KR20150111304A - Method of forming pattern - Google Patents

Abstract

Provided is a method for forming a pattern by using a positive-type photosensitive resin composition, capable of forming a resist pattern in a desired sectional form with a small amount of light exposure, and forming a pattern with excellent chemical resistance. The photosensitive resin composition uses a material containing a compound for generating an imidazole compound by (D) heating, and forms a pattern by heating the patterned coating film at a fixed temperature, in a state of containing a component having an acid group among coating films composed of the photosensitive resin composition patterned by light exposure and development.

Description

[0001] METHOD OF FORMING PATTERN [0002]

The present invention relates to a pattern forming method.

In the lithography technique, for example, a resist film made of a resist material is formed on a substrate, and the resist film is subjected to selective exposure with radiation such as light or electron rays through a mask having a predetermined pattern formed thereon, A step of forming a resist pattern having a predetermined shape by performing a developing process on the resist film is performed.

A resist material in which the exposed part changes in characteristics to be dissolved in the developer is referred to as a positive type and a resist material in which the exposed part changes to a property not dissolved in the developing solution is referred to as a negative type.

BACKGROUND ART [0002] In the recent years, in the production of semiconductor devices and liquid crystal display devices, miniaturization of patterns is progressing rapidly by the progress of lithography technology.

As a technique of refinement, generally, the exposure light source has been shortened in wavelength. Specifically, conventionally, ultraviolet rays represented by g-line and i-line have been used, but at present, mass production of semiconductor devices using KrF excimer laser or ArF excimer laser has been started. Further, F2 excimer lasers of shorter wavelengths, electron beams, EUV (extreme ultraviolet rays), and X-rays than these excimer lasers have also been studied.

Resist materials are required to have lithography properties such as sensitivity to resolution of these exposure light sources and resolving ability to reproduce patterns of fine dimensions.

A chemically amplified resist containing a base resin whose alkali solubility is changed by the action of an acid and an acid generator which generates an acid by exposure is used as a resist material satisfying such a demand. For example, a positive-type chemically amplified resist contains a base resin having a resin capable of increasing the alkali solubility by the action of an acid and an acid generator, and when the resist pattern is formed, acid is generated from the acid generator by exposure , The exposed portion becomes alkali-soluble.

As specific examples of such positive-type chemically amplified resists, it is known that a resin having a structural unit derived from a (meth) acrylic ester having an acid dissociable, dissolution inhibiting group is contained as a base resin (see Patent Documents 1 and 2 ).

Japanese Patent Application Laid-Open No. 2003-241385 Japanese Patent Application Laid-Open No. 2006-096965

However, in the case of forming a pattern using a positive resist composition, since the polymerization reaction and the crosslinking reaction do not occur in the pattern, the chemical resistance of the pattern necessarily formed is inferior to the pattern formed using the negative resist composition .

In the case of forming a pattern using a positive resist composition as described in Patent Documents 1 and 2, in the case of not carrying out the post-exposure baking (PEB) or in the case of the PEB process at a low temperature, It may be difficult or difficult to form a pattern having a desired cross-sectional shape. If a good pattern can be formed by PEB treatment or low-temperature PEB treatment, the throughput of various products or semi-finished products having a resist pattern can be improved by shortening the pattern formation time.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a positive resist composition which can form a resist pattern having a desired sectional shape at a low exposure dose, And a method thereof.

The present inventors have found that a photosensitive resin composition comprising (D) a substance containing a compound which generates an imidazole compound by heating is used as a coating film comprising a photosensitive resin composition patterned by exposure and development, The present invention has been accomplished on the basis of the finding that the above problems can be solved by heating the patterned coating film to a predetermined temperature to form a pattern. Specifically, the present invention provides the following.

An aspect of the present invention relates to a coating film forming process for forming a coating film by applying a positive photosensitive resin composition whose solubility in an alkali developing solution is increased by exposure to a support,

An exposure process for positively selectively exposing the coating film,

A developing step of developing the exposed coated film with an alkali developer,

A baking process for baking a coating film patterned by development

A method for forming a pattern,

Wherein the positive photosensitive resin composition comprises (D)

[Chemical Formula 1]

(Wherein R ^d1 , R ^d2 and R ^d3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, , A sulfonate group, a phosphinyl group, a phosphonate group or an organic group.

A compound capable of generating an imidazole compound,

The baking temperature of the coating film in the baking step is preferably at least the temperature at which the compound generating the imidazole compound represented by (D1) by heating (D) generates an imidazole compound represented by the formula (D1) by pyrolysis,

The coating film in the baking step is a pattern forming method characterized by including a component having an acidic group.

