JP2002311586A - Negative type resist composition for electron beam or x-ray - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problem of a performance enhancing technique in the microfabrication of a semiconductor device using electron beams or X-rays and to provide a negative type chemical amplification type resist composition for electron beams or X-rays satisfying such characteristics as sensitivity, resolution and resist shape when electron beams or X-rays are used. SOLUTION: The negative type resist composition contains (A) a sulfonium salt and/or an iodonium salt which generates an acid when irradiated with electron beams or X-rays and has at least one phenyl group, (B) a resin soluble in an aqueous alkali solution, (C) a crosslinker which causes crosslinking with the resin (B) under the action of the acid and (D) a compound which breaks its own bond and/or cleaves another component when irradiated with electron beams or X-rays but does not generates a phenyl radical as an intermediate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative resist composition suitable for use in ultra microlithography processes such as the production of ultra LSIs and high capacity microchips, and other photofabrication processes. More specifically, the present invention relates to a negative type photoresist composition capable of forming a pattern with high definition using X-rays, electron beams and the like, and is particularly suitable for fine processing of a semiconductor device using high energy rays such as electron beams. The present invention relates to a negative resist composition which can be used for a resist composition.

[0002]

2. Description of the Related Art The degree of integration of integrated circuits is increasing, and in the manufacture of semiconductor substrates such as VLSI, processing of ultrafine patterns having a line width of less than half a micron is required. Have been. In order to meet the need, the wavelength of an exposure apparatus used for photolithography is becoming shorter and shorter, and now far ultraviolet light and excimer laser light (XeCl, KrF, ArF, etc.) have been studied. . Further, formation of finer patterns by electron beams or X-rays has been studied.

In particular, electron beams or X-rays are positioned as a next-generation or next-next-generation pattern forming technology, and development of a negative resist capable of achieving a high sensitivity, a high resolution and a rectangular profile is desired. In electron beam lithography, energy is supplied to a compound in a process where an accelerated electron beam causes collision and scattering with atoms constituting a resist material to cause a reaction of the resist material to form an image. The use of a highly accelerated electron beam increases the straightness, reduces the effects of electron scattering, and makes it possible to form a high-resolution rectangular pattern.On the other hand, the electron beam permeability increases, The sensitivity decreases. As described above, in electron beam lithography, there is a trade-off between sensitivity, resolution, and resist shape, and it has been a problem how to achieve both. As a resist material for these, for the purpose of improving sensitivity, a chemically amplified resist mainly using an acid catalyzed reaction is used, and as a main component for a negative resist, an alkali-soluble resin, an acid generator, and A chemically amplified composition comprising an acid crosslinking agent has been effectively used.

Conventionally, for a negative chemically amplified resist,
Various alkali-soluble resins have been proposed. For example, Japanese Patent No. 2505053, JP-A-3-170554 and JP-A-6-118646 disclose novolak-type phenol resins, JP-A-7-31463, and JP-A-8-29255.
No. 9 discloses a polyvinyl phenol resin having a narrowed molecular weight distribution, JP-A-3-87746, JP-A-8-44061 discloses a phenol resin partially converted to a cyclic alcohol structure by hydrogenation, JP-A-7-295200, Kaihei 8
JP-A-152717 discloses a resin in which a part of OH groups of polyvinyl phenol is protected by an alkyl group.
No. 86 describes a polyvinyl phenol resin having an acid-inactive protecting group such as an acyl group. JP-A-6-67431 and JP-A-10-10733 describe a polyvinylphenol resin copolymerized with styrene, Discloses a polyvinyl phenol resin copolymerized with (meth) acrylate monomers, and JP-A-8-240911 discloses a resin having a carboxy group.

The acid generator is disclosed in Japanese Patent Publication No. 8-36.
No. 35 discloses an organic halogen compound, JP-A-2-52348.
Nos. 4 and 5 include aromatic compounds substituted with Br and Cl.
No. 368864 and JP-A-4-366865 describe Br,
Cl-substituted aromatic compounds having alkyl or alkoxy groups, JP-A-2-150848, JP-A-6-19
No. 9770, iodonium and sulfonium compounds, JP-A-3-87746, haloalkanesulfonate compounds, JP-A-4-210960, JP-A-4-2172
No. 49, a diazodisulfone compound or a diazosulfone compound; JP-A-4-336454, Br and I-substituted alkyltriazine compounds; JP-A-4-291258, a sulfonamide, sulfonimide compound;
JP-A-291259 discloses a sulfonic acid compound of a polyhydric phenol, JP-A-4-291260 and JP-A-4-29126.
No. 1 and JP-A-6-202320 disclose a naphthoquinonediazide-4-sulfonate compound.
No. 9 discloses a disulfone compound, JP-A-6-236024 discloses an N-oxyimidosulfonate compound, and U.S. Pat. No. 5,344,742 discloses a benzylsulfonate compound.

Further, with respect to acid crosslinking agents, see JP-A-3-75.
652, JP-A-5-181277, JP-A-7-14
No. 6556, a methoxymethylmelamine compound, JP-A-4-281455, JP-A-5-232702, JP-A-6-83055, a compound having an alkoxymethyl ether group, JP-A-5-281715, an oxazine compound, JP-A-5-134412, JP-A-6-38
No. 25 discloses an aromatic compound having an alkoxyalkyl group, and JP-A-6-194838 discloses, in addition to a trioxane compound, an alkoxymethyluryl compound described in JP-A-1-293339. However, in any combination of these compounds, it is difficult to obtain a sufficiently high sensitivity under electron beam irradiation or X-ray irradiation under a high accelerating voltage condition, and the high sensitivity and the resist shape can be satisfied. Balancing at the level was a challenge.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the problem of a technique for improving the performance in microfabrication of a semiconductor device using an electron beam or an X-ray. An object of the present invention is to provide a negative chemically amplified resist composition for electron beams or X-rays, which satisfies the characteristics of sensitivity, resolution and resist shape. Highly sensitive electron beam or X-ray that can be used in next-generation EB irradiators (EB block irradiators or EB steppers (sequential reduction projection irradiators) aimed at improving throughput) that are suitable for mass production of semiconductor devices To provide a negative type chemically amplified resist composition.

[0008]

In order to achieve high sensitivity, a method of increasing the amount of the acid generator is generally employed. On the other hand, in a negative type, the more the acid generator is added, the more the line is added. There is a tendency for the pattern shape to deteriorate, such as a skirted shape, and it has been difficult to achieve both high sensitivity and pattern shape. According to this study, it was confirmed that pattern shape degradation tends to be remarkable especially when an acid generator that generates a phenyl radical is used as an intermediate. As a result, they have found that these problems can be solved by using a compound that cleaves its own bond or causes cleavage of other components but does not generate a phenyl radical as an intermediate, and has reached the present invention. That is, the present invention has the following configuration.

(1) (A) a sulfonium salt and / or iodonium salt having at least one phenyl group which generates an acid upon irradiation with an electron beam or X-ray; (B) a resin soluble in an aqueous alkali solution; (C) an acid (B) a cross-linking agent that forms a cross-link with the resin due to the action of (D) an electron beam or X-ray irradiation cleaves its own bond and / or causes cleavage of other components, but does not generate a phenyl radical as an intermediate A negative resist composition for electron beams or X-rays, comprising a compound.

(2) (D) A compound which cleaves its own bond by irradiation with an electron beam or X-ray and / or causes cleavage of others but does not generate a phenyl radical species as an intermediate is (a) Aromatic or alicyclic ketones, (b)
Selected from the group consisting of organic peroxides, (c) hexaarylbiimidazole compounds, (d) ketoxime ester compounds, (e) azinium compounds, (f) active ester compounds, and (g) compounds having a carbon-halogen bond. The negative resist composition for electron beams or X-rays according to the above (1), wherein the composition is at least one kind.

(3) (D) A compound which cleaves its own bond by irradiation with an electron beam or X-ray and / or causes cleavage of others but does not generate a phenyl radical species as an intermediate is represented by (h) Photochromic compounds, (i) benzyl carbamates, (j) sulfonamides,
(K) The negative resist composition for electron beam or X-ray according to the above (1) or (2), which is at least one selected from the group consisting of acyloxyiminos.

(4) The negative resist composition for electron beam or X-ray according to any one of (1) to (3), further comprising (E) a nitrogen-containing basic compound. (5) The negative resist composition for electron beam or X-ray according to any one of the above (1) to (4), further comprising (F) a surfactant.

Hereinafter, preferred embodiments will be described. (6) (A) The sulfonium salt and / or iodonium salt having at least one phenyl group and generating an acid upon irradiation with an electron beam or X-ray is at least one sulfonium salt or iodonium salt containing fluorine. The negative resist composition for an electron beam or X-ray according to any one of the above (1) to (5). (7) The negative resist composition for an electron beam or X-ray according to any one of the above (1) to (6), further comprising (G) a spectral sensitizing dye or dye.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail. [1] Resin soluble in aqueous alkali solution of the present invention (B) (hereinafter also referred to as alkali-soluble resin)

The alkali-soluble resin used as the alkali-soluble resin of the component (B) is not particularly limited, and those well-known in conventional electron beam negative resist compositions can be used. Examples of such an alkali-soluble resin include a novolak resin obtained by condensing a phenol such as phenol, m-cresol, p-cresol, xylenol, and trimethylphenol with an aldehyde such as formaldehyde under an acidic catalyst, and hydroxystyrene. Polyhydroxystyrene resins such as homopolymers of styrene or copolymers of hydroxystyrene with other styrene monomers, copolymers of hydroxystyrene with acrylic acid or methacrylic acid or derivatives thereof, acrylic acid or methacrylic acid Examples thereof include alkali-soluble resins such as acrylic acid or methacrylic acid-based resins, which are copolymers of styrene and its derivatives, and resins in which some of the hydroxyl groups of polyhydroxystyrene are protected with acid-dissociable substituents.

The styrene monomers to be copolymerized with the above-mentioned hydroxystyrene include styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene and p-methylstyrene.
Methoxy styrene, p-chlorostyrene and the like can be mentioned. Examples of the derivatives of acrylic acid or methacrylic acid include, for example, methyl acrylate, ethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, acrylamide, acrylonitrile, and corresponding methacrylic acid derivatives. On the other hand, examples of the acid dissociable substituent include a tertiary alkyloxycarbonyl group such as a tert-butoxycarbonyl group and a tert-amyloxycarbonyl group;
Tertiary alkyloxycarbonylalkyl groups such as t-butoxycarbonylmethyl group; tertiary alkyl groups such as tert-butyl group; alkoxyalkyl groups such as ethoxyethyl group and methoxypropyl group; tetrahydropyranyl group; tetrahydrofuranyl Examples include an acetal group such as a group, a benzyl group, and a trimethylsilyl group. The protection ratio of the hydroxyl group by these acid-dissociable substituents is usually 1 to 60 mol% of the hydroxyl group in the resin, particularly 1
It is preferable that the content be in the range of 0 to 50 mol% because of excellent contrast between the exposed portion and the unexposed portion.

