JP2824209B2 - Photosensitive composition and pattern forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a photosensitive composition and a method of forming a pattern useful for a circuit formation of an electronic device, a printing material, and the like using the photosensitive composition.

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 may lack resolution when a very fine pattern needs to be formed. As a method for increasing the resolving power, CEL (Contrast Enhanced Layer) is applied. However, when CEL is applied, the photosensitivity is reduced, the exposure takes a long time, and the working efficiency is reduced, which is not preferable.

Further, since the principle of development utilizes the difference in solubility between exposed and unexposed areas, development conditions are delicate, and strict control of development conditions is required to obtain good reproducibility. Since the unexposed portion is not completely insoluble in the developing solution, the unexposed resist film partially dissolves or swells during the developing process, and the resistance of the formed pattern to the etching solution is reduced. However, there are drawbacks such as the accuracy of the formed pattern is likely to be reduced.

On the other hand, an acid is generated in the pattern latent image portion by irradiation with ultraviolet rays, electron beams, or the like, and the acid is used as a catalyst to cause a elimination reaction in the polymer in a chain, whereby the irradiated portion and the non-irradiated portion are separated. A material for forming a pattern by changing the solubility in a developing solution and a pattern forming method using the same are disclosed in US Pat.
-45439, JP-A-63-250542 and the like.

In these compositions, the photon yield is higher than that using quinonediazide as a photosensitizer, and the photosensitivity is improved. However, the principle of development is the same as that using quinonediazide. There is a problem.

An object of the present invention is to solve the above-mentioned drawbacks of the conventional positive type photosensitive composition and based on a novel principle, a photosensitive composition particularly useful as a positive type photoresist, a printing material and the like. And a method for manufacturing a pattern using the same.

The present inventors have conducted intensive studies on a method for overcoming the above-mentioned drawbacks of the positive photosensitive composition. As a result, this time, a polymer containing a carboxyl group and a phenolic hydroxyl group, a polyvinyl ether compound, and A composition comprising a compound capable of decomposing upon irradiation with energy rays to generate an acid; a polymer containing a carboxyl group, a polymer containing a hydroxyphenyl group, a polyvinyl ether compound, and decomposing upon irradiation with active energy rays to generate an acid When a coating formed from the compound is heated, a coating film formed from the compound is crosslinked by an addition reaction between a carboxyl group and / or a hydroxyphenyl group and a vinyl ether group, and becomes insoluble in a solvent or an aqueous alkali solution, and further has an active energy Irradiation of X-rays and heating after the irradiation cause the catalytic action of the generated acid. It found that a photosensitive composition structure is cut by irradiating portion functioning quite a new mechanism that again becomes soluble in the solvent and an alkaline aqueous solution, thereby completing the present invention.

Thus, according to one aspect of the present invention, A)
Photosensitive composition containing, as essential components, a polymer containing a carboxyl group and a hydroxyphenyl group, B) a compound containing two or more vinyl ether groups in one molecule, and C) a compound that generates an acid upon irradiation with active energy rays. And a method of forming a pattern using the same.

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 two or more vinyl ether groups in one molecule, and C) a compound that generates an acid upon irradiation with active energy rays. Provided are a photosensitive composition containing the composition as an essential component, and a method for forming a pattern using the composition.

According to the composition of the present invention, the unexposed portion has a crosslinked structure, so that the unexposed portion is completely insolubilized in a solvent or an aqueous alkali solution used for development. Since this does not occur, there is no problem that occurs in the conventional positive resist described above.

Further, the composition of the present invention does not require the use of a large amount of a functional group having a high extinction coefficient unlike a resist using quinonediazide as a photosensitizer, so that the transparency to active energy rays can be increased. In addition, the acid generated in the irradiated portion acts as a catalyst during heating and cuts the cross-linking structure in a chain, so that the sensitivity of the positive-working photosensitive composition can be increased.

Further, the pattern formed by the composition of the present invention has an extremely high contrast, and is therefore extremely useful as a resist for a fine pattern.

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

A) Carboxyl group and hydroxyphen
Polymer Containing a Nyl Group The polymer A) used in the photosensitive composition according to the first aspect of the present invention is a film-forming polymer containing at least one carboxyl group and hydroxyphenyl group in one molecule. A copolymer of hydroxystyrene such as p-hydroxystyrene and a polymer unsaturated monomer containing a carboxyl group; and a copolymer of hydroxystyrene and the carboxyl group-containing monomer with another polymer And copolymers with possible monomers.

The polymerizable unsaturated monomer containing a carboxyl group includes, for example, 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) 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.

