JPH11153858A - Visible light sensitive composition and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve heat stability and to shorten a heating time at the time of coating a substrate with a photosensitive composition and cross-linking the coated composition by using naphthalimidylsulfonate as a compound to be decomposed to generate an acid by irradiation with a visible light and using it in combination with this compound. SOLUTION: The photosensitive composition contains (A) a polymer having carboxyl; groups and, when needed, further having hydroxyphenyl groups, (B) a compound having >=2 vinylether groups, (C) a compound to be allowed to generate an acid by irradiation with visible light and represented by formula I, and (D) a sensitizing dye. In formula I, R is a group represented by formula II, and in formula II, each of R1 -R3 is, independently, an H or F atom. This composition has high sensitivity to light in the visible wavelength region, especially, Ar laser beams having a stable emission wavelength in 488 nm or 514.5 nm, and it has good heat stability in the pattern formation process.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a visible light-sensitive composition and a method for producing a pattern useful for forming a circuit of an electronic device and a material for printing using the composition.

[0002]

2. Description of the Related Art At present, positive photoresists are widely used for forming circuit patterns of electronic devices and the like.
As the positive resist composition used for these applications, in many cases, a combination of an alkali-soluble novolak resin and a quinonediazide compound as a photosensitive agent is used.

This composition utilizes a reaction in which a quinonediazide group is photolyzed by irradiation with ultraviolet rays to form indenecarboxylic acid via ketene.

[0004] However, a resist using this quinonediazide compound has low visible light reactivity, and has problems such as insufficient resolution when a very fine pattern needs to be formed.

The present inventors have proposed, as an alternative, a positive photosensitive composition, a visible light comprising a polymer containing a carboxyl group, a poly (vinyl ether) compound, and a compound which decomposes upon irradiation with active energy rays to generate an acid. (Japanese Patent Application Laid-Open No. 6-295064), a visible light-sensitive composition comprising a polymer having a carboxyl group and a hydroxyphenyl group, a polyvinyl ether compound and a compound capable of decomposing upon irradiation with active energy rays to generate an acid. Composition (Japanese Unexamined Patent Publication No. Hei 7-146552 = US Patent 54966)
78) was proposed earlier. When these coatings are heated, a coating film formed therefrom is crosslinked by an addition reaction between a carboxyl group and a vinyl ether group, becomes insoluble in a solvent or an aqueous alkali solution, and is further irradiated with active energy rays and irradiated. When heated afterwards, the photosensitive composition functions by a mechanism whereby the crosslinked structure is cut by the catalytic action of the generated acid, and the irradiated portion becomes soluble again in a solvent or an aqueous alkaline solution.

[0006] These compositions do not require the use of a large amount of functional groups having a high extinction coefficient, unlike resists using quinonediazide as a photosensitizer, so that the transparency to active energy rays can be increased. The acid generated in the irradiated part acts as a catalyst at the time of heating, and has a merit that the sensitivity of the photosensitive composition acting positively can be increased because the crosslinked structure is cut in a chain.

[0007]

However, when these photosensitive compositions are applied to a substrate and crosslinked by heating, it is required to shorten the heating time from the viewpoint of productivity. Therefore 1
If an attempt is made to shorten the time by heating at a high temperature of 00 ° C. or more, the photoacid generating compound present in the photosensitive composition generates an acid before irradiation with visible light, and the entire film formed during development dissolves. There is a problem of doing. Therefore, there is a strong demand in the art for improving the thermal stability of the photosensitive composition.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies on a method for solving the problems of the above-mentioned photosensitive composition, and as a result, this time, it is decomposed by irradiation with visible light to generate an acid. By using naphthalimidyl sulfonate as a compound and using it in combination with a sensitizing dye, the inventors have found that the above problems can be solved, and have completed the present invention.

Thus, according to one aspect of the present invention,
(A) a polymer containing a carboxyl group and optionally further containing a hydroxyphenyl group;
(B) a compound containing at least two vinyl ether groups in one molecule; (C) a general formula for generating an acid upon irradiation with visible light

[0010]

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Where R is

[0012]

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A group wherein R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or a fluorine atom;

[0014]

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A compound represented by the formula: and (D)
A visible light-sensitive composition comprising a sensitizing dye and a method for forming a pattern using the same are provided.

According to another aspect of the present invention,
(A ′) a polymer containing a carboxyl group; (A ″) a polymer containing a hydroxyphenyl group; (B) a compound containing at least two vinyl ether groups in one molecule; (C) visible light irradiation And (D) a sensitizing dye, and a visible light-sensitive composition comprising the compound represented by the general formula (I) and a method for forming a pattern using the same. .

The composition of the present invention can be used in visible light, especially at a wavelength of 48.
Since it is highly sensitive to an Ar laser having a stable oscillation line in the visible region of 8 nm or 514.5 nm and has good thermal stability even in the pattern manufacturing process,
There is no problem of film dissolution at the time of development, the contrast of the formed pattern is large, and it is useful for applications such as positive photoresists and printing materials.

Hereinafter, the present invention will be described in more detail.

(A) Carboxyl group-containing and case
May further contain a hydroxyphenyl group
Polymer : The polymer (A) used in the visible light-sensitive composition of the first aspect of the present invention contains at least one carboxyl group in one molecule and optionally further contains a hydroxyphenyl group. A film-forming polymer that may be contained, wherein the polymer containing only a carboxyl group includes, for example, a homopolymer of a polymer unsaturated monomer containing a carboxyl group; A copolymer of a monomer containing and another copolymerizable monomer; a polyester-based, polyurethane-based, polyamide-based resin or the like having a carboxyl group in the molecular chain or at the molecular terminal; Examples of the polymer containing both a hydroxyl group and a hydroxylphenyl group include hydroxystyrene such as p-hydroxystyrene, and a polymer containing a carboxyl group. Copolymers of polymerizable unsaturated monomers;
Examples include hydroxystyrene and copolymers of the carboxyl group-containing monomer and other copolymerizable monomers.

Examples of the above-mentioned polymerizable unsaturated monomer containing a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, and itaconic acid. As the body, for example, methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
(Meth) acrylate, nonyl (meth) C ₁ -C ₁₂ alkyl esters of (meth) acrylic acid such as decyl acrylate; (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxypropyl, (meth) C ₂ -C ₆ hydroxyalkyl esters of (meth) acrylic acid such as 3-hydroxypropyl acrylate and hydroxybutyl (meth) acrylate; styrene, α-methylstyrene, p
Vinyl aromatic compounds such as -tert-butylstyrene;
Examples thereof include vinyl acetate, (meth) acrylonitrile, (meth) acrylamide, and vinylpyrrolidone. These monomers may be used alone or in combination of two or more. In particular, the use of vinyl aromatic compounds such as styrene, α-methylstyrene, C ₁ -C ₆ alkyl-substituted styrenes (eg p-tert-butylstyrene) as said other monomers can be achieved. This is suitable in terms of the accuracy of the image pattern to be obtained, the etching resistance, and the like.