Among these alkali-soluble resins, those having a molecular weight distribution (Mw / Mn ratio) of 3.5 or less are preferred because of their excellent resist pattern shape. Such resins are called monodispersed resins and are easily commercially available. Can be obtained.
In the case of a novolak resin having an Mw / Mn ratio of more than 3.5, the low molecular weight portion may be removed by a known fractional precipitation treatment, and the Mw / Mn ratio may be adjusted to 3.5 or less.

In the present invention, the component (B) is preferably polyhydroxystyrene, polyhydroxystyrene having a hydroxyl group protected by an acid-dissociable substituent, a copolymer of hydroxystyrene and styrene, and a cresol novolak resin. In particular, the molecular weight distribution (Mw / Mn
Cresol novolak resin having a ratio of 3.5 or less, polyhydroxystyrene having a molecular weight distribution (Mw / Mn ratio) of 1.5 or less, a copolymer of hydroxystyrene and styrene, and a part of hydroxyl groups of polyhydroxystyrene having tert-butoxycarbonyl. The resin protected by the group is suitable for forming a resist pattern having excellent heat resistance and contrast. The weight average molecular weight (Mw) and number average molecular weight (Mn)
Means gel permeation chromatography (GP
C) in terms of polystyrene. In the present invention, the alkali-soluble resin of the component (B) may be used alone or in combination of two or more.

In the present invention, the alkali-soluble resin is preferably a resin containing a repeating unit containing a phenol structure having at least one OH group at a meta position from a site linked to the main chain skeleton of the resin, and having a molecular weight distribution. It is an alkali-soluble resin in the range of 1.0 to 1.5. In a chemically amplified negative resist, a cross-linking agent and an alkali-soluble resin react by an action of an acid catalyst generated by irradiation with actinic rays, radiation, or an electron beam to form a cross-linked structure and become insoluble in an alkali developer. In this case, when an alkali-soluble resin containing a phenol structure having at least one OH group at the meta position is used, the molecular weight distribution of the resin is further reduced, and when a resin having a more uniform molecular weight is used, specific It was found that the crosslinking efficiency was improved and the sensitivity was increased.

As such a resin, preferably, m-
Polyvinyl phenol resin, a copolymer having a structural unit derived from m-vinyl phenol, a resin obtained by partially protecting or modifying the m-polyvinyl phenol resin, a (meth) acrylate polymer having an m-phenol skeleton, and the like. Although resins can be widely used, more preferred are phenolic resins containing a repeating structural unit represented by the following general formula (a).

[0021]

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In the general formula (a), R ₁ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an oxyalkyl group or a haloalkyl group which may have a substituent. x
Represents an integer of 0 to 3. R ₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group or an acyl group which may have a substituent. When R ₂ there are a plurality, the plurality of R ₂ may be the same or different. R ₃ is a hydrogen atom, a halogen atom,
A cyano group, or an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group,
Alternatively, it represents an aryl group. When there are a plurality of R ₃ ,
A plurality of R ₃ may be the same or different. Further, _two of the plurality of R ₂ , two of the plurality of R ₃ , or R ₂ and R ₃ may be combined to form a ring.

A ₁ may have a single bond or a substituent,
Valent alkylene group, alkenylene group, cycloalkylene group or arylene group, or -O -, - SO ₂ -,
_{-O-CO-R 5 -,} - CO-O-R 6 -, - CO-N
(R ₇ ) represents —R ₈ —. R ₅ , R ₆ , and R ₈ may be the same or different and may have a single bond, an ether group, an ester group, an amide group, a urethane group, or a ureide group, or may have a substituent. Good represents a divalent alkylene group, alkenylene group, cycloalkylene group, or arylene group. R ₇ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group which may have a substituent.

The alkyl group for R _{1 to} R ₃ and R ₇ is preferably an alkyl group having 1 to 8 carbon atoms,
For example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group,
An octyl group can be mentioned. The cycloalkyl groups of R _{2 to} R ₃ and R ₇ may be monocyclic or polycyclic. Preferred examples of the monocyclic type include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group each having 3 to 8 carbon atoms. Preferred examples of the polycyclic type include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an α-pinel group, and a tricyclodecanyl group.

The alkenyl group of R _{2 to} R ₃ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group and a cyclohexenyl group. The aryl group of R _{2 to} R ₃ and R ₇ is preferably an aryl group having 6 to 15 carbon atoms, for example, a phenyl group, a tolyl group, a dimethylphenyl group, a 2,4,6-trimethylphenyl group, Naphthyl group,
And an anthryl group. R _{2 to} R ₃ , R ₇
The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

The oxyalkyl group for R ₁ is preferably an oxyalkyl group having 1 to 4 carbon atoms, for example, an alkoxy group having 1 to 4 carbon atoms such as a hydroxy group, a methoxy group, an ethoxy group and a butoxy group. And an oxymethyl group, an oxyethyl group, an oxypropyl group, and an oxybutyl group substituted by an acyl group having 1 to 4 carbon atoms such as an acetoxy group, a propanoyloxy group and a butanoyloxy group. As the haloalkyl group for R ₁ ,
It is preferably a haloalkyl group having 1 to 4 carbon atoms, and examples thereof include a chloromethyl group, a chloroethyl group, a chloropropyl group, a chlorobutyl group, a bromomethyl group, and a bromoethyl group. The acyl group for R ₂ is preferably an acyl group having 1 to 10 carbon atoms, and examples thereof include a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pivaloyl group, and a benzoyl group.

The alkylene group of A ₁ , R ₅ , R ₆ and R ₈ is preferably an alkylene group having 1 to 8 carbon atoms,
Examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. The alkenylene group preferably has 2 to 2 carbon atoms.
These are six alkenylene groups, for example, an ethenylene group, a propenylene group, a butenylene group and the like.
The cycloalkylene group preferably has 5 to 8 carbon atoms.
Cycloalkylene groups, for example, a cyclopentylene group, a cyclohexylene group and the like. The arylene group is preferably an arylene group having 6 to 12 carbon atoms, for example, a phenylene group, a tolylene group,
Examples include a xylylene group and a naphthylene group.

Further, these groups may further have a substituent. Examples of the substituent include those having active hydrogen such as an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), and an alkoxy group. Groups (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), thioether group, acyl group (acetyl group, propanoyl group, benzoyl group, etc.), acyloxy group (acetoxy group, propanoyloxy group, benzoyloxy group, etc.), Examples include an alkoxycarbonyl group (a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, etc.), a cyano group, a nitro group, and the like.
Particularly, those having active hydrogen such as an amino group, a hydroxyl group and a carboxyl group are preferable.

Further, two of a plurality of R ₂ , a plurality of R ₃
And the ring which may be formed by combining R ₂ and R ₃ may be a ring which may contain a 4- to 7-membered hetero atom (oxygen atom, nitrogen atom, sulfur atom) Specific examples of the formed structure preferably include a benzofuran ring, a benzodioxonol ring, a benzopyran ring, an indole ring, a benzimidazole ring, a benzopyrazole ring, and a benzothiophene ring.

The resin of the present invention (B) may be a resin comprising only the repeating structural unit of the general formula (a), but for the purpose of further improving the performance of the negative resist of the present invention,
Other polymerizable monomers may be copolymerized.

The copolymerizable monomers that can be used include those shown below. For example, acrylates other than the above, acrylamides, methacrylates, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, addition polymerizable unsaturated bonds selected from crotonates and the like. It is a compound having one.

Specifically, for example, acrylic esters such as alkyl (the alkyl group has 1 to 1 carbon atoms)
Acrylates (eg, methyl acrylate, ethyl acrylate, propyl acrylate, t-butyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate) , Chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2
-Dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.) aryl acrylate (for example, phenyl acrylate);

Methacrylic esters, for example, alkyl (preferably having 1 to 10 carbon atoms in the alkyl group) methacrylate (for example, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, t-butyl methacrylate,
Amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate,
Chlorbenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate , Furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.),
Aryl methacrylates (eg, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.);

Acrylamides, for example, acrylamide, N-alkylacrylamide, (alkyl having 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, butyl, t-butyl, heptyl) Group, octyl group, cyclohexyl group, benzyl group, hydroxyethyl group, benzyl group, etc.), N-arylacrylamide (aryl group includes, for example, phenyl group, tolyl group, nitrophenyl group, naphthyl group,
Examples include a cyanophenyl group, a hydroxyphenyl group, and a carboxyphenyl group. ), N, N-dialkylacrylamide (an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a butyl group, an isobutyl group, an ethylhexyl group, a cyclohexyl group, etc.), N-diarylacrylamide (an aryl group includes, for example, a phenyl group), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like ;

Methacrylamides, for example, methacrylamide, N-alkylmethacrylamide (an alkyl group having 1 to 10 carbon atoms, for example, methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl Group, cyclohexyl group, etc.), N
-Aryl methacrylamide (an aryl group includes a phenyl group and the like), N, N-dialkyl methacrylamide (an alkyl group includes an ethyl group, a propyl group and a butyl group), N, N-diaryl Methacrylamide (an aryl group includes a phenyl group and the like), N-hydroxyethyl-N-methylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-ethyl-N-phenylmethacrylamide and the like;
Allyl compounds, for example, allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyloxyethanol Such;

Vinyl ethers such as alkyl vinyl ethers (for example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether,
Ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, Tetrahydrofurfuryl vinyl ether, etc.), vinyl aryl ethers (for example, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-
2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether, etc.);

Vinyl esters, for example, vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate , Vinylphenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-
Phenylbutyrate, vinylcyclohexylcarboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like;

Styrenes such as styrene, alkyl styrene (eg, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl Styrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc., alkoxystyrene (eg, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrene (eg, chlorostyrene, dichlorostyrene) , Trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluors Ren, trifluoromethyl styrene, 2
-Bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.), carboxystyrene, vinylnaphthalene;

Crotonic esters, for example, alkyl crotonates (for example, butyl crotonate, hexyl crotonate, glycerin monocrotonate, etc.); dialkyl itaconates (for example, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.) ); Dialkyl esters of maleic acid or fumaric acid (eg,
Dimethyl maleate, dibutyl fumarate, etc.), maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleilenitrile and the like. In addition, generally, any addition-polymerizable unsaturated compound that can be copolymerized may be used.