As the polymer A), phenol carboxylic acids such as hydroxybenzoic acid, gallic acid and resorcinic acid, or phenol, mono- or di-alkylphenols having 1 to 18 carbon atoms or naphthols, resorcinol, catechol Polymers obtained by condensing a mixture of one or more phenols selected from the above with formaldehyde can also be used.

The polymers A) generally comprise from about 500 to about 10
It preferably has a number average molecular weight in the range of 0000, especially about 1500 to about 30,000. On the other hand, the content of the carboxyl group is generally 0.5 per kg of the polymer.
It may be in the range of 10 to 10 equivalents, especially 0.5 to 5.0 equivalents, and the hydroxyphenyl groups may be in the range of at least 1.0 equivalent, especially 2.0 to 8.0 equivalents per kg of polymer. desirable. When the content of carboxyl group is 0.5 equivalent /
If the amount is less than 10 kg, the degree of crosslinking of the film formed by heating before irradiation with actinic rays is not sufficient, and the solubility of the exposed portion in an alkaline developer tends to be low and the developability tends to decrease. / Kg, the storage stability of the composition tends to decrease. On the other hand, if the content of the hydroxyphenyl group is less than 1.0 equivalent / kg, the degree of crosslinking at the time of crosslinking may not be sufficient.

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 ′) Polymer Containing Carboxyl Group The polymer A ′) used in the photosensitive composition according to the second aspect of the present invention forms a film containing at least one carboxyl group in one molecule. A homopolymer of a polymerizable unsaturated monomer containing a carboxyl group; a copolymer of the carboxyl group-containing monomer and another copolymerizable monomer; Examples thereof include polyester-based, polyurethane-based, and polyamide-based resins having a carboxyl group in the chain or at the molecular terminal.

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 ') generally has a number average molecular weight in the range of about 3,000 to about 100,000, especially about 5,000 to about 30,000. Is a polymer 1
Generally 0.5 to 10 equivalents per kg, especially 0.5 to 5.0
It is desirable to be within the equivalent range. 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 actinic light is not sufficient, and the solubility of the exposed portion 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.

It is preferable that the polymer A ') 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 ″) heavy containing a hydroxyphenyl group
The present polymer A ″) used in the photosensitive composition according to the second aspect of the present invention is a polymer containing at least one hydroxyphenyl group in one molecule, and is, for example, monofunctional or polyfunctional. Condensates of phenol compounds, alkylphenol compounds or mixtures thereof with carbonyl compounds such as formaldehyde and acetone; homopolymers of hydroxy-containing vinyl aromatic compounds such as p-hydroxystyrene; Copolymers of the compound with other copolymerizable monomers and the like can be mentioned.

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 type which becomes insoluble and infusible as the condensation proceeds. And condensed with an acid catalyst to obtain a soluble and fusible novolak type. In the present invention, the latter novolak-type phenol resin can usually be used. The molecular weight of the novolak-type phenolic resin increases as the condensation proceeds. In general, it is preferable that the molecular weight obtained by condensing in a reaction time of 1 to 3 hours is in the range of 500 to 2,000. Further, as the other monomer copolymerizable with the hydroxy group-containing vinyl aromatic compound, another copolymerizable monomer similar to that exemplified for the copolymer in the polymer A ′) may be used. Can be.

Such a hydroxyphenyl group-containing polymer A ″) is generally from about 500 to about 1,000,000, in particular from about 1 to about 1,000,000.
It preferably has a number average molecular weight in the range of 000 to about 30,000.

The content of the hydroxyphenyl group in the polymer A ″) is generally 1.0 to 10 per kg of the polymer.
Conveniently, it is in the range of equivalents, especially 2.0 to 8.0 equivalents. When the content of the hydroxyphenyl group is 1.0 equivalent /
If the amount is less than kg, the degree of crosslinking of the film formed by heating before irradiation with actinic rays tends to be insufficient, and if it exceeds 10 equivalents / kg, the resist film tends to become brittle.

The polymer A ″) also has a glass transition temperature (Tg) of 0 ° C. or higher, particularly 5 ° C., similarly to the polymers A) and A ′).
Preferably it is in the range of -70 ° C. Tg is 0 ° C
When it is less than 3, the coating film shows tackiness, dust and dirt are easily adhered, and it tends to be difficult to handle.

B) Two or more vinyl ethers per molecule
The compound B) contains a compound of the formula -RO-CH = CH in one molecule.
₂ wherein R represents a linear or branched alkylene group having 1 to 6 carbon atoms such as ethylene, propylene, butylene, etc., containing at least 2, preferably 2 to 4 vinyl ether groups Polyphenol compounds such as bisphenol A, bisphenol F, bisphenol S, and phenolic resins, and polyols such as ethylene glycol, propylene glycol, trimethylolpropane, trimethylolethane, and pentaerythritol. With polyhalogenated alkyl vinyl ethers such as chloroethyl vinyl ether; polyisocyanates such as tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate And compound, a reaction product of hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether. In particular, a condensate of the above 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 have etching resistance,
This is preferable from the viewpoint of the accuracy of the formed pattern and the like.