According to the present invention, it is possible to provide a pattern forming method using a positive photosensitive resin composition capable of forming a resist pattern having a desired sectional shape at a low exposure dose as well as a pattern having excellent chemical resistance .

«Pattern formation method»

In the pattern forming method according to the present invention,

A coating film forming step of forming a coating film by applying a positive-working photosensitive resin composition which is exposed to an alkali developing solution to increase its solubility in an alkali developer,

An exposure step of positively selectively exposing the coating film,

A developing step of developing the exposed coated film with an alkali developer,

A baking process for baking a coating film patterned by development

And a pattern forming method.

The positive photosensitive resin composition (hereinafter, also referred to as photosensitive resin composition) using the pattern forming method according to the present invention essentially contains a compound (D) which generates an imidazole compound having a specific structure by heating. The coated film of the photosensitive resin composition patterned by exposure and development is baked at a predetermined temperature in a state containing a component having an acidic group.

Hereinafter, each step included in the pattern forming method according to the present invention will be described in order.

[Coating film forming step]

The method of applying the photosensitive resin composition on a support is not particularly limited, and for example, a spinner is suitably used. The formed photosensitive resin film is pre-baked if necessary. Prebaking is performed at, for example, 80 to 120 DEG C for 40 to 120 seconds.

The support is not particularly limited as long as it is used for forming a resist pattern. As a preferable support, for example, a substrate for electronic parts and a substrate having a predetermined wiring pattern formed thereon can be exemplified. More specifically, examples thereof include substrates made of metal such as silicon wafers, copper, chromium, iron and aluminum, and glass substrates. As the material of the wiring pattern, for example, copper, aluminum, nickel, gold and the like can be used.

As the support, an inorganic and / or organic film may be provided on the substrate as described above. The inorganic film may be an inorganic anti-reflection film (inorganic BARC). The organic film may be an organic anti-reflection film (organic BARC).

[Photosensitive resin composition]

Hereinafter, the photosensitive resin composition will be described. As described above, the photosensitive resin composition essentially contains a compound (D) which generates an imidazole compound having a specific structure by heating. The coating film of the photosensitive resin composition patterned by exposure and development is baked at a predetermined temperature in a state containing a component having an acidic group.

Suitable examples of the acidic group contained in the coating film composed of the photosensitive resin composition baked at a predetermined temperature include a carboxyl group and a phenolic hydroxyl group. Further, the acidic group may be formed on the resin in the bake. These acid groups cause a condensation reaction by the action of an imidazole compound generated in a baking step to be described later, and improve the chemical resistance of the baked pattern at a predetermined temperature.

The photosensitive resin composition satisfying these conditions includes a photosensitive resin composition comprising a component having an acid group protected by a protecting group which is removable by exposure or heating or an alkali soluble component having an acidic group and is exposed to an alkali developer And the solubility of the photosensitive resin composition increases. Examples of the component having an acidic group include a resin having an acidic group or a compound having an acidic group (sometimes referred to as a non-polymerized or non-polymerized system). Examples of the alkali-soluble component include (A) an alkali-soluble resin or (A ') an alkali-soluble compound.

Suitable examples of such a photosensitive resin composition include those containing (A) an alkali-soluble resin and / or (A ') an alkali-soluble compound and (B) a non-alkali-soluble resin having a specific functional group described below. As such a photosensitive resin composition, it is preferable to include (A) an alkali-soluble resin and (B) a non-alkali-soluble resin having a specific functional group described below. Such a photosensitive resin composition may contain (C) a compound which generates an acid or a radical by the action of light. The photosensitive resin composition may further contain (S) solvent. Hereinafter, the components containing the above-mentioned suitable photosensitive resin composition will be described in order.

<(A) Alkali-soluble resin>

The photosensitive resin composition contains (A) an alkali-soluble resin. Here, the alkali-soluble resin is a resin film having a thickness of 1 占 퐉 formed on a substrate by a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by weight, When it is immersed in minute, it means that it dissolves by 0.01 탆 or more.

The alkali-soluble resin (A) is preferably at least one resin selected from the group consisting of (A1) novolak resins, (A2) polyhydroxystyrene resins, (A3) acrylic resins and (A4) Do.