Among these, monomers having a carboxyl group such as carboxystyrene, N- (carboxyphenyl) acrylamide, N- (carboxyphenyl) methacrylamide, and monomers improving the alkali solubility such as maleimide are copolymer components. Is preferred. The content of the other polymerizable monomer in the resin in the present invention is preferably 50 mol% or less, more preferably 30 mol% or less, based on all repeating units.

Specific examples of the resin having a repeating structural unit represented by the general formula (a) are shown below, but the present invention is not limited thereto.

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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In the above specific examples, n represents a positive integer. x,
y and z represent the molar ratio of the resin composition, and x = 30 to 95, y = 5 to 70, and preferably x =
It is used in the range of 50 to 90, y = 10 to 50. In a resin consisting of three components, x = 30 to 90, y = 5 to 65,
z = 5 to 65, preferably x = 50 to 90, y = 5 to 4
5, used in the range of z = 5-45.

The preferred molecular weight of the resin of the present invention (B), preferably the resin having a repeating unit represented by the general formula (a), is 1,000 by weight average (polystyrene standard).
~ 50,000, preferably 2,000 ~ 30,000
0, and more preferably in the range of 2,500 to 15,000. The molecular weight distribution (Mw / Mn) is 1.0-1.
5, and more preferably in the range of 1.0 to 1.2. The smaller the molecular weight distribution, the higher the crosslinking efficiency and the higher the sensitivity. Further, the effect of excellent resolution and pattern edge roughness is exhibited. Here, the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) are obtained by gel permeation chromatography (polystyrene conversion value). The content of the repeating structural unit represented by the general formula (a) is 5 to 1
The amount is 00 mol%, preferably 50 to 100 mol%, and more preferably 70 to 100 mol%.

The resin used in the present invention (B) is described, for example, in JP-A-4-195138 and JP-A-4-350657.
JP-A-4-350658, JP-A-6-41222
No., JP-A-6-65333, Polym.
J. , 18, 1037 (1986), Poly.
m. J. , Vol. 22, p. 386 (1990), Makr
omol. Chem. Suppl. , Vol. 15, p. 167 (1989). That is, the desired alkali-soluble resin can be obtained by a so-called living anion polymerization method. Further, it can also be obtained by combining a resin synthesized by radical polymerization with a soluble good solvent and a poor solvent and performing molecular weight fractionation or fractionation by gel chromatography.
These resins may be used alone or in combination of two or more.

The alkali dissolving rate of the alkali-soluble resin is preferably 20 ° C./sec or more as measured at 23 ° C. with 0.26N tetramethylammonium hydroxide (TMAH). Particularly preferably, it is 200 ° / sec or more. The alkali-soluble resin of the present invention may be used alone or in combination with another alkali-soluble resin. The proportion of the alkali-soluble resin of the present invention is 1
Up to 100 parts by weight of another alkali-soluble resin other than the present invention can be used together with 00 parts by weight. Examples of the resins that can be used are shown below. For example, cresol, xylenol, a novolak resin of formaldehyde with a suitable combination of trimethylphenol, hydrogenated novolak resin, acetone-pyrogallol resin, p-hydroxystyrene resin and its copolymer, styrene-maleic anhydride copolymer, carboxy Examples of the group-containing (meth) acrylic resin and its copolymer include, but are not limited to, these.

The amount of the resin (B) to be added is 30 to 95% by weight, preferably 40 to 90% by weight, based on the total solid content of the composition, including the amount of other alkali-soluble resins that can be used together. Preferably, it is used in the range of 50 to 80% by weight.

[2] The compound (photoacid generator) which generates an acid upon irradiation with an electron beam or X-ray as the component (A) will be described. The photoacid generator used in the present invention includes at least one photoacid generator that generates an acid upon irradiation with an electron beam or X-ray.
Any compound can be used as long as it is a sulfonium salt and / or iodonium salt having two phenyl groups. An iodonium salt represented by the following general formula (PAG3) or a sulfonium salt represented by the following general formula (PAG4) Is preferred. The sulfonium salt and / or iodonium salt having at least one phenyl group is at least one
Although two phenyl groups are contained in the cation part and / or the anion part of the salt, those containing at least the cation part of the salt are preferred.

[0056]

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Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. R ²⁰³ , R ²⁰⁴ ,
R ²⁰⁵ each independently represents a substituted or unsubstituted alkyl group or aryl group. Z ⁻ represents a counter anion, for example, BF ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , Si
_{^{F 6 2-, ClO 4 -,}} CF 3 SO 3 - perfluoroalkane sulfonate anion such as, pentafluorobenzenesulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid Examples of the dye include an anion and a sulfonic acid group-containing dye, but are not limited thereto.

Further, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded through a single bond or a substituent. Specific examples include the following compounds, but are not limited thereto.

[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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The onium salts represented by the general formulas (PAG3) and (PAG4) are known, and are described, for example, in US Pat.
It can be synthesized by the methods described in 2,807,648 and 4,247,473, JP-A-53-101,331 and the like.

Among the photoacid generators including the iodonium salt represented by the general formula (PAG3) or the sulfonium salt represented by the general formula (PAG4), an example of a photoacid generator that can be effectively used is an anion having a fluorine anion. A photoacid generator having an atom is exemplified.

[0069] For example, the cation portion is composed of iodonium or sulfonium, anionic part R ^F SO ₃ ^- (wherein, the R ^F is, a fluorine-substituted alkyl group having 1 to 10 carbon atoms) represented by A photoacid generator selected from sulfonates composed of anions is used.
The fluorine-substituted alkyl group represented by R ^F may be linear, branched, or cyclic. Preferred R ^F
Is a fluorine-substituted linear alkyl group represented by CF ₃ (CF ₂ ) y, wherein y is an integer of 0 to 9. The cation moiety of the photoacid generator preferably has the following general formula (I) to (II)
I).

[0070]

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In the above general formulas (I) to (III), R ₁
To R ₃₇ are the same or different and each represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group, a halogen atom or -S
—R represents a ₃₈ group. R ₃₈ represents a linear, branched or cyclic alkyl group or aryl group. R _{1 to} R ₁₅ , R ₁₆ to
Two or more of R ₂₇ , R _{28 to} R ₃₇ are bonded to form a ring containing one or more selected from a single bond, a carbon atom, an oxygen atom, a sulfur atom and a nitrogen atom; Is also good.

In the general formulas (I) to (III), R _{1 to} R
The linear or branched alkyl group of ₃₈ may have a substituent and may have a carbon number such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, and a t-butyl group. 1-4 are mentioned. Examples of the cyclic alkyl group include those having 3 to 8 carbon atoms which may have a substituent, such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group. Examples of the linear or branched alkoxy group for R _{1 to} R ₃₇ include a methoxy group, an ethoxy group,
Those having 1 to 4 carbon atoms such as a hydroxyethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a t-butoxy group are exemplified. Examples of the cyclic alkoxy group include a cyclopentyloxy group, for example, a cyclopentyloxy group and a cyclohexyloxy group. Examples of the halogen atom for R _{1 to} R ₃₇ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the aryl group for R ₃₈ include those having 6 to 14 carbon atoms which may have a substituent such as a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group.

As these substituents, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom,
A chlorine atom, an iodine atom), an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cyano group, a hydroxy group, a carboxy group, an alkoxycarbonyl group, and a nitro group.

Further, R _{1 to} R ₁₅ , R _{16 to} R ₂₇ , R _{28 to} R
Of _37, two or more of formed by combining a single bond, carbon, oxygen, one selected sulfur, and nitrogen or 2
Examples of the ring containing more than one kind include a furan ring, a dihydrofuran ring, a pyran ring, a trihydropyran ring, a thiophene ring, a pyrrole ring, and the like. Specific examples (A1-1) to (A) of the photoacid generator that can be used in the present invention.
1-64) is shown below.

[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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The amount of the photoacid generator (A) is usually in the range of 0.001 to 40% by weight, preferably 0.01 to 20% by weight, based on the solid content in the composition. And more preferably in the range of 0.1 to 10% by weight. When the addition amount of the photoacid generator is less than 0.001% by weight, the sensitivity is lowered. When the addition amount is more than 40% by weight, the light absorption of the resist becomes too high, and the deterioration of the profile and the process (particularly baking) ) The margin is undesirably narrow.

[3] Acid Crosslinking Agent of the Present Invention (C) In the present invention, a compound capable of being crosslinked by an acid (hereinafter, appropriately referred to as an acid crosslinking agent or simply a crosslinking agent) is used together with an alkali-soluble resin and an acid generator. use. Here, a known acid crosslinking agent can be effectively used. Preferably,
One or more hydroxymethyl, alkoxymethyl, acyloxymethyl or alkoxymethyl ether groups, more preferably 2 to 16, more preferably 4 to 1
It is a compound or resin having zero or an epoxy compound.

More preferably, alkoxymethylated, acyloxymethylated melamine compounds or resins, alkoxymethylated, acyloxymethylated urea compounds or resins, hydroxymethylated, alkoxymethylated, acyloxymethylated phenol compounds or resins, and alkoxymethyl Examples include etherified phenol compounds and resins.

(I) As the phenol compound,
Preferably, it has a molecular weight of 1200 or less, contains 3 to 5 benzene rings in the molecule, further has two or more hydroxymethyl groups or alkoxymethyl groups in total, and has at least one of the hydroxymethyl group and the alkoxymethyl group. Phenol derivatives formed by concentrating on a benzene ring or binding by distribution can be given. By using such a phenol derivative, the effects of the present invention can be made more remarkable. The alkoxymethyl group bonded to the benzene ring preferably has 6 or less carbon atoms. Specifically, a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an i-propoxymethyl group, an n-butoxymethyl group, an i-butoxymethyl group,
A sec-butoxymethyl group and a t-butoxymethyl group are preferred. Further, an alkoxy-substituted alkoxy group such as a 2-methoxyethoxy group and a 2-methoxy-1-propyl group is also preferable. Among these phenol derivatives, particularly preferred ones are listed below.

[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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(Wherein L ^{1 to} L ⁸ may be the same or different and each represents a hydroxymethyl group, a methoxymethyl group or an ethoxymethyl group.) A phenol derivative having a hydroxymethyl group is A phenol compound having no hydroxymethyl group (compound wherein L ^{1 to} L ⁸ are hydrogen atoms in the above formula) and formaldehyde are reacted in the presence of a base catalyst. At this time, the reaction is preferably performed at a reaction temperature of 60 ° C. or lower in order to prevent resinification and gelation. Specifically, JP-A-6-282067 and JP-A-7-64
No. 285, for example.