The polymer (A) containing both a carboxyl group and a hydroxyphenyl group includes phenol carboxylic acids such as hydroxybenzoic acid, gallic acid and resorcinic acid;
A polymer obtained by condensing a mono- or di-alkylphenol or a mixture with one or more phenols selected from naphthols, resorcinol, catechol and the like with formaldehyde can also be used.

The polymer (A) is generally used in an amount of about 500 to about 1
It preferably has a number average molecular weight in the range of from about 0.00000, especially from about 1,000 to about 50,000, and more particularly from about 1,500 to about 30,000. On the other hand, the content of the carboxyl group is generally 0.5 to 10 per kg of the polymer.
Equivalents, particularly 0.5 to 8 equivalents, more particularly 0.5 to 5 equivalents.
It is generally desirable to be in the range of 1 to 10 equivalents, especially 2 to 8 equivalents, more particularly 3 to 6 equivalents per kg. When the content of the carboxyl group is less than 0.5 equivalent / kg,
If the degree of crosslinking of the film formed by heating before irradiation with visible light is not sufficient, the solubility of the exposed part in an alkaline developer tends to be low, and the developability tends to decrease. If it exceeds 10 equivalents / kg, The storage stability of the composition tends to decrease. On the other hand, if the content of the hydroxyphenyl group is less than 1 equivalent / kg, the degree of crosslinking at the time of crosslinking may be insufficient, and if it exceeds 10 equivalents / kg, high temperature heating is required for heating before irradiation with visible light. there is a possibility.

Further, the polymer A) preferably has a glass transition temperature (Tg) of 0 ° C. or higher, particularly in the range of 5 to 70 ° C. If the Tg is lower than 0 ° C., the coating film tends to be sticky, and it is easy for dust and dirt to adhere to the film, which tends to be difficult to handle.

(A ′) Polymerization Containing Carboxyl Group
Body : The present polymer (A ′) used in the visible light-sensitive composition of the second aspect of the present invention is a film-forming polymer containing at least one carboxyl group in one molecule, for example, , A homopolymer of a polymerizable unsaturated monomer containing a carboxyl group; a copolymer of the carboxyl group-containing monomer and another copolymerizable monomer; a carboxyl group in the molecular chain or at a molecular terminal And polyester-based, polyurethane-based, polyamide-based resins and the like.

Examples of the polymerizable unsaturated monomer containing a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, and itaconic acid, and are copolymerizable with these carboxyl group-containing monomers. Examples of other monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate,
(Meth) acrylic acid such as butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, and decyl (meth) acrylate C ₁ ~
C ₁₂ alkyl ester; hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
3-hydroxypropyl (meth) acrylate, (meth)
C ₂ -C ₆ hydroxyalkyl esters of (meth) acrylic acid such as hydroxybutyl acrylate; styrene, α-
Vinyl aromatic compounds such as methylstyrene and p-tert-butylstyrene; vinyl acetate, (meth) acrylonitrile, (meth) acrylamide, vinylpyrrolidone, etc., and these monomers may be used alone or 2 More than one species can be used in combination. In particular,
Styrene, α-methylstyrene, C
₁ -C ₆ alkyl substituted styrenes (e.g., p-ter
Use of a vinyl aromatic compound such as (t-butylstyrene) is preferable in terms of the accuracy of the formed image pattern, etching resistance, and the like.

The carboxyl group-containing polymer (A ') is generally used in an amount of about 3,000 to about 100,000, especially about 4,000.
0 to about 65,000, more particularly about 5,000 to about 30,
It is preferable to have a number average molecular weight in the range of 000, and the content of carboxyl group is 1 kg of polymer.
In general, the amount is preferably in the range of 0.5 to 10 equivalents, particularly 0.5 to 8 equivalents, more preferably 0.5 to 5.0 equivalents. When the content of the carboxyl group is less than 0.5 equivalent / kg, the degree of crosslinking of the film formed by heating before irradiation with visible light is not sufficient, and the solubility of the exposed part in an alkaline developing solution is low and the developing property is low. On the other hand, when it exceeds 10 equivalents / kg, the storage stability of the composition tends to decrease.

Further, the polymer (A ') preferably has a glass transition temperature (Tg) of 0 ° C. or more, particularly in the range of 5 to 70 ° C. If the Tg is lower than 0 ° C., the coating film tends to be sticky, and it is easy for dust and dirt to adhere to the film, which tends to be difficult to handle.

(A ″) containing a hydroxyphenyl group
Polymer: the polymer in a visible light sensitive composition of the second aspect of the present invention (A ') in combination with the polymer used (A ") is at least one hydroxyphenyl group in the molecule And a condensate of a monofunctional or polyfunctional phenol compound, an alkylphenol compound or a mixture thereof with a carbonyl compound such as formaldehyde or acetone; containing a hydroxy group such as p-hydroxystyrene. Homopolymers of vinyl aromatic compounds; and copolymers of the hydroxyl group-containing vinyl aromatic compounds with other copolymerizable monomers.

The monofunctional or polyfunctional phenol compound includes, for example, phenol, o-cresol, m
-Cresol, p-cresol, 3,5-xylenol, 2,6-xylenol, 2,4-xylenol, catechol, resorcinol, pyrogallol, bisphenol A
And the like, and a compound having 1 to 3 hydroxyl groups on a benzene ring. Examples of the alkylphenol compound include p-isopropylphenol and p-isopropylphenol.
Alkyl phenol compounds having 1 to 10, preferably 1 to 4 carbon atoms in the alkyl moiety, such as tert-butylphenol, p-tert-amylphenol, and p-tert-octylphenol are exemplified.

The condensation reaction of these compounds with a carbonyl compound such as formaldehyde or acetone can be carried out by a method known per se. In general, when condensation is carried out with an alkali catalyst, the resol becomes insoluble and infusible as the condensation proceeds. A mold is obtained and, when condensed with an acid catalyst, a soluble and fusible novolak form is obtained. In the present invention, the latter novolak-type phenol resin can usually be used. The molecular weight of the novolak type phenol resin increases as the condensation proceeds, but generally, the molecular weight obtained by condensation in a reaction time of 1 to 3 hours is 500 to 2,000, especially 7
Those in the range of 00 to 1,500 are preferred.