The compound B) is liquid at room temperature or has a melting point or softening point of 150 ° C. or lower, particularly 130 ° C. or lower, when the polymer A) or the polymer A is heated upon heating before irradiation with active energy rays. ) And / or A ″), which is easily added to the carboxyl group and / or phenolic hydroxyl group in the polymer A) or the polymer A ′) and / or A ″) and the vinyl ether group of the compound B). It is preferable because the reaction easily occurs.

C) Generates acid by irradiation with active energy rays
The resulting compound C) is decomposed by irradiation with an active energy ray described below, and the polymer A) or the polymer A ′) and / or
Or a compound capable of generating an acid having sufficient strength to cleave a crosslinked structure formed between A ″) and compound B)
"It may be referred to as a" photoacid generating compound ") and includes, for example, those represented by the following formula.

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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Wherein R ₁ and R ₂ each independently represent an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.

[0043]

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Wherein R ₁ and R ₂ have the same meaning as described above.

[0045]

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Photosensitive Composition The photosensitive composition according to the first embodiment of the present invention comprises the above-mentioned polymer A) containing a carboxyl group and a hydrophenyl group, a compound B) containing a vinyl ether group and a photoacid generating compound C).
And the mixing ratio thereof can be varied over a wide range depending on the use of the composition, but the vinyl ether group-containing compound B) is a polymer A). Generally 5 to 1 for 100 parts by weight
It is preferable to use 50 parts by weight, particularly 10 to 100 parts by weight, and the photoacid generator compound C) is 100 parts by weight in total of the polymer A) and the vinyl ether group-containing compound B).
0.1 to 40 parts by weight, especially 0.2 to 40 parts by weight,
It is suitable to use within the range of 20 parts by weight.

The photosensitive composition according to the second embodiment of the present invention comprises the above-mentioned carboxyl group-containing polymer A ′), hydroxyphenyl group-containing polymer A ″), vinyl ether group-containing compound B), It contains four components of the acid-generating compound C) as essential components, and the mixing ratio thereof can be varied over a wide range depending on the use of the composition and the like. The hydroxyphenyl group-containing polymer A ″) is generally defined as a polymerization ratio of A ′) / A ″) of 90/10 to 10/90, particularly 70/3.
It can be used within the range of 0 to 30/70,
The vinyl ether group-containing compound B) is generally used in an amount of 5 to 15 parts by weight based on 100 parts by weight of the total amount of the carboxyl group-containing polymer A ′) and the hydroxyphenyl group-containing polymer A ″).
It is preferably used in an amount of 0 parts by weight, particularly 10 to 100 parts by weight, and the photoacid generating compound C) is a carboxyl group-containing polymer A ′), a hydroxyphenyl group-containing polymer A ″) and a vinyl ether Generally 0.1 to 40 parts by weight, based on 100 parts by weight of the total amount of the group-containing compound B),
In particular, it is suitable to use within the range of 0.2 to 20 parts by weight.

The photosensitive composition of the present invention may optionally contain a sensitizing dye. Examples of the sensitizing dye that can be used include phenothiazine, anthracene, coronene, and benzanthracene. Examples include perylene, pyrene, merocyanine, and ketocoumarin dyes.

The compounding amount of these sensitizing dyes is as follows.
The amount is suitably in the range of 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, based on 100 parts by weight or based on 100 parts by weight of the total amount of the polymers A ') and A "). .

Further, in order to impart appropriate flexibility and non-adhesiveness to the formed film, a plasticizer such as phthalic acid ester, a polyester resin, an acrylic resin and the like are added to the composition of the present invention. May be. The addition amount thereof is usually 100 parts by weight of the total amount of the polymer A), the vinyl ether group-containing compound B) and the photoacid generator compound C) or the amount of the polymer A ′), the polymer A ″), the vinyl ether group The content is preferably 50 parts by weight or less based on 100 parts by weight of the total amount of the compound B) and the photoacid generating compound C).

Further, the composition of the present invention may optionally contain a fluidity regulator, 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. There are no particular restrictions on the solvent that can be used at this time, 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, and acetic acid Esters such as butyl; 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; these glycols and methanol , Ethanol, butanol,
Glycol ethers such as mono- or diethers with hexanol, octanol, benzyl alcohol, and phenol or esters of the monoether; cyclic ethers such as dioxane and tetrahydrofuran; cyclic carbonates such as ethylene carbonate and propylene carbonate; And aromatic hydrocarbons. These solvents can be used alone or as a mixture of two or more, if necessary.