A phenol derivative having an alkoxymethyl group can be obtained by reacting a corresponding phenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst. At this time, the reaction is preferably performed at a reaction temperature of 100 ° C. or less in order to prevent resinification and gelation. Specifically, it can be synthesized by a method described in European Patent EP632003A1 or the like. A phenol derivative having a hydroxymethyl group or an alkoxymethyl group synthesized as described above is preferable in terms of stability during storage, but a phenol derivative having an alkoxymethyl group is particularly preferable from the viewpoint of stability during storage.
Such a phenol derivative having two or more hydroxymethyl groups or alkoxymethyl groups in total and concentrated or linked to any benzene ring may be used alone. A combination of the above may be used.

(Ii) N-hydroxymethyl group, N-
As a compound having an alkoxymethyl group or an N-acyloxymethyl group, European Patent Publication (hereinafter referred to as “E
No. 0,133,216, West German Patent Nos. 3,634,671 and 3,711,264, and monomer-oligomer-melamine-formaldehyde condensates; Examples include urea-formaldehyde condensate and benzoguanamine-formaldehyde condensate disclosed in the alkoxy-substituted compound disclosed in EP-A-0,212,482. More preferred examples include, for example, melamine-formaldehyde derivatives having at least two free N-hydroxymethyl groups, N-alkoxymethyl groups, or N-acyloxymethyl groups, among which N-alkoxymethyl derivatives are particularly preferred. .

(Iii) Examples of the epoxy compound include monomer, dimer, oligomer, and polymer epoxy compounds containing one or more epoxy groups. For example, a reaction product of bisphenol A with epichlorohydrin, a reaction product of a low molecular weight phenol-formaldehyde resin with epichlorohydrin, and the like can be mentioned. In addition, US Pat. No. 4,026,705,
Epoxy resins described and used in British Patent No. 1,539,192 can be mentioned.

The crosslinking agent is used in an amount of generally 3 to 65% by weight, preferably 5 to 50% by weight, based on the total solid content of the resist composition. If the amount of the cross-linking agent is less than 3% by weight, the residual film ratio decreases, and if it exceeds 65% by weight, the resolving power decreases, and the stability of the resist solution during storage is not so preferable.

In the present invention, the above-mentioned (i) phenol compound may be added to, for example, another crosslinking agent (ii) as described above,
(Iii) can also be used in combination. The ratio of other cross-linking agents that can be used in combination with the phenol derivative is from 100/0 to 20/80, preferably from 90/10 to 4 in a molar ratio.
0/60, more preferably 80/20 to 50/50.

[4] (D) a compound that cleaves its own bond by irradiation with an electron beam or X-ray and / or causes cleavage of other components but does not generate a phenyl radical as an intermediate (hereinafter referred to as “( (D) Component) The component (D) used in the present invention includes (D) cleavage of its own bond by irradiation with an electron beam or X-ray, and / or cleavage of other components. Any compound can be used as long as it does not generate a phenyl radical as a compound, but a photo radical generator or a photo base generator is preferable.

Here, the fact that the bond itself is cleaved by irradiation with an electron beam or X-ray means that the covalent bond in the molecule is cleaved after receiving energy or electrons, as shown in the following formula.

[0103]

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In the formula, ¹ (DMPA) ^* represents a singlet excited state molecule of (DMPA), and ³ (DMPA) ^* represents (DMP
A) represents the triplet excited state molecule of A).

[0105] In addition, "to cause cleavage of another component by irradiation with an electron beam or X-ray" means that after receiving energy or electrons, it reacts with another molecule and causes cleavage of a bond of another molecule without dissociation itself. Means that. For example,
When a hydrogen donor is added to an aromatic ketone (the following formula), the following hydrogen abstraction reaction occurs between two molecules, and a ketyl radical is generated.

[0106]

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[0107] In the formula, Ph ₂ C = O ¹ denotes a singlet excited state molecule of _{Ph 2 C = O, Ph 2} C = O 3 is Ph ₂ C =
Represents a triplet excited state molecule of O.

The phenyl radical means a component (component (2) in the following formula) generated by cleavage of a bond directly connected to a benzene ring as shown in the following formula.

[0109]

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Further, a compound that does not generate a phenyl radical as an intermediate refers to a compound in which cleavage of the bond by electron beams and X-rays is suppressed because the bond directly linked to the benzene ring is relatively stable. .

The photo-radical generator is preferably (a) an aromatic or alicyclic ketone, (b) an organic peroxide, (c) a hexaarylbiimidazole compound,
(D) ketoxime ester compounds, (e) azinium compounds, (f) active ester compounds, (g) compounds having a carbon-halogen bond, and the like.

Preferred examples of component (D) (a) aromatic or alicyclic ketones include “RADIATION CU”.
RING IN POLYMER SCIENCE AND TECHNOLOGY '' JPFOUASS
Compounds having a benzophenone skeleton or thioxanthone skeleton described in IERJ.F.RABEK (1993), pp. 77-117. As (a) aromatic or alicyclic ketones, aromatic ketones are preferred. Below, (a)
Specific examples of aromatic or alicyclic ketones will be described, but the present invention is not limited thereto.

[0113]

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[0114]

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[0115]

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[0116]

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Preferred examples of the aromatic ketones include α-thiobenzophenone compounds described in JP-B-47-6416 and benzoin ether compounds described in JP-B-47-3981.

[0118]

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An α-substituted benzoin compound described in JP-B-47-22326, for example,

[0120]

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Benzoin derivatives described in JP-B-47-23664, aroylphosphonic esters described in JP-A-57-30704, dialkoxybenzophenones described in JP-B-60-26483, for example,

[0122]

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JP-B-60-26403, JP-A-62-8
Benzoin ethers described in 1345, for example,

[0124]

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Japanese Patent Publication No. 1-34242, US Patent No. 4,3
18,791 and α-aminobenzophenones described in EP 0284561A1, for example,

[0126]

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P-Di (dimethylaminobenzoyl) benzene described in JP-A-2-21452, for example,

[0128]

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A thio-substituted aromatic ketone described in JP-A-61-194062, for example,

[0130]

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The acylphosphine sulfide described in JP-B-2-9597, for example,

[0132]

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An acylphosphine described in JP-B-2-9596, for example,

[0134]

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The thioxanthones described in JP-B-63-61950 and the coumarins described in JP-B-59-42864 can be exemplified.

(B) "Organic peroxide" which is another example of the component (D) used in the present invention includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. However, examples thereof include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,
5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane,
1,1-bis (tert-butylperoxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramethane hydroperoxide Oxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, ditertiary butyl peroxide, tertiary butyl cumyl peroxide, dicumyl peroxide , Bis (tert-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy)
Hexane, 2,5-xanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, meta-toluoyl peroxide, diisopropylperoxydicarbonate, di-2
-Ethylhexyl peroxydicarbonate, di-2-
Ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tertiary butylperoxyacetate, tertiary butylperoxypivalate, tertiary butylperoxyneo Decanoate, tertiary butyl peroxyoctanoate, tertiary butyl peroxy-
3,5,5-trimethylhexanoate, tertiary butyl peroxylaurate, tertiary carbonate, 3,3'4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3'4 4'-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3'4,4 '
-Tetra- (t-octylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (cumylperoxycarbonyl) benzophenone, 3,3'4,4 '
-Tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate), carbonyldi (t-hexylperoxydihydrogen diphthalate) and the like.

Of these, 3,3'4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3'4
Peroxide esters such as 4'-tetra- (cumylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, di-t-butyldiperoxyisophthalate Systems are preferred.

Examples of (c) hexaarylbiimidazole compounds which are other examples of the component (D) used in the present invention include JP-B-45-37377 and JP-B-44-8651.
Lophine dimers described in No. 6, for example, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) -4 , 4 ', 5,5'-Tetraphenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis ( o-chlorophenyl) -4,
4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2, 2'-bis (o-nitrophenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole, 2,
2'-bis (o-methylphenyl) -4,4 ', 5
5'-tetraphenylbiimidazole, 2,2'-bis (o-trifluorophenyl) -4,4 ', 5,5'-
And tetraphenylbiimidazole.

Other examples of the component (D) used in the present invention, which is (d) a ketoxime ester compound, include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentane-
3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyimiminobtan-2-one, 2- Ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

Another example of the component (D) of the present invention is (e).
Examples of azinium salt compounds are described in JP-A-63-138.
No. 345, JP-A-63-142345, JP-A-63-142345
No. 142346, JP-A-63-143537 and JP-B-46-43363.

Examples of the active ester compound (f), which is another example of the component (D), include imide sulfonate compounds described in JP-B-62-6223, JP-B-63-14340,
Active sulfonates described in JP-A-59-174831 can be mentioned.

Preferred examples of the compound (g) having a carbon-halogen bond, which is an example of the component (D), include those represented by the following general formulas [IV] to [X].

[0143]

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(Wherein X ² represents a halogen atom; Y ²
Represents _{^{-CX 2, -NH 2, -NHR 32}} -NR 32, an -OR ^32. Here, ^R32 represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. R ³¹ is -CX
^{2 represents} an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group. ).

[0145]

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(Where R ³³ is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a halogen atom, an alkoxy group, a substituted alkoxyl group, a nitro group or a cyano group; ^Two
Is a halogen atom, and n is an integer of 1 to 3. ).

[0147]

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(Where R ³⁴ is an aryl group or a substituted aryl group, and R ³⁵ is

[0149]

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Or Z ² is —C (＝ O)
—, —C (＝ S) — or —SO ₂ —, and R ³⁶ , R ³⁷
Is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group;
³⁸ is the same as R ³² in the general formula [IV], X ³ is a halogen atom, and m is 1 or 2. ).

[0151]

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In the formula, R ³⁹ is an aryl group or a heterocyclic group which may be substituted, and R ⁴⁰ is carbon atom 1
A trihaloalkyl or trihaloalkenyl group having up to 3; and p is 1, 2 or 3.

[0153]

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(Where L is a hydrogen atom or a compound of the formula: CO—
^{_{(R 41) q (CX 3}} 4) are substituents of _r, Q is sulfur, selenium or oxygen atom, a dialkyl methylene group, alkene -
A 1,2-ylene group, a 1,2-phenylene group or an NR group, M is a substituted or unsubstituted alkylene group or alkenylene group, or a 1,2-arylene group;
R ⁴² is an alkyl group, an aralkyl group or an alkoxyalkyl group; R ⁴¹ is a carbocyclic or heterocyclic divalent aromatic group; X ⁴ is a chlorine, bromine or iodine atom; And r = 1 or q = 1 and r = 1 or 2. A) a carbonylmethylene heterocyclic compound having a trihalogenomethyl group;

[0155]

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(Where X ⁵ is a halogen atom, t
Is an integer of 1 to 3, s is an integer of 1 to 4, R ⁴³
A hydrogen atom or a CH _3-t X ⁵ _t group, R ⁴⁴ is represented by a is) s-valent optionally substituted unsaturated organic group, 4- halogeno-5- (halogenomethyl-phenyl) -
-Oxazole derivatives.