The alkali-soluble resin preferably has an unsaturated double bond and / or an epoxy group. The alkali-soluble resin usually has an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group. For example, by reacting a phenolic hydroxyl group with a compound containing an unsaturated double bond or an epoxy group, such as allyl bromide, (meth) acrylic acid halide, epichlorohydrin, and etherifying or acylating a phenolic hydroxyl group, An unsaturated double bond or an epoxy group can be introduced into an alkali-soluble resin having a hydroxyl group. When the alkali-soluble resin is a resin having a carboxyl group, by reacting an unsaturated double bond such as a (meth) acrylic acid ester containing a carboxyl group and an epoxy group with a compound having an epoxy group, an unsaturated double bond is added to the resin having a carboxyl group Can be introduced.

The alkali-soluble group such as the phenolic hydroxyl group or the carboxyl group of the alkali-soluble resin (A) may be protected by a protecting group, a part or all of which is deprotected by exposure. In this case, the protecting group is preferably a group represented by the following formula (I), which is a water repellent protecting group essential for the (B) non-alkali-soluble resin.

Examples of the unit having a protected alkali-soluble group include a unit derived from (meth) acrylic acid in which a carboxyl group is protected by a group represented by the formula (I), a unit derived from a (meth) And a unit derived from hydroxystyrene in which the phenolic hydroxyl group is protected by a group represented by the formula (I).

(A) When a part or all of the alkali-soluble group of the alkali-soluble resin is protected by a protecting group, in order to promote deprotection at the time of exposure, the photosensitive resin composition may contain an acid Or a compound which generates radicals.

[(A1) Novolak Resin]

(A1) The novolak resin is obtained, for example, by subjecting an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "phenol") and an aldehyde to addition condensation under an acid catalyst.

Examples of the phenol include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, Phenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5- Methylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, chloroglycinol, hydroxydiphenyl, bisphenol A, Gallic acid, gallic acid ester,? -Naphthol,? -Naphthol, and the like.

Examples of the aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde.

The catalyst for the addition condensation reaction is not particularly limited. For example, in the acid catalyst, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid and the like are used.

It is also possible to further improve the flexibility of the novolak resin by using o-cresol, substituting the hydrogen atom of the hydroxyl group in the resin with another substituent, or using bulky aldehydes.

The weight average molecular weight of the novolak resin (A1) is not particularly limited within the range not impairing the object of the present invention, but is preferably 1,000 to 50,000.

A part of the hydroxyl groups of the (A1) novolac resin may be converted into a group represented by the formula (I) included in the later-described (B) non-alkali-soluble resin. The group represented by the formula (I) described later produces a phenolic hydroxyl group by pyrolysis at a temperature close to the temperature at which the compound generating the imidazole compound by heating (D) generates an imidazole compound by pyrolysis. Therefore, when the photosensitive resin composition containing the novolak resin is heated in a baking step described later, a phenolic hydroxyl group, which is an acidic group, is formed on the novolak resin.

[(A2) polyhydroxystyrene resin]

Examples of the hydroxystyrene compound constituting the polyhydroxystyrene resin (A2) include p-hydroxystyrene,? -Methylhydroxystyrene,? -Ethylhydroxystyrene and the like.

The polyhydroxystyrene resin (A2) is preferably a copolymer of a hydroxystyrene-based compound and a styrene-based compound. Examples of the styrene compound constituting the styrene resin include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, and? -Methylstyrene.

The weight average molecular weight of the polyhydroxystyrene resin (A2) is not particularly limited within a range that does not impair the object of the present invention, but it is preferably 1,000 to 50,000.

A part of the hydroxyl groups of the polyhydroxystyrene resin (A2) may also be converted to a group represented by the following formula (I), like the (A1) novolak resin.

[(A3) acrylic resin]

The (A3) acrylic resin is preferably a resin obtained by copolymerizing (meth) acrylic acid with a monomer having an unsaturated bond. Examples of the monomer copolymerizable with (meth) acrylic acid include unsaturated carboxylic acids other than (meth) acrylic acid, (meth) acrylic esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, And an epoxy group-containing unsaturated compound having no alicyclic group.

Preferable examples of the unsaturated carboxylic acid other than (meth) acrylic acid include monocarboxylic acids such as crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; And anhydrides of these dicarboxylic acids.

Examples of the (meth) acrylic esters include linear or branched alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate and t- Branched alkyl (meth) acrylates; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono Acrylate, perfluoro (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and phenyl (meth) acrylate.