[0053] Formation of a pattern using the photosensitive composition of the formation the present invention a pattern may be carried out 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 a PS plate, a printed circuit board laminated with a copper foil, or a silicon wafer of a semiconductor material. It is applied 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 treated with a polymer A)
Alternatively, at a temperature and for a time at which a crosslinking reaction between the polymer A ') and / or A ") and the vinyl ether group-containing compound B) substantially occurs, for example, at a temperature of about 60 to about 150 ° C for about 1 hour. Heat for about 30 minutes to crosslink and cure the coating.

Next, the cured coating film on the substrate is image-irradiated with active energy rays using a positive photomask, a reduction projection exposure machine, a direct drawing machine or the like. The active energy ray that can be used here is selected depending on the type of the photoacid generator compound C) blended in the photosensitive composition and the like. For example, an electron beam, a monochromatic ray having a wavelength of 200 to 600 nm, or A mixed light thereof can be used.

The substrate irradiated with the active energy ray 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, from about 60 to about 150. Heat at a temperature of about 1 to about 30 minutes to substantially cut the crosslinked structure of the coating in the irradiated area.

By treating the substrate thus heated, irradiated and heated with a developing solution, a pattern can be formed on the substrate. Examples of the developer include a liquid capable of dissolving the polymer A) or the polymer A '), for example, a water-soluble organic base, for example, hydroxyammonium salts such as alkanolamine and tetraethylammonium hydroxide; an inorganic alkali, for example, caustic soda , Sodium carbonate, sodium metasilicate and the like.

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 of 0.05 to 10% by weight.
Further, if necessary, the solvent described as a solvent that can be used in the production of the photosensitive 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 carried out 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 photosensitive composition of the present invention can be used as a dry film type resist.

For example, the photosensitive composition obtained by the above-mentioned method is coated on a transparent and flexible support film capable of transmitting active rays such as a polyethylene terephthalate film, and the composition is subjected to heat treatment if necessary. The solvent in the product is removed to create a dry film type resist. If necessary, a release film may be attached to the resist surface of the formed film to form a protective layer. Alternatively, a resist film may be formed on the release film in advance by the above-described method, and then a support film may be attached. In general, the support film and the release film preferably have a thickness of about 10 to about 250 μm from the viewpoint of handling.

The adhesive force between the release film and the resist film is generally one of the adhesive force between the support film and the resist film.
It is preferably about / 10 or less. When the adhesive force of the release film is large, the operation of peeling the release film from the dry film becomes difficult. In addition, the dry film is laminated on a substrate by a method described later, and the adhesive force between the heat-crosslinked and exposed resist film and the support film is required to remove the support film before development. It is desirable that it is about 1/3 or less of the adhesive force with the substrate. For this purpose, the surface of the support film may be subjected to a treatment such as a normal easy peeling treatment, or the substrate surface may be subjected to a treatment such as physical polishing or chemical soft etching.

Further, the photosensitive composition of the present invention can be used as a transfer film type resist as follows.

That is, the transfer film type resist can be prepared by the same method as the dry film type resist. However, in the case of the dry film type resist, the adhesive force between the supporting film and the resist film is different from the transfer film type resist. It is desirable that the adhesive strength between the substrate and the resist film when the resist is laminated, or the substrate and the resist film after further heat-crosslinking the resist is about 1/3 or less. However, the present invention is different from the above in that it is possible to use a film having a low or opaque light transmittance, such as a film containing a dye or a pigment, or a metal foil. In order to satisfy the condition of the adhesive force between the respective layers, the same treatment as in the case of the dry film type resist can be performed.

In the case of a transfer film type resist, the support film is peeled off before the exposure, so that the adhesiveness of the resist film surface is reduced, and the resist surface during exposure is prevented from becoming dirty and the photo tool from being contaminated. For this reason, a glass transition temperature of 2 which does not show tackiness at room temperature on a support film 2
The first layer having a temperature of 0 ° C. or more and the second layer having a glass transition temperature of not more than
May be formed.

In this case, the first layer may be composed of the photosensitive composition of the present invention, or may be composed of a non-photosensitive composition that can be removed by a developer.

In general, the thickness of the photosensitive resist film in the dry film type and transfer film type resists described above is suitably in the range of about 0.5 to about 15 μm.

In the case of a transfer film type resist having two resist film layers, the thickness of the first layer is usually about 0.1 to 5 μm.
Suitably, it is in the range of m.