[0157]

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(Where X ⁶ is a halogen atom;
Is an integer of 1 to 3, u is an integer of 1 to 4, R ⁴⁵
Is a hydrogen atom or a CH _3-v X ⁶ _v group, R ⁴⁶ is an unsaturated organic group which may be substituted for u-valent. ), A 2- (halogenomethyl-phenyl) -4-halogeno-oxazole derivative.

Specific examples of such a compound having a carbon-halogen bond are described, for example, in Wakabayashi et al., Bull.
em. Soc. Japan, 42 , 2924 (1969), for example, 2-phenyl 4,6-bis (trichloromethyl) -S-triazine, 2- (p-chlorophenyl) -4,6-bis ( Trichloromethyl) -S-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S -Triazine, 2- (2 ', 4'-dichlorophenyl) -4,6
-Bis (trichloromethyl) -S-triazine, 2,
4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6-bis (trichloromethyl)-
S-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -S-triazine, 2- (α, α, β-
Trichloroethyl) -4,6-bis (trichloromethyl) -S-triazine and the like. Other compounds described in GB 1388492, for example, 2
-Styryl-4,6-bis (trichloromethyl) -S-
Triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-
(Methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl)
Compounds described in JP-A-53-133428, such as -4-amino-6-trichloromethyl-S-triazine, for example, 2- (4-methoxy-naphth-1-yl) -4,6
-Bis-trichloromethyl-S-triazine, 2- (4
-Ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl -S-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine), 2- (acenaphth-5-
Yl) -4,6-bis-trichloromethyl-S-triazine, such as the compounds described in DE 3337024, for example,

[0160]

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[0161]

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And the like. Also, FC Sc
Haefer et al., J. Org. Chem. 29, 1527 (196
The compounds described in 4), for example, 2-methyl-4,6-bis (tribromomethyl) -S-triazine, 2,4,6-
Tris (tribromomethyl) -S-triazine, 2,
4,6-tris (dibromomethyl) -S-triazine,
2-amino-4-methyl-6-tribromomethyl-S-
Triazine, 2-methoxy-4-methyl-6-trichloromethyl-S-triazine and the like can be mentioned. Further, compounds described in JP-A-62-58241, for example,

[0163]

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[0164]

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And the like. Further, Japanese Patent Laid-Open No. 5-
No. 281,728, for example,

[0166]

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[0167]

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And the like. Or even more
Jo by MP Hutt, EF Elslager and LM Herbel
urnalof Heterocyclic chemistry ", Vol. 7 (No.
3) The following compound groups that can be easily synthesized by those skilled in the art according to the synthesis methods described on pages 511 et seq. (1970).

[0169]

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[0170]

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[0171]

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[0172]

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[0173]

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[0174]

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Alternatively, compounds such as described in DE-A-2641100, for example 4- (4-methoxy-styryl) -6- (3,3,3-trichloropropenyl) -2-pyrone and 4- (3,4,5-trimethoxy-styryl) -6-trichloromethyl-2-pyrone or the compounds described in DE 33 33 450, for example,

[0176]

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In the formula, R ⁴¹ represents a benzene ring, and R ⁴² represents an alkyl group, an aralkyl group or an alkoxyalkyl group.

[0178]

[Table 1]

Alternatively, a group of compounds described in German Patent No. 3021590,

[0180]

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[0181]

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Alternatively, a group of compounds described in German Patent No. 3021599, for example,

[0183]

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The following can be mentioned.

The photobase generator preferably includes (h) a photochromic compound, (i) a benzyl carbamate, (j) a sulfonamide, and (k) an acyloxyimino.

(H) Examples of the photochromic compound include spiropyrans and spirooxazines. Specific examples include the following compounds. 1,3,3-trimethylindolinobenzopyrrospirane, 1,3,3-trimethylindolino-8'-methoxybenzopyrrolospirane, 1,3,3-trimethylindolino-β-naphthopyrrolospirane, 1,3,3-
Trimethylindolinonaphthospiroxazine, 1,
3,3-trimethylindonori-6'-nitrobenzopyrrospirane, 1,3,3-trimethylindonori
6'-bromobenzopyrrolospirane, 1,3,3-trimethylindonori-6'-hydroxybenzopyrrolospirane and the like.

(I) Examples of benzyl carbamates include those having a carbamate group represented by the following general formula. These generate a base amine by irradiation with an electron beam or X-ray, for example, by the following reaction.

[0188]

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[0189]

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In the above formula, Ar represents a nitro-substituted aromatic group or an aromatic group, R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group or an aromatic group, and X represents an alkylene group.

The alkyl group for R ¹ , R ² and R ³ is preferably an alkyl group having 1 to 20 carbon atoms. Specifically, methyl, ethyl, propyl, isopropyl and n-
Butyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, tert-amyl group, hexyl group, heptyl group, octyl group, cyclopentyl group,
Examples include cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, adamantyl, decanyl, lauryl, partimyl, stearyl, and the like.

The aromatic groups represented by Ar, R ¹ , R ² and R ³ are preferably those having 6 to 20 carbon atoms.
Phenyl group, naphthyl group, biphenyl group, phenanthrenyl group, anthranyl group, fluorenyl group, pyrene group, etc., p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p
-Tert-butoxyphenyl group, alkoxyphenyl group such as m-tert-butoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, alkylphenyl group such as dimethylphenyl group, methylnaphthyl group, alkylnaphthyl group such as ethylnaphthyl group, methoxynaphthyl group, alkoxynaphthyl group such as ethoxynaphthyl group, dimethylnaphthyl group, diethylnaphthyl group and the like Examples thereof include dialkoxynaphthyl groups such as dialkylnaphthyl group, dimethoxynaphthyl group, and diethoxynaphthyl group. Examples of the alkylene group for X include a methylene group, an ethylene group, a trimethylene group, a propylene group, and a tetramethylene group.

(I) Specific examples of benzyl carbamates include nitrobenzylcyclohexyl carbamate,
Nitrobenzylcyclohexyl carbamate, 3,5-
Dimethoxybenzylcyclohexyl carbamate, 3-
Nitrophenylcyclohexyl carbamate, benzylcyclohexyl carbamate, 2,5-dinitrobenzylcyclohexyl carbamate, [[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine,
[[(2-nitrobenzyl) oxy] carbonyl] piperidine, bis [[(2-nitrobenzyl) oxy] carbonyl] piperazine, bis [[(2-nitrobenzyl)
Oxy] carbonyl] hexene-1,6-diamine,
[[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] hexene-1,6-
Diamine, N-[[(2-nitrophenyl) -1-methylmethoxy] carbonyl] cyclohexylamine, N-
[[(2-nitrophenyl) -1-methylmethoxy] carbonyl] octadecylamine, bis [[(α-methyl-2-nitrobenzyl) oxy] carbonyl] hexane-1,6-diamine, N-[[(2 , 6-Dinitrophenyl) -1-methylmethoxy] carbonyl] cyclohexylamine, N-[[(2-nitrophenyl) -1-
(2'-nitrophenyl) methoxy] carbonylcyclohexylamine, N-[[(2,6-dinitrophenyl) -1- (2 ', 6'-dinitrophenyl) methoxy] carbonyl] cyclohexylamine and the like. Among the above, nitrobenzylcyclohexyl carbamate and 2,5-dinitrobenzylcyclohexyl carbamate are more preferred.

(J) Examples of the sulfonamides include those having a sulfonamide group represented by the following general formula. These generate a base amine by irradiation with an electron beam or X-ray, for example, by the following reaction.

[0195]

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In the above formula, Ar represents a nitro-substituted aromatic group or an aromatic group, and R ² and R ³ represent a hydrogen atom, an alkyl group or an aromatic group.

The alkyl group for R ² and R ³ has 1 carbon atom.
To 20 are preferred, and specifically, methyl, ethyl, propyl, isopropyl, n-butyl, s
ec-butyl, tert-butyl, pentyl, isopentyl, tert-amyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4
-Methylcyclohexyl group, cyclohexylmethyl group,
Examples thereof include a norbornyl group, an adamantyl group, a decanyl group, a lauryl group, a partimyl group, and a stearyl group.

As the aromatic groups for Ar, R ² and R ³ ,
Those having 6 to 20 carbon atoms are preferable, and specifically, a phenyl group, a naphthyl group, a biphenyl group, a phenanthrenyl group, an anthranyl group, a fluorenyl group, a pyrene group, and the like,
p-methoxyphenyl group, m-methoxyphenyl group, o
-Methoxyphenyl group, ethoxyphenyl group, p-te
an alkoxyphenyl group such as an rt-butoxyphenyl group, an m-tert-butoxyphenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group,
Ethylphenyl group, 4-tert-butylphenyl group,
4-butylphenyl group, alkylphenyl group such as dimethylphenyl group, methylnaphthyl group, alkylnaphthyl group such as ethylnaphthyl group, methoxynaphthyl group, alkoxynaphthyl group such as ethoxynaphthyl group, dimethylnaphthyl group, diethylnaphthyl group and the like Dialkylnaphthyl group,
Examples include dialkoxynaphthyl groups such as dimethoxynaphthyl group and diethoxynaphthyl group.

(J) Specific examples of the sulfonamides include N-cyclohexyl-4-methylphenylsulfonamide, N-cyclohexyl-2-naphthylsulfonamide, N, N'-diethyl-4-methylphenylsulfonamide and the like. Is mentioned. Among the above, N-cyclohexyl-4-methylphenylsulfonamide, N, N '
-Diethyl-4-methylphenylsulfonamide is more preferred.

(K) Examples of the acyloxyimino include those having an acyloxyimino group represented by the following general formula.

[0201]

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In the above formula, R, R 'and R "represent a hydrogen atom, an alkyl group or an aromatic group.

The alkyl group for R, R 'and R "is preferably an alkyl group having 1 to 20 carbon atoms.
Ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, tert-amyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, Examples thereof include a cycloheptyl group, a cyclopropylmethyl group, a 4-methylcyclohexyl group, a cyclohexylmethyl group, a norbornyl group, an adamantyl group, a decanyl group, a lauryl group, a partimyl group, and a stearyl group.