As the alkali-soluble resin (A), it is also preferable to have an epoxy group. For this reason, as the (meth) acrylic acid ester, a (meth) acrylic acid ester containing an epoxy group is also preferable. Preferable examples of the epoxy group-containing (meth) acrylic acid ester include, for example, alicyclic epoxy group-containing unsaturated compounds having the structures represented by the following formulas (a3-1) to (a3-16). Among them, the compounds represented by the following formulas (a3-1) to (a3-6) are preferable, and the compounds represented by the following formulas (a3-1) to (a3-4) are more preferable.

(2)

(3)

[Chemical Formula 4]

Wherein R ^a4 represents a hydrogen atom or a methyl group, R ^a5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ^a6 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and n represents 0 to 10 Lt; / RTI &gt; As R ^a5 , a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group or a hexamethylene group is preferable. Examples of R ^a6 include methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, phenylene, cyclohexylene, -CH ₂ -Ph-CH ₂ - And Ph represents a phenylene group).

Also, an epoxy group-containing unsaturated compound not having an alicyclic group is very suitably used as a monomer for introducing an epoxy group into the (A3) acrylic resin. Examples of the epoxy group-containing unsaturated compound having no alicyclic group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (Meth) acrylate; (meth) acrylic acid epoxy alkyl esters such as (meth) acrylate; ? -alkylacrylic acid epoxyalkyl esters such as glycidyl? -ethyl acrylate, glycidyl? -n-propyl acrylate, glycidyl? -n-butyl acrylate, and 6,7-epoxyheptyl? -ethylacrylate; And the like. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate and 6,7-epoxyheptyl (meth) acrylate are preferred.

Examples of the (meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (Meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide and N-hydroxyethyl-N-methyl (meth) acrylamide.

Examples of the allyl compound include allyl esters such as allyl acetate, allyl caprylate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; Allyloxyethanol; And the like.

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2- But are not limited to, ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether Alkyl vinyl ethers such as methyl vinyl ether; Vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether and vinyl anthranyl ether; And the like.

Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethylacetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinylphenylacetate , Vinyl acetoacetate, vinyl lactate, vinyl-beta-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate and vinyl naphthoate.

Examples of the styrenes include styrene; Examples of the monomer include methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, , And acetoxymethylstyrene; Alkoxystyrene such as methoxystyrene, 4-methoxy-3-methylstyrene, and dimethoxystyrene; It is possible to use at least one member selected from the group consisting of chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, urethostyrene, fluorostyrene, trifluorostyrene, 2-bromo- , And 4-fluoro-3-trifluoromethylstyrene; And the like.

The proportion of the unit containing a carboxyl group in the (A3) acrylic resin is preferably 5 to 70% by weight, and more preferably 10 to 40% by weight.

A part of the carboxyl group of the (A3) acrylic resin may also be converted to a group represented by the following formula (I), similarly to the hydroxyl group of the novolac resin (A1).

[(A4) Cardo resin]

(A4) Cardo resin is a resin having a cardo structure. The (A4) cardo resin as the alkali-soluble resin (A) is not particularly limited and may be appropriately selected from those conventionally compounded in the photosensitive composition. Among them, a resin represented by the following formula (a-1) which is a resin having a (meth) acryloyl group is preferable.

[Chemical Formula 5]

In the formula (a-1), X ^a represents a group represented by the following formula (a-2) or (a-2 ').

[Chemical Formula 6]

The formula (a2) and the formula (a2 ') of, R ^a1 is, each independently represents a hydrocarbon group, or a halogen atom, a hydrogen atom, the carbon atom 1 ~ 6, R ^a2 are each independently A hydrogen atom or a methyl group, and W ^a represents a group represented by the following formula (a-3).

(7)

In the above formula (a-1), Y ^a represents a residue other than an acid anhydride group (-CO-O-CO-) from a dicarboxylic acid anhydride. Examples of the dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorenedic anhydride, methyltetrahydrophthalic anhydride , And anhydrous glutaric acid.

In the above formula (a-1), Z ^a represents a residue other than the two acid anhydride groups in the tetracarboxylic acid dianhydride. Examples of the tetracarboxylic acid dianhydride include pyromellitic acid dianhydride, benzophenonetetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, and biphenyl ether tetracarboxylic acid dianhydride.

In the above formula (a-1), x represents an integer of 0 to 20.

The weight average molecular weight (Mw: value measured by gel permeation chromatography (GPC) in terms of polystyrene conversion) of the alkali-soluble resin (A) described above is preferably 1,000 to 50,000, more preferably 3,000 to 10,000.

The weight average molecular weight of the (A4) cardo resin is preferably 1000 to 40000, more preferably 2,000 to 30,000.

