JPH11143072A - Deep ultraviolet-ray sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a deep UV sensitive resin compsn. suitable for use as a circuit pattern forming material for a semiconductor integrated circuit, etc., and suitable for use also as a permanent film forming material for an interlayer insulating film, a protective film for a color filter, etc. SOLUTION: The deep UV sensitive resin compsn. contains [A] a copolymer of (a-1) an unsatd. carboxylic acid, (a-2) an epoxy group-contg. radical polymerizable compd. and, optionally, (a-3) other radical polymerizable compd. copolymerizable with the compds. (a-1) and (a-2) and [B] an adhesion assistant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a deep UV-sensitive resin composition. More specifically, it is suitable as a material for forming a circuit pattern of a semiconductor integrated circuit (hereinafter referred to as “IC”) and the like, and is also suitable as a material for forming a permanent film such as an interlayer insulating film and a protective film for a color filter. It relates to a resin composition.

[0002]

2. Description of the Related Art In the production of semiconductor integrated circuits, there is a demand for a deep UV-sensitive resin composition which can be used as a resist having high resolution and high sensitivity. Conventionally, a positive resist containing a novolak resin and a 1,2-quinonediazide compound has been known as a resist used in the manufacture of ICs. However, this positive resist has excellent resolution, but has sufficiently satisfactory chemical resistance to withstand wet etching, furthermore, sensitivity, adhesion to a substrate, heat resistance, and the like. Not really.

In recent years, among LCDs that have rapidly developed, an active matrix type LCD (hereinafter, referred to as “AM-
LCD ”) is the favorite of next-generation display devices to replace cathode-ray tubes due to its high response speed, and the display screen area is increasing. The AM-LCD TF
A resist is used for the formation of the T circuit as in the case of the IC, and further, a permanent film such as an interlayer insulating film and a protective film for a color filter, which is conventionally formed using a thermosetting resin composition. Has been attempted to be formed with the same composition as the resist.

However, the permanent film of such an LCD includes:
Chemical resistance, adhesion to the substrate, heat resistance, transparency in the visible light region, etc. are required, but conventional positive resists containing novolak resins and quinonediazide compounds as described above are sufficient for the above reasons. A satisfactory permanent film could not be formed. In this regard, as can be seen in JP-A-7-248629, the above-mentioned various properties are greatly improved by using a vinyl polymer instead of the novolak polymer and combining it with a 1,2-quinonediazide compound. However, with the recent high quality and high performance of LCD, higher transparency,
High resolution is needed.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel deep UV-sensitive resin composition. Another object of the present invention is to produce a circuit such as a TFT circuit for an IC or LCD, which is excellent in chemical resistance, sensitivity, developability, residual film ratio, heat resistance and adhesion to a substrate, and is excellent in alkali aqueous solution. Another object of the present invention is to provide a deep UV-sensitive resin composition suitable as a resist developable with a developing solution. Still another object of the present invention is to form a permanent film such as an interlayer insulating film, a color filter protective film, and a circuit protective film of an LCD, and has a heat resistance, an adhesion to a substrate, and a visible light region. An object of the present invention is to provide a deep UV-sensitive resin composition capable of providing a permanent film having excellent transparency, chemical resistance and the like.

[0006] Other objects and advantages of the present invention will become apparent from the following description.

[0007]

According to the present invention, the above objects and advantages of the present invention are as follows: [A] (a-1) an unsaturated carboxylic acid, (a-2) a radical polymerizable compound containing an epoxy group. Compound and, if necessary, (a-3) the compound (a
This is achieved by a deep UV-sensitive resin composition comprising a copolymer of another radically polymerizable compound copolymerizable with -1) and (a-2) and [B] an adhesion aid. . Hereinafter, the present invention will be described in detail, and other objects, advantages and effects of the present invention will become apparent. Hereinafter, first, each component contained in the deep UV-sensitive resin composition according to the present invention will be described.