The aromatic group represented by R, R 'and R "is preferably an aromatic group having 6 to 20 carbon atoms.
Naphthyl group, biphenyl group, phenanthrenyl group, anthranyl group, fluorenyl group, pyrene group and the like, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, alkoxyphenyl groups such as m-tert-butoxyphenyl group, 2-methylphenyl group, 3
Alkylphenyl groups such as -methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group and dimethylphenyl group; alkylnaphthyl groups such as methylnaphthyl group and ethylnaphthyl group Alkoxynaphthyl groups such as methoxynaphthyl group and ethoxynaphthyl group; dialkylnaphthyl groups such as dimethylnaphthyl group and diethylnaphthyl group; and dialkoxynaphthyl groups such as dimethoxynaphthyl group and diethoxynaphthyl group.

Specific examples of the (k) acyloxyimino include, for example, the following (k) -1 to (k) -3, but the present invention is not limited to these specific examples. .

[0206]

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Among these, (k) -1 is more preferred.

More preferred examples of the component (D) in the present invention include the above-mentioned (a) aromatic ketones, (c) hexaarylbiimidazole compound, (f) active ester compound, and (g) carbon-halogen bond. A compound having
(H) a photochromic compound and (i) a benzyl carbamate, and most preferably, (c) a hexaarylbiimidazole compound,
(G) a compound having a carbon-halogen bond, and (i) benzyl carbamates. Component (D) in the present invention is suitably used alone or in combination of two or more.

The amount of the compound (D) to be added is usually in the range of 0.001 to 40% by weight, preferably 0.01 to 20% by weight, more preferably 0.01 to 20% by weight, based on the solid content in the composition. Preferably, it is used in the range of 0.1 to 10% by weight. If the amount of the compound (D) is less than 0.001% by weight, the effect of the addition cannot be obtained. If the amount is more than 40% by weight, the light absorption of the resist becomes too high, and the profile deteriorates, The process (especially baking) margin is unfavorably reduced.

[5] (E) Nitrogen-Containing Basic Compound The resist composition of the present invention preferably contains, as the component (E), a nitrogen-containing basic compound having no acidic group. This has the effect of improving the resolution. The preferred organic basic compound having no acidic group that can be used in the present invention is a compound that is more basic than phenol. The acidic groups that the organic basic compound does not have include phenolic hydroxyl groups, sulfonic acid groups, and phosphoric acid groups. In particular, a nitrogen-containing basic compound having no acidic group is preferable, and examples thereof include compounds having the following structures.

[0211]

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Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl having 1 to 6 carbon atoms. A substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ²⁵¹ and R ²⁵² may be bonded to each other to form a ring.

[0213]

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(Wherein R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R
²⁵⁶ independently represent an alkyl group having 1 to 6 carbon atoms.) Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule,
Particularly preferred are compounds containing both a substituted or unsubstituted amino group and a ring structure containing a nitrogen atom, or compounds having an alkylamino group. Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazol, substituted or unsubstituted Pyrazole, substituted or unsubstituted pyrazine,
Substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted aminomorpholine, substituted or unsubstituted amino And alkyl morpholine. Preferred substituents are an amino group, an aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group,
A hydroxyl group and a cyano group.

Preferred specific examples of the nitrogen-containing basic compound include guanidine, 1,1-dimethylguanidine,
1,3,3, -tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine,
-Dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-
Amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-amino Ethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) Pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-
3-methyl-1-p-tolylpyrazole, pyrazine, 2
-(Aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-
Aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-diazabicyclo [4.3.0] nona-
5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabicyclo [2.2.2]
Octane, 2,4,5-triphenylimidazole, N
-Methylmorpholine, N-ethylmorpholine, N-hydroxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholinoethylthiourea (CHMET
U) and other tertiary morpholine derivatives, JP-A-11-5257
No. 5 hindered amines (for example, those described in the gazette [0005]) and the like, but are not limited thereto.

Particularly preferred specific examples are 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabicyclo [2.2.2] Tertiary morpholines such as octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, pyrroles, pyrazoles, imidazoles, pyridazines, pyrimidines, CHMETU, etc., and bis Hindered amines such as (1,2,2,6,6-pentamethyl-4-piperidyl) sebagate and the like can be mentioned.

Among them, 1,5-diazabicyclo [4.
3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabicyclo [2.2.2] octane, 4-dimethylaminopyridine, hexamethylene Preferred are tetramine, CHMETU, and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate.

These basic compounds having no acidic group are used alone or in combination of two or more.
The amount used is usually from 0.001 to 10% by weight, preferably from 0.01 to 5% by weight, based on the solid content of the total composition of the radiation-sensitive resist composition. If the amount is less than 0.001% by weight, the effect of the addition of the basic compound cannot be obtained. Meanwhile, 1
If it exceeds 0% by weight, the sensitivity tends to decrease and the developability of the unexposed area tends to deteriorate.

[6] (F) Surfactant The resist composition of the present invention contains, as the component (F), a fluorine-containing surfactant, a silicon-containing surfactant and a surfactant containing both a fluorine atom and a silicon atom. Either or 2
Preferably, it contains more than one species. This is effective in reducing the particle initial value when the resist component is dissolved in the solvent.

As these surfactants, for example, those described in
No. 62-36663, JP-A-61-226746, JP-A-61-226745,
JP-A-62-170950, JP-A-63-34540, JP-A-7-23016
No. 5, JP-A-8-62834, JP-A-9-54432, JP-A-9-598
No. 8, U.S. Pat.No. 5,405,720, No. 5360692, No. 5529881,
No. 5296330, No. 5436098, No. 5576143, No. 5294511
And the surfactants described in Nos. 5824451 and 5824451, and the following commercially available surfactants can be used as they are. As commercially available surfactants, for example, F-top EF301, EF303, (manufactured by Shin-Akita Chemical Co., Ltd.), Florad FC43
0, 431 (Sumitomo 3M Limited), Mega Fuck F171, F1
73, F176, F189, R08 (Dai Nippon Ink Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Troysol S-366 (Troy Chemical Co., Ltd.) )) Or a silicon-based surfactant. Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicon-based surfactant.

The compounding amount of the fluorine-based and / or silicon-based surfactant is usually 0.001% by weight to 2% by weight, preferably 0.1% by weight, based on the solid content in the composition of the present invention.
It is from 01% by weight to 1% by weight. These surfactants may be added alone or in some combination.

Examples of the surfactant that can be used in addition to the above include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether and the like. Polyoxyethylene alkyl allyl ethers such as ethylene alkyl ethers, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostea Sorbitan esters such as sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene Nonionics such as fatty acid esters of polyoxyethylene sorbitan such as rubitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Surfactants and the like.

The amount of these other surfactants is usually 2% by weight or less, preferably 1% by weight or less, more preferably 0.01% by weight, based on the solid content in the composition of the present invention.
１1% by weight.

[7] (G) Spectral Sensitizing Dye or Dye The resist composition of the present invention preferably further contains a known spectral sensitizing dye or dye as the component (G). Examples of preferred spectral sensitizing dyes or dyes include polynuclear aromatics (eg, pyrene, perylene, triphenylene) and xanthenes (eg, fluorescein, eosin,
Erythrosine, rhodamine B, rose bengal cyanines (eg, thiacarbocyanine, oxacarbocyanine) merocyanines (eg, merocyanine, carbomerocyanine) thiazines (eg, thionin, methylene blue, toluidine blue) acridines (eg, acridine orange, Chloroflavin, acriflavin) phthalocyanines (eg, phthalocyanine, metal phthalocyanine) porphyrins (eg, tetraphenylporphyrin, porphyrin substituted with a central metal) chlorophylls (eg, chlorophyll, chlorophyllin, chlorophyll substituted with a central metal) metal complexes, eg,

[0225]

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Anthraquinones, for example, (anthraquinone) squariums, for example, (squarium). More preferred examples of the spectral sensitizing dye or dye of the component (G) include styryl dyes described in JP-B-37-13034, for example,

[0227]

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The cationic dyes described in JP-A-62-143044, for example,

[0229]

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A quinoxalinium salt described in JP-B-59-24147, for example,

[0231]

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A new methylene blue compound described in JP-A-64-33104, for example,

[0233]

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Anthraquinones described in JP-A-64-56767, for example,

[0235]

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Benzoxanthene dyes described in JP-A-2-1714. JP-A-2-226148 and JP-A-2-2-2
No. 26149, acridines, for example,

[0237]

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Pyrylium salts described in JP-B-40-28499, for example,

[0239]

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Cyanines described in JP-B-46-43363, for example,

[0241]

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The benzofuran dyes described in JP-A-2-63053, for example,

[0243]

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JP-A-2-85858, JP-A-2-21
No. 6154 conjugated ketone dyes, for example

[0245]

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Dyes described in JP-A-57-10605. Azocinnamylidene derivatives described in JP-B-2-30321, for example,

[0247]

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Cyanine dyes described in JP-A-1-287105, for example,

[0249]

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JP-A-62-31844, JP-A-62-31844
No. 31848, Xanthene dyes described in JP-A-62-143043, for example,

[0251]

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An aminostyryl ketone described in JP-B-59-28325, for example,

[0253]

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The merocyanine dyes represented by the following formulas [1] to [8] described in JP-B-61-9621, for example,

[0255]

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In the general formulas [3] to [8], X ⁸
Is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxy group, an aryl group, a substituted aryl group, an aryloxy group,
Represents an aralkyl group or a halogen atom. General formula [2]
In the above, Ph represents a phenyl group. In the general formulas [1] to [8], R ⁴⁸ , R ⁴⁹ and R ⁵⁰ each represent an alkyl group, a substituted alkyl group, an alkenyl group, an aryl group, a substituted aryl group or an aralkyl group. Good. The following general formula described in Japanese Patent Application Laid-Open No. 2-179643

Dyes represented by [9] to [11], for example,

[0257]

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A: oxygen atom, sulfur atom, selenium atom,
Represents a tellurium atom, an alkyl or aryl substituted nitrogen atom or a dialkyl substituted carbon atom. Y ^{3 represents a} hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an acyl group, or a substituted alkoxycarbonyl group. R ⁵¹ and R ⁵² : a hydrogen atom, an alkyl group having 1 to 18 carbon atoms,
Alternatively, as a substituent, R ⁵³ O—,

[0259]

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-(CH ₂ CH ₂ O) w-R ⁵³ , a substituted alkyl group having 1 to 18 carbon atoms and having a halogen atom (F, Cl, Br, I). However, R ⁵³ is a hydrogen atom or a carbon number of 1 to 1.
0 represents an alkyl group, B represents a dialkylamino group,
Represents a hydroxyl group, an acyloxy group, a halogen atom, and a nitro group. w represents an integer of 0 to 4, and x represents an integer of 1 to 20. The following general formula [1] described in JP-A-2-244050
2) a merocyanine dye represented by, for example,

