattern over time. It is preferable. As the amines, for example, diethanolamine, triethanolamine, tributanolamine, which is difficult to volatilize from the resist film by heating during prebaking,
Examples thereof include secondary or tertiary alkanolamines such as triisopropanolamine, and secondary or tertiary alkylamines such as diethylamine, triethylamine, dibutylamine and tributylamine. The blending amount is
The amount is preferably 0.01 to 5 parts by weight, particularly preferably 0.1 to 1 part by weight, based on 100 parts by weight of the component (A).

Examples of the organic solvent used in the present invention include acetone, methyl ethyl ketone, cyclohexanone, isobutyl methyl ketone, isoamyl methyl ketone, 1,
Ketones such as 1,1-trimethylacetone; ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monoacetate or diethylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monoisopropyl ether, monobutyl ether or monophenyl ether, etc. Polyhydric alcohols and derivatives thereof; cyclic ethers such as dioxane; and methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, ethyl 3-ethoxypropionate, etc. Esters can be mentioned. These may be used alone or in combination of two or more.

In the resist composition for a chemically amplified positive type liquid crystal device of the present invention, if necessary, compatible additives such as the performance of a resist film are improved as long as the object of the present invention is not impaired. Additional resins, plasticizers, stabilizers,
Contains a surfactant, a colorant for making the developed image more visible, a sensitizer for improving the sensitizing effect, an antihalation dye, and a conventional additive such as an adhesion improver. be able to.

The chemically amplified positive type liquid crystal device resist composition of the present invention is prepared by dissolving the components (A), (B), (C) and, if necessary, other components in an organic solvent. It can be prepared.

The resist pattern for a liquid crystal element of the present invention is
It is obtained using such a chemically amplified resist composition for a positive type liquid crystal element. That is, first, the resist composition for a chemically amplified positive type liquid crystal element is applied onto a glass square substrate using a spinner or the like to form a coating film. This is pre-baked on, for example, a hot plate and dried, and then exposed through a mask pattern. After this is heat-treated (PEB), a resist pattern is formed by applying an alkali developing solution such as TMAH by a curtain flow method or immersing in an alkali developing solution, washing and drying.

[0035]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

Example 1 As the component (A), an m-cresol form novolak resin having a weight average molecular weight of 10,000 was obtained by adding oxalic acid and formalin to 100 mol% of m-cresol and conducting a condensation reaction. The alkali solubility of this resin in a 2.38 wt% TMAH aqueous solution was 750 Å / sec.
As the component (B),

[0037]

[Chemical 8]

Was used. 100 parts by weight of component (A),
6 parts by weight of the component (B), 8 parts by weight of cyclohexanedimethanol divinyl ether as the component (C), 0.2 parts by weight of triisopropanolamine as the component (D), and a nonionic fluorine-silicone surfactant (trade name: Mega Fuck R-08 (manufactured by Dainippon Ink and Chemicals, Inc.)) 0.0
4 parts by weight was dissolved in 395 parts by weight of propylene glycol monomethyl ether acetate to prepare a chemically amplified resist composition for positive type liquid crystal device. Then, the prepared chemically amplified resist composition for a positive type liquid crystal device was applied onto a glass substrate with a chrome film (150 mm × 150 mm) by spinner coating so as to have a film thickness of 1.5 μm, and then the temperature of the hot plate was adjusted to 130. ℃ (pre-bake),
It was dried for 90 seconds to obtain a dry coating film. Then, it was exposed through a test chart mask using a mirror projection aligner MPA-600FA (manufactured by Canon Inc.). Next, the temperature of the hot plate is set to 120 ° C. and 90
After the second exposure, a heat treatment (PEB) was performed. Then, it was immersed in a 2.38 wt% TMAH aqueous solution at 23 ° C. for 60 seconds,
The exposed portion was removed by rinsing with pure water for 30 seconds and drying to form a resist pattern on the substrate.

The resist pattern thus obtained was observed with a scanning electron microscope. Table 1 shows the limit resolution and the exposure amount at that time as the sensitivity. Further, similarly, Table 1 shows the resist pattern size in which the cross-sectional shape of the resist pattern is rectangular. Further, in the above pattern forming process, when the developing time is 120 seconds, the change in the film thickness of the unexposed portion before and after the development is shown in Table 1 as the film reduction amount. In the pattern formation process, only the prebaking temperature was changed within the range of 10 ° C., and the dimensional change amount of the resist pattern per unit temperature was determined as the prebaking margin from the resist pattern size obtained at each temperature. The results are shown in Table 1. Further, in the above pattern forming process, only the developing process was changed from immersion to the curtain opening type, and the difference between the resist pattern size at the start of development and the resist pattern size at the end of development was determined as a development margin. The results are shown in Table 1. Further, after the pattern forming process, post-baking at 200 ° C. is performed to form a resist-altered film, and the alteration film is required to be stripped by a typical resist stripping solution ST-106 (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.). The time was evaluated as peelability. The results are shown in Table 1.