As the other monomer copolymerizable with the hydroxy-containing vinyl aromatic compound, the same copolymerizable monomers as those exemplified for the polymers (A) and (A ') can be used. Other monomers can be used.

The hydroxyphenyl group-containing polymer (A ″) generally has a number within the range of about 500 to about 100,000, especially 750 to about 65,000, and more particularly about 1,000 to about 30,000. It preferably has an average molecular weight.

The content of the hydroxyphenyl group in the polymer (A ″) is generally in the range of 1 to 10 equivalents, preferably 2 to 8 equivalents, more preferably 3 to 6 equivalents per kg of the polymer. If the content of the hydroxyphenyl group is less than 1.0 equivalent / kg, the degree of crosslinking of the film formed by heating before irradiation with visible light tends to be insufficient, and if it exceeds 10 equivalent / kg. In addition, the resist film tends to be brittle.

The polymer (A ″) is also a polymer (A),
The glass transition temperature (Tg) is 0 ° C. as in (A ′).
As described above, it is particularly preferable that the temperature be in the range of 5 to 70 ° C. If the Tg is lower than 0 ° C., the coating film tends to be sticky, and it is easy for dust and dirt to adhere to the film, which tends to be difficult to handle.

(B) Two or more vinyl esters per molecule
Compound containing a ter group : The compound (B) is
[Wherein, R 'is ethylene, propylene, linear or branched chain represents an alkylene group having 1 to 6 carbon atoms such as butylene] formula -R'-O-CH = CH ₂ vinyl ether groups represented by At least two, preferably 2-4
Low molecular weight or high molecular weight compound containing, for example, bisphenol A, bisphenol F, bisphenol S, polyphenol compounds such as phenolic resin, ethylene glycol, propylene glycol, trimethylolpropane, trimethylolethane, Condensates of polyols such as pentaerythritol with halogenated alkyl vinyl ethers such as chloroethyl vinyl ether; polyisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and hydroxyalkyl such as hydroxyethyl vinyl ether Reaction products with vinyl ether and the like can be mentioned.
In particular, a condensate of the above-mentioned polyphenol compound and a halogenated alkyl vinyl ether and a reaction product of a polyisocyanate compound having an aromatic ring and a hydroxyalkyl vinyl ether are preferable from the viewpoint of etching resistance, accuracy of a formed pattern, and the like.

The compound (B) is liquid at ordinary temperature or has a melting point or softening point of 150 ° C. or less, especially 130 ° C.
The following are easily transferred into the polymer (A) or the polymer (A ') and / or (A ") upon heating before irradiation with visible light, and the polymer (A) or the polymer (A') as well as/
Alternatively, the addition reaction between the carboxyl group and / or phenolic hydroxyl group in (A ″) and the vinyl ether group of compound B) is preferred because it easily occurs.

(C) Generating an acid by irradiation with visible light
Compound : The compound (C) is decomposed by irradiation of visible light described below, and the polymer (A) or the polymer (A ′) is decomposed.
And / or a compound that generates an acid of sufficient strength to cleave the cross-linking structure formed between (A ″) and compound (B) (hereinafter sometimes referred to as a “photoacid generating compound”). And those represented by the following general formula (I) are included.

[0038]

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Where R is

[0040]

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A group wherein R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or a fluorine atom;

[0042]

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Represents

Specific examples of the compound represented by the above formula (I) include, for example,

[0045]

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And the like.

(D) Sensitizing dye : The sensitizing dye (D) used in the visible light-sensitive composition of the present invention is 400 to 7
It is excited by absorbing light (visible light) in a wavelength region of 00 nm, and the above-mentioned polymers (A), (A ′),
(A ″), a compound having an interaction with the compound (B) and the photoacid generator compound (C), and having the following general formula (II):
And (III), cyanine dyes, merocyanine dyes, coumarin dyes, and the like. Among these, in particular, the general formulas (II) and (II)
Compounds represented by I) are preferred. The term "interaction" as used herein includes energy transfer and electron transfer from the excited sensitizing dye to other components.

[0048]

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Wherein R ₄ , R ₅ , R ₆ and R ₇ each independently represent a methyl, ethyl, propyl or isopropyl group, preferably a methyl group, and R ₈
And R ₉ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms,
5, an alkoxycarbonyl group, a dialkylamino group having 1 to 4 carbon atoms in each alkyl moiety, Cl, Br, CN, N
O ₂ or SO ₂ CH ₃ , preferably hydrogen or methyl.

[0050]

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In the formula, R ₁₀ , R ₁₁ and R ₁₂ each independently represent a methyl group, ethyl group, propyl group or isopropyl group, preferably R ₁₀ and R ₁₁ are methyl groups, and R ₁₂ is An ethyl group and R ₁₃ and R ₁₄
Are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, and each of the alkyl portions having 1 to 4 carbon atoms.
Represents a dialkylamino group, Cl, Br, CN, NO ₂ or SO ₂ CH ₃ , and is preferably a hydrogen or methyl group.

As the cyanine dye, merocyanine dye and coumarin dye other than the compounds represented by (II) and (III), those known per se can be used. For example, cyanine dyes and merocyanine dyes can be used. The dyes described in JP-A-61-213838 are described as dyes, and the coumarin dyes are described in JP-A-61-9138.
No. 7,650, JP-A-3-223759.

Visible light-sensitive composition : The visible light-sensitive composition according to the first aspect of the present invention may contain the above-mentioned carboxyl group and optionally further contain a hydroxyphenyl group. A polymer (A), a compound containing a vinyl ether group (B), a photoacid generator compound (C) and a sensitizing dye (D) as essential components.
The compounding ratio can be varied over a wide range depending on the use of the composition and the like. Generally, the vinyl ether group-containing compound (B) is generally added in an amount of 5 parts by weight per 100 parts by weight of the polymer (A). It is preferably used in an amount of from 150 to 150 parts by weight, particularly from 10 to 100 parts by weight, more preferably from 20 to 80 parts by weight, and the photoacid generating compound (C) contains the polymer (A) and a vinyl ether group-containing compound. Total amount of compound (B) 1
In general, 0.1 to 40 parts by weight, especially 0.1 part by weight, per 100 parts by weight.
It is suitable to use in the range of 2 to 20 parts by weight, more particularly 0.5 to 15 parts by weight. Further, a sensitizing dye (D)
Is a polymer (A) and a vinyl ether group-containing compound (B)
Can be used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, and more preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the total amount.