When the photosensitive composition of the present invention is used as a dry film type resist, the dry film type resist is pressed on the substrate by using a laminator, a press or the like. At the time of press bonding, the substrate and / or the press roll and the press plate may be heated to a temperature of up to about 250 ° C. Then, if necessary, for crosslinking and curing,
The required temperature and time conditions, for example, about 60 to about 150 ° C.
For about 1 to about 30 minutes.

In the case of performing pressure bonding under heating, since the crosslinking reaction proceeds sufficiently at the time of pressure bonding, the heat treatment after the pressure bonding may be omitted in some cases.

The transfer film type resist can be pressure-bonded onto the substrate in the same manner as the dry film type resist. However, in the case of the transfer film type resist, the support film is applied after the pressure bonding or after the pressure-heat treatment and before the exposure. Peel off from the resist film surface.

The substrate on which the dry film type resist or the transfer film type resist has been pressed in this manner is subjected to heating-selective irradiation-heating-development treatment in the same manner as in the case of the photosensitive composition coated substrate described above. A pattern can be formed thereon. However, in the case of a dry film type resist, the support film is peeled from the resist film surface after exposure and before development.

Further, when the substrate can be etched, similarly to the photosensitive composition coated substrate, the exposed substrate portion is removed with an appropriate etching agent, and if necessary, the remaining film is removed with an appropriate release agent. , A relief image can be obtained.

The pattern formed in this way is a very fine pattern and has excellent contrast, and is therefore advantageous for the production of printing plates, reliefs, displays, etc., which require fine images, and printed circuit boards. Can be used for

In particular, the photosensitive composition of the present invention has a crosslinked structure in the unexposed portion of the resist film, so that the unexposed portion has excellent resistance to a developing solution and an etching solution as compared with a conventional positive type photoresist. The precision of the formed pattern is excellent, and therefore, the printed circuit board having a fine pattern, L
Extensive applications are expected in fields such as semiconductor precision processing such as SI and metal fine processing.

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

Production Example 1 Synthesis of Carboxyl- and Hydroxyphenyl-Group-Containing Polymer A-1 600 parts of o-hydroxybenzoic acid, 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 carboxyl group- and hydroxyphenyl group-containing polymer A-2 200 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
and the precipitate formed is separated off.
After dissolving in 00 ml of acetone, 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-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 consisting 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 over 2 hours in 600 parts of heated and stirred methyl isobutyl ketone, 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 comprising 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 was prepared. Heated to 110 ° C and stirred 2
After dropping over 2 hours in 1000 parts of butoxyethanol, the temperature was maintained for another 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 72 parts of acrylic acid 650 parts of styrene 100 parts of ethyl acrylate 178 parts of n-butyl acrylate A mixture of 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 45.6 g of bisphenol A, 80 ml of 2-chloroethyl vinyl ether and 100 ml of toluene
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 aqueous layer, and the aqueous layer was removed. Further, 400 parts of deionized water was added, the resin was washed at 75 ° C., the aqueous layer was removed, and the same washing operation was repeated twice. After that, about 120
Drying at ℃ yielded a novolak phenolic resin. A vinyl ether compound B-2 was obtained in exactly the same manner as in Production 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 polyisocyanate obtained by reacting 1 mol of trimethylolpropane with 3 mol of tolylene diisocyanate
875 parts of ethylene glycol dimethyl ether solution and 2
-Hydroxyethyl vinyl ether (264 parts) was reacted at 35 ° C for 3 hours in the presence of 1 part of dibutyltin diacetate to obtain a vinyl ether compound B-3. This compound contained three vinyl ether groups in one molecule. About 81% solids. Example 1 A mixture of 100 parts of polymer A-1 and 60 parts of vinyl ether compound B-1 and 10 parts of photoacid generating compound C-1 (Note 1) was dissolved in diethylene glycol dimethyl ether to form a 20% by weight solution.

A silicon wafer was coated with a spin coater to a dry film thickness of 1 μm, and dried at 90 ° C. for 10 minutes.

The substrate was irradiated with ultraviolet light having a wavelength of 356 nm while changing the irradiation amount stepwise, heated at 120 ° C. for 20 minutes, and then developed using a 2.38% aqueous solution of tetramethylammonium hydroxide.

The γ value (Note 2) obtained from the residual ratio curve of the film after development with respect to the amount of ultraviolet irradiation is 11.0, which is an extremely high contrast value, and no decrease or swelling of the film in the unexposed portion is observed. I couldn't.

Similarly, a 1 μm film was formed on a silicon wafer and irradiated with 365-nm ultraviolet light at a light exposure of 8 mj / cm ² using a pattern mask, and then processed exactly as described above to obtain a line / space. = 1/1 μm image was formed. 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 is 89
Degree and a very excellent pattern shape. The minimum exposure for image formation was 6 mj / cm ² .