Example 2 Each characteristic was evaluated in the same manner as in Example 1 except that the composition of the resist composition for a chemically amplified positive type liquid crystal element of Example 1 was changed as follows. As the component (A), a cresol form novolak resin having a weight average molecular weight of 4000, which was obtained by adding oxalic acid and formalin to 35 mol% of m-cresol and 65 mol% of p-cresol and conducting a condensation reaction, was used. The alkali solubility of this resin in a 2.38 wt% TMAH aqueous solution was 500Å / sec. (B)
The component, the component (C) and the component (D) are the same as in Example 1. 100 parts by weight of component (A), 3 parts by weight of component (B),
4 parts by weight of the component (C), 0.1 parts by weight of the component (D) and a nonionic fluorine-silicone surfactant (trade name: Megafac R-08 (manufactured by Dainippon Ink and Chemicals, Inc.)) 0.0
4 parts by weight was dissolved in 395 parts by weight of propylene glycol monomethyl ether acetate to prepare a chemically amplified resist composition for positive type liquid crystal device. The results are shown in Table 1.

Comparative Example 1 (Naphthoquinonediazide type resist) Each characteristic was obtained in the same manner as in Example 1 except that the composition of the resist composition for a chemically amplified positive type liquid crystal device of Example 1 was changed as follows. evaluated. 35 mol% of m-cresol and p
-A cresol form novolak resin having a weight average molecular weight of 4,000, which was obtained by adding oxalic acid and formalin to 65 mol% of cresol, was used as an alkali-soluble resin component. 2.38% by weight of this resin TMAH
The alkali solubility in the aqueous solution was 500Å / sec. As a photosensitive component, naphthoquinone-1,2 was added to 1 mol of 2,3,4,4'-tetrahydroxybenzophenone.
An esterified product obtained by reacting 2.4 mol of diazide-5-sulfonic acid chloride was used. 100 parts by weight of the resin,
25 parts by weight of the photosensitive component, 10 parts by weight of bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane as a sensitizer, nonionic fluorine.
Silicone type surfactant (Brand name Megafac R-08
(Manufactured by Dainippon Ink and Chemicals, Inc.)) 0.04 parts by weight of propylene glycol monomethyl ether acetate 39
It was dissolved in 5 parts by weight to prepare a chemically amplified resist composition for positive type liquid crystal element. The results are shown in Table 1.

Comparative Example 2 (Three-Component Chemically Amplified Positive Resist) The same as Example 1 except that the composition of the chemically amplified positive type liquid crystal element resist composition of Example 1 was changed as follows. , Each characteristic was evaluated. Oxalic acid and formalin were added to 100 mol% of m-cresol, and a cresol novolak resin having a weight average molecular weight of 10,000 obtained by condensation reaction was used as an alkali-soluble resin component. The alkali solubility of this resin in a 2.38 wt% TMAH aqueous solution was 750 Å / sec. The acid generator component is the same as in Example 1. The dissolution inhibitor component 1 is

[0043]

[Chemical 9]

Part or all of the hydrogen atoms of the hydroxyl groups of
A compound substituted with a butoxycarbonylmethyl group was used. As the dissolution inhibitor component 2, a compound in which a part or all of hydrogen atoms of a carboxyl group and a hydroxyl group of deoxycholic acid were substituted with a 1-ethokin-1-ethyl group was used. The amine component is the same as in Example 1. Alkali-soluble resin component 100 parts by weight, acid generating component 5 parts by weight, dissolution inhibitor component 1 8 parts by weight, dissolution inhibitor component 2 8 parts by weight, triisopropanolamine 0.1 parts by weight, nonionic fluorine-silicone interface Activator (Brand name Megafac R-0
8 (manufactured by Dainippon Ink and Chemicals, Inc.) 0.04 parts by weight of propylene glycol monomethyl ether acetate 39
It was dissolved in 5 parts by weight to prepare a chemically amplified resist composition for positive type liquid crystal element. The results are shown in Table 1.