[0261]

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(Wherein R ⁵⁴ and R ⁵⁵ each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxycarbonyl group, an aryl group, a substituted aryl group or an aralkyl group. A ² represents an oxygen atom, a sulfur atom , A selenium atom, a tellurium atom, an alkyl- or aryl-substituted nitrogen atom, or a dialkyl-substituted carbon atom, and X ⁹ represents a group of non-metallic atoms necessary to form a nitrogen-containing 5-membered heterocyclic ring. ⁴ represents a substituted phenyl group, an unsubstituted or substituted polynuclear aromatic ring, or an unsubstituted or substituted heteroaromatic ring, and Z ³ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group,
Represents an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, a substituted amino group, an acyl group, or an alkoxycarbonyl group, which may be mutually bonded to Y ⁴ to form a ring. Preferred specific examples are

[0263]

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A merocyanine dye represented by the following formula [13] described in JP-B-59-28326, for example,

[0265]

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In the above formula, R ⁵⁶ and R ⁵⁷ each represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group,
Represents a substituted aryl group or an aralkyl group, which may be the same or different from each other. X ¹⁰ is Hammett (Hamm
ett) represents a substituent within the range of -0.9 to +0.5. A merocyanine dye represented by the following general formula [14] described in JP-A-59-89303, for example,

[0267]

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(Wherein R ⁵⁸ and R ⁵⁹ each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or an aralkyl group. X ¹¹ is Hammett's sigma (σ). Values from -0.9 to +0.
Represents up to 5 substituents. Y ⁵ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an acyl group or an alkoxycarbonyl group. As a preferred specific example,

[0269]

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A merocyanine dye represented by the following general formula [15] described in Japanese Patent Application No. 6-269047, for example,

[0271]

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(Wherein R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁸ ,
R ⁶⁹ , R ⁷⁰ and R ⁷¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group,
Substituted aryl group, hydroxyl group, substituted oxy group, mercapto group, substituted thio group, amino group, substituted amino group, substituted carbonyl group, sulfo group, sulfonato group, substituted sulfinyl group, substituted sulfonyl group, phosphono group, substituted phosphono group, phosphonato group, a substituted phosphonato group, a cyano group, or a nitro group, or, R ⁶⁰ and R ^61, R ⁶¹ and R ^62, R ⁶² and R ^63, R ⁶⁸ and R ^69, R ⁶⁹ and R ^70, R ⁷⁰ And R
⁷¹ may combine with each other to form an aliphatic or aromatic ring, R ⁶⁴ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group; R ⁶⁵ represents a substituted or unsubstituted group; substituted alkenyl group, or a substituted or unsubstituted alkynyl group, R ^66, R ⁶⁷
Are each independently a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group,
Preferred examples of the substituted carbonyl group)

[0273]

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A benzopyran-based dye represented by the following formula [16] described in Japanese Patent Application No. 7-164585, for example,

[0275]

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(Wherein, R ^{72 to} R ⁷⁵ independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group or an amino group; and R ^{72 to} R ⁷⁵
May form a ring consisting of a nonmetallic atom together with the carbon atoms to which they can each be attached. R ⁷⁶ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaromatic group, a cyano group, an alkoxy group, a carboxy group or an alkenyl group. R ⁷⁷
Is a group represented by R ⁷⁶ or —ZR ⁷⁶ , and Z represents a carbonyl group, a sulfonyl group, a sulfinyl group, or an arylenedicarbonyl group. R ⁷⁶ and R ⁷⁷ may together form a ring composed of a non-metallic atom. A is O atom, S
Represents an atom, NH or an N atom having a substituent. B is O
Represents an atom or a group of ＣC (G ¹ ) (G ² ). G ¹ , G ²
May be the same or different, and represent a hydrogen atom, a cyano group,
Represents an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an arylcarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or a fluorosulfonyl group. However, G ¹ and G ² are not simultaneously hydrogen atoms. G ¹ and G ² may form a ring composed of a nonmetallic atom together with the carbon atom). And the like.

More preferred examples of the component (G) in the present invention include the merocyanine dyes described in JP-B-61-9621, the merocyanine dyes described in JP-A-2-179463, and JP-A-2-244050. Merocyanine dyes, merocyanine dyes described in JP-B-59-28326, merocyanine dyes described in JP-A-59-89303, merocyanine dyes described in Japanese Patent Application No. 6-269047, and benzopyran-based dyes described in Japanese Patent Application No. 7-164585. Can be mentioned. (G) in the present invention
The components are suitably used alone or in combination of two or more.

Further, to the photopolymerizable composition of the present invention, a known compound having an action of further improving sensitivity or suppressing polymerization inhibition by oxygen may be added as a co-sensitizer.

Examples of such co-sensitizers include amines, for example, MR Sander et al., Journal of Polymer Soc.
Society, Vol. 10, p. 3173 (1972);
No. 20189, JP-A-51-82102, JP-A-52
-134692, JP-A-59-138205, JP-A-60-84305, JP-A-62-18537, JP-A-64-33104, Research Disclosure 3382
No. 5 and the like, and specific examples include triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

Other examples of the co-sensitizer include thiols and sulfides, for example, thiol compounds described in JP-A-53-702, JP-B-55-500806, and JP-A-5-142772; No. 75643, specifically, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, and the like. Is raised.

As another example, amino acid compounds (eg, N-phenylglycine, etc.) and JP-B-48-429 may be used.
No. 65, organometallic compounds (eg, tributyltin acetate, etc.), hydrogen donors described in JP-B-55-34414, and sulfur compounds described in JP-A-5-91089 (eg,
Trithiane, etc.), phosphorus compounds described in Japanese Patent Application No. 5-32147 (diethyl phosphite, etc.), and Japanese Patent Application No. 6-1916.
And Si-H and Ge-H compounds described in No. 05.

When the above-mentioned co-sensitizer is used, it is usually used in an amount of preferably 0.01 to 50% by weight, more preferably 0.02 to 20% by weight, based on the solid content in the composition.
%, Most preferably 0.05 to 10% by weight.

The composition of the present invention is dissolved in a solvent in which each of the above components is dissolved, and coated on a support. As the solvent used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethyl Formamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable. Or mixed to use.

In the manufacture of precision integrated circuit elements, the pattern formation step on a resist film is performed by forming a negative (the negative) of the present invention on a substrate (eg, a silicon / silicon dioxide skin cover, a glass substrate, a transparent substrate such as an ITO substrate, etc.). A photoresist pattern is formed by applying a photoresist composition and then irradiating with an electron beam (under an acceleration voltage of 75 keV or more) or an X-ray lithography apparatus, and heating, developing, rinsing, and drying to form a good resist pattern. can do.

Examples of the developer for the negative photoresist composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; ethylamine;
primary amines such as n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, Aqueous solutions of alkalis such as quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, and cyclic amines such as pyrrole and piperidine can be used. Further, an appropriate amount of an alcohol such as isopropyl alcohol or a surfactant such as a nonionic surfactant may be added to an aqueous solution of the above alkalis. Of these developers, quaternary ammonium salts are preferred, and tetramethylammonium hydroxide and choline are more preferred.

[0286]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the contents of the present invention are not limited thereto.

[Synthesis Example 1 (Synthesis of Resin Example (1))] 500 ml of dehydrated tetrahydrofuran was added with n as a polymerization catalyst.
After adding 0.004 mol of -butyllithium and cooling to -78 ° C, a solution of 35 g (0.20 mol) of 3-t-butoxystyrene, also cooled to -78 ° C, in 20 ml of tetrahydrofuran was added and stirred for 1 hour. Was. Thereafter, 10 ml of methanol was added to the reaction solution to stop the polymerization reaction. The resulting reaction solution was poured into methanol with stirring to precipitate a white resin. The precipitated resin was filtered and dried, and then dissolved in acetone (300 ml).
% Hydrochloric acid was added, and the mixture was heated and stirred at 60 ° C. for 8 hours. Thereafter, the mixture was poured into 2 L of ion-exchanged water with stirring to precipitate a white resin. After washing with deionized water and drying under reduced pressure, 19.2 g of the resin (1) of the present invention was obtained.
I got By NMR measurement, it was confirmed that the structure of the resin was Compound Example (1), and when the molecular weight was measured by GPC, the weight average (Mw: in terms of polystyrene) was 5,100, and the molecular weight distribution (Mw / Mn). Was 1.1.

[Synthesis Example 2 (Synthesis of Resin Example (19))] In place of 35 g of 3-t-butoxystyrene in Synthesis Example 1,
24.7 g (0.14 mol) of 3-t-butoxystyrene
18.6 g (0.06 mol) of 4-t-butoxystyrene and 18.6 g of the resin (19) of the present invention were synthesized in the same manner as in Synthesis Example 1 except for the above. NMR measurement confirmed that the structure of the resin was Compound Example (1),
When the molecular weight was measured by GPC, the weight average (M
w: 4,900 in terms of polystyrene; molecular weight distribution (M
(w / Mn) was 1.1.

[Synthesis Example 3 (Synthesis of Resin Example (24))] Instead of 35 g of 3-t-butoxystyrene in Synthesis Example 1,
30 g (0.17 mol) of 3-t-butoxystyrene and 4.9 g (0.03 mol) of 3,4-dimethoxystyrene
In the same manner as in Synthesis Example 1, 19.6 g of the resin (24) of the present invention was synthesized. NMR measurement confirmed that the structure of the resin was Compound Example (1).
When the molecular weight was measured with a PC, the weight average (Mw: in terms of polystyrene) was 4,500, and the molecular weight distribution (Mw / M
n) was 1.2.

[Synthesis Example 4 (Synthesis of Resin Example (35))] 3
-T-butoxystyrene 30 g (0.17 mol), 1-
4.6 g (0.03 mol) of vinylnaphthalene, 50 m of polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.)
g was dissolved in 1-methoxy-2-propanol (80 ml) and added dropwise over 2 hours to 1-methoxy-2-propanol (20 ml) heated to 70 ° C under a nitrogen stream and stirring. After 2 hours, 50 mg of an initiator was added, and the reaction was further performed for 2 hours. Thereafter, the temperature was raised to 90 ° C., and stirring was continued for 1 hour.
After allowing the reaction solution to cool, it was poured into 1 L of ion exchanged water with vigorous stirring to precipitate a white resin. After filtering and drying the obtained resin, it was dissolved in 300 ml of acetone,
3 ml of 36% hydrochloric acid was added, and the mixture was heated and stirred at 60 ° C. for 8 hours. Thereafter, the mixture was poured into 2 L of ion-exchanged water with stirring to precipitate a white resin. Washing with ion-exchanged water, drying under reduced pressure, dissolving in methanol and reprecipitating in hexane were repeated twice, and the resin of the present invention (3
5) 15.8 g were obtained. By NMR measurement, it was confirmed that the structure of the resin was Compound Example (35), and when the molecular weight was measured by GPC, the weight average (Mw: in terms of polystyrene) was 6,800, and the molecular weight distribution (Mw / Mn). Was 1.3. Hereinafter, the resin of the present invention (B) was synthesized in the same manner.