The photosensitive composition according to the second embodiment of the present invention comprises the above-mentioned carboxyl group-containing polymer (A '),
It contains the hydroxyphenyl group-containing polymer (A ″), vinyl ether group-containing compound (B), photoacid generator compound (C) and sensitizing dye (D) as essential components. In general, the carboxyl group-containing polymer (A ′) and the hydroxyphenyl group-containing polymer (A ″) can be changed over a wide range depending on the use of the composition and the like. The polymerization ratio of (A ″) is generally 90/10 to 10/90, especially 70/30 to 3
0/70, more particularly within the range of 60/40 to 40/60, and the vinyl ether group-containing compound (B) comprises a carboxyl group-containing polymer (A ′) and a hydroxyphenyl group-containing polymer. (A ″) and the total amount 10
5 to 150 parts by weight, especially 10 to 10 parts by weight,
It is preferably used in an amount of 100 parts by weight, more preferably 10 to 80 parts by weight, and the photoacid generating compound (C)
Is generally 0.1 part by weight based on 100 parts by weight of the total amount of the carboxyl group-containing polymer (A '), hydroxyphenyl group-containing polymer (A ") and vinyl ether group-containing compound (B).
It is suitable to use in the range of 1 to 40 parts by weight, particularly 0.2 to 20 parts by weight, more particularly 0.5 to 15 parts by weight.

Further, the sensitizing dye (D) was used in an amount of 100 parts by weight based on the total amount of the carboxyl group-containing polymer (A ′), hydroxyphenyl group-containing polymer (A ″) and vinyl ether group-containing compound (B). 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, more preferably 0.5 to 3 parts by weight.

In the composition of the present invention, an acid hydrolysis reaction is caused in an exposed portion by an acid generated when a film to be formed is exposed, and water is present in order for the acid hydrolysis reaction to proceed smoothly. It is desirable to do. For this reason, in the composition of the present invention, by incorporating a hydrophilic resin such as polyethylene glycol, polypropylene glycol, methylcellulose, and ethylcellulose, the water required for the above reaction can be easily incorporated into the formed coating film. You can do so. The amount of the hydrophilic resin to be added is usually 100 parts by weight of the total amount of the components (A), (B), (C) and (D) or (A ′),
(A ″), total amount of components (B), (C) and (D) 10
In general, the amount can be set to 20 parts by weight or less, preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 0 parts by weight.

Further, in order to impart appropriate flexibility and non-adhesiveness to a film formed using the composition of the present invention, a plasticizer such as a phthalate ester is added to the composition of the present invention. A polyester resin, an acrylic resin, or the like can be added.
The amount of these additives is usually 100 parts by weight of the total amount of the components (A), (B), (C) and (D) or (A ′), (A ″), (B), (C) ) And 50 parts by weight, especially 0.1 part by weight, per 100 parts by weight of the total of components (D)
It is preferably from 1 to 30 parts by weight.

Further, the composition of the present invention may optionally contain a fluidity modifier, a coloring agent such as a dye or a pigment, and the like.

The photosensitive composition of the present invention can be prepared by mixing the above-mentioned components as they are or, if necessary, in a solvent. The solvent that can be used at that time is not particularly limited as long as it can dissolve each component of the composition. For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone; methyl acetate, ethyl acetate, Esters such as butyl acetate; aliphatic alcohols having 1 to 10 carbon atoms such as methanol, ethanol and propanol; aromatic group-containing alcohols such as benzyl alcohol; glycols such as ethylene glycol and propylene glycol; And mono- or diethers such as methanol, ethanol, butanol, hexanol, octanol, benzyl alcohol and phenol or glycol ethers such as esters of the monoether; cyclic ethers such as dioxane and tetrahydrofuran Ethylene carbonate, cyclic carbonates such as propylene carbonate, aliphatic and aromatic hydrocarbons, and the like. These solvents can be used alone or as a mixture of two or more, if necessary.

Pattern formation : Pattern formation using the visible light-sensitive composition of the present invention can be performed as described below.

First, the composition of the present invention is spin-coated, spray-coated, roll-coated on a substrate, for example, an aluminum plate for PS plate, a substrate for a printed circuit laminated with copper foil, or a substrate such as a silicon wafer of a semiconductor material. Coating is performed by a coating method known per se such as coating, curtain flow coating, and printing. The thickness of the applied film at that time is not strictly limited, and can be changed according to the purpose of use of the formed pattern, etc., but usually, the dry film thickness is preferably in the range of about 0.5 to about 15 microns. It is.

The substrate coated with the composition is substantially crosslinked with polymer (A) or polymer (A ′) and / or (A ″) and vinyl ether group-containing compound (B). Under conditions of temperature and time that occur, for example, from about 60 to about 15
Heat at a temperature of 0 ° C., preferably about 80 to about 140 ° C. for about 1 to about 30 minutes to crosslink and cure the coating.

Next, the cured coating film on the substrate is selectively image-irradiated with visible light using a positive photomask, a reduction projection exposure machine, a direct drawing machine or the like. The visible light that can be used here is selected depending on the type of the photoacid generator compound (C) and the sensitizing dye (D) incorporated in the photosensitive composition, and for example, the wavelength is 400 to 600 nm. A monochromatic light beam in the visible region, a mixed light beam thereof, an Ar laser having an oscillation line in the visible region, or the like can be used.

The substrate irradiated with visible light is then subjected to temperature and time conditions such that the crosslinked structure of the cured coating film is cut in the presence of the acid generated by the irradiation, for example,
The coating is heated at a temperature of about 60 to about 150C, preferably about 80 to about 140C for about 1 to about 30 minutes to substantially cut the crosslinked structure of the irradiated portion of the coating film. In this case, the substrate irradiated with visible light is preferably brought into contact with water in advance. An acid is easily generated by contact with water, and the subsequent cleavage reaction of the crosslinked structure is facilitated. The contact with water can be performed by immersing the substrate in normal temperature water or hot water, or by spraying water vapor.

By treating the substrate which has been thus heated, irradiated and, if necessary, contacted with water and heated, with a developing solution, a pattern can be formed on the substrate. As the developer, a liquid capable of dissolving the polymer (A) or the polymer (A ′) and the polymer (A ″), for example, a water-soluble organic base such as alkanolamine, tetraethylammonium hydroxide, etc. Hydroxyammonium salts; inorganic alkalis, for example, basic aqueous solutions such as caustic soda, sodium carbonate, and sodium metasilicate can be used.

These basic substances may be used alone or in combination of two or more. The concentration of these substances is usually preferably in the range from 0.05 to 10% by weight, in particular from 1 to 8% by weight. If necessary, the solvent described as a solvent that can be used in producing the visible light-sensitive composition of the present invention may be added at a concentration within a range that can be mixed with the developer.