Copolymer [A] The copolymer [A] used in the present invention comprises (a-1) an unsaturated carboxylic acid and (a-2) a radical polymerizable compound containing an epoxy group, and (A-3) The above (a)
-1) and (a-2) are copolymers with other radically polymerizable compounds copolymerizable with (a). Unsaturated carboxylic acid (a-
As 1), an unsaturated carboxylic acid having an ethylenically unsaturated double bond can be mentioned as a preferable example.

Specific examples of such unsaturated carboxylic acids (a-1) include monocarboxylic acids such as methacrylic acid, acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid and p-vinylbenzoic acid. Carboxylic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 1,4
-Cyclohexene dicarboxylic acid, 3-vinylphthalic acid,
4-vinylphthalic acid, methyl-5-norbornene-2,
Examples thereof include dicarboxylic acids such as 3-dicarboxylic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, and dimethyltetrahydrophthalic acid.
Of these, methacrylic acid, acrylic acid, itaconic acid and the like are preferably used.

In the present invention, the unsaturated carboxylic acid (a
As -1), a partially esterified or partially amidated unsaturated carboxylic acid, for example, a half ester or half amide of an unsaturated dicarboxylic acid, in which a part of the carboxylic acid group remains free, can also be used. . As such a half ester or half amide of an unsaturated carboxylic acid, monomethyl itaconate, monobutyl itaconate and the like are preferably used. These unsaturated carboxylic acids can be used alone or in combination of two or more.

Examples of the radical polymerizable compound (a-2) containing an epoxy group include glycidyl (meth) acrylate, α-ethyl glycidyl (meth) acrylate, α-n-propyl glycidyl (meth) acrylate, -N-butyl glycidyl (meth) acrylate, 2-methyl glycidyl (meth) acrylate, 2-ethyl glycidyl (meth) acrylate, 2-propyl glycidyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, 3, Methacrylic esters such as 4-epoxyheptyl (meth) acrylate and α-ethyl-6,7-epoxyheptyl (meth) acrylate; o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether , Α-methyl -O-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2,6
Diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5-triglycidyloxymethylstyrene Styrenes such as glycidyloxymethylstyrene and 2,4,6-triglycidyloxymethylstyrene are exemplified. Of these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like are preferably used. These compounds (a-2)
They can be used alone or in combination of two or more.

Specific examples of other radically polymerizable compounds (a-3) which may be used in the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid. n-propyl, i-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, (meth)
Tert-butyl acrylate, (meth) acrylic acid-
2-ethylhexyl, lauryl (meth) acrylate,
Dodecyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate,
Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, (meth) acrylic acid Phenyl, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, cyclopentyl (meth) acrylate, furyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate, (meth) acrylic acid Benzyl, phenesyl (meth) acrylate, cresyl (meth) acrylate, -1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate,
Perfluoro-n-propyl (meth) acrylate, Perfluoro-i-propyl (meth) acrylate, (meth)
Triphenylmethyl acrylate, cumyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate,
(Meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-amide, (meth) acrylic acid-N, N
-(Meth) acryloyl group-containing radical polymerizable compounds such as -dimethylamide, (meth) acrylic acid-N, N-dipropylamide, (meth) acrylic acid-anilide, (meth) acrylonitrile; acrolein, vinyl chloride,
Vinylidene chloride, N-vinyl pyrrolidone, vinyl acetate,
Styrene, α-methylstyrene, o-methylstyrene,
m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-methoxymethylstyrene, p-ter
Vinyl group-containing radically polymerizable compounds such as t-butoxystyrene, chloromethylstyrene, butadiene, 2,3-dimethylbutadiene and isoprene; unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate; Can be

Of these, styrene, α-methylstyrene, p-tert-butoxystyrene, dicyclopentanyl (meth) acrylate, methyl (meth) acrylate, tert-butyl (meth) acrylate, (meth) )
2-Hydroxyethyl acrylate, benzyl (meth) acrylate, butadiene, isoprene and the like are preferably used. By using these compounds as copolymer components, it is possible to control the alkali solubility, glass transition temperature, dielectric constant, etc. of the polymer, and as a result, the resist performance such as resolution and residual film ratio, and transparency In some cases, the performance as a permanent film such as heat resistance is easily improved. These compounds (a-3) can be used alone or in combination of two or more.
Further, in the above copolymerization, a molecular weight regulator such as α-methylstyrene dimer may be added.

The copolymer [A] used in the present invention can be obtained by copolymerizing the above compounds. The copolymer contains the unsaturated carboxylic acid (a-1) component in an amount of preferably 5 to 50% by weight, particularly preferably 10 to 40% by weight, and contains an epoxy group-containing radical polymerizable compound (a-2).
Is preferably from 5 to 90% by weight, particularly preferably from 30 to 90% by weight.
70% by weight, and polymerized units of the other radically polymerizable compound (a-3), preferably 70% by weight or less,
Particularly preferably, it is contained in an amount of 20 to 60% by weight.

If the content of the unsaturated carboxylic acid (a-1) component is less than 5% by weight, the resulting coating film has poor solubility in a developing solution composed of an aqueous alkali solution, thereby deteriorating the developing property and the sensitivity. May be. On the other hand, if it exceeds 50% by weight, the obtained coating film has too high solubility in an aqueous alkali solution, and the residual film ratio of the obtained resist pattern may be deteriorated. Further, an epoxy group compound (a-
2) If the content of the component is less than 5% by weight, the resulting coating film may have insufficient crosslink density and thus may have poor heat resistance and chemical resistance, while if it exceeds 90% by weight, the resulting coating film may have an alkaline aqueous solution. In some cases, the solubility of the compound may be reduced to deteriorate the developability or the sensitivity may be reduced. Further, when the content of the other radically polymerizable compound (a-3) exceeds 70% by weight, the solubility of the polymer in a developing solution composed of an alkaline aqueous solution is poor, and patterning may be difficult. is there.

The copolymer [A] used in the present invention has a weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) of usually 2 × 10 ³ to 1 × 10 ⁵ , preferably 5 ×.
Desirably, it is 10 ^{3 to} 5 × 10 ⁴ . Mw is 2 × 1
If it is less than 0 ³ , the resulting film may have poor developability, residual film ratio, and the like, and may be inferior in pattern shape and heat resistance. On the other hand, if it exceeds 1 × 10 ⁵ , sensitivity will decrease. And the pattern shape may be inferior. The copolymer [A] used in the present invention as described above comprises an unsaturated carboxylic acid (a-1), an epoxy group-containing radical polymerizable compound (a-2), and optionally another radical polymerizable compound. The compound (a-3) is obtained by copolymerizing the compound (a-3) by various polymerization methods, and a method of copolymerizing the compound (a-3) in a solvent in the presence of a catalyst (polymerization initiator) is preferable.

Specific examples of the solvent used in the copolymerization include alcohols such as methanol, ethanol, propanol and butanol; cyclic ethers such as tetrahydrofuran and dioxane; cellosolve esters such as methyl cellosolve acetate and ethyl cellosolve acetate; ethylene. Glycol ethers such as glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and propylene glycol monomethyl ether; propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene Glico Propylene glycol alkyl ether acetates such as propyl ether acetate; aromatic hydrocarbons such as benzene, toluene, and xylene; ketone, cyclohexanone, 2-
Ketones such as heptanone and 4-hydroxy-4-methyl-2-pentanone; ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate;
Ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, Esters such as methyl 3-ethoxypropionate, ethyl acetate and butyl acetate; aprotic polar solvents such as dimethylformamide and N-methyl-2-pyrrolidone. These solvents include polymerizable compounds [(a-1), (a-2) and (a
-3)], usually 20 to 10 with respect to 100 parts by weight in total.
It is used in an amount of 00 parts by weight.

As the catalyst, those generally known as radical polymerization initiators can be widely used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobisisobutyronitrile
2'-azobis (2,4-dimethylvaleronitrile),
Azo compounds such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis (t-butyl) Peroxy)
Organic peroxides such as cyclohexane and hydrogen peroxide can be used. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox polymerization initiator.

The copolymer [A] has a carboxyl group derived from the unsaturated carboxylic acid (a-1) and an epoxy group derived from the epoxy group-containing compound (a-2), and is alkali-soluble. And self-crosslinking properties. Further, the copolymer [A] has appropriate solubility in an aqueous alkaline solution, and gives a deep-sensitive ultraviolet-sensitive resin composition excellent in high sensitivity, high residual film ratio, developability, and the like. Further, the resist pattern obtained by using the copolymer [A] is excellent in various properties such as heat resistance, adhesion to a substrate, transparency in a visible light region, and chemical resistance.

Adhesion Aid [B] The adhesion aid [B] used in the present invention is preferably a trialkoxysilane having a reactive functional group, for example, vinyltrimethoxysilane, vinyltriethoxysilane,
Vinyltris (2-methoxyethoxy) silane, N-
(2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-
Methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like can be mentioned.
Of these, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane are preferably used.

Other Components The deep UV-sensitive resin composition of the present invention contains a non-radical polymerizable compound having at least two epoxy groups in a molecule for the purpose of further improving heat resistance. You may go out. Such compounds include, for example, Epikote 1001, 1002, 1003, 100
4, 1007, 1009, 1010, 828
Bisphenol A type epoxy resin such as (trade name; Yuka Shell Epoxy Co., Ltd.); bisphenol F type epoxy resin such as Epicoat 807 (trade name; Yuka Shell Epoxy Co., Ltd.); Epicoat 152, 154 ( Product name: Yuka Shell Epoxy Co., Ltd.), EPPN20
Phenol novolak type epoxy resins such as 1, 202 (trade name; manufactured by Nippon Kayaku Co., Ltd.); EOCN102, 103S, 104S, 1020, 1025, 1027
(Trade name; manufactured by Nippon Kayaku Co., Ltd.), Epikote 180S7
Cresol novolak type epoxy resin such as 5 (trade name; Yuka Shell Epoxy Co., Ltd.); Epicoat 1032
Polyphenol type epoxy resins such as H60 and XY-4000 (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.); C
Y-175, 177, 179, Araldite CY-
182, 192, 184 (trade name; manufactured by Ciba Geigy Co., Ltd.), ERL-4234, 4299, 4221,
4206 (trade name; manufactured by UCC), Shodyne 50
9 (trade name; manufactured by Showa Denko KK), Epicron 200,
400 (trade name; manufactured by Dainippon Ink Co., Ltd.), Epicoat 871, 872 (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.), ED-5661, and 5662 (trade name: Celanese Coating Co., Ltd.) And aliphatic polyglycidyl ethers such as Epolite 100MF (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and Epiol TMP (manufactured by NOF Corporation). These compounds are based on 100 parts by weight of the copolymer [A].
It is used as needed in an amount of 50 parts by weight or less.

Further, the deep UV-sensitive resin composition of the present invention may contain a surfactant for the purpose of preventing striation (after coating streaks) and improving developability. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether. Ethylene aryl ethers; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; DC
11PA, SH28PA, ST94PA, ST103P
A, SH190, 192, 194, SF2902
L, 2904, 2908, 2909, SRX28
0A, 294A, 298 (Dow Corning Toray)
Polysiloxane surfactants such as Silicone Co., Ltd .; F-Top EF301, 303, and 352 (Shin-Akita Chemical Co., Ltd.), Megafac F-171, and F-1
72, F-173 (Dainippon Ink and Chemicals, Inc.)
FC-430, FC-431 (manufactured by Sumitomo 3M Limited), Asahigard AG710, Surflon S-382, SC-101, SC-102,
Fluorinated surfactants such as SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 57, 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) and the like. The surfactant is used as needed in an amount of 2% by weight or less, preferably 1% by weight or less based on the solid content of the deep UV-sensitive resin composition. Furthermore, the deep UV-sensitive resin composition according to the present invention contains an antistatic agent, a storage stabilizer, an antifoaming agent, if necessary,
It may contain pigments, dyes and the like.

Deep ultraviolet rays In the present invention, deep ultraviolet rays have a wavelength of about 190 to about 26.
Refers to an electromagnetic wave of 0 nm.

Deep UV Sensitive Resin Composition The deep UV sensitive resin composition of the present invention comprises the above-mentioned copolymer [A], adhesion promoter [B] and, if necessary, other components. It is desirable that the adhesion aid [B] be contained in an amount of preferably 1 to 50 parts by weight, particularly preferably 3 to 20 parts by weight, based on 100 parts by weight of the polymer [A]. The amount of the adhesion auxiliary agent in the deep UV-sensitive resin composition is less than that of the copolymer [A] 1.
If the amount is less than 1 part by weight with respect to 00 parts by weight, the effect of improving the adhesion between the coating film formed from the composition and the substrate cannot be obtained. In some cases, the solubility in a developing solution composed of an alkaline aqueous solution is lowered, the developing property is deteriorated, and the sensitivity is lowered.

The deep UV-sensitive resin composition of the present invention can be easily prepared by uniformly mixing the above components, and is usually used in the form of a solution after being dissolved in an appropriate solvent. For example, the copolymer [A] is dissolved in a solvent,
By mixing the adhesion aid [B] and other components as required at a predetermined ratio with this solution, a deep UV-sensitive resin composition in a solution state can be prepared. As the solvent, the same solvent as that used in producing the copolymer [A] can be used. In addition, other N-
Methylformamide, N, N-dimethylformamide,
N-methylformanilide, N-methylacetamide,
N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether,
Dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-
Nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate,
γ-butyrolactone, ethylene carbonate, propylene carbonate,
A solvent such as phenyl cellosolve acetate can also be used.

Among these solvents, glycol ethers such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether; ethyl cellosolve acetate;
Ethylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate; esters such as ethyl lactate and ethyl 2-hydroxypropionate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether; Ketones such as 2-heptanone are preferably used.

The deep UV-sensitive resin composition of the present invention is applied to a substrate as a solution dissolved in a solvent so that the solid content concentration is preferably 20 to 40% by weight. Also,
It is preferable that the deep UV-sensitive resin composition solution prepared as described above is used after being filtered using a filter having a pore size of about 0.2 μm. The deep UV-sensitive resin composition solution prepared in this way has excellent long-term storage stability.

Method of Use The above-mentioned UV-sensitive resin composition solution is applied to the surface of a substrate, and the solvent is removed by heating to form a coating film. As a method for applying the radiation-sensitive resin composition solution to the substrate surface, various methods such as a spray method, a roll coating method, and a spin coating method can be employed. Next, the formed coating film is heated (prebaked). The heating conditions vary depending on the type of each component, the mixing ratio, and the like, but are usually from 60 to 120 ° C. and from 10 to 60 ° C.
It is about 0 seconds. Next, the heated coating film is irradiated with deep ultraviolet rays through a mask having a predetermined pattern, and then developed with a developer to remove unnecessary portions. Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, N- Methylpyrrolidone, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,
8-diazabicyclo [5.4.0] -7-undecene,
An alkaline aqueous solution containing an alkali such as 1,5-diazabicyclo [4.3.0] -5-nonane can be used. The concentration of the alkali water-soluble is usually 0.1 to 2.5% by weight, preferably 0.2 to 0.5% by weight.

In addition, methanol,
An aqueous solution to which an appropriate amount of a water-soluble organic solvent such as ethanol, a surfactant or the like has been added can also be used as the developer. The development time is usually from 30 to 180 seconds, and the development method may be any of a puddle method and a dipping method. After the development, the substrate is washed with running water for 30 to 90 seconds and air-dried with compressed air or compressed nitrogen to remove moisture on the substrate and form a patterned film. Subsequently, a heating device such as a hot plate or an oven is used to set a predetermined temperature,
For example, at 150 to 250 ° C. for a predetermined time, for example, 5 to 30 minutes on a hot plate, and 30 to 90 in an oven.
By performing the heat treatment for a minute, a patterned crosslinked film can be obtained.

[0030]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.
In the examples, parts and% are by weight unless otherwise specified.

Synthesis of Copolymer [A] Synthesis Example 1 (Synthesis of Copolymer [A-1]) A separable flask equipped with a stirrer, a cooling pipe, a nitrogen inlet pipe, and a thermometer was prepared as shown in Table 1. Charge compound, 3
After purging with nitrogen for 0 minutes, the separable flask was immersed in an oil bath, and the polymerization reaction was carried out for 5 hours while maintaining the internal temperature at 70 ° C. The solid concentration of the obtained polymer solution was 33.1% by weight, and it was confirmed that the polymerization reaction proceeded 100%. The Mw of the copolymer [A-1] is 2.35 × 1
0 was ^4. In addition, Mw is GPC (gel permeation chromatography) (Tosoh Corporation HLC-8)
020) (polystyrene equivalent molecular weight) (hereinafter the same). Table 1 shows the results.

Synthesis Examples 2 to 6 (Copolymers [A-2] to [A
Synthesis of -5]) In the same manner as in Synthesis Example 1, except that the components, solvents and polymerization conditions shown in Table 1 were used in the amounts and conditions shown in Table 1, the copolymer [A] was used. -2] to [A-
5] was obtained. Table 1 shows the solid content concentration and Mw of each of the obtained polymer solutions.

[0033]

[Table 1]

Preparation of Deep UV Sensitive Resin Composition Example 1 100 parts by weight (solid content) of the copolymer [A-1] obtained in Synthesis Example 1, 3-glycidoxypropyltrimethoxy as an adhesion promoter 10 parts by weight of silane ([B-1]) and 0.01 part by weight of SH28PA as a surfactant were mixed and dissolved in diethylene glycol ethyl methyl ether so as to have a solid concentration of 30% by weight. The solution was filtered through a 2 μm millipore filter to prepare a deep UV-sensitive resin composition solution.

Examples 2 to 19 and Comparative Examples 1 and 2 The procedure of Example 1 was repeated, except that the components shown in Table 3 were used, to prepare a deep UV-sensitive resin composition solution. did. In Table 3, abbreviations of components indicate the following compounds. [B-1] ... 3-glycidoxypropyltrimethoxysilane, [B-2] ... 3-glycidoxypropylmethyldimethoxysilane, [B-3] ... 3-methacryloxypropyltri Methoxysilane, [C-1]
・ SH28PA (manufactured by Dow Corning Toray Silicone Co., Ltd.), [C-2] ··· MegaFac F-172
(D-Nippon Ink Co., Ltd.), [C-3]: Florado FC-430 (Sumitomo 3M Co., Ltd.), [D-
1] ··· 1,1,3-tris (2,5-dimethyl-4-
Condensation product of (hydroxyphenyl-3-phenyl) propane (1 mol) and 1,2-quinonediazido 5-sulfonic acid chloride (1.9 mol).

Evaluation of Deep UV Sensitive Resin Composition The deep UV sensitive resin compositions obtained in Examples and Comparative Examples were evaluated by forming a patterned film as described below. Table 3 shows the results. (I) After applying the deep UV-sensitive resin composition solution obtained in each example to a 4-inch silicon wafer using a spinner, the solution was heated at 90 ° C. for 2 minutes on a hot plate to form a film having a thickness of 2. A 0 μm coating was formed. (Ii) Using the obtained coating film as NSR-20 manufactured by Nikon Corporation
05 EX8A reduction projection exposure machine (NA = 0.50, λ =
After exposure to 60 mJ / cm ^{2 at} 248 nm).
It developed at 25 degreeC for 1 minute using the tetramethylammonium hydroxide aqueous solution of weight%, rinsed with water, and dried, and formed the pattern-like film on the silicon wafer.