Synthesis of Crosslinking Agent [HM-1] 20 g of 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] -4- [α, α-bis (4-hydroxyphenyl) ethyl] benzene (Honshu Chemical Industry Co., Ltd. T
risp-PA) was added to a 10% aqueous potassium hydroxide solution, and the mixture was stirred and dissolved. Then, while stirring this solution, 3
60 ml of a 7% aqueous formalin solution was gradually added at room temperature over 1 hour. After stirring at room temperature for 6 hours, the mixture was thrown into a dilute aqueous sulfuric acid solution. The precipitate was filtered, washed sufficiently with water, and recrystallized from 30 ml of methanol to obtain 20 g of a white powder of a phenol derivative having a hydroxymethyl group [HM-1] having the following structure. The purity was 92% (liquid chromatography method).

[0292]

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Synthesis of Crosslinking Agent [MM-1] 20 g of the phenol derivative having a hydroxymethyl group [HM-1] obtained in the above Synthesis Example was added to 1 liter of methanol, and the mixture was heated and stirred to dissolve. Next, 1 ml of concentrated sulfuric acid was added to this solution, and the mixture was heated under reflux for 12 hours. After the completion of the reaction, the reaction solution was cooled, and 2 g of potassium carbonate was added. After sufficiently concentrating this mixture, 300 ml of ethyl acetate was added. The solution was washed with water and concentrated to dryness to obtain 22 g of a white solid of a phenol derivative having a methoxymethyl group [MM-1] having the following structure. 90 purity
% (Liquid chromatography method).

[0294]

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Further, the following phenol derivatives were synthesized in the same manner.

[0296]

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[Examples 1 to 18 and Comparative Examples 1 to 8] (1) Coating of resist 2.0 g of resin shown in Table 2 below, 0.035 g of photoacid generator shown in Table 2 and crosslinking shown in Table 2 1.6 g of the agent, 0.020 g of the compound (D) shown in Table 2, 0.0015 g of the nitrogen-containing basic compound shown in Table 2, and 0.1 g of the surfactant shown in Table 2.
001 g and 0.020 g of the component (G) shown in Table 2.
g was dissolved in a solvent shown in Table 2 to prepare a resist composition of the present invention.

Each sample solution was treated with 0.1 μm Teflon (R).
After filtration with a filter made by Co., Ltd., it was applied on a silicon wafer treated with hexamethyldisilazane by a spin coater, and dried by heating on a vacuum-contacting hot plate at 110 ° C. for 90 seconds to form a resist having a thickness of 0.3 μm. A membrane was obtained.

[0299]

[Table 2]

In Table 2, resins (1), (4),
(8), (19), (20), (24), (25),
The compositions (molar ratios) and molecular weights of (35), (40), (44) and (52) are as follows.

(1): Mw = 5,000, Mw / Mn = 1.3 (4): Mw = 5,500, Mw / Mn = 1.2 (5): Mw = 12,300, Mw / Mn = 1.8 (8): Mw = 6,400, Mw / Mn = 1.2 (19): x / y = 70/30, Mw = 4,900, Mw / Mn = 1.1 (20): x / y = 85/15, Mw = 5,800, Mw / Mn = 1.1 (24): x / y = 85/15, Mw = 4,500, Mw / Mn = 1.2 (25): x / y = 85/15, Mw = 5,200, Mw / Mn = 1.2 (35): x / y = 85/15, Mw = 6,800, Mw / Mn = 1.3 (40): x / y = 80/20, Mw = 6,300, Mw / Mn = 1.1 (44): x / y / z = 85/10/5, Mw = 4,600 Mw / Mn = 1.2 (52): x / y = 80/20, Mw = 7,200, Mw / Mn = 1.3

The ratio in the case of using two kinds of acid generators in Table 2 is a weight ratio. Further, the crosslinking agents CL-1, CL-2
Is:

[0303]

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The compounds (D) in Table 2 are as follows.

[0305]

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[0306]

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The nitrogen-containing basic compounds in Table 2 are as follows. 1: 1,8-diazabicyclo [4.3.0] nona-5
-Ene 2: 2,6-diisopropylaniline 3: 4-dimethylaminopyridine 4: 2,4,5-triphenylimidazole 5: triethylamine 6: 1,5-diazabicyclo [4.3.0] nona-5
-Ene 7: 1,5-diazabicyclo [2.2.2] octane 8: hexamethylenetetramine 9: CHMETU 10: bis (1,2,2,6,6-pentamethyl-4)
-Piperidyl) sebagate 11: piperazine 12: phenylguanidine

The surfactants in Table 2 are as follows. W1: Megafac F176 (manufactured by Dainippon Ink and Chemicals, Inc.) (fluorine) W2: Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.) (fluorine and silicone) W3: Polysiloxane polymer KP-341 (Manufactured by Shin-Etsu Chemical Co., Ltd.) W4: polyoxyethylene triphenyl ether W5: Troysol S-366 (Troy Chemical Co., Ltd.)
Made)

The compounds of (G) in Table 2 are as follows.

[0310]

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The solvents in Table 2 are as follows. S1: propylene glycol monomethyl ether acetate S2: propylene glycol monomethyl ether propionate S3: ethyl lactate S4: butyl acetate S5: 2-heptanone S6: propylene glycol monomethyl ether S7: ethoxytyl propionate S8: γ-butyrolactone S9 : Ethylene carbonate S10: propylene carbonate S11: cyclohexanone

(2) Preparation of resist pattern An electron beam lithography system (acceleration voltage 50 Ke
Irradiation was performed using V). 110 ° C each after irradiation
Heating for 60 seconds with a vacuum adsorption type hot plate,
It was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with water for 30 seconds, and dried. The cross-sectional shape of the obtained pattern was observed with a scanning electron microscope. Sensitivity, resolution, PED
The stability and the particle initial value were evaluated as follows.

[Resolution] First, the sensitivity (Eth) was determined. Next, a 0.15 μm line and space of 1: 1
The exposure amount resolved by the above is defined as the optimum exposure amount (Eopt), and the minimum line width (μm) of the separated line and space at this exposure amount was evaluated and defined as the resist resolution.

[PED stability]: 0.15 μm
Radiation dose (eg, electron beam: 8 μC /
cm ² ), and the wafer subjected to the irradiation step was left in a clean room for 2 hours. Subsequently, development was carried out following baking after radiation irradiation, and the deviation of the 0.15 μm line and space pattern from the designed dimensions was measured. | Design dimension-Actual dimension | / Design dimension × 100 (%) It was judged that the smaller the value, the better.

[Number of Particles and Increase in Number of Particles after Storage over Time]: Immediately after the preparation of the radiation-sensitive positive resist composition solution (coating solution) prepared as described above (initial value of particles), and at 4 ° C. The particles in the liquid after standing for one week (the number of particles after aging) were counted by a particle counter manufactured by Rion. Along with the initial particle value, (number of particles after aging)
-The particle increase calculated by (initial value of particles) was evaluated. Table 3 shows the results of the performance evaluation.

[0316]

[Table 3]

From the results shown in Table 3, the negative resist composition obtained by combining the composition of the present invention has higher resolution and resolution than the comparative example.
It can be seen that the profile and PED stability are improved, and the particle initial value is also reduced.

[Examples 19 to 23 and Comparative Example 9] A resist film formed in the same manner as described above using the composition of Examples 2, 7, 8, 10, and 11 and Comparative Example 2 was used.
Irradiation was performed using an electron beam lithography apparatus under the condition of an acceleration voltage of 0 KeV. After irradiation, heating, development, and rinsing were performed in the same manner as in the above example, and the obtained pattern was observed with a scanning electron microscope. Table 4 shows the results of the evaluation performed in the same manner as in the above example.

[0319]

[Table 4]

From the results shown in Table 4, it can be seen that the negative resist composition of the present invention has a better resolution than the composition of Comparative Example 3 even when irradiated with an electron beam at a high accelerating voltage.
It can be seen that PED stability is improved and the particle initial value is also reduced.

[0321]

According to the negative resist composition for an electron beam and an X-ray of the present invention, sensitivity and sensitivity can be improved even under high accelerating voltage conditions.
A negative resist composition having excellent resolution and a rectangular profile can be provided.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA01 AA02 AA03 AB16 AC05 AC06 BE07 CB13 CB14 CB17 CB29 CC04 CC17 CC20 FA17

Claims (5)

[Claims] (A) a sulfonium salt and / or iodonium salt having at least one phenyl group which generates an acid upon irradiation with an electron beam or X-ray; (B) a resin soluble in an aqueous alkali solution; (B) a crosslinking agent that forms a crosslink with the resin by action (D) a compound that cleaves its bond by irradiation with an electron beam or X-ray and / or causes cleavage of other components but does not generate a phenyl radical as an intermediate And a negative resist composition for electron beam or X-ray. 2. Compounds which (D) cleave their bonds by irradiation with an electron beam or X-ray and / or cause cleavage of others but do not generate a phenyl radical species as an intermediate are (a) aromatic compounds An aromatic or alicyclic ketone, (b) an organic peroxide, (c) a hexaarylbiimidazole compound,
2. The compound according to claim 1, wherein the compound is at least one selected from the group consisting of (d) a ketoxime ester compound, (e) an azinium compound, (f) an active ester compound, and (g) a compound having a carbon-halogen bond. 3. The negative resist composition for electron beam or X-ray according to item 1. 3. A compound which (D) cleaves its own bond by irradiation with an electron beam or X-ray and / or causes the cleavage of others, but does not generate a phenyl radical species as an intermediate, comprises (h) a photochromic 3. The electron beam according to claim 1, wherein the compound is at least one selected from the group consisting of a compound, (i) benzyl carbamates, (j) sulfonamides, and (k) acyloxyiminos. 4. X-ray negative resist composition. 4. The negative resist composition for electron beams or X-rays according to claim 1, further comprising (E) a nitrogen-containing basic compound. 5. The negative resist composition for electron beam or X-ray according to claim 1, further comprising (F) a surfactant.