JP2003286278A - Methylenedioxolane compound, actinic ray composition by using the same and method for forming pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition capable of forming a resist film excellent in actinic ray sensitivity. <P>SOLUTION: This actinic ray composition is characterized by containing (A) a methylenedioxolane compound or its derivative and (B) at least 1 kind of a polymer selected from (a) a polymer containing 0.1-10 equivalent hydroxyphenyl group/1 kg of the polymer, and having 3,000-100,000 range number-average molecular weight and ≥0°C glass transition point, (b) a polymer containing 1-10 equivalent hydroxyphenyl group/1 kg of the polymer, and having 500-100,000 range number-average molecular weight and ≥0°C glass transition point and (c) a polymer containing 0.1-20 equivalent hydroxyphenyl and carboxyl group/1 kg of the polymer, and having 500-100,000 range number-average molecular weight and ≥0°C glass transition point, as indispensable components. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel methylenedioxolane compound, an active energy ray composition using the same, and a pattern forming method obtained by 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. Many of positive resist compositions used for these purposes use a combination of an alkali-soluble novolac resin and a quinonediazide compound as a photosensitizer. This composition utilizes a reaction in which a quinonediazide group is photolyzed by irradiation of ultraviolet rays to form an indenecarboxylic acid via ketene.

However, the resist using the quinonediazide compound may have insufficient resolution when it is necessary to form a very fine pattern. On the other hand, in JP-A-6-295064, a photosensitive composition comprising a polymer containing a carboxyl group, a compound containing two or more vinyl ether groups in one molecule, and a compound generating an acid upon irradiation with active energy rays. Is disclosed. When a coating film formed from this composition is heated (primary heating), the polycarboxylic acid resin is crosslinked due to the addition reaction between the carboxyl group and the vinyl ether group and becomes insoluble in the solvent or the alkaline aqueous solution. When irradiation is performed after irradiation with radiation (secondary heating), the cross-linking structure is cleaved by the catalytic action of the acid generated by irradiation with active energy rays, and the irradiated area becomes soluble again in the solvent or alkaline aqueous solution. A resist pattern is formed by removing.

The above-mentioned method of forming a circuit pattern by heating by generating an acid by irradiation of an active energy ray with a polycarboxylic acid resin, a polyfunctional vinyl ether compound and a polyfunctional vinyl ether compound is basically required in recent years to form a very fine circuit pattern. Can be said to be able to meet. However, by-products (outgas) such as acetaldehyde are generated during the reaction caused by heating, which causes problems such as contamination of the exposure device, contamination of the photomask, and deterioration of the working environment. Therefore, a reaction system that does not generate outgas such as acetaldehyde as a by-product is desired.

[0005]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that the composition containing the above-mentioned vinyldioxolane skeleton group-containing compound is particularly effective after irradiation with active energy. The inventors have found that a stable positive resist pattern having excellent sensitivity and resolution and capable of forming a stable positive resist pattern can be formed without generating acetaldehyde in the reaction of, and thus completed the present invention.

That is, the present invention is 1, formula (1)

[0007]

[Chemical 5]

And equation (2)

[0009]

[Chemical 6]

And equation (3)

[0011]

[Chemical 7]

And equation 4

[0013]

[Chemical 8]

(In the above formulas (1) to (4), R ₁ ,
R ₉ , R _{10 and} R ₁₈ are the same or different and each represents a monovalent hydrocarbon group having 1 to 24 carbon atoms, which may have a carbocyclic structure, an aromatic ring or a heterocyclic structure, and R ₂ to R ₇ ,
_{R 11 ~R 16, R 20 ~R} 2 8, R 30 ~R 32, R
_{34 to} R ₃₆ or R _{38 to} R ₄₀ are the same or different and each represents a monovalent hydrocarbon bond having 1 to 24 carbon atoms or a hydrogen atom which may have a carbocyclic structure, an aromatic ring or a heterocyclic structure. shown, R _19, R ₃₃ or _{R 37} is a divalent carbon atoms 1 to 24 or a hydrocarbon group, R _8, R ₁₇ or R
₂₉ represents a hydrocarbon group having 1 to 24 carbon atoms. At least one methylenedioxolane compound or a derivative thereof (hereinafter, may be collectively abbreviated as “methylenedioxolane compound (A)”), 2, the above methylenedioxolane compound (A), polymer Polymer (a) containing 0.1 to 10 equivalents of carboxyl group per kg and having a number average molecular weight in the range of 3000 to 100000 and a glass transition temperature of 0 ° C. or higher, and at least 1 to 1 kg of the polymer. 10
Contains an equivalent amount of hydroxyphenyl groups, and
Polymer (b) and polymer 1k having a number average molecular weight in the range of 100,000 and a glass transition temperature of 0 ° C. or higher
contains at least 0.1 to 20 equivalents of hydroxyphenyl and carboxyl groups per gram, and 500 to 1
Active energy ray characteristic, containing at least one polymer (B) selected from polymers (c) having a number average molecular weight in the range of 00000 and a glass transition temperature of 0 ° C. or higher as an essential component. Composition, 3. The active energy ray composition, wherein the active energy ray composition comprises a photoacid generator compound (C), 4. The substrate is coated with the active energy ray composition. Step, step of heating the substrate, step of irradiating active energy rays so that a pattern can be formed with active energy rays, step of performing no heating after irradiation, or performing heat treatment at a temperature lower than 140 ° C., base Pattern forming method, characterized in that the steps of developing with a positive developing solution are sequentially carried out. 5. The active energy ray-permeable composition is transmitted through the active energy ray. That was coated on a transparent support film, making formation allowed active energy ray dry film resist coating layer of dried active energy ray composition step,
A step of pressing the active energy ray coating layer of the dry film resist onto a substrate on which a resist pattern is formed,
The step of heating the substrate, the step of irradiating the active energy ray through the supporting film with the active energy ray, the supporting film is peeled off, and heating is not performed after the irradiation, or 1
A pattern forming method, which comprises sequentially performing a heat treatment step at a temperature of less than 40 ° C., and then performing a developing step with a basic developing solution. 6. The above active energy ray composition on a transfer film And then dried to form an active energy ray coating layer to form a transfer film resist, a step of pressure-bonding the photosensitive active energy ray layer of the transfer film resist to a substrate, a step of heating the substrate, and peeling off the support film. ,
A step of irradiating with an active energy ray so that a desired pattern is formed, a step of performing no heat treatment after irradiation, or a step of performing heat treatment under the condition of less than 140 ° C., and a step of developing with a basic developing solution The present invention relates to a pattern forming method characterized by being performed.