The content of the alkali-soluble resin (A) in the photosensitive resin composition is not particularly limited within the range not hindering the object of the present invention. Soluble resin (A) relative to the total of the weight of the alkali-soluble resin (A), the weight of the non-alkali-soluble resin (B) and the weight of the other non- Is preferably 30% by weight or more, more preferably 50% by weight or more, and particularly preferably 50 to 70% by weight.

When the alkali-soluble compound (A ') is used instead of or in addition to the alkali-soluble resin (A) in the photosensitive resin composition, the alkali-soluble compound may be a low molecular weight compound having an acidic group.

(A ') Examples of the low-molecular weight compound having an acid group suitable as an alkali-soluble compound include acrylic acid, methacrylic acid and a compound represented by the following formula (A'1-1).

[Chemical Formula 8]

(D + e + f), d is an integer of 1 to 3, and e is an integer of 0 to 3 (in the formula (A'1-1), R ^a1 is a hydrogen atom or a methyl group, R ^a2 is And f is an integer of 1 to 3.)

When R ^a2 is an organic group, the organic group may be a combination of an aliphatic group and an aromatic group in combination of an aliphatic group and an aromatic group. The organic group may contain a hetero atom such as N, S, O, P or a halogen atom. As R ^a2 , an aliphatic group which may contain an ether bond (-O-) or an ester bond (-CO-O-) is preferable. When R ^a2 is an aliphatic group which may contain an ether bond (-O-) or an ester bond (-CO-O-), the number of carbon atoms thereof is not particularly limited, but is preferably 1 to 20, More preferably 1 to 8 carbon atoms.

As the combination of d, e and f, it is preferable that d and f are 1 and e is 0.

Among the compounds represented by the above formula (A'1-1), the compounds represented by the following formula (A'1-2) are preferable.

[Chemical Formula 9]

(Wherein R ^a1 is a hydrogen atom or a methyl group, R ^a3 and R ^a4 are alkylene groups having 1 to 20 carbon atoms, L is -O-, -CO-O- or - O-CO-, and g is an integer of 0 to 5.)

R ^a3 and R ^a4 in the formula (A'1-2) are preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms. Methylene group, 1,2-ethanediyl group, 1,3-propanediyl group, 1,2-propanediyl group, 1,4-butanediyl group, 1,5-pentanediyl group, .

G in formula (A'1-2) is preferably an integer of 0 to 3, preferably 0 or 1.

(A ') Compounds having an acid group of a non-condensation system having a carboxyl group and a (meth) acryloyl group, which are suitably used as an alkali-soluble compound, can be prepared by reacting all of the hydroxyl groups of a compound containing at least one hydroxyl group and a carboxyl group, Acylating agent according to the acylating agent giving the (meth) acryloyl group described above.

Further, a compound having an acid group of a non-condensation system having a carboxyl group, a hydroxyl group and a (meth) acryloyl group may be prepared by reacting a part of the hydroxyl group of a compound containing two or more hydroxyl groups and at least one carboxyl group with the By acylating according to the acylating agent giving a diary.

Among the compounds having an acid group of a non-condensed system, compounds having an acid group of a non-condensation system having a carboxyl group and a (meth) acryloyl group are preferable from the standpoint of preparation and availability.

Among the compounds containing a hydroxyl group and a carboxyl group, which are used for preparing a compound having an acid group of a non-condensation system having a carboxyl group and a (meth) acryloyl group, a hydroxy acid having one hydroxyl group and a carboxyl group is preferable. As such a hydroxy acid, an aliphatic hydroxy acid which may contain an ether bond (-O-) or an ester bond (-CO-O-) is preferable.

Specific examples of such aliphatic hydroxy acids include glycolic acid, lactic acid, hydroxybutyric acid, mono-2-hydroxyethyl esters of oxalic acid, mono-2-hydroxyethyl ester of malonic acid, mono-2-hydroxyethyl ester of succinic acid, Mono-2-hydroxyethyl ester of tartaric acid and mono-2-hydroxyethyl ester of adipic acid.

The content of the alkali-soluble compound (A ') in the photosensitive resin composition is not particularly limited within the range not hindering the object of the present invention. The proportion of the weight of the alkali-soluble compound (A ') to the total of the weight of the alkali-soluble compound (A') and the weight of the non-alkali-soluble resin (B) in the photosensitive resin composition is preferably 30 wt% , More preferably 50 wt% or more, and particularly preferably 50 to 70 wt%.