The development can be performed by a method known per se, such as immersing the substrate in a developing solution or spraying the developing solution on the substrate. After pattern formation, the substrate can be washed with water and / or dried by heating, if necessary.

Further, when the substrate can be etched, a relief image is obtained by removing the exposed substrate portion with an appropriate etching agent and, if necessary, removing the remaining coating with an appropriate release agent. Can be.

The pattern formed in this manner is a very fine pattern and has excellent contrast, which is advantageous for the production of a printing plate, relief, display, etc., which require a fine image, and a printed circuit board. Can be used for

In particular, the visible light-sensitive composition of the present invention is excellent in thermal stability at the time of heat crosslinking, so that it can be crosslinked by heating at a high temperature of 100 ° C. or higher for a short time. Since the part has a cross-linked structure, the unexposed part has better resistance to developing solutions and etching solutions, and the precision of the formed pattern is superior to that of the conventional positive type photoresist. Extensive applications are expected in the fields of precision processing of semiconductors such as circuit boards and LSIs, and fine metal processing.

[0071]

The present invention will be described more specifically with reference to the following examples. “Parts” and “%” are based on weight.

Production Example 1 Synthesis of Polymer A-1 Containing Carboxyl and Hydroxyphenyl Groups 600 parts of o-hydroxybenzoic acid, 90 parts of o-cresol 90
0 parts, 30% formalin 1145 parts, deionized water 13
0 parts and 6.5 parts of oxalic acid were placed in a flask and heated to reflux for 60 minutes. Thereafter, 13.5 parts of 15% hydrochloric acid was added, and the mixture was heated under reflux for 40 minutes. Then 400 parts of about 15 ° C. deionized water were added to keep the contents at about 50 ° C. to precipitate the resin. After adding 400 parts of deionized water and washing the resin at 50 ° C., the aqueous layer was removed, and the same washing operation was repeated three times, followed by drying under reduced pressure at about 120 ° C. to obtain a novolak phenol resin ( Polymer A-1) was obtained. A molecular weight of about 650, a carboxyl group content of 2.8 mol / kg polymer, and a hydroxyphenyl group content of 5.4 mol / kg polymer.

Production Example 2: Synthesis of Polymer A-2 Containing Carboxyl Group and Hydroxyphenyl Group 200 parts of tetrahydrofuran, 65 parts of p-hydroxystyrene, 28 parts of n-butyl acrylate, acrylic acid 1
One part and 3 parts of azobisisobutyronitrile were put in a flask, and the inside of the vessel was replaced with nitrogen and heated at 100 ° C. for 2 hours with stirring. The product was poured into 1500 ml of toluene, the resulting precipitate was separated, dissolved in 300 ml of acetone, and 1500 ml of the solution was again poured into toluene. The precipitate was dried at 60 ° C. under reduced pressure to obtain a polymer A-2.
Molecular weight about 5200, acrylic acid / n-butyl acrylate / p-hydroxystyrene = 17/37/50 (weight ratio), carboxyl group content 1.8 mol / kg polymer,
A polymer having a hydroxyphenyl group content of 4.6 mol / kg.

Production Example 3: Synthesis of carboxyl group- and hydroxyphenyl group-containing polymer A-3 200 parts of tetrahydrofuran, 93.5 parts of p-hydroxystyrene, 6.5 parts of acrylic acid and 3 parts of azobisisobutyronitrile were used. The flask was placed in a flask, and the inside of the vessel was replaced with nitrogen and heated at 100 ° C. for 2 hours with stirring. 1500 products
pour into ml of toluene and separate the precipitate formed,
After dissolving in 300 ml of acetone, 1500 ml again
Was also poured into toluene. The precipitate was dried at 60 ° C. under reduced pressure to obtain a polymer A-3. A molecular weight of about 2300, a carboxyl group content of 1.0 mol / kg polymer, and a hydroxyphenyl group content of 7.0 mol / kg polymer.

Production Example 4: Synthesis of Carboxyl Group-Containing Polymer A-4 A mixture of 216 parts of acrylic acid, 500 parts of styrene, 284 parts of n-butyl methacrylate, and 50 parts of azobisisobutyronitrile (AIBN) was heated to 80 ° C. After dropping into 600 parts of heated and stirred methyl isobutyl ketone over 2 hours, polymer A-4 was maintained at that temperature for another 2 hours. Solid content: about 62.5%, carboxyl group 3mol / k
g, aromatic ring content: 34.6 parts by weight / 100 parts by weight.

Production Example 5: Synthesis of Carboxyl Group-Containing Polymer A-5 A mixture of 288 parts of acrylic acid, 300 parts of styrene, 255 parts of n-butyl acrylate, 157 parts of 2-hydroxyethyl acrylate, and 100 parts of t-butyl peroxybenzoate, Heated to 110 ° C and stirred 2
After dropping in 1000 parts of butoxyethanol in 2 hours, the temperature was further maintained for 2 hours to obtain a polymer A-5. Solid content about 50%, carboxyl group 4 mol / kg,
Polymer having an aromatic ring content of 20.7 parts by weight / 100 parts by weight.

Production Example 6: Synthesis of Carboxyl Group-Containing Polymer A-6 A mixture of 72 parts of acrylic acid, 650 parts of styrene, 100 parts of ethyl acrylate, 178 parts of n-butyl acrylate, and 75 parts of AIBN was polymerized in exactly the same manner as in Production Example 1. do it,
Polymer A-6 was obtained. Solid content: about 62.5%, carboxyl group content: 1 mol / kg, aromatic ring content: 45 parts by weight /
100 parts by weight polymer.

Production Example 7: Synthesis of hydroxyphenyl group-containing polymer A-7 1490 parts of o-cresol, 30% formalin 114
5 parts, 130 parts of deionized water and 6.5 parts of oxalic acid were placed in a flask and heated to reflux for 60 minutes. Then add 15% hydrochloric acid to 1
After adding 3.5 parts and heating under reflux for 40 minutes, 400 parts of deionized water at about 15 ° C. were added to keep the contents at about 75 ° C. to precipitate the resin. The aqueous layer was removed after neutralization by adding a 35% sodium hydroxide solution, and 400 parts of deionized water was added.
After washing the resin at 5 ° C., the aqueous layer was removed, and the same washing operation was repeated twice, followed by drying at about 120 ° C. under reduced pressure to obtain a novolak phenol resin (polymer A-7).
Molecular weight 600.