[0015]

Hereinafter, the present invention will be described in more detail. First, the methylenedioxolane compound (A) of the present invention will be described.

Methylenedioxolane compound (A): The vinyldioxolane compound (A) of the present invention contains 1 to 4 vinyl groups in one molecule, and an oxolane group formula (5) represented by the following formula.

[0017]

[Chemical 9]

It is a compound having 1 to 4 units in one molecule.

The vinyldioxolane compound (A) is a compound represented by the following formulas (1) to (4). Formula (1)

[0020]

[Chemical 10]

And equation (2)

[0022]

[Chemical 11]

And equation (3)

[0024]

[Chemical 12]

And equation 4

[0026]

[Chemical 13]

(In the above formulas (1) to (4), R ₁ ,
R ₉ , R _{10 and} R ₁₈ are the same or different and each represents a monovalent hydrocarbon group having 1 to 24 carbon atoms, which may have a carbocyclic structure, an aromatic ring or a heterocyclic structure, and R ₂ to R ₇ ,
_{R 11 ~R 16, R 20 ~R} 2 8, R 30 ~R 32, R
_{34 to} R ₃₆ or R _{38 to} R ₄₀ are the same or different and each represents a monovalent hydrocarbon bond having 1 to 24 carbon atoms or a hydrogen atom which may have a carbocyclic structure, an aromatic ring or a heterocyclic structure. shown, R _19, R ₃₃ or _{R 37} is a divalent carbon atoms 1 to 24 or a hydrocarbon group, R _8, R ₁₇ or R
₂₉ represents a hydrocarbon group having 1 to 24 carbon atoms. In the formulas (1) to (4), examples of the monovalent hydrocarbon group having 1 to 24 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a heptyl group, an octyl group, Examples thereof include a decanyl group and a dodecanyl group. These groups may be linear or branched.
In the formulas (1) to (4), the carbocyclic structure includes a cyclohexyl group, a phenyl group and the like. The heterocyclic structure includes, for example, pyrans, pyrones, pyrroles, pyrrolines, pyrrolidines, imidazolines,
Imidazolidines Pyrazolidines, piperidines, piperazines, morpholines, indolines, chromans and the like are included.

Examples of the methylenedioxolane compounds represented by the formulas (1) to (4) include the following compounds.

[0029]

[Chemical 14]

[0030]

[Chemical 15]

[0031]

[Chemical 16]

[0032]

[Chemical 17]

[0033]

[Chemical 18]

Polymer (B): Polymer containing a carboxyl group (a): A film-forming polymer containing at least one carboxyl group in one molecule, for example, a polymerizable group containing a carboxyl group. Homopolymer of saturated monomer; Copolymer of the carboxyl group-containing monomer and other copolymerizable monomer; Polyester type, polyurethane type, polyamide having a carboxyl group in the molecular chain or at the molecular end Examples of such resins include resins.

Examples of the above-mentioned polymerizable unsaturated monomer containing a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, itaconic acid and the like, and are copolymerizable with these carboxyl group-containing monomers. Examples of the 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; (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl, (meth) C ₂ of (meth) acrylic acid such as hydroxyethyl acrylate-butyl ~ C ₆ hydroxyalkyl ester; styrene,
Vinyl aromatic compounds such as α-methylstyrene and p-tert-butylstyrene; vinyl acetate, (meth) acrylonitrile, (meth) acrylamide, vinylpyrrolidone and the like, and these monomers may be used alone. Alternatively, two or more kinds can be used in combination. In particular, as the other monomer, styrene, α-methylstyrene, C ₁ -C ₆ alkyl-substituted styrene (for example, p
The use of vinyl aromatic compounds such as -tert-butyl styrene) may improve the accuracy of the image pattern formed,
It is suitable in terms of etching resistance and the like.