&Lt; (B) Non alkali soluble resin &gt;

The photosensitive resin composition suitably used in the present invention contains (B) a non-alkali soluble resin. (B) The alkali-soluble resin includes an OH group protected by a water-repellent protecting group of a specific structure, which is deprotected by exposure. Therefore, the photosensitive resin composition containing the (B) non-alkali-soluble resin is very difficult to be miscible with the alkaline developer in the unexposed state, and is hardly dissolved in the alkaline developer even though it contains the alkali-soluble resin (A) Do not.

With respect to the OH group protected by the water-repellent protecting group which is deprotected by exposure, the OH group may be a hydroxyl group or an OH group contained in the carboxyl group.

When the (B) non-alkali-soluble resin is exposed, part or all of the aforementioned water-repellent protecting groups are deprotected. As a result, when the photosensitive resin composition is exposed, it is easy to be blended into an alkali developing solution.

The (B) non-alkali-soluble resin has a hydrophilic functional group with a specific structure in a deprotected state. Such a hydrophilic functional group contributes to enhancement of contrast and promotes dissolution of the alkali-soluble resin (A) into an alkali developing solution. As a result, when the photosensitive resin composition containing (B) the non-alkali soluble resin is exposed, the alkali developer is well mixed with the photosensitive resin composition, and (A) the alkali soluble resin is dissolved in the alkaline developer in a satisfactory manner , The exposed portions in the photosensitive resin composition are well removed by the alkali developing solution.

The OH group protected by the above-described water-repellent protecting group which is deprotected by exposure is specifically a group represented by the following formula (I).

[Chemical formula 10]

(In the formula (I), R ¹ is a hydrogen atom or a hydrocarbon group of 1 to 20 carbon atoms which may be interrupted by -O- or -S-; R ² and R ³ are each independently -O- or -O-; R ¹ and R ² may be bonded to each other to form a ring, and R ² and R ³ may be bonded to each other to form a ring.

In the formula (I), R ¹ , R ² and R ³ are hydrocarbon groups having 1 to 20 carbon atoms. The number of carbon atoms of the hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 6. The hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

When R ¹ , R ² and R ³ are aliphatic hydrocarbon groups, the aliphatic hydrocarbon groups may be in the form of chain, cyclic structure or cyclic structure. The aliphatic hydrocarbon group may have an unsaturated bond. The aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group.

When R ¹ , R ² and R ³ are chain aliphatic hydrocarbon groups, specific examples thereof include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, Butyl group, n-pentyl group, isopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-heptadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-heptadecyl, Decyl group and n-icosyl group.

Specific examples of the cyclic aliphatic hydrocarbon group represented by R ¹ , R ² and R ³ as the cyclic aliphatic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group , A cyclononyl group, a cyclodecyl group, a cyclododecyl group, and a cyclododecyl group.

Specific examples of the case where R ¹ , R ² and R ³ are cyclic aliphatic hydrocarbon groups and the cyclic aliphatic hydrocarbon group is a polycyclic group include groups excluding one hydrogen atom from the following polycyclic aliphatic hydrocarbon.

(11)

When R ¹ , R ² and R ³ are aromatic hydrocarbon groups, specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a biphenylyl group, a phenanthrenyl group and a fluorenyl group.

When R ¹ , R ^2, and R ³ are groups obtained by combining an aliphatic hydrocarbon group and an aromatic hydrocarbon group, examples of such groups include an aralkyl group. Specific examples of the aralkyl group include a benzyl group, a phenethyl group, a 3-phenyl-n-propyl group, a 4-phenyl-n-butyl group, Ethyl group and 2- (β-naphthyl) ethyl group.

When R ¹ , R ² and R ³ are a hydrocarbon group containing an aromatic ring, the aromatic ring may be a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, An alkanoyl group having 1 to 10 carbon atoms, and an alkanoyloxy group having 2 to 10 carbon atoms. When a plurality of substituents are present on the aromatic ring, the plurality of substituents may be the same or different.

In formula (I), R ¹ is preferably a hydrogen atom. R ² is preferably a methyl group. As R ³ , an ethyl group, an isobutyl group, a cyclohexyl group, a 2-ethyl-n-hexyl group or an octadecyl group is preferable.

When R ² and R ³ are bonded to each other to form a ring, the ring is a heterocyclic ring containing an oxygen atom bonded to R ³ . For the heterocyclic ring containing an oxygen atom, the number of carbon atoms thereof is preferably from 3 to 7, more preferably from 4 to 6. The heterocyclic ring may further include a hetero atom other than the oxygen atom bonded to R &lt; ³ &gt;. Examples of the heteroatom in this case include an oxygen atom, a sulfur atom, and a nitrogen atom.