Production Example 8: Synthesis of hydroxyphenyl group-containing polymer A-8 60 parts of tetrahydrofuran, p-hydroxystyrene 2
One part, 9 parts of n-butyl acrylate and 3 parts of azobisisobutyronitrile were placed in a flask, the inside of the vessel was replaced with nitrogen, and heated at 100 ° C. for 2 hours with stirring. Product 7
The resulting precipitate was separated by pouring into 00 ml of toluene, and dissolved in 100 ml of acetone.
1 was also poured into toluene. The precipitate was dried under reduced pressure at 60 ° C. to obtain a polymer A-8. Molecular weight about 14000; n-butyl acrylate / p-hydroxystyrene = 35/6
5 (polymerization ratio).

Production Example 9: Synthesis of vinyl ether compound B-1 250 ml of bisphenol A 45.6 g, 2-chloroethyl vinyl ether 80 ml and toluene 100 ml
After the replacement with nitrogen, 20 g of sodium hydroxide was added thereto, and the mixture was heated at 80 ° C. for 30 minutes. Then 4.56g
Of tetrabutylammonium bromide in 20 ml of 2
-A solution dissolved in chloroethyl vinyl ether was charged, and the mixture was heated and reacted at 95 ° C for 5 hours. After washing the reaction three times with deionized water, the oil layer was separated. The oil layer was distilled to remove unreacted 2-chloroethyl vinyl ether and toluene to obtain a vinyl ether compound B-1. This compound contained two vinyl ether groups in one molecule.

Production Example 10: Vinyl ether compound B-2
Synthesis of o-cresol 1490 parts, 30% formalin 114
5 parts, 130 parts of deionized water and 6.5 parts of oxalic acid were placed in a flask and heated to reflux for 60 minutes. Then add 15% hydrochloric acid to 1
3.5 parts was added and the mixture was heated under reflux for 40 minutes. Then 400 parts of deionized water at about 15 ° C. were added to keep the contents at about 75 ° C. to precipitate the resin. Next, a 35% sodium hydroxide solution was added to neutralize the solution, and the aqueous layer was removed. Further, 400 parts of deionized water was added to wash the resin at 75 ° C., and the aqueous layer was removed. The same washing operation was repeated twice. After that, about 120
After drying at ℃, a novolak phenol resin was obtained. The molecular weight was about 600.

A vinyl ether compound B-2 was obtained in exactly the same manner as in Preparation Example 9 except that 15 g of the resin was used instead of 45.6 g of bisphenol A. This compound contained about 3.5 vinyl ether groups in one molecule.

Production Example 11: Vinyl ether compound B-3
Of Trimethylolpropane and Tolylene Diisocyanate
75% of polyisocyanate reacted with 3 moles
875 parts of ethylene glycol dimethyl ether solution and 2
-Hydroxyethyl vinyl ether (264 parts)
Reaction at 35 ° C. for 3 hours in the presence of 1 part of rutin diacetate
Thus, a vinyl ether compound B-3 was obtained. This compound is 1
The molecule contained three vinyl ether groups. Solid content approx.
81%. Example 1 Copolymer A-4 (solid content 62.5%) 160 parts Vinyl ether compound B-1 70 parts Polyethylene glycol (average molecular weight 400) 2 parts Photoacid generator C-1 (Note 1) 10 parts Sensitizing dye-1 (Note 2) Dissolve 1 part of the mixture in diethylene glycol dimethyl ether.
Disassembled to give a 20% by weight solution.

[0086] The resultant was coated on a silicon wafer with a spin coater so as to have a dry film thickness of 1 µm, and then dried at 120 ° C for 8 minutes.

This substrate was irradiated with visible light having a wavelength of 488 nm while changing the irradiation amount in a stepwise manner, heated at 120 ° C. for 10 minutes, and then developed using a 2.38% aqueous solution of tetramethylammonium hydroxide.

The γ value (Note 3) obtained from the residual ratio curve of the film after development with respect to the irradiation amount of visible light is 10.5, which is an extremely high contrast value. I was not seen.

Similarly, a 1 μm film was formed on a silicon wafer, irradiated with 488 nm visible light at a light exposure of 8 mj / cm ² using a pattern mask, and then immersed in room temperature water for 1 minute. Then, the same processing as described above was performed to form an image having a line / space of 1/1 μm. The cross-sectional shape of the image pattern was evaluated based on the angle between the wafer surface and the image pattern wall. The angle was 88 degrees, which was an extremely excellent pattern shape. Minimum exposure for image formation is 6m
j / cm ² .

(Note 1) Photoacid generator C-1: NAI-100 manufactured by Midori Kagaku Co., Ltd. represented by the following formula was used.

[0089]

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(Note 2) Sensitizing Dye-1: NKX-1595 manufactured by Japan Photographic Dye Laboratories represented by the following formula was used.

[0091]

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(Note 3) γ value: an index representing the contrast, the larger the value, the higher the contrast. The measurement was carried out according to the method described in "Photopolymer Handbook, Photopolymer Handbook, pp. 101-103, (1989) Industrial Research Committee".

Example 2 Copolymer A-5 (solid content: 50%) 200 parts Vinyl ether compound B-2 20 parts Polyethylene glycol (average molecular weight: 400) 2 parts Photoacid generator C-2 (Note 4) 7.5 Part of sensitizing dye-2 (Note 5) 1 part of the mixture was dissolved in the same manner as in Example 1, applied to a silicon wafer by a spin coater so as to have a dry film thickness of 3 μm, and dried at 120 ° C. for 5 minutes.

This substrate was subjected to γ
The value was determined. The γ value was 10.0, indicating a very high contrast value, and no decrease or swelling of the film in the unexposed portion was not observed at all.

Next, Example 1 was repeated except that visible light of 488 nm was used as the irradiation light and the exposure amount was 3 mj / cm ^2.
The shape of the image pattern was evaluated in exactly the same manner as described above. The angle was 88 degrees, which was a very excellent pattern shape. The minimum exposure for image formation was ² mj / cm ² .

(Note 4) Photoacid generator C-2: NAI-105 of Midori Kagaku Co., Ltd. represented by the following formula was used.

[0097]

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(Note 5) Sensitizing Dye 2: A sensitizing dye of the following formula, manufactured by Japan Photographic Dye Laboratories, was used.

[0099]

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Example 3 Copolymer A-6 (solid content: 62.5%) 160 parts Vinyl ether compound B-3 15 parts Photoacid generator C-3 (Note 6) 5 parts Sensitizing dye-3 (Note 7) 1 part of the mixture was dissolved in the same manner as in Example 1 and coated on a substrate obtained by laminating a 18 μm copper foil on a polyimide film to a dry film thickness of 5 μm using a roll coater.
Dry at 8 ° C. for 8 minutes.