(Note 1) Photoacid generating compound C-1: The compound having the following formula was used.

[0095]

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(Note 2) 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, edited by Photopolymer Handbook, pp. 101-103, (1989) Industrial Research Committee".

Example 2 100 parts of polymer A-2 25 parts of vinyl ether compound B-2 7.5 parts of photoacid generator compound C-2 (Note 3) 7.5 parts 1 part of sensitizing dye 1 (Note 4) It was melted in the same manner as in No. 1 and coated on a silicon wafer by a spin coater so as to have a dry film thickness of 3 μm, and dried at 50 ° C. for 10 minutes.

The γ value was determined in exactly the same manner as in Example 1 except that this substrate used 488 nm visible light. The γ value was 10.1 and the contrast was extremely high, 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 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 87 degrees, which was an extremely excellent pattern shape. The minimum exposure for image formation was ² mj / cm ² .

(Note 3) Photoacid generating compound C-2: The compound having the following formula was used.

[0101]

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(Note 4) Sensitizing dye 1: The following sensitizing dye was used.

[0103]

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Example 3 Polymer A-3 100 parts Vinyl ether compound B-3 (solid content 81%) 20 parts Photoacid generator compound C-3 (Note 5) 5 parts A mixture of 5 parts was dissolved in the same manner as in Example 1. Then, the substrate was prepared by laminating an 18 μm copper foil on a polyimide film, and coated with a roll coater to a dry film thickness of 5 μm.
Dry at 10 ° C. for 10 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.

Then, a line / space = 12 mj / c was applied on a substrate prepared in the same manner as above using a line / space = 50/50 μm photomask at 365 nm with an ultra-high pressure mercury lamp.
After exposure to m ^{2, the} film was heated at 130 ° C. for 15 minutes. Next, after developing with a 3% aqueous sodium carbonate solution, the exposed copper is etched using copper chloride, and then the film on the substrate is removed with a 3% aqueous sodium hydroxide solution, whereby an excellent etching pattern is formed on the substrate. Was.

(Note 5) Photoacid generating compound C-3: The compound having the following formula was used.

[0108]

Embedded image

Example 4 Polymer A-4 (solid content: 62.5%) 80 parts Polymer A-7 65 parts Vinyl ether compound B-1 60 parts Photoacid generator compound C-1 10 parts A mixture of 10 parts was mixed with diethylene glycol dimethyl ether. Dissolve to give a 20% by weight solution.

[0110] The resultant was coated on a silicon wafer by a spin coater so as to have a dry film thickness of 1 µm, and then dried at 90 ° C for 10 minutes.

The substrate was irradiated with ultraviolet light having a wavelength of 356 nm while changing the irradiation amount stepwise, heated at 120 ° C. for 20 minutes, and then developed 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 amount of ultraviolet irradiation was 10.2, indicating an extremely high contrast value, and no reduction or swelling of the film in the unexposed portion was observed.

Similarly, a 1 μm film was formed on a silicon wafer, irradiated with 365 nm ultraviolet light at a light exposure of 8 mj / cm ² using a pattern mask, and processed in the same manner as described above to obtain a line / space. = 1/1 μm image was formed. 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 is 89
Degree and a very excellent pattern shape. The minimum exposure for image formation was 6 mj / cm ² .

Example 5 Polymer A-5 (solid content: 50%) 200 parts Polymer A-8 100 parts Vinyl ether compound B-2 100 parts Photoacid generator compound C-2 7.5 parts Sensitizing dye 1 1 part 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 50 ° C. for 10 minutes.

The γ value was determined in exactly the same manner as in Example 4 except that this substrate used 488 nm visible light. The γ value was 11.3, 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 an irradiation light beam, and the exposure amount was 2
mj / cm ^2, and the shape of the image pattern was evaluated in exactly the same manner as in Example 4 except that the heating conditions after exposure were 90 ° C. and 10 minutes. The angle was 88 degrees, which was an extremely excellent pattern shape. The minimum exposure for image formation is 1.5 mj /
cm ² .

Example 6 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 5 parts Was dissolved in the same manner as in Example 4 and applied to 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 15 ° C. for 15 minutes.

The γ value of this substrate was determined in exactly the same manner as in Example 4. The γ value was extremely high at 9.8.

Next, a line / space = 50/50 μm was applied on a substrate prepared in the same manner as above at a light amount of 10 mj / c monitored at 365 nm with a super high pressure mercury lamp through a photomask.
After exposure to m ^{2, the} film was heated at 100 ° C. for 15 minutes. Then, after developing with a 3% aqueous sodium carbonate solution, the exposed copper is etched using copper chloride, and then the film on the substrate is removed with a 3% aqueous sodium hydroxide solution to form an excellent etching pattern on the substrate. Was done.