When R ¹ and R ² are bonded to each other to form a ring, the ring is preferably a saturated aliphatic hydrocarbon ring of 3 to 12 atoms. When the ring formed by combining R ¹ and R ² is a 6-membered saturated aliphatic hydrocarbon ring, the group represented by formula (I) is a group represented by the following formula. In the formula, R ³ is the same as the formula (I).

[Chemical Formula 12]

Suitable examples of the group represented by formula (I) are shown below.

[Chemical Formula 13]

As the group represented by the formula (I), it is preferable that R ² and R ³ are bonded to each other to form a ring containing an oxygen atom. Accordingly, among the groups represented by the formula (I), the following groups are preferred.

[Chemical Formula 14]

Among the groups containing a ring containing these oxygen atoms, the following groups are more preferable.

[Chemical Formula 15]

When the photosensitive resin composition is exposed, the (B) non-alkali-soluble resin preferably satisfies the following formulas (II-1) to (II-3)

-R ⁴ -OH ... (II-1)

_{^{- (R 5 -O) m -R}} 6 ... (II-2)

- (R ⁷ -SO ₂ ) _n -R ⁸ - (II-3)

(Wherein (II-1), R ⁴ is a carbon atom number of 1 to 20 alkyl group. In the formula (II-2) of, R ⁵ is a carbon atom number of 2 to 4 alkylene group, R ⁶ is a hydrogen atom , A hydrocarbon group having 1 to 50 carbon atoms or -R ⁹ -C (= O) -OH wherein R ⁹ is a divalent organic group, and m is an integer of 2 to 20. In the formula (II-3) , R ⁷ is an alkylene group having 1 to 4 carbon atoms, R ⁸ is a hydrocarbon group having 1 to 50 carbon atoms, and n is an integer of 1 to 20. A plurality of R ⁵ in the formula (II-2) When n is an integer of 2 to 20 in the formula (II-3), a plurality of R ⁷ in the formula (II-3) may be the same or different.)

Lt; 2 &gt;

The group represented by the above formulas (II-1) to (II-3) is a hydrophilic functional group which contributes to an improvement in contrast at the time of development. When the exposed photosensitive resin composition is in contact with an alkali developer, Thereby promoting dissolution of the soluble resin into an alkali developer.

When the end of the group represented by the formula (II-1) or (II-2) is an OH group, the non-alkali soluble resin (B) -2). &Lt; / RTI &gt;

Further, the group represented by the formula (II-1) or the formula (II-2) in which the terminal is an OH group is protected with a protecting group which can be protected by exposure to light, Resin may be used. In this case, when the non-alkali soluble resin (B) is exposed, a group represented by the formula (II-1) or (II-2) wherein the terminal is an OH group is produced.

In the formula (II-1), R ⁴ is an alkylene group having 1 to 20 carbon atoms. The alkylene group may be linear or branched. As the alkylene group, a straight chain alkylene group is preferable. Specific examples of the straight chain alkylene group having 1 to 20 carbon atoms include a methylene group, an ethane-1,2-diyl group, an n-propane-1,3-diyl group, n-pentane-1,5-diyl group, n-hexane 1,6-diyl group, n-heptane-1,7-diyl group, N-decane-1,10-diyl group, n-undecane-1,11-diyl group, n-dodecane-1,12-diyl group, n-tridecane- n-pentadecane-1,15-diyl group, n-hexadecane-1,16-diyl group, n-heptadecane-1,17-diyl group, n -Octadecane-1,18-diyl group, n-nonadecane-1,19-diyl group and n-icoic acid-1,20-diyl group.

Preferred examples of the group represented by the formula (II-1) include a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group, a 4-hydroxy- N-hexyl group, 7-hydroxy-n-heptyl group, 8-hydroxy-n-octyl group, 9-hydroxy-n-nonyl group and 10- . Of these, preferred are a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group, a 4-hydroxy-n-butyl group, a 5-hydroxy-n-pentyl group and a 6-hydroxy- More preferable.

In the formula (II-2), R ⁵ is an alkylene group having 2 to 4 carbon atoms, R ⁶ is a hydrogen atom, a hydrocarbon group having 1 to 50 carbon atoms, or -R ⁹ -C (═O) -OH [R ⁹ is a divalent organic group].