The polymer (a) is about 3000 to about 1000.
00, especially a number average molecular weight in the range of about 5,000 to about 30,000, and the content of the carboxyl group is generally 0.1 to 1 per 1 kg of the polymer.
It is desirable that the amount is within the range of 0 equivalent, particularly 0.5 to 5.0 equivalent. Carboxyl group content is 0.5 equivalent / kg
If it is less, the degree of cross-linking of the film formed by heating before actinic ray irradiation is not sufficient, and the solubility of the exposed portion in an alkaline developing solution is low and the developability tends to decrease, while 10 equivalent / If it exceeds kg, the storage stability of the composition tends to decrease.

The polymer (a) has a glass transition temperature (hereinafter, this may be simply referred to as "Tg").
Is preferably 0 ° C. or higher, and particularly preferably in the range of 5 to 70 ° C. If the Tg is less than 0 ° C., the coating film becomes tacky, and dust and dirt are likely to adhere to it, which tends to make it difficult to handle.

Polymer containing hydroxyphenyl groups
(B): The polymer (b) is a polymer containing at least one hydroxyphenyl group in one molecule, and includes, for example, a monofunctional or polyfunctional phenol compound, an alkylphenol compound or a mixture thereof, and formaldehyde,
Condensate with carbonyl compound such as acetone; Homopolymer of hydroxy group-containing vinyl aromatic compound such as p-hydroxystyrene; Copolymerization of the hydroxyl group-containing vinyl aromatic compound with other copolymerizable monomer Examples include coalescence.

Examples of the monofunctional or polyfunctional phenol compound include phenol, o-cresol, and m.
-Cresol, p-cresol, 3,5-xylenol, 2,6-xylenol, 2,4-xylenol, catechol, resorcin, pyrogallol, bisphenol A
And compounds having 1 to 3 hydroxyl groups on the benzene ring.

Examples of the alkylphenol compound include p-isopropylphenol and p-ter.
Examples thereof include alkylphenol compounds having 1 to 10, preferably 1 to 4 carbon atoms in the alkyl moiety such as t-butylphenol, p-tert-amylphenol, and p-tert-octylphenol.

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. Generally, when the condensation reaction is carried out with an alkali catalyst, it becomes insoluble and infusible as the condensation proceeds. And a soluble and fusible novolak type is obtained by condensation with an acid catalyst.

The molecular weight of the novolac type phenol resin usually increases as the condensation proceeds, but the molecular weight obtained by condensing in the reaction time of 1 to 3 hours is 500 to 2
Those within the range of 000 are preferable.

Further, as the other monomer copolymerizable with the hydroxy group-containing vinyl aromatic compound, the same copolymerizable other monomer as the above-mentioned other monomer copolymerizable with the carboxyl group-containing monomer can be used. Can be used.

Such hydroxyphenyl group-containing polymer (b) is generally about 500 to about 1,000,000, especially about 1
It is preferred to have a number average molecular weight in the range of 000 to about 30,000.

The content of hydroxyphenyl group in the polymer (b) is generally 1.0 to 10 per 1 kg of the polymer.
It is expedient to be in the range of equivalents, especially 2.0 to 8.0 equivalents. When the content of hydroxyphenyl groups is less than 1.0 equivalent / kg, the degree of crosslinking of the film formed by heating before actinic ray irradiation tends to be insufficient, and when it exceeds 10 equivalents / kg, the resist film is formed. It easily becomes brittle.

The polymer (b) is also the same as the polymer (a).
It is preferable that the Tg is 0 ° C. or higher, particularly 5 to 70 ° C. If the Tg is less than 0 ° C., the coating film becomes tacky, and dust and dirt are likely to adhere to it, which tends to make it difficult to handle.

Carboxyl group and hydroxyphenyl group
Polymer (c) containing: The polymer (c) is a film-forming polymer containing at least one carboxyl group and hydroxyphenyl group in one molecule, and is, for example, a hydroxy group such as p-hydroxystyrene. Copolymers of styrene and a polymer unsaturated monomer containing a carboxyl group; examples thereof include hydroxystyrene and a copolymer of the carboxyl group-containing monomer and another copolymerizable monomer. .

Examples of the above-mentioned polymerizable unsaturated monomer containing a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, and the like. 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) C2-C6 hydroxyalkyl ester of (meth) acrylic acid such as 3-hydroxypropyl acrylate and hydroxybutyl (meth) acrylate; styrene, α-methylstyrene,
Vinyl aromatic compounds such as p-tert-butylstyrene; vinyl acetate, (meth) acrylonitrile, (meth)
Examples thereof include acrylamide and vinylpyrrolidone. These monomers may be used alone or in combination of two or more kinds.

Further, as the polymer (c), phenolcarboxylic acids such as hydroxybenzoic acid, gallic acid and resorcinic acid, or these, and phenol, mono- or di-alkylphenols having 1 to 18 carbon atoms or naphthols, resorcin, A polymer obtained by condensing a mixture of one or more phenols selected from catechol and the like with formaldehyde can also be used.

The polymer (c) is generally about 500 to about 1.
It is preferred to have a number average molecular weight in the range of 00000, especially about 1500 to about 30,000.

In the polymer (c), the content of carboxyl group in the polymer is generally 0.1 per 1 kg of the polymer.
To 20 equivalents, especially 0.5 to 5.0 equivalents,
The hydroxyphenyl group of the polymer is preferably at least 1.0 equivalent, and particularly preferably 2.0 to 8.0 equivalents per kg of the polymer.

When the content of the carboxyl group of the polymer (c) is less than 0.5 equivalent / kg, the degree of crosslinking of the film formed by heating before actinic ray irradiation is not sufficient, and
The solubility of the exposed part in an alkaline developing solution is low and the developability tends to be low, while when it exceeds 10 equivalents / kg, the storage stability of the composition tends to be low, which is not preferable.

When the content of the hydroxyphenyl group in the polymer (c) is less than 1.0 equivalent / kg, the degree of crosslinking at the time of crosslinking is not sufficient, which is not preferable.

The polymer (c) has a Tg of 0 ° C. or higher,
It is particularly preferable that the temperature is within the range of 5 to 70 ° C. Tg
Is less than 0 ° C., the coating film exhibits tackiness, dust and dirt are likely to be attached, and handling tends to be difficult.

Photoacid generator compound C: Photoacid generator compound C
Is a compound which decomposes upon irradiation with the following active energy rays to generate an acid having a sufficient strength to cleave the crosslinked structure formed between the polymer B and the divinyl ether compound A, Known materials can be used.

Examples of compounds and mixtures used as photoacid generator compound C include diazonium, phosphonium,
Sulfonium and Iodonium Salts: Halogen Compounds: Organometallic / Organohalogen Combinations: Strong Acids such as Benzoin and 0-Nitrobenzyl Esters of Toluenesulfonic Acid: and N-Hydroxyamides and N-Hydroxyimide Sulfonates as Described in US Pat. No. 4,371,605. Kind is included. Also included are aryl naphthoquinone diazide-4-sulfonates. Suitable photosolubilizers are diaryliodonium or triarylsulfonium salts.

They are generally present in the form of salts of complex metal halide ions, such as tetrafluoroborate, hexafluoroantimonate, hexafluoroarsenate and hexafluorophosphate. Another useful group of photolabile acid generators includes oligomers and polymers to which anionic groups having an aromatic onium acid generator as the positive counterion are attached. Examples of the above polymers include US Pat.
1,429 columns 9, lines 1-68 and columns 10,
Included are the polymers described at lines 1-14. It is desirable to add a sensitizer to this system in order to adjust the spectral sensitivity to the available wavelengths of actinic radiation. This need depends on the requirements of the system and the particular photosensitive compound used. For example, for iodonium and sulfonium salts that respond only to wavelengths below 300 nm, benzophenone and its derivatives, polycyclic aromatic hydrocarbons such as perylene, pyrene and anthracene, and their derivatives can be used to
It can be exposed to longer wavelengths. Decomposition of diallyl iodonium and triaryl sulfonium salts is also described by bis- (p-N, N-dimethylaminobenzylidene)
-Acetone can be sensitized. Sulfonium salts linked to anthracene having a chain length of 3 to 4 atoms are effective photosolubilizers. MG. Tilley Ph.D. Thesis, North Dakota State University, Fargo, ND (198
8) [Diss. Abstr. Lnt. B, 49, 8791 (1989): Chem. Abst.
r., 111, 39942u] are suitable types of photosolubilizers. Other suitable acid generators are ATAS
S, ie 3- (9-anthracenyl) propyl diphenylsulfonium hexafluoroantimonate. In this compound, the anthracene and sulfonium salt are linked by a chain of 3 carbons.

Additional examples of photoacid generator compound C which may be used herein are diphenyl iodonium tosylate,
Benzoin tosylate, and triarylsulfonium hexafluoroantimonate. In addition to the above, for example, iron-allene complexes, ruthenium allene complexes, silanol-metal chelate complexes, triazine compounds, diazidonaphthoquinone compounds, sulfonic acid esters, sulfonic acid imide esters, Halogen compounds and the like can be used. Furthermore, JP-A-7-1
The acid generators described in Japanese Patent No. 46552 and Japanese Patent Application No. 9-289218 can also be used.

The photoresist composition of the present invention is used as an organic solvent-based or water-based type in which the above-mentioned components are dispersed or dissolved in an organic solvent (if a pigment is used as a coloring agent, the pigment is finely dispersed). be able to.

The blending ratio of the photoresist composition can be varied over a wide range depending on the use of the composition and the like, but the divinyl ether compound A is the polymer B10.
About 5 to 150 parts by weight, especially 10 to 10 parts by weight
It is preferable to use within the range of 0 parts by weight. The photoacid generator compound C is used in an amount of about 0.1 to 40 parts by weight, particularly 0.2 to 20 parts by weight, based on 100 parts by weight of the total amount of the polymer B and the divinyl ether compound A. Appropriate.

A sensitizing dye may be added to the photoresist composition of the present invention if necessary. Examples of sensitizing dyes that can be used include phenothiazine-based, anthracene-based, coronene-based, benzanthracene-based, perylene-based,
Examples include dyes of pyrene type, merocyanine type, ketocoumarin type, and the like.

The blending amount of these sensitizing dyes is the same as that of polymer B10.
0.1 to 10 parts by weight, preferably 0.
A range of 3 to 5 parts by weight is suitable.

A colorant may be added to the photoresist composition of the present invention if necessary, and as the colorant which can be used, for example, a combination of a leuco dye and a halogen compound is often used. Examples of leuco dyes include tris (4-dimethylamino-phenyl) methane hydrochloride “leuco crystal violet”, bis (4-dimethylaminophenyl) phenylmethane hydrochloride “leuco malachite green” and the like. On the other hand, as the halogen compound, amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzayl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2, 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-
2,2-bis (P-chlorophenyl) ethane, hexachloroethane and the like can be mentioned. Coloring agents other than those shown here may be contained.

In the photoresist composition of the present invention, a plasticizer such as phthalate ester, a polyester resin, an acrylic resin, etc. may be added in order to impart appropriate flexibility and non-adhesiveness to the resist film, if necessary. May be added. Usually, the addition amount thereof is preferably 50 parts by weight or less based on 100 parts by weight of the total amount of the divinyl ether compound A and the polymer B.

If necessary, a flowability modifier may be added to the photoresist composition of the present invention.

The photoresist composition of the present invention can be prepared by mixing the above-mentioned components as they are or in a solvent if necessary. The solvent that can be used in that case is not particularly limited as long as it can dissolve each component of the composition, and examples thereof include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone; methyl acetate, ethyl acetate, acetic acid. Esters such as butyl; aliphatic alcohols having 1 to 10 carbon atoms such as methanol, ethanol, propanol; alcohols containing an aromatic group such as benzyl alcohol; glycols such as ethylene glycol and propylene glycol; these glycols and methanol , Glycol ethers such as monoether or diether with ethanol, butanol, hexanol, octanol, benzyl alcohol, phenol, etc., or esters of the monoether; cyclic ethers such as dioxane, tetrahydrofuran, etc. Ethylene carbonate, cyclic carbonates such as propylene carbonate, aliphatic and aromatic hydrocarbons, and the like. These solvents may be used alone or in combination of two or more, if necessary.

Next, the pattern forming method of the present invention will be described below.

Pattern forming method 1: The pattern forming method according to claim 3, wherein the step of applying the active energy ray composition to a substrate, the step of heating the substrate, and the pattern of active energy rays can be formed. Thus, it can be formed by sequentially performing the step of irradiating with active energy rays, the step of performing no heating after irradiation, or the step of performing heat treatment at a temperature of less than 140 ° C., and the step of developing with a basic developer.

Pattern formation method 2: The pattern formation method according to claim 4, wherein the active energy ray composition is applied onto a transparent support film which can transmit active energy rays and dried to obtain active energy ray characteristics. A step of forming a coating layer of the composition to form an active energy ray-type dry film resist, a step of pressing the active energy ray-type coating layer of the dry film resist to a substrate on which a resist pattern is formed, a step of heating the substrate, an active energy ray Of irradiating active energy rays through the support film, without heating after irradiation, or at 140 ° C
It can be formed by sequentially performing a step of performing a heat treatment under the condition of less than that, and then sequentially performing a step of peeling off the supporting film and developing with a basic developing solution.

Pattern forming method 3: The pattern forming method according to claim 5, wherein the active energy ray composition is applied onto a transfer film and dried to form an active energy ray coating layer to form a transfer film resist. A step of producing, a step of press-bonding the photosensitive active energy ray layer of the transfer film resist to a substrate, a step of heating the substrate, a step of peeling the transfer film after heating, and an active energy ray so that a desired pattern is formed. The step of irradiating, the step of performing no heating after irradiation, or the step of performing heat treatment under the condition of less than 140 ° C., peeling the support film,
It can be formed by sequentially performing the steps of developing with a basic developer.

The materials and methods used in the steps of the above-mentioned pattern forming methods 1 to 3 will be described below.

As the substrate to which the active energy ray-based composition is applied, for example, a copper-clad laminated substrate or the like can be used.

Means for applying the active energy ray composition to the substrate include, for example, a roller, a roll coater,
Spin coater, curtain roll coater, spray,
It can be applied by means of electrostatic coating, dip coating, silk printing, spin coating and the like.

The conditions for heating the coated substrate are as follows:
In a hot air drying oven at 60 ℃ ~ 150 ℃ 1 minute ~ 1 hour, preferably
A coating film can be formed by heating at 80 ° C to 120 ° C for 5 minutes to 30 minutes.

As a light source for irradiating an active energy ray so that a pattern can be formed with the active energy ray, a light source conventionally used, for example, ultrahigh pressure, high pressure, medium pressure,
Oscillates in the visible region or the visible region by cutting the light source obtained from each light source such as low-pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, sunlight, etc. with an ultraviolet cut filter. Various lasers with lines can be used. As a high-power and stable laser light source, the second harmonic (532 nm) of an argon laser or a YAG laser is preferable.

As the basic developing solution, the liquid developing treatment is
For example, the developing solution is about 10 to 80 ° C., preferably about 15 to
Liquid temperature of 50 ° C for about 10 seconds to 60 minutes, preferably about 3
A pattern can be formed on the resin layer for film formation by spraying or dipping for 0 seconds to 30 minutes.

The liquid developing treatment is carried out, for example, by monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, monobutylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, diethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, diethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, triethanolamine, diethanolamine, triethanolamine, triethanolamine. Examples thereof include aqueous solutions such as ethanolamine, dimethylaminoethanol, diethylaminoethanol, ammonia, caustic soda, caustic potash, sodium metasilicate, potassium metasilicate, sodium carbonate, and tetraethylammonium hydroxide. Polyethylene terephthalate or the like can be used as the transparent support film that can transmit active energy rays.

A method for press-bonding the active energy ray coating layer of the dry film resist to a substrate on which a resist pattern is formed is, for example, 60 ° C. to 10 ° C. in advance.
It can be pressure-bonded by heating at 0 ° C. and applying pressure at a temperature of 30 to 150 ° C.

Next, as a condition for heating the pressure-bonded substrate, a method of heating at a temperature of 60 ° C. or less may be adopted.

Examples of the transfer film include polyethylene terephthalate.

As a method for pressure-bonding the photosensitive active energy ray layer of the transfer film resist to the substrate, for example, the substrate is heated to 60 ° C. to 100 ° C. in advance and pressure-bonded at a temperature of 30 to 150 ° C. it can.

The composition of the present invention is a known photosensitive material such as paint, ink, adhesive, resist material, printing plate material (plate making material for flat plates and relief printing plates, PS plate for offset printing, etc.), information recording material. It can be used in a wide range of applications such as relief image forming materials. The method of the present invention can be applied without any particular limitation such as use, as long as it includes the above steps.

Examples of the use include, for example, by industrial field:
Electric parts, lighting, electric elements, semiconductors,
Electricity such as printing, printed circuit, electronic communication, electric power; measurement, optics, display, acoustics, control, vending, signal, information recording, etc .; inorganic chemistry , Organic chemistry, polymer chemistry, metallurgy, fiber chemistry / metallurgy / fibers; separation / mixing, metal working, plastic working, printing, container, packaging, etc. Classes: Agricultural and fisheries related products, food related products, fermentation related products, household products related products, health / entertainment related products, and mechanical engineering products.

Examples of the above-mentioned electricity include a black matrix insulating coating forming method, a build-up insulating coating forming method, a solder resist insulating coating forming method, a display panel partition wall forming method, a display panel black belt forming method, and a color. A method for forming a colored insulating film of a filter, a display panel phosphor, a hologram pattern, a CD mastering, a coil, and the like; physical examples include optical fiber processing, a floppy disk, a magnetic tape, a magnetic card, an optical component, an electromagnetic wave absorber, and the like; Examples of metallurgy / fibers include inorganic, glass, cement, and ceramic insulators; examples of treatment / transportation include printed matter, printing original plates, diffraction gratings, markings, barcodes, masks, filters, etching, defrosters, Cement processing, stone processing, fiber processing, plastic Click processing, labels, etc., as the life outfits, such as carriers, cosmetic, fermentation industry such as; the mechanical engineering such, micromachine components, and the like, for example.

[0085]

The methylenedioxolane compound or derivative thereof of the present invention is obtained by applying a mixture of a polycarboxylic acid resin and / or a phenol compound and a photoacid generator to a substrate,
The formed film can be irradiated with active energy rays to generate an acid, and then a circuit pattern can be formed by heating, but since byproducts such as acetaldehyde (outgas) do not occur in the reaction caused by the above heating. There is no problem such as stains on the exposure device, stains on the photomask, and deterioration of working environment.

[0086]

EXAMPLES The present invention is not limited to the examples described below. Parts and% are based on weight.

Synthesis of Polymer Containing Carboxyl Group 7.8 parts of acrylic acid, 50 parts of methyl methacrylate, 12.2 parts of ethyl acrylate, 30 parts of phenoxyethylene glycol acrylate, tertiary butyl peroxy 2-ethylhexanoate (polymerization initiation It was obtained by polymerizing a mixture of 1 part of the agent.

Synthesis of polymer containing hydroxyphenyl group 1490 parts of O-cresol, 114% of formalin 114
5 parts, 130 parts of deionized water and 6.5 parts of oxalic acid were placed in a flask and refluxed for 60 minutes. Then add 15% hydrochloric acid to 13.5
After adding 40 parts and refluxing for 40 minutes, 400 parts of about 15 ° C. deionized water was added to keep the content at about 75 ° C. to precipitate the resin.
Then, a 35% sodium hydroxide solution was added to neutralize, 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 novolac phenol resin.

Carboxyl group and hydroxyphenyl group
Synthesis of polymer containing O-hydroxybenzoic acid 600 parts, O-cresol 900
Part, 30% formalin 1145 parts, deionized water 130
And 6.5 parts of oxalic acid were placed in a flask and refluxed for 60 minutes. Then, 13.5 parts of 15% hydrochloric acid was added and refluxed for 40 minutes, then 400 parts of deionized water of about 15 ° C. was added to keep the content at about 50 ° C. to precipitate the resin. After adding 400 parts of deionized water and washing the resin at 50 ° C., the water layer is removed,
Furthermore, after repeating the same washing operation three times, the pressure was reduced to about 1
It was dried at 20 ° C. to obtain a novolac phenol resin. Molecular weight about 650, carboxyl group content 2.8 mol / kg
Polymer, hydroxyl phenyl group content 5.4 mol / k
g polymer.

Example 1 100 parts of polymer, 4,4'-dimethylene- [2,2 '
-Propylenebis (1,3-dioxolane)] (Note 1)
A mixture of 53 mmol / 100 g of the polymer and 2 parts of a photo-acid generator (the same applies to UVAC 1591 manufactured by Daicel UCB Co., Ltd.) was dissolved in cyclohexanone to give a 30 wt% solution.

It is coated on a copper foil with a bar coater so as to have a dry film thickness of 10 μm and dried at 100 ° C. for 10 minutes to carry out an addition reaction of a carboxyl group and dimethylenedioxolane.

This substrate was irradiated with ultraviolet light of 365 nm through a step tablet (21 steps, manufactured by Hitachi), left at room temperature for 10 minutes, and then developed using a 0.75% sodium carbonate aqueous solution at 25 ° C. (Note 1)

[0093]

[Chemical 19]

Table 1 shows the attributions of the compound measured by ¹ H-NMR analysis. Table 1

[0095]

[Table 1]

Table 2 shows the results of the measurement of the compound by infrared spectroscopy (IR). Table 2

[0097]

[Table 2]

Example 2 100 parts of polymer, 4,4'-dimethylene- [2,2 '
-Propylene bis (1,3-dioxolane)] 53mm
A mixture of 100 g of ol / polymer and 2 parts of a photo-acid generator was dissolved in cyclohexanone to prepare a 30 wt% solution. It is coated on a copper foil with a bar coater to a dry film thickness of 10 μm and dried at 100 ° C. for 10 minutes to carry out an addition reaction of a carboxyl group and vinyl ether. This substrate was irradiated with ultraviolet light of 365 nm through a step tablet (21 steps, manufactured by Hitachi), left at room temperature for 10 minutes, and then developed using a 0.75% sodium carbonate aqueous solution at 25 ° C.

Example 3 100 parts of polymer, 4,4'-dimethylene- [2,2 '
-Propylene bis (1,3-dioxolane)] 53mm
A mixture of 100 g of ol / polymer and 2 parts of a photo-acid generator was dissolved in cyclohexanone to prepare a 30 wt% solution. It is coated on a copper foil with a bar coater to a dry film thickness of 10 μm and dried at 100 ° C. for 10 minutes to carry out an addition reaction of a carboxyl group and vinyl ether. This substrate was irradiated with ultraviolet light of 365 nm through a step tablet (21 steps, manufactured by Hitachi), left at room temperature for 10 minutes, and then developed using a 0.75% sodium carbonate aqueous solution at 25 ° C.

Example 4 On an untreated polyethylene terephthalate film having a thickness of 38 μm, 100 parts of polymer, 4,4′-dimethylene-
[2,2'-Propylenebis (1,3-dioxolane)]
A mixture of 53 mmol / 100 g of the polymer and 2 parts of the photo-acid generating compound was dissolved in cyclohexanone to obtain a 30 wt% solution.

The resist was applied by a roll coater to a dry film thickness of 10 μm, and then dried at 100 ° C. for 10 minutes. Then, a 20 μm thick untreated polypropylene film was attached to the resist surface to obtain a dry film type resist.

This dry film type resist was formed to a thickness of 1
A substrate obtained by laminating a copper foil of 18 μm on a polyimide film of 00 μm was pressure bonded using a laminator with a roll temperature of 100 ° C. This substrate was exposed in the same manner as in Example 1 and allowed to stand at room temperature for 10 minutes, then the supporting film was peeled off, and the photosensitivity was measured in the same manner as in Example 1.

Example 5 100 parts of polymer, 4,4'-dimethylene-on a non-treated polyethylene terephthalate film having a thickness of 38 μm.
[2,2'-Propylenebis (1,3-dioxolane)]
A mixture of 53 mmol / 100 g of the polymer and 2 parts of the photo-acid generating compound was dissolved in cyclohexanone to obtain a 30 wt% solution.

The resist was applied by a roll coater to a dry film thickness of 10 μm, and dried at 100 ° C. for 10 minutes to obtain a transfer film type resist.

This transfer film type resist was formed to a thickness of 10
A laminator with a roll temperature of 100 ° C. was used for pressure bonding to a substrate obtained by laminating a 18 μm copper foil on a 0 μm polyimide film. The support film was peeled off, and the substrate was exposed in the same manner as in Example 1 and allowed to stand at room temperature for 10 minutes.
The photosensitivity was measured in exactly the same manner as in Example 1.

Example 6 After irradiation with ultraviolet light having the same composition as in Example 1 and heating at 100 ° C. for 10 minutes, development was performed using a 0.75% aqueous sodium carbonate solution at 25 ° C.

Example 7 The same composition as in Example 2 was irradiated with ultraviolet light and heated at 100 ° C. for 10 minutes, followed by development with a 0.75% aqueous sodium carbonate solution at 25 ° C. Example 8 After irradiation with ultraviolet light having the same composition as in Example 3, heating was conducted at 100 ° C. for 10 minutes, and development was performed using a 0.75% aqueous sodium carbonate solution at 25 ° C.

Example 9 After irradiation with ultraviolet light having the same composition as in Example 4 and heating at 100 ° C. for 10 minutes, development was carried out using a 0.75% aqueous sodium carbonate solution at 25 ° C.

Example 10 The same composition as in Example 5 was irradiated with ultraviolet light, heated at 100 ° C. for 10 minutes, and developed using a 0.75% aqueous sodium carbonate solution at 25 ° C.

Performance evaluation: Drying property after finger-drying after finger-drying: Drying property against finger-sticking after coating and drying the above-mentioned Examples 1 to 10 was evaluated according to the following criteria.
○: No stickiness at all, △: Only slightly sticky, ×: Sticky sensitivity: After applying and drying the above Examples 1 to 10 or pressing on a substrate, an ultraviolet light of 365 nm was used as a step tablet (Hitachi). Made 2
(1 step), Examples 1 to 5 were left at room temperature for 10 minutes, and then developed using a 0.75% aqueous sodium carbonate solution at 25 ° C. Examples 6 to 10 were heated at 100 ° C. for 10 minutes and then at 25 ° C.
Development was performed using a 75% sodium carbonate aqueous solution to prepare an evaluation substrate.

Etching resistance: Each of the evaluation substrates prepared as described above was visually evaluated with a cupric chloride etching solution for peeling of the coating film according to the following criteria. ◯: No peeling, Δ: Slightly peeling, ×: Peeling peelability: The evaluation substrate prepared as described above was immersed in a 3% sodium hydroxide aqueous solution at 50 ° C. and visually observed. The removability and peelability of the coating film were evaluated according to the following criteria. ◯: No residue at all, Δ: Slightly residual residue, ×: Resist remained on the entire surface Table 1 shows the results of the above tests. As is clear from the results in Table 1, the coating film formed from the photosensitive resin composition of the present invention was excellent in sensitivity and etching resistance, and was also excellent in peelability.

Table 3

[0113]

[Table 3]

Table 4

[0115]

[Table 4]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI theme code (reference) G03F 7/38 501 G03F 7/38 501 H05K 3/06 H05K 3/06 J F term (reference) 2H025 AB01 AB15 AB16 AB17 AB20 AC01 AC08 AD03 BE00 CB10 CB13 CB14 CB17 CB29 CB43 CB45 CB55 CB60 CC20 FA01 FA03 FA12 FA17 2H096 AA01 AA25 AA26 AA27 AA30 BA11 BA20 DA01 EA02 EA02 EA02 CE03 5E06 BE13 BB06 CB16 CB06 CB02

Claims (6)

[Claims] 1. Formula (1): And the formula (2) And the formula (3) And Equation 4 (In the above formulas (1) to (4), R ₁ , R ₉ , R ₁₀
Or R ₁₈ is the same or different and represents a monovalent hydrocarbon group having 1 to 24 carbon atoms, which may have a carbocyclic structure, an aromatic ring or a heterocyclic structure, and R _{2 to} R ₇ and R ₁₁ ~ R _{16
, R 20 ~R 2 8, R} 30 ~R 32, R 34 ~R 36
Or R _{38 to} R ₄₀ are the same or different and each represents a monovalent hydrocarbon bond having 1 to 24 carbon atoms or a hydrogen atom which may have a carbocyclic structure, an aromatic ring, or a heterocyclic structure;
R ₁₉ , R ₃₃ or R ₃₇ represents a divalent hydrocarbon group having 1 to 24 carbon atoms, and R ₈ , R ₁₇ or R ₂₉ has 1 carbon atom.
~ 24 hydrocarbon groups. At least one methylenedioxolane compound selected from the following) or a derivative thereof. 2. A methylenedioxolane compound or a derivative thereof (A) according to claim 1, and 0.1% per 1 kg of the polymer.
Contains 1 to 10 equivalents of carboxyl groups, and 300
Number average molecular weight in the range of 0 to 100,000 and 0 ° C
Polymer (a) having the above glass transition temperature, containing at least 1 to 10 equivalents of a hydroxyphenyl group per kg of the polymer, and having a number average molecular weight in the range of 500 to 100,000 and a glass transition temperature of 0 ° C. or higher. (B) having at least 0.1 to 20 equivalents of hydroxyphenyl group and carboxyl group per 1 kg of the polymer, and having a number average molecular weight in the range of 500 to 100,000 and a glass transition temperature of 0 ° C. or higher. An active energy ray composition comprising as an essential component at least one polymer (B) selected from the polymers (c) having 3. The photoacid generator compound (C) is contained in the active energy ray composition.
The active energy ray-based composition as described in 1. 4. A step of applying the active energy ray composition according to claim 2 or 3 to a substrate, a step of heating the substrate, a step of irradiating the active energy ray so that a pattern can be formed. A pattern forming method, characterized in that heating is not performed after irradiation, or a step of performing heat treatment under the condition of less than 140 ° C. and a step of developing with a basic developing solution are sequentially performed. 5. The active energy ray-sensitive composition according to claim 2 or 3 is applied onto a transparent support film which can transmit active energy rays and dried to form a coating layer of the active energy ray composition. Step of making an energy ray dry film resist, step of pressing the active energy ray film layer of the dry film resist to a substrate on which a resist pattern is formed, step of heating the substrate, irradiation of active energy ray through supporting film The step of peeling the support film, performing no heating after irradiation, or performing a heat treatment at a temperature of less than 140 ° C., and then performing a step of developing with a basic developing solution are sequentially performed. And a pattern forming method. 6. A step of coating a transfer film with the active energy ray-sensitive composition according to claim 2 or 3, followed by drying to form an active energy ray-type coating layer to form a transfer film resist, and a photosensitive activity of the transfer film resist. A step of pressure-bonding the energy ray-sensitive layer to the substrate, a step of heating the substrate, a step of peeling the support film and irradiating with active energy rays so that a target pattern is formed, or no heating after irradiation, or A pattern forming method, which comprises sequentially performing a heat treatment step under a condition of less than 140 ° C. and a step of developing with a basic developing solution.