Comparative Example 1 Carboxyl group-containing polymer 1 A mixture of 288 parts of acrylic acid 300 parts of styrene 300 parts of n-butyl acrylate 112 parts of 2-hydroxyethyl acrylate 100 parts of t-butyl peroxybenzoate was heated to 110 ° C. Stirring 2
After dripping into 1000 parts of butoxyethanol over 2 hours, the temperature was maintained for 2 hours to obtain polymer 1. Solid content: about 50%, carboxyl group: 4 mol / kg, aromatic ring content: 20.7 parts by weight / 100 parts by weight.

Polymer 1 (solid content 50%) 200 parts Photosensitive agent 1 (Note 6) 30 parts was made into a 20% solution with diethylene glycol dimethyl ether and applied on a silicon wafer with a spin coater to a dry film thickness of 1.3 μm. After drying at 120 ° C. for 20 minutes, a characteristic curve was obtained in the same manner as in Example 1. The γ value was 2.1, and about 30% of the unexposed portion was dissolved when the exposed portion was completely dissolved.

The gamma value was measured in the same manner except that the developing solution was changed to a 0.5% aqueous sodium carbonate solution. The γ value was 3.3, and the unexposed portion was dissolved by about 3% when the exposed portion was completely dissolved.

A pattern was formed on a substrate in exactly the same manner as in Example 1 except that the exposure amount was 80 mj / cm ^2, and a 0.5% aqueous sodium carbonate solution was used as a developing solution, and the cross section was observed. The angle between the substrate and the pattern was 79 degrees. In this example, an image could not be formed at an exposure amount of 60 mj / cm ² or less.

(Note 6) Photosensitive agent 1: The following formula was used.

[0125]

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Comparative Example 2 Polymer 2 1490 parts of o-cresol 30% formalin 1145
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 13.
Five parts were 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 after neutralization, the aqueous layer was removed. Further, 400 parts of deionized water was added, the resin was washed at 75 ° C, the aqueous layer was removed, and the same washing operation was repeated twice. After drying under reduced pressure at about 120 ° C., a novolak phenol resin (polymer 2) was obtained. The molecular weight was about 600.

100 parts of Polymer 2 and 20 parts of Photosensitive Agent 1 were dissolved in the same manner as in Comparative Example 1 to form a 1.3 μm film on a silicon wafer. The γ value was measured in exactly the same manner as in Example 1.

The γ value was 4.6. When the exposed portion was completely dissolved, the unexposed portion was dissolved by about 15%. Next, a pattern was formed in the same manner as in Example 1 except that the exposure amount was set to 80 mj / cm ^2, and the cross section was observed. The angle between the substrate and the pattern was 82 degrees. In this example, 55 mj /
If it was less than cm ² , no pattern could be formed.

Example 7 100 parts of polymer A-2 30 parts of vinyl ether compound B-1 30 parts of photoacid generation on a polyethylene terephthalate film having a surface of 75 μm in thickness and subjected to a 3 μm-thick aminoalkyd resin film-based easy peeling treatment Dissolve 8 parts of compound C-1 in ethylene glycol monoethyl ether and add 3 parts
A 0 wt% solution of the resist was applied by a roll coater to a dry film thickness of 5 μm, and dried at 50 ° C. for 10 minutes. Next, a thickness of 100 which has been release-treated with silicone.
A μm polyethylene terephthalate film was mounted on the resist surface to obtain a dry film type resist.

The dry film type resist was applied to a thickness of 1
Using a laminator with a roll temperature of 100 ° C., the substrate was pressure-bonded to a substrate obtained by laminating a 18 μm copper foil on a 00 μm polyimide film.

After exposing the substrate to light in the same manner as in Example 1, the support film was peeled off, and the substrate was heated at 110 ° C. for 10 minutes, and then the γ value was determined in the same manner as in Example 1. As a result, the γ value was extremely high at 8.5, and no decrease or swelling of the film in the unexposed portion was observed.

Next, an etching pattern was formed on the substrate in exactly the same manner as in Example 3 except that the support film was peeled off after exposing the substrate prepared in the same manner. as a result,
An excellent etching pattern without pattern defects was obtained.

Example 8 Measurement of γ value and etching were performed in exactly the same manner as in Example 7, except that the resist film was pressed onto the substrate and then the supporting film was peeled off to form a transfer resist film on the substrate. A pattern was formed. As a result, the γ value was extremely high at 8.7, no reduction or swelling of the unexposed portions was observed, and the obtained etching pattern was excellent without defects.