The γ value of this substrate was determined in exactly the same manner as in Example 1. The γ value was extremely high at 9.5.

Next, a pattern of line / space = 30/30 μm was drawn on the resist film on the substrate formed in the same manner with an energy density of ² mJ / cm ² by a direct drawing machine using an argon ion laser beam having a wavelength of 488 nm. . Then, after heating at 100 ° C. for 10 minutes, development is performed with a 3% aqueous sodium carbonate solution, the exposed copper is etched with copper chloride, and then the coating on the substrate is removed with a 3% aqueous sodium hydroxide solution to obtain an excellent etching pattern. Was formed on the substrate.

(Note 6) Photoacid generator C-3: NAI-101 manufactured by Midori Kagaku Co., Ltd. represented by the following formula was used.

[0104]

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(Note 7) Sensitizing dye-3: LS-5 manufactured by Mitsui Toatsu Co., Ltd. represented by the following formula was used.

[0106]

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Example 4 Polymer A-1 100 parts Vinyl ether compound B-1 60 parts Polyethylene glycol (average molecular weight 400) 2 parts Photoacid generator compound C-1 (Note 1) 10 parts Sensitizing dye-1 (Note 2) 0.5 part of the mixture was dissolved in diethylene glycol dimethyl ether to give a 20% by weight solution.

[0108] The resultant was coated on a silicon wafer by a spin coater so as to have a dry film thickness of 1 µm, and dried at 120 ° C for 8 minutes.

This substrate was subjected to γ
The value was determined. The γ value was 11.5, indicating a very high contrast value, and no decrease or swelling of the film in the unexposed portion was observed.

Then, the visible light exposure was reduced to 7 mj / cm ^2.
The shape of the image pattern was evaluated in the same manner as in Example 1 except for the above. The angle was 89 degrees, which was an extremely excellent pattern shape. The minimum exposure for image formation was 5 mj / cm ² .

Example 5 Polymer A-2 100 parts Vinyl ether compound B-2 25 parts Polyethylene glycol (average molecular weight 400) 2 parts Photoacid generator compound C-2 (Note 4) 7.5 parts Sensitizing dye-4 ( Note 8) One part of the mixture was dissolved in the same manner as in Example 4, applied to a silicon wafer by a spin coater so as to have a dry film thickness of 3 μm, and dried at 120 ° C. for 5 minutes.

This substrate was subjected to γ
The value was determined. The γ value was 10.2, indicating an extremely high contrast, and no decrease or swelling of the film in the unexposed portion was observed.

Next, Example 1 was repeated except that 488 nm visible light was used as the irradiation light beam and the exposure amount was 3 mj / cm ^2.
The shape of the image pattern was evaluated in exactly the same manner as described above. The angle was 89 degrees, which was an extremely excellent pattern shape. The minimum exposure for image formation was ² mj / cm ² .

(Note 8) Sensitizing Dye 4: A dye represented by the following formula and manufactured by Japan Photosensitive Dye Laboratories was used.

[0115]

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Example 6 Polymer A-3 100 parts Vinyl ether compound B-3 (solid content 81%) 20 parts Photoacid generator compound C-3 (Note 6) 5 parts Sensitizing dye-3 (Note 7) 1 part Was dissolved in the same manner as in Example 1 and applied to a substrate obtained by laminating a 18 μm copper foil on a polyimide film with a roll coater to a dry film thickness of 5 μm.
Dry at 8 ° C. for 8 minutes.

The γ value of this substrate was determined in exactly the same manner as in Example 1. The γ value was extremely high at 9.8.

Next, a pattern of line / space = 30/30 μm was drawn on the resist film on the substrate formed in the same manner with an energy density of ² mj / cm ² by a direct drawing machine using an argon ion laser beam having a wavelength of 488 nm. . Then, after heating at 130 ° C. for 10 minutes, development was performed with a 3% aqueous sodium carbonate solution. Thereafter, the exposed copper was etched using copper chloride, and the coating on the substrate was removed with a 3% aqueous sodium hydroxide solution, whereby an excellent etching pattern was formed on the substrate.

Example 7 Polymer A-4 (solid content: 62.5%) 80 parts Polymer A-7 65 parts Vinyl ether compound B-1 60 parts Polyethylene glycol (average molecular weight 400) 2 parts Photoacid generator compound C- 1 (Note 1) 10 parts Sensitizing dye-1 (Note 2) 1 part of the mixture was dissolved in diethylene glycol dimethyl ether to obtain a 20% by weight solution.

This was coated on a silicon wafer by a spin coater so as to have a dry film thickness of 1 μm.
Dry at 0 ° C. for 8 minutes.

The substrate was irradiated with visible light having a wavelength of 488 nm while changing the irradiation amount in a stepwise manner.
After heating for 0 minutes, development was performed using a 2.38% aqueous solution of tetramethylammonium hydroxide.

The γ value obtained from the residual ratio curve of the film after development with respect to the irradiation amount of visible light was 10.5, which was an extremely high contrast value, and no decrease or swelling of the film in the unexposed portion was observed. .

Next, the shape of the image pattern was evaluated in the same manner as in Example 1 except that the exposure amount of visible light was changed to 7 mj / cm ² . The angle was 88 degrees, which was an extremely excellent pattern shape. The minimum exposure for image formation was 5 mj / cm ² .

Example 8 Polymer A-5 (solid content 50%) 200 parts Polymer A-8 100 parts Vinyl ether compound B-2 100 parts Polyethylene glycol (average molecular weight 400) 2 parts Photoacid generator compound C-2 ( Note 4) 7.5 parts of sensitizing dye-2 (Note 5) 1 part of the mixture was dissolved in the same manner as in Example 1 and coated on a silicon wafer by a spin coater so as to have a dry film thickness of 3 μm. For 5 minutes.

This substrate was subjected to γ
The value was determined. The γ value was 11.0, indicating a very high contrast value, and no decrease or swelling of the film in the unexposed portion was observed.

Next, the substrate coated and dried under the above conditions was irradiated with 488 nm visible light as the irradiation light, and the exposure amount was 2
The shape of the image pattern was evaluated in exactly the same manner as in Example 1 except that mj / cm ² was used. The angle was 88 degrees, which was an extremely excellent pattern shape. The minimum exposure for image formation was 1.5 mj / cm ² .