As R ⁵ , ethane-1,2-diyl group, n-propane-1,2-diyl group, n-propane-1,3-diyl group and n-butane- -1,2-diyl group and n-propane-1,2-diyl group are more preferable.

When R ⁶ in the formula (II-2) is a hydrocarbon group, the number of carbon atoms of the hydrocarbon group is 1 to 50, preferably 1 to 12, and more preferably 1 to 8. The hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

When R ⁶ is an aliphatic hydrocarbon group, the aliphatic hydrocarbon group may be in the form of a chain, a ring, or a chain structure and a cyclic structure. The aliphatic hydrocarbon group may have an unsaturated bond. The aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group. A suitable example of R ^{6 as} a hydrocarbon group is the same as a suitable example of a hydrocarbon group of R ¹ , R ² and R ³ .

R ⁹ in the formula (II-2) is a divalent organic group. This organic group may contain a hetero atom such as N, S, O, or a halogen atom. The organic group may include a chain structure and a cyclic structure, either as a chain or as a cyclic structure. The number of carbon atoms of the organic group is preferably 1 to 50, more preferably 1 to 12. As such an organic group, a hydrocarbon group not containing a hetero atom is preferable, and an aliphatic hydrocarbon group is preferable. When R ⁹ is a divalent aliphatic hydrocarbon group, the aliphatic hydrocarbon group is preferably an alkylene group, more preferably a linear alkylene group. A suitable example of the case where R ⁹ is a linear alkylene group is the same as R ⁴ described above. When R ⁹ is a straight chain alkylene group, a straight chain alkylene group having 1 to 6 carbon atoms is particularly preferable.

In the formula (II-3), R ⁷ is an alkylene group having 1 to 4 carbon atoms and R ⁸ is a hydrocarbon group having 1 to 50 carbon atoms. A suitable example of R ⁷ is the same as R ⁵ in the formula (II-2). A suitable example of R ⁸ is the same as R ⁶ in the formula (II-2).

(B) the alkali-soluble resin has at least one group represented by formulas (II-1) to (II-3) in the exposed state and has a group represented by formula (I) It does not. For example, the main skeleton may be a linear shape, a star shape, or a tree shape (brush shape).

Preferable main skeletons include a skeleton of a carbon-carbon bond contained in a polymer of a monomer having an unsaturated bond, and a skeleton of an acetylene diol derivative.

Among them, a main skeleton composed of a carbon-carbon bond contained in a polymer of a monomer having an unsaturated bond is preferable. Examples of the polymer of the monomer having an unsaturated bond having such a main skeleton include a copolymer of a monomer having an unsaturated bond including a (meth) acrylic acid ester, a polymer of an unsaturated alicyclic compound such as (poly) cycloolefin, a polymer of a maleimide derivative And a copolymer of the unsaturated alicyclic compound and the maleimide derivative. When the copolymer is a copolymer, it may be copolymerized with maleic anhydride.

Examples of the (B) non-alkali-soluble resin which is a polymer of a monomer having an unsaturated bond include a linear polymer capable of being produced by polymerizing a monomer having an unsaturated double bond by a reaction between unsaturated double bonds, As the linear polymer,

(III-1): &lt; EMI ID =

[Chemical Formula 16]

, X ¹ (wherein (III-1) is a trivalent organic group derived from a monomer having an unsaturated double bond, R ¹⁰ is the above-mentioned formula (II-1) ~ (II -3), and the following formula ( II-4) to the following formula (II-7):

-R ⁴ -OR ¹¹ ... (II-4)

_{^{- (R 5 -O) m -R}} 12 ... (II-5)

-R ⁴ -OR ¹³ -C (= O) -OR ¹¹ (II-6)

- (R ⁵ -O) _m -R ¹⁴ -C (= O) -OR ¹² (II-7)

And R &lt; 2 &gt;

In formula (II-4) and formula (II-6), R ⁴ is an alkylene group having 1 to 20 carbon atoms, R ¹¹ is a protecting group which can be deprotected when the photosensitive resin composition is exposed, R ¹³ is a divalent organic group,

In the formulas (II-5) and (II-7), R ⁵ is an alkylene group having 2 to 4 carbon atoms, a plurality of R ^{5 s} may be the same or different, m is an integer of 2 to 20, R ¹² is a protecting group that can be deprotected when the photosensitive resin composition is exposed, and R ¹⁴ is a divalent organic group.)

(III-2): &lt; EMI ID =

[Chemical Formula 17]

(In the formula (III) -2, X ² is a trivalent organic group derