JPH0643633A - Chemical amplification type resist composition - Google Patents

Abstract

PURPOSE:To obtain the resist composition forming a positive or negative resist high in sensitivity to light, especially, in the visible light to ultraviolet rays by incorporating a specified squarium compound. CONSTITUTION:This resist composition contains an acid-photogenerator and a binder and the squarium compound represented by formula I or II in which each of R<1> and R<2> is, independently, aminophenyl or 9-durolidyl or Y=CH- each optionally substituted by 1-3 alkyl, alkoxy, or aryl groups each independent of each other; Y is an optionally substituted N-containing heterocyclic group, such as indolin-2-ylidene, benz[e]indolin-2-ylidene, or benzothiazolinylidene; and each of Z<1> and Z<2> is, independently, optionally substituted phenyl.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chemically amplified resist composition which provides a positive resist or a negative resist with high sensitivity to light rays in the visible to near infrared region. The chemically amplified resist composition is useful as a material for PS plates for laser direct plate making, dry film resists, digital proofs, holograms and the like.

[0002]

2. Description of the Related Art A chemically amplified type which uses a photo-acid generator as a photosensitizer and causes a secondary chemical reaction by the catalytic action of an acid generated by exposure to cause a change in the dissolution rate in a developing solution to form a pattern. Resist compositions are known (organic synthetic chemistry, 49 , 437 (1991), textile and industry,
47 , 358 (1991)].

The squarylium compound is used as a resist material in the coexistence with an ethylenically unsaturated compound (JP-A-63-142346, JP-A-2-306247), photolabile blocked surface activity. Image forming system in the coexistence with a developing agent (JP-A-60-243653), a charge generating agent for electrophotographic photoreceptors (Dyes and Pigments, 9 , 85
(1988), Japanese Unexamined Patent Publication No. 52-55643, Japanese Unexamined Patent Publication No. 60-224674), and media materials for optical memory disks (Japanese Unexamined Patent Publication No. 3-1492).
63), a resin plate material for condensing light (Japanese Patent Laid-Open No. 63-235370), a material for an LB (Langmuir-Brodget) film (Nikkei New Material, October 26, 1987), and the like.

[0004]

The present invention particularly provides a chemically amplified resist composition which gives a positive resist or a negative resist with high sensitivity to light rays in the visible to near infrared region.

[0005]

The present invention provides a compound of formula (I)

[0006]

[Chemical 3]

[In the formula, R ¹ and R ² are the same or different and each is a substituted or unsubstituted aminophenyl,
9-julolidyl, Y = CH- (wherein Y represents a substituted or unsubstituted nitrogen-containing heterocyclic group) or

[0008]

[Chemical 4]

(Wherein Z ¹ and Z ² are the same or different and each represents a substituted or unsubstituted phenyl), and a chemically amplified resist composition containing a squarylium compound, a photoacid generator and a binder. Regarding things. Examples of the nitrogen-containing heterocyclic group of Y in the formula (I) include indoline-2-ylidene, benz [e] indoline-2-ylidene, 2-benzothiazolinylidene, naphtho [2,1-
d] thiazole-2 (3H) -ylidene, naphtho [1,
2-d] thiazole-2 (1H) -ylidene, 1,4-
Dihydroquinoline-4-ylidene, 1,2-dihydroquinoline-2-ylidene, 2,3-dihydro-1H-imidazo [4,5-b] quinoxaline-2-ylidene, 2-
Examples thereof include benzoselenazolinylidene.

The substituents on the aminophenyl, phenyl, 9-julolidyl and nitrogen-containing heterocyclic groups are the same or different and have 1 to 3 substituents, for example, alkyl, alkoxy, aryl, aralkyl, halogen, nitro, hydroxy, amino and the like. Can be given. Examples of alkyl include alkyl having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, amyl and hexyl.

Examples of alkoxy include alkoxy having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, pentyloxy and hexyloxy.
The aryl includes, for example, phenyl and naphthyl having 6 to 10 carbon atoms, the aralkyl includes, for example, benzyl, phenylethyl and phenylpropyl having 7 to 10 carbon atoms, and the halogen includes fluorine, Examples thereof include chlorine, bromine and iodine.

The squarylium [compound (I)] represented by the formula (I) is a known compound (for example, JP-A-63-142346).
JP-A-2-306247) and novel compounds, which are produced, for example, by the following method. Manufacturing method 1

[0013]

[Chemical 5]

(Wherein R ¹ and R ² are as defined above, X is chlorine, bromine, iodine or

[0015]

[Chemical 6]

This reaction is represented by R¹H (or R
¹H₂ ⁺・ X^-) And equimolar R²H (or R ²H₂ ⁺
・ X^-) Equimolar squaric acid and, if necessary, equimolar
~ 2 times the molar amount of the basic compound in the solvent, 90 ~ 1
The reaction is carried out at 10 ° C and the reaction is completed in 1 to 24 hours. As a solvent
Is only an alcohol solvent having 4 to 6 carbon atoms, or
Mixed solvent with zen or toluene (alcohol solvent
50% or more), or acetic acid is used.

Examples of the basic compound include triethylamine, quinoline, pyridine and the like. The compound (I) is obtained by removing the solvent from the reaction mixture or filtering the product. Manufacturing method 2

[0018]

[Chemical 7]

[Wherein R ¹ , R ² and X have the same meanings as defined above, R ⁰ represents chlorine or OR ³ (in the formula, R ³ represents alkyl having 1 to 4 carbon atoms)] Carbon Number 1-4
Examples of the alkyl include methyl, ethyl, propyl, butyl and the like. Compound (III) is R ¹ H (or R ¹ H
₂ ⁺ .X ⁻ ) and equimolar compound (II) and, if necessary, equimolar basic compound or metallic sodium are reacted in a solvent at 10 to 35 ° C. for 5 minutes to 5 hours.

As the basic compound, the same compounds as described above are used. Examples of the solvent include chloroform, dichloromethane, 1,2-dichloroethane, diethyl ether, diisopropyl ether, tetrahydrofuran, toluene, benzene, dimethylformamide, dimethyl sulfoxide and the like. The compound (III) is isolated by distilling the solvent from the reaction mixture or filtering the product.

Compound (IV) is the same as Compound (III) in the range of 50-90.
(Wt%) in aqueous acetic acid solution at 90-110 ° C for 1-24
It is obtained by reacting for a time. Isolation of compound (IV) is the same as described above. Compound (I) is a compound (IV) equimolar R ² H (or R ² H ₂ ⁺ · X ⁻ ) and, if necessary, an equimolar basic compound in a solvent at 90 to 110 ° C.
Obtained by reacting for -24 hours. As the basic compound, the same compounds as described above are used. As the solvent, only an alcohol solvent having 4 to 6 carbon atoms or a mixed solvent with benzene or toluene (50% or more of alcohol solvent) is used.

Isolation of compound (I) is as described above,
Furthermore, the compound (I) can be purified by a method such as a recrystallization method, a forced precipitation method, or a column chromatography. Next, Table 1 shows typical examples of the compound (I).

[0023]

[Table 1]

[0024]

[Table 2]

As the photoacid generator, s-triazine compounds substituted with at least one trihalomethyl group [2,4,6-tris (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) ) -4,6-Bis (trichloromethyl) -s-triazine, 2- (4-methoxy-1-naphthalenyl) -4,6-bis (trichloromethyl) -s-triazine, etc.], iron-arene compounds [ (Η ⁶ -Isopropylbenzene) (η ⁵ -Cyclopentadienyl) iron (II)

[0026]

[Chemical 8]

Salts, etc.], onium salts [diaryliodonium salts [8-anilinenaphthalene-1-sulfonic acid diphenyliodonium salts, etc.], triarylsulfonium salts, triarylselenonium salts, dialkylphenacylsulfonium salts, dialkyl-4- Hydroxyphenylsulfonium salts, iodonium salts, etc.}, aryldiazonium salts, diazoketones, o
-Nitrobenzyl esters [9,10-diethoxyanthracene-2-sulfonic acid-p-nitrobenzyl ester, etc.], Sulfonic acid esters [α-hydroxymethylbenzoinsulfonic acid ester, N-hydroxyimide sulfonate, etc.], silanol -Aluminum complexes and the like. Among these, s-triazine compounds substituted with at least one trihalomethyl group are preferable, and these can be obtained by the method described in JP-A-2-306247, for example.

As the binder, acrylic acid, its esterified product, methacrylic acid, its esterified product, (anhydrous) maleic acid, its esterified product, acrylonitrile, styrene, α-alkylstyrene, α-acetoxystyrene, hydroxystyrene, α- Alkylhydroxystyrene, α-acetoxyhydroxystyrene, a protective group (for example, a trialkylsilyl group, a tetrahydropyranyl group, a t-butoxycarbonyl group) whose hydroxyl group is easily dissociated by acid treatment, or a cyclic compound thereof. Analogs, vinyl acetate, vinyl chloride, vinylidene chloride, butadiene, crotonic acid, itaconic acid, N-
Substituted maleimide, vinyl benzoic acid, homopolymers or copolymers of these ester compounds, polyethylene oxide,
Polyvinylpyrrolidone, polyamide, polyurethane, polyethylene terephthalate, acetyl cellulose, methyl cellulose, ethyl cellulose, polyvinyl butyral, chlorinated polyolefin, polyalkylene, polyaldehyde, polycarbonate, epoxy resin, cresol novolac resin, melamine resin, alkyd resin, modified polyvinyl alcohol alone Alternatively, a block or graft copolymer or a modified product by a combination may be used.

In order to improve plasma resistance during development, a silicon-containing substituent may be introduced into these binders before or after exposure. The ratio of the compound (I) is 1 to 60 parts with respect to 100 parts by weight of the photoacid generator (hereinafter, "parts" means "parts by weight"), and the amount of the binder is 2 with respect to 1 part of the photoacid generator. 100 parts, preferably 5-5
It is 0.

Further, in particular, when a negative resist is obtained by a thermal crosslinking reaction in the presence of an acid, a crosslinking agent can be contained. As the cross-linking agent, an amino compound having at least two alkoxymethyl groups, methylol groups, acetoxymethyl groups or the like as functional groups, for example, melamine derivatives [hexamethoxymethylated melamine (Mitsui Cyanamid Co., Ltd. Cymel 300 series (1) ), Etc.], benzoguanamine derivative [methyl / ethyl mixed alkylated benzoguanamine resin (Cymel 1100 series (2) manufactured by Mitsui Cyanamid Co., Ltd.)], glycoluril derivative [tetramethylolglycoluril (Cymel 1100 series manufactured by Mitsui Cyanamid Co., Ltd.) (3))
Etc.], and at least a disubstituted aromatic compound having an alkoxymethyl group, a methylol group, an acetoxymethyl group or the like as a functional group, for example, 1,3,5-trihydroxymethylbenzene, 1,3,5-triacetoxy. Methylbenzene, 1,2,4,5-tetraacetoxymethylbenzene and the like are mentioned, and these are Polym. Mater. Sci. En
g., 64 , 241 (1991).

The amount of the cross-linking agent is 0.1 with respect to 1 part of the photo-acid generator.
-100 parts, preferably 0.2-50 parts. further,
Depending on the intended use of the chemically amplified resist, a solvent (such as ethyl cellosolve), a dissolution inhibitor (such as silyl ether), a plasticizer (such as dioctyl phthalate), a sensitivity improver (such as a tertiary amine), a dark reaction inhibitor, You may contain the coloring agent etc. which consist of organic or inorganic dyes and pigments.

The chemically amplified resist composition of the present invention can be obtained, for example, by mixing the compound (I), a photoacid generator, a binder, and optionally a crosslinking agent. Furthermore, by applying a solution prepared by dissolving the chemically amplified resist composition of the present invention in a solvent (such as ethyl cellosolve) to a surface-treated aluminum plate, silicon wafer, glass plate or the like and drying the solution, particularly from visible light. A photosensitive sample having high sensitivity to light rays in the near infrared region can be obtained.

As a light source of light rays in the visible to near-infrared region, for example, a compound (I) such as a mercury lamp, carbon arc, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, halogen lamp, light emitting diode, laser beam is absorbed. Any possible source of light can be used. The temperature of the heat treatment to be carried out after the light irradiation is preferably below the melting point (decomposition point) of the photosensitive sample obtained from room temperature, particularly in the temperature range of 50 to 120 ° C. In the development for forming the final image, wet development using a solvent (for example, dilute alkaline aqueous solution), dry etching using heating, plasma, accelerated ions or the like can be used depending on the composition.

[0034]

EXAMPLES Examples and reference examples will be shown below. Example 1 100 parts of poly-p-hydroxystyrene [resin M manufactured by Maruzen Petroleum Co., Ltd.], 40 parts of hexamethoxymethylated melamine [CYMEL 301 manufactured by Mitsui Cyanamid Co., Ltd.], 2, 4,
8 parts of 6-tris (trichloromethyl) -s-triazine and 11 parts of the compound were dissolved in 900 ml of ethyl cellosolve to obtain a solution of the chemically amplified resist composition. This solution was applied to a grained and anodized aluminum plate using a spin coater so that the dry film thickness was 1 μm, and dried with a warm air dryer. A step tablet with an optical density difference of 0.15 was placed on the obtained photosensitive sample, and a heat ray absorption filter HA-30 (HOYA
Manufactured by Toshiba Glass Co., Ltd.) (light manufactured by Toshiba Glass Co., Ltd.) (I ₀ = 80.5 μJ / cm ² · s).
Was irradiated. Subsequently, it was heat-treated in an oven at 100 ° C. for 5 minutes, further developed with a 2 wt% sodium metasilicate aqueous solution, and then an ink was applied using a PS plate development ink PI-2 (manufactured by Fuji Photo Film Co., Ltd.) to attach the ink. When the amount of energy required for curing was calculated from the number of curing stages, it was 0.7
It showed a high sensitivity of mJ / cm ² .

Example 2 As in Example 1, except that 1 part of compound 1 and 1 part of heat treatment (100 ° C., 5 minutes) were replaced with 1 part of compound 4 and heat treatment conditions (90 ° C., 10 minutes). When carried out, a sensitivity of 1.4 mJ / cm ² was obtained.

Example 3 In Example 1, the heat treatment condition (100 ° C., 5 minutes) was changed to 9
When performed in the same manner as in Example 1 except that the temperature was 0 ° C. for 10 minutes, a very high sensitivity of 0.24 mJ / cm ² was obtained.

Example 4 Instead of 8 parts of 2,4,6-tris (trichloromethyl) -s-triazine in Example 1, (η ⁶ -isopropylbenzene) (η ⁵ -cyclopentadienyl) iron (II ) of

[0038]

[Chemical 9]

The same procedure as in Example 1 was carried out except that 8 parts of salt was used, and a sensitivity of 3.4 mJ / cm ² was obtained.

Example 5 As in Example 1, except that 1 part of compound 1 and 1 part of compound 3 and heat treatment conditions (100 ° C., 5 minutes) were changed to 1 part of compound 3 and heat treatment conditions (90 ° C., 10 minutes). When carried out, a sensitivity of 4 mJ / cm ² was obtained.

Example 6 As in Example 1, except that 1 part of compound 1 and 1 part of heat treatment (100 ° C., 5 minutes) were replaced by 1 part of compound 2 and heat treatment conditions (90 ° C., 10 minutes). When carried out, a sensitivity of 4.5 mJ / cm ² was obtained.

Example 7 In Example 1, 100 parts of poly-p-hydroxystyrene [resin M manufactured by Maruzen Petroleum Co., Ltd.] was replaced with 100 parts of poly-p-hydroxystyrene [PHS Marker Linker H3F manufactured by Maruzen Petrochemical Co., Ltd.]. Parts, 1 part of compound 1 to 1 part of compound 6 obtained in Reference Example 1, heat treatment conditions of 100 ° C., 5
The temperature was changed from 90 minutes to 90 ° C for 10 minutes, and 600 without using the interference filter KL-63 (manufactured by Toshiba Glass Co., Ltd.).
A sensitivity of 5 mJ / cm ² was obtained in the same manner as in Example 1 except that light having a wavelength of about 800 nm (I ₀ = 2.46 mJ / cm ² · s) was exposed.

Example 8 The same procedure as in Example 7 was repeated except that 1 part of the compound 6 obtained in Reference Example 1 in Example 7 was replaced with 1 part of the compound 7 obtained in Reference Example 2, and the result was 5 mJ / cm ^2. The sensitivity of was obtained.

Example 9 A sensitivity of 18 mJ / cm ² was obtained in the same manner as in Example 7 except that 1 part of the compound 6 obtained in Reference Example 1 was replaced with 1 part of the compound 5. .

Example 10 In Example 1, 100 parts of poly-p-hydroxystyrene [resin M manufactured by Maruzen Petroleum Co., Ltd.] was added to 100 parts of polymethacrylic acid ester polymer, and the heat treatment condition after exposure was 100 ° C. When the same procedure as in Example 1 was carried out except that the temperature was changed from 5 minutes to 90 ° C. for 6 minutes, a sensitivity of 0.9 mJ / cm ² was obtained.

Example 11 In Example 1, 100 parts of poly-p-hydroxystyrene [resin M manufactured by Maruzen Petroleum Co., Ltd.] was replaced with 100 parts of poly-p-hydroxystyrene [PHS Marker Linker H3F manufactured by Maruzen Petrochemical Co., Ltd.]. Hexamethoxymethylated melamine [Cymel 301 manufactured by Mitsui Cyanamid Co., Ltd.] 4
A solution of the chemically amplified resist composition prepared in the same manner as in Example 1 was replaced with 40 parts of hexamethoxymethylated melamine [Cymel 300 manufactured by Mitsui Cyanamid Co., Ltd.], and the solution was spun onto the surface-treated glass. Apply
A photosensitive sample having a film thickness of 1 μm was obtained by drying. The light of He-Ne laser is added to this with a beam splitter.
Divided into luminous flux, angle θ = 7 from the same plane with respect to the photosensitive sample
It was incident at 4 °. After completion of the exposure, heat treatment was performed for 15 minutes in an oven at 90 ° C., followed by development with a 2ωt% sodium metasilicate aqueous solution, washing with water and drying to obtain a bright surface hologram.

Example 12 In Example 1, 100 parts of poly-p-hydroxystyrene [resin M manufactured by Maruzen Petroleum Co., Ltd.] was added to 100 parts of metacresol type novolak resin (m / p = 6/4), and
Heat treatment conditions after exposure are 100 ° C, 5 minutes to 90 ° C, 1
The same procedure as in Example 1 except that the time was changed to 0 minutes.
A sensitivity of 0.7 mJ / cm ² was obtained.

Example 13 In Example 1, 100 parts of poly-p-hydroxystyrene (resin M manufactured by Maruzen Petroleum Co., Ltd.) was added to 100 parts of styrene-monoisobutyl maleate copolymer, and heat treatment conditions after exposure. Was carried out in the same manner as in Example 1 except that the temperature was changed from 100 ° C. for 5 minutes to 90 ° C. for 1 minute.
A sensitivity of ² was obtained.

Example 14 In Example 7, 40 parts of hexamethoxymethylated melamine [Cymel 301 manufactured by Mitsui Cyanamid Co., Ltd.] to 42 parts of hexamethoxymethylated melamine [Cymel 300 manufactured by Mitsui Cyanamid Co., Ltd.] 8 parts of 4,6-tris (trichloromethyl) -s-triazine
Aniline naphthalene-1-sulfonic acid diphenyliodonium salt 9 parts, compound 6 1 part obtained in Reference Example 1 to compound 11 parts, further heat treatment after exposure to 90 ° C.
Example 7 except changing from 10 minutes to 90 ° C. for 6 minutes
A sensitivity of 43 mJ / cm ² was obtained in the same manner as in.

Example 15 In Example 1, 8 parts of 2,4,6-tris (trichloromethyl) -s-triazine was added to 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-. Triazine to 8 parts, and heat treatment conditions after exposure to 100 ° C.
A sensitivity of 3 mJ / cm ² was obtained in the same manner as in Example 1 except that the temperature was changed from 5 minutes to 90 ° C. for 12 minutes.

Example 16 100 parts of an alkali-insoluble fluorine-containing polyimide having a hydroxy group protected by a tetrahydropyranyl group, 2,4,6
-Tris (trichloromethyl) -s-triazine (8.4 parts) and compound 1 (0.9 parts) were dissolved in 900 ml of ethyl cellosolve to obtain a chemically amplified resist composition solution. This solution was applied to a grained and anodized aluminum plate using a spin coater so that the dry film thickness was 1 μm, and dried with a warm air dryer. A step tablet with an optical density difference of 0.15 was placed on the obtained photosensitive sample, and a heat ray absorption filter HA-3 was used from a 3KW ultra-high pressure mercury lamp.
0 (manufactured by HOYA) and light of about 610 nm obtained through a colored glass filter R-61 (manufactured by Toshiba Glass Co., Ltd.) were irradiated. Subsequently, after heat treatment for 15 minutes in an oven at 120 ° C., development was carried out with PS plate developer DN3C (manufactured by Fuji Photo Film Co., Ltd.), and the light-irradiated portion was dissolved to obtain a positive image.

Example 17 In Example 1, 100 parts of poly-p-hydroxystyrene [Resin M manufactured by Maruzen Petroleum Co., Ltd.] was replaced with 100 parts of poly-p-hydroxystyrene [PHS Marker Linker H3F manufactured by Maruzen Petrochemical Co., Ltd.]. Hexamethoxymethylated melamine [Cymel 301 manufactured by Mitsui Cyanamide Co., Ltd.] 40
Hexamethoxymethylated melamine [K & K] 40.
8 parts to 2,4,6-tris (trichloromethyl) -s
-Triazine 8 parts to 7.6 parts, compound 1 1 part to compound 6 obtained in Reference Example 1 to 1.02 parts, heat ray absorption filter HA-30 (manufactured by HOYA) from a 3 KW ultra-high pressure mercury lamp,
Color glass filter R-61 and interference filter KL
-63 (both manufactured by Toshiba Glass Co., Ltd.) was irradiated with light of about 630 nm (I ₀ = 80.5 μJ / cm ² · s) for 3 times.
KL-78 from W super high pressure mercury lamp [Toshiba Glass Co., Ltd.]
Light around 780 nm (I ₀ = 162 μJ
/ Cm ² · s) and a heat treatment condition of 100 ° C. for 5 minutes to 90 ° C. for 10 minutes, and a sensitivity of 2.0 mJ / cm ² was obtained.

Example 18 Compound 6 1.0 obtained in Reference Example 1 in Example 17
When 2 parts was added to 1.25 parts of the compound 7 obtained in Reference Example 2 and the heat treatment conditions were 90 ° C., 10 minutes to 90 ° C., and 11 minutes, the procedure of Example 17 was repeated.
A sensitivity of mJ / cm ² was obtained.

Example 19 The compound 6 obtained in Reference Example 1 in Example 17 1.
Example 2 was carried out in the same manner as in Example 17 except that 02 parts were added to 1.1 parts of the compound 8 obtained in Reference Example 3 and the heat treatment conditions were 90 ° C., 10 minutes to 90 ° C., and 13 minutes.
A sensitivity of / cm ² was obtained.

Example 20 In Example 1, 100 parts of poly-p-hydroxystyrene [Resin M manufactured by Maruzen Petroleum Co., Ltd.] and 100 parts of poly-p-hydroxystyrene [PHS Marker Linker H3F manufactured by Maruzen Petroleum Co., Ltd.] were used. 40 parts of hexamethoxymethylated melamine [CYMEL 301 manufactured by Mitsui Cyanamid Co., Ltd.] to 48 parts of hexamethoxymethylated melamine (manufactured by K & K) and 1 part of Compound 1 obtained in Reference Example 4 as Compound 9 1.
1 part, further heat treatment conditions 100 ℃, 5 minutes to 90
The same procedure as in Example 1 except that the temperature was 8 ° C. for 8 minutes
A sensitivity of 3.4 mJ / cm ² was obtained.

Example 21 The compound 9 1. obtained in Reference Example 4 in Example 20.
1 part of compound 10 having the following structure (Japanese Patent Application Laid-Open No. 2-306)
Compound of No. 247) 1.1 Example
When the same procedure as in Example 0 was performed, a sensitivity of 1.9 mJ / cm ² was obtained.

[0057]

[Chemical 10]

Example 22 In Example 20, 48 parts of hexamethoxymethylated melamine (manufactured by K & K) was added to 40 parts, 1.1 parts of compound 9 was added to 1.0 part of compound 11 and a heat ray absorption filter from a 3 KW ultra-high pressure mercury lamp. Light around 630 nm (I ₀ = 80.5 μJ / cm ² · s) obtained through HA-30 (manufactured by HOYA), colored glass filter R-61 and interference filter KL-63 [all manufactured by Toshiba Glass Co., Ltd.] Instead of the 3 kW ultra-high pressure mercury lamp heat ray absorption filter HA-30 (HOY
A) and a colored glass filter R-66 (manufactured by Toshiba Glass Co., Ltd.) to obtain light of 660 nm or more (I ₀ = 2.
55 mJ / cm ² · s), and further heat treatment conditions 90
Example 2 except that the temperature was changed from 8 minutes to 90 ° C. for 18 minutes.
When the same procedure as in Example 0 was performed, a sensitivity of 4.9 mJ / cm ² was obtained.

Example 23 In Example 20, 48 parts of hexamethoxymethylated melamine (manufactured by K & K) was added to 40 parts, and 1.1 parts of compound 9 was added to compound 12 (the compound described in JP-A-3-149263) .1.
To part 0 Heat ray absorption filter H from 3KW ultra high pressure mercury lamp
A-30 (made by HOYA), colored glass filter R-61
And light around 630 nm (I ₀ = 8) obtained through the interference filter KL-63 (both manufactured by Toshiba Glass Co., Ltd.)
0.5 μJ / cm ² · s) instead of 3 kW ultra high pressure mercury lamp heat ray absorption filter HA-30 (manufactured by HOYA), colored glass filter R-66 and interference filter KL-6
8 obtained through Toshiba Glass Co., Ltd. 6
Irradiation with light of around 80 nm (I ₀ = 112 μJ / cm ² · s) and heat treatment conditions of 90 ° C. for 8 minutes to 90 ° C., 5
The procedure of Example 20 was repeated except that the time was changed to 3.3.
A sensitivity of mJ / cm ² was obtained.

[0060]

[Chemical 11]

Reference Example 1 3,4-dichloro-3-cyclobutene-1,2-dione [compound described in Tetrahedron Lett. No. 10, P.781 (1970)] 0.3 g was added with 15 ml of dichloromethane, At room temperature, 0.54 g of 1,1-bis (p-dimethylaminophenyl) ethylene was added and stirred. After 1 hour, dichloromethane was distilled off from the reaction mixture on a rotary evaporator. Add 7.6 ml of acetic acid and 10 ml of water to the residue, and add 10
Heated on 0 ° C. oil bath. After heating for 1 hour, acetic acid and water were distilled off by a rotary evaporator.
20 ml of n-butanol and 20 ml of benzene were added to the residue,
1,3-di-n-hexyl-2-methylimidazo [4,
5-b] quinoxalinium tosylate (1.05 g) and quinoline (0.27 g) were added, and the mixture was heated for 2 hours. Then, after concentrating with a rotary evaporator, it was purified by column chromatography to obtain 0.45 g of Compound 6. Melting point: 147 ° C (decomposition) Elemental analysis value: Calculated value (%): C 75.83 H 7.52 N 12.06 Measured value (%): C 76.13 H 7.54 N 12.26

Reference Example 2 3,4-diisopropoxy-3-cyclobutene-1,2
After stirring a mixture of 1.98 g of -dione, 2.99 g of N-ethylrepidinium iodide and 20 ml of isopropanol in room temperature, 0.23 g of sodium was added thereto and stirred for 4 hours. Then, the insoluble matter was filtered off, the filtrate was concentrated, and the residue was purified by column chromatography. After adding 30 ml of acetic acid and 10 ml of water to this purified product, 9
Heat at 5 ° C. for 1.5 hours. After the reaction was completed, the volatile matter was concentrated and dried. Then, 13 ml of n-butanol was added to the dried product.
Then, 0.92 g of 1,3-di-n-butyl-2-methylimidazo [4,5-b] quinoxalinium chloride and 0.27 g of quinoline were added, and the mixture was heated under reflux for 4 hours. Then, the solvent and the produced water were distilled off by the rotary evaporator. The residue was purified by column chromatography to obtain 0.31 g of compound 7. Melting point: 237 to 238 ° C (decomposition) Elemental analysis value: Calculated value (%): C 74.84 H 6.47 N 12.83 Measured value (%): C 75.13 H 6.52 N 12.94

Reference Example 3 3,4-diisopropoxy-3-cyclobutene-1,2
After stirring a mixture of 1.98 g of -dione, 2.99 g of N-ethylrepidinium iodide and 20 ml of isopropanol at room temperature, 0.23 g of sodium was added thereto and stirred for 4 hours. Then, the insoluble matter was filtered off, the filtrate was concentrated, and the residue was purified by column chromatography. After adding 30 ml of acetic acid and 10 ml of water to this purified product, 9
Heat at 0-100 ° C for 1.5 hours. After the reaction was completed, the volatile matter was concentrated and dried. After that, 1,3,3-
Trimethyl-2-methylene indoline (0.37 g), n-butanol (21 ml) and benzene (21 ml) were added, and the mixture was heated under reflux for 5 hours. Then, the volatile matter was concentrated, and the residue was purified by column chromatography to obtain 80.24 g of a compound represented by the following structural formula.

[0064]

[Chemical 12]

The melting point and elemental analysis values of Compound 8 were as follows. Melting point: 260-263 ° C (decomposition) Elemental analysis value: Calculated value (%): C 79.59 H 6.20 N 6.63 Actual value (%): C 79.90 H 6.15 N 6.80

Reference Example 4 3,4-Dichloro-3-cyclobutene-1,2-dione
After adding 20 ml of dichloromethane to 1.5 g, 1,3,3-trimethyl-2-methyleneindoline under ice-water cooling 1.
7 g was added dropwise, and after 2 hours, the precipitate was filtered and dried.
To this dried product, 35 ml of acetic acid and 50 ml of water were added, and the mixture was heated on an oil bath at 100 ° C. for 1 hour, and acetic acid and water were distilled off by a rotary evaporator. To the residue was added 100 ml of n-butanol, 1,3-di-n-hexyl-2-methylimidazo [4,5-b] quinoxalinium tosylate 5.2.
5 g and 1.01 g of triethylamine were added, and the mixture was heated under reflux for 3 hours. Then, the volatile matter was concentrated, and the residue was purified by column chromatography to obtain 3.57 g of a compound 9 represented by the following structural formula.

[0067]

[Chemical 13]

The melting point and elemental analysis values of Compound 9 were as follows. Melting point: 173.5 to 174.9 ° C Elemental analysis value: Calculated value (%): C 75.59 H 7.51 N 11.60 Measured value (%): C 73.99 H 7.47 N 11.17

Reference Example 5 In Reference Example 3, 1,1,2,3-tetramethyl-1H-benz [e] indolium iodide 0.7 was used instead of 1,3,3-trimethyl-2-methyleneindoline.
0.17 g of compound 11 represented by the following structural formula was obtained in the same manner except that 2 g and 0.28 g of quinoline were added.

[0070]

[Chemical 14]

The melting point and elemental analysis values of Compound 11 were as follows. Melting point: 266-267.6 ° C (decomposition) Elemental analysis value: Calculated value (%): C 81.33 H 5.97 N 5.93 Measured value (%): C 81.52 H 6.06 N 5.97

[0072]

The chemically amplified resist composition of the present invention has excellent photosensitivity.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification number Internal reference number for FI Technical indication G03F 7/039 501 G03H 1/02 8106-2K H01L 21/027

Claims (1)

[Claims] 1. A compound represented by the formula (I): [In the formula, R ¹ and R ² are the same or different and each is a substituted or unsubstituted aminophenyl, 9-julolidyl, Y = CH- (in the formula, Y represents a substituted or unsubstituted nitrogen-containing heterocyclic group). Or [Chemical 2] (Wherein Z ¹ and Z ² are the same or different and represent substituted or unsubstituted phenyl), and a chemically amplified resist composition containing a squarylium compound, a photoacid generator and a binder.