The evaluation items and evaluation methods are shown below. [Resolution] The size of the smallest space pattern that was resolved was measured with a scanning electron microscope. [Residual film ratio] (film thickness after development / film thickness before development) × 100 was determined, and 90% or more was evaluated as ○, and less than 90% was evaluated as x. [Developability] The surface roughness of the patterned film after development and the presence or absence of peeling of the remaining pattern were observed with a scanning electron microscope. When peeling was not recognized, it was evaluated as ○, and when it was recognized, it was evaluated as x. [Pattern Shape] The cross-sectional shape of the patterned film at the optimal exposure time was observed with a scanning electron microscope. Table 2 shows the evaluation criteria for the cross-sectional shape. When the shape was a square or a rectangle like A, it was judged as good (○), and when it was recognized that the shape was different from A as B or C, it was judged as bad (x).

[0038]

[Table 2]

[Heat resistance] The patterned coating heated at a temperature of 220 ° C. was further heated for 1 hour, and when the film loss due to thermal decomposition was less than 5%, it was evaluated as ○. % Or more was evaluated as x. [Light transmittance] A pattern-like film of about 100 μm × 100 μm was formed on a Corning 7059 glass substrate.
Heated at 220 ° C. 400 nm to 78 of this pattern
The light transmittance at 0 nm was measured, and those having a minimum transmittance of 95% or more were evaluated as ○, those from 90% to less than 95% as Δ, and those less than 90% as x. [Adhesion] Using a 0.66 μm silicon wafer with a thermal oxide film, a 5.0 μmL / S patterned film was formed.
Heated on a hot plate at 220 ° C. for 5 minutes. The heated silicon wafer is immersed for 6 minutes in a 25 ° C. etching solution that is a 6: 1 (volume ratio) mixture of a 40% by weight aqueous solution of ammonium fluoride and a 50% by weight aqueous solution of hydrogen fluoride,
The undercut of the patterned film (the difference between the pattern widths at the top and bottom of the pattern shape shown in Table 2) was observed with a scanning electron microscope.
m and less than 1.3 μm, Δ: 1.3 μm or more. [Storage stability] The deep UV-sensitive resin composition solution was added at 5 ° C for 3 hours.
After storing for a month, a patterned film was formed by the above method, and the same evaluation was performed as described above, and the result was compared with that of the deep UV-sensitive resin composition immediately after preparation. The case where the deep UV-sensitive resin composition immediately after the preparation gave the same evaluation result was judged as good.

[0040]

[Table 3]

Comparative Examples 3 to 5 Evaluations were made in the same manner as in Example 1 except that the resin composition used in Example 1 was patterned at the exposure wavelength shown in Table 4. Table 4 shows the results.

[0042]

[Table 4]

[0043]

The deep UV-sensitive resin composition according to the present invention is excellent in sensitivity, developability, residual film ratio, heat resistance, and adhesion to a substrate, and is free from the use of a 1,2-quinonediazide compound. In particular, a film (pattern) having excellent transparency can be formed. Such a deep UV-sensitive resin composition of the present invention can be used for a thin film transistor (TF) for a semiconductor integrated circuit (IC) and a liquid crystal display (LCD).
T) It is suitable not only as a circuit but also as a positive resist for forming a mask for circuit manufacture and the like, and also as a material for forming a permanent film such as an interlayer insulating film and a protective film for a color filter.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C09D 4/00 C09D 4/00

Claims (1)

[Claims] [A] (a-1) an unsaturated carboxylic acid,
(A-2) a radical polymerizable compound containing an epoxy group and, if necessary, (a-3) another radical polymerizable compound copolymerizable with the compounds (a-1) and (a-2). A deep UV-sensitive resin composition comprising a polymer and [B] an adhesion aid.