Example 9 A 2 μm-thick polyvinyl alcohol coating layer was formed as a first layer on a 75 μm-thick polyethylene terephthalate film, and 200 parts of polymer A-5 (solid content: 50%) was further formed thereon. A-8 100 parts Vinyl ether compound B-2 100 parts Photoacid generator compound C-2 7.5 parts Sensitizing dye 1 1 part was dissolved in methoxypropanol to 25% by weight so that a solution having a dry film thickness of 8 μm was obtained. It was applied with a roll coater and dried at 60 ° C. for 5 minutes to obtain a transfer film type resist.

A roll temperature of 75 was formed on the same substrate as in Example 6.
The support film was peeled off after the transfer film type resist was pressure-bonded using a laminator at ℃. Next, Example 5
The γ value was determined in exactly the same manner as in the above. As a result, the γ value is 1
The value was extremely high at 1.1. Also, no decrease or swelling of the film in the unexposed portion was observed.

Next, the transfer film resist film formed on the substrate in the same manner was applied with a direct drawing machine using an argon ion laser beam having a wavelength of 488 nm at 2 mJ / cm.
Line / space = 30 μm / 3 at energy density of ²
A 0 μm pattern was drawn. Then, after heating at 100 ° C. for 15 minutes, development with a 3% aqueous sodium carbonate solution was performed, the exposed copper was etched using cupric chloride, and the resist film remaining on the substrate was removed with a 3% aqueous sodium hydroxide solution. An excellent etching pattern without any defects was formed on the substrate.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-106038 (JP, A) JP-A-55-12995 (JP, A) JP-A-48-89003 (JP, A) JP-A-5-129 100428 (JP, A) JP-A-5-100429 (JP, A) JP-A-6-161110 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03F 7/00-7 / 18

Claims (9)

(57) [Claims] 1. A) 0.5 to 10 per kg of polymer
It contains carboxyl groups in the range of equivalents and at least one equivalent of hydroxyphenyl groups per kg of polymer and has a number average molecular weight in the range of
A photosensitive polymer comprising: a polymer having a glass transition temperature of at least 2 ° C .; B) a compound having at least two vinyl ether groups in one molecule; and C) a compound capable of generating an acid upon irradiation with active energy rays. Composition. 2. The compound (B) containing a vinyl ether group,
Formula -R-O-CH = CH ₂ [where R is 1 to 6 carbon atoms
Which is a low- or high-molecular-weight compound containing 2 to 4 vinyl ether groups represented by the following formulas: 3. The composition according to claim 1, wherein the vinyl ether group-containing compound B) is contained in an amount of 5 to 150 parts by weight per 100 parts by weight of the polymer A). 4. The photoacid generator compound (C) is represented by the following formula (I):
~ (XIV) Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image [Wherein, R ₁ and R ₂ each independently have 1 to 12 carbon atoms.
Represents an alkyl group or an alkoxy group having 1 to 12 carbon atoms.] Wherein R ₁ and R ₂ have the same meaning as described above. The composition according to any one of claims 1 to 3, which is selected from the group consisting of: 5. The photoacid generating compound C) is contained in an amount of 0.1 to 40 parts by weight based on 100 parts by weight of the total of the polymer A) and the vinyl ether group-containing compound B).
The composition according to any one of claims 4 to 4. 6. A sensitizing dye selected from the group consisting of phenothiazine, anthracene, coronene, benzanthracene, perylene, pyrene, merocyanine and ketocoumarin based on 100 parts by weight of polymer A). 0.1 to 10 parts by weight.
A composition according to any one of the preceding claims. 7. A step of applying the photosensitive composition according to claim 1 to a substrate, a step of heating the substrate, a step of selectively irradiating an active energy ray, and a step of irradiating the substrate after irradiation. Wherein the step of heating is followed by the step of developing with a basic developer. 8. The photosensitive composition according to any one of claims 1 to 6, which is coated on a transparent support film through which actinic rays can pass, and dried to form a photosensitive coating layer. A step of forming a film resist, a step of pressing the photosensitive film layer of the dry film type resist onto a substrate, a step of heating the substrate, a step of selectively irradiating active energy rays through a support film, and heating the substrate after the irradiation. A method for forming a pattern, comprising sequentially performing a step of removing the support film after the step of heating and a step of developing with a basic developer. 9. A step of applying the photosensitive composition according to any one of claims 1 to 6 on a transfer film and drying to form a photosensitive film layer, thereby forming a transfer film type resist. Pressing the photosensitive film layer of the film type resist onto the substrate, heating the substrate, peeling the transfer film after heating, selectively irradiating the active energy ray, heating the substrate after the irradiation, base A step of sequentially developing with a neutral developer.