[0045]

[Table 1]

As is clear from Table 1, Examples 1 and 2 were superior to Comparative Examples 1 and 2 in all the items.

[0047]

The resist pattern for a liquid crystal element using the chemically amplified positive type liquid crystal element resist composition of the present invention is
It has the following effects. (1) It has three characteristics: high resolution, high sensitivity, and reduction of film loss. In the conventional naphthoquinone diazide-based non-chemically amplified positive resist, there is a trade-off relationship that the film loss becomes large when the sensitivity is increased, and it was difficult to satisfy both of them. It has become possible to satisfy. In addition, the composition of the present invention can achieve a high limit resolution. The limit resolutions of Examples 1 and 2 are about 1.3 μm. The limiting resolution of the conventional naphthoquinonediazide type non-chemically amplified positive resist for liquid crystal device production was about 1.4 μm. The limit resolution of the three-component chemically amplified positive resist is about 2.5μ.
It was m. (2) Improvement of rectangularity of resist pattern shape (3) Improvement of pre-bake margin: The amount of change in resist pattern size could be reduced to 1/3 or less of that in the conventional case. The amount of change in resist pattern size per temperature of the conventional resist was 0.41 μm / ° C. On the other hand, in Examples 1 and 2, 0.08 to 0.12 μm / ° C. could be achieved. (4) Improvement of development margin: A resist pattern size deviation can be significantly reduced. The conventional resist pattern size deviation was 0.75 μm. On the other hand, in Examples 1 and 2, 0.03 to 0.04 μm could be suppressed. (5) Improvement of peelability: Deterioration of the resist pattern can be significantly suppressed. In the case of the conventional resist, the time required for stripping the deteriorated film formed at 160 ° C. post bake at the stripping solution temperature of 60 ° C. was 10 minutes, whereas in the composition of the present invention, the deteriorated film formed at 200 ° C. post bake was used. The time required for peeling was 2 minutes or less at the peeling liquid temperature of 23 ° C. (6) Cost reduction: There is a strong demand for cost reduction of resists for liquid crystal elements, which is affected by price reductions of electronic devices equipped with liquid crystal devices such as personal computers. The resist composition for a chemically amplified liquid crystal element of the present invention has the characteristics (1) to (5) described above, and can be manufactured at low cost. Commercialization of products has become easier.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Chisaburo Aoki             150 Nakamaruko, Nakahara-ku, Kawasaki-shi, Kanagawa East             Within Kyoka Kogyo Co., Ltd. F-term (reference) 2H025 AA02 AA04 AB16 AB17 AC01                       AD03 BE00 BE10 BG00 CB29                       CC17 FA17

Claims (6)

[Claims] 1. The following components (A) to (C), (A) 2.3.
An alkali-soluble resin consisting of a novolak resin having an alkali solubility in an aqueous solution of 8% by weight of tetramethylammonium hydroxide in the range of 375 to 1000 Å / sec,
A resist composition for a chemically amplified positive type liquid crystal element, which is obtained by dissolving (B) a compound that generates an acid upon irradiation with radiation, and (C) a crosslinkable polyvinyl ether compound in an organic solvent. 2. The alkali solubility of the component (A) is 500
The chemically amplified positive type liquid crystal element resist composition according to claim 1, which is an m-cresol form novolac resin in the range of 750 Å / sec. 3. The component (B) is g (436 nm) line, h (40 nm)
5. The resist composition for a chemically amplified positive type liquid crystal device according to claim 1 or 2, which is a compound which generates an acid upon irradiation with either of the 5) line and the i (365 nm) line. 4. An alcohol represented by the following general formula (I) wherein the component (C) is: (In the formula, R is a group in which n hydrogen atoms have been removed from an alkane containing a linear group, a branched group, or a cyclic group, and n is 2, 3 or 4
The chemical amplification type positive type liquid crystal device resist composition according to any one of claims 1 to 3, which is a compound in which a part or all of the hydroxyl groups of (4) are etherified with vinyl groups. 5. The composition according to claim 1, further comprising 0.01 to 5 parts by weight of amines as the component (D) with respect to 100 parts by weight of the component (A). A chemically amplified positive resist composition for liquid crystal devices. 6. A coating film is provided on a glass square substrate using the resist composition for a chemically amplified positive type liquid crystal device according to claim 1, dried, and then dried through a mask pattern. A resist pattern for a liquid crystal element, which is obtained by the steps of exposure, heat treatment after exposure, and then alkali development.