Example 9 Polymer A-6 (solid content: 62.5%) 112 parts Polymer A-8 30 parts Vinyl ether compound B-3 (solid content: 81%) 15 parts Photoacid generator compound C-3 (Note 6) 5 parts of Sensitizing Dye-3 (Note 7) 1 part of the mixture was dissolved in the same manner as in Example 1, and a polyimide film laminated with 18 μm copper foil was dried with a roll coater to a dry film thickness of 5 μm. Painted on, 120
Dry at 8 ° C. for 8 minutes.

The γ value of this substrate was determined in exactly the same manner as in Example 1. The γ value was extremely high at 9.9.

Next, a pattern of line / space = 30/30 μm was drawn on the resist film on the substrate formed in the same manner with an energy density of ² mj / cm ² by a direct drawing machine using an argon ion laser beam having a wavelength of 488 nm. . Then, after heating at 130 ° C for 10 minutes, 3%
Development was performed with an aqueous solution of sodium carbonate. Thereafter, the exposed copper was etched using copper chloride, and the coating on the substrate was removed with a 3% aqueous sodium hydroxide solution, whereby an excellent etching pattern was formed on the substrate.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/033 G03F 7/033 7/039 601 7/039 601 7/38 511 7/38 511 H01L 21/027 C09D 5/32 // C09D 5/32 H01L 21/30 502R 569F

Claims (26)

[Claims] (A) a polymer containing a carboxyl group and optionally further containing a hydroxyphenyl group; (B) a compound containing at least two or more vinyl ether groups in one molecule (C) a general formula for generating an acid upon irradiation with visible light; In the formula, R is Groups (where R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or a fluorine atom); A visible light-sensitive composition comprising: a compound represented by the formula: and (D) a sensitizing dye. (A ′) a polymer containing a carboxyl group; (A ″) a polymer containing a hydroxyphenyl group;
(B) a compound containing at least two vinyl ether groups in one molecule; (C) a general formula that generates an acid upon irradiation with visible light. Wherein R is A group (wherein R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or a fluorine atom); A visible light-sensitive composition comprising: a compound represented by the formula: and (D) a sensitizing dye. 3. The polymer (A) has a content of about 500 to about 100,0.
The composition of claim 1 having a number average molecular weight of 00. 4. The composition according to claim 1, wherein the polymer (A) contains 0.5 to 10 equivalents of a carboxyl group per 1 kg of the polymer. 5. The composition according to claim 1, wherein the polymer (A) contains 1 to 10 equivalents of a hydroxyphenyl group per 1 kg of the polymer. 6. The composition according to claim 1, wherein the polymer (A) has a glass transition temperature (Tg) of 0 ° C. or higher. 7. The polymer (A ') has a content of about 3,000 to about 10
3. It has a number average molecular weight of 000.
Composition. 8. The composition according to claim 2, wherein the polymer (A ') contains 0.5 to 10 equivalents of a carboxyl group per kg of the polymer. 9. The polymer (A ″) has a polymer content of about 500 to about 100,
3. The composition of claim 2, which contains a number average molecular weight of 000. 10. The composition according to claim 2, wherein the polymer (A ″) contains 1 to 10 equivalents of hydroxyphenyl group per 1 kg of the polymer. 11. The composition according to claim 2, wherein the polymers (A ′) and (A ″) each have a glass transition temperature (Tg) of 0 ° C. or higher. 12. A compound (B) containing a vinyl ether group
Is represented by -R'-O-CH = CH ₂ [wherein
R 'represents a linear or branched alkylene group having 1 to 6 carbon atoms].
3. The composition according to claim 1, which is a compound having a low molecular weight or a high molecular weight. 13. A compound (B) containing a vinyl ether group
Is a condensate of a polyphenol compound and a halogenated alkyl vinyl ether or a reaction product of a polyisocyanate compound having an aromatic ring and a hydroxyalkyl vinyl ether. 14. The photoacid generating compound (C) is represented by the following formula: 3. The composition of claim 1 or 2 selected from the group consisting of: 15. The sensitizing dye (D) has a general formula: In the formula, R ₄ , R ₅ , R ₆ and R ₇ each independently represent a methyl group, an ethyl group, a propyl group or an isopropyl group, and R ₈ and R ₉ each independently represent a hydrogen atom, a carbon number 1-4. An alkyl group, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, a dialkylamino group having 1 to 4 carbon atoms in each alkyl portion, Cl,
Represents Br, CN, NO ₂ or SO ₂ CH ₃ , In the formula, R ₁₀ , R ₁₁ and R ₁₂ each independently represent a methyl group, an ethyl group, a propyl group or an isopropyl group, R ₁₃ and R ₁₄ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, An alkoxy group having 1 to 4 carbon atoms, an alkylcarbonyl group having 2 to 5 carbon atoms, a dialkylamino group having 1 to 4 carbon atoms in each alkyl portion, Cl, Br, C
The composition according to claim 1, wherein the composition is selected from the group consisting of a compound represented by N, NO ₂ or SO ₂ CH ₃ , a cyanine dye, a merocyanine dye, and a coumarin dye. 16. The composition according to claim 1, comprising 5 to 150 parts by weight of the vinyl ether group-containing compound (B) based on 100 parts by weight of the polymer (A). 17. The photoacid generator compound (C) is converted into a polymer (A).
The composition according to claim 1, which is contained in an amount of 0.1 to 40 parts by weight based on 100 parts by weight of the total amount of the compound (B) and the vinyl ether group-containing compound (B). 18. The composition according to claim 1, wherein the sensitizing dye (D) is contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total of the polymer (A) and the vinyl ether group-containing compound (B). 19. The composition of claim 2 wherein the weight ratio of polymer (A ') to polymer (A ") is 90/10 to 10/90. 20. The composition according to claim 2, comprising 5 to 150 parts by weight of the vinyl ether group-containing compound (B) based on 100 parts by weight of the total of the polymer (A ′) and the polymer (A ″). 21. The photoacid generator compound (C) is used in an amount of 0.1 to 40 parts by weight based on 100 parts by weight of the total of the polymer (A ′), the polymer (A ″) and the vinyl ether group-containing compound (B).
3. The composition of claim 2 which contains parts by weight. 22. The sensitizing dye (D) is contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the polymer (A '), the polymer (A ") and the vinyl ether group-containing compound (B). 3. The composition of claim 2, wherein 23. The method according to claim 1, further comprising a hydrophilic resin.
Or the composition of 2. 24. A step of applying the visible light-sensitive composition according to claim 1 or 2 to a substrate; a step of heating the substrate; a step of image-selectively irradiating visible light; and a step of heating the substrate after irradiation. And a step of sequentially developing with a basic developer. 25. The method of claim 24, further comprising the step of contacting the substrate with water after the step of image-selectively irradiating visible light. 26. A pattern formed by the method according to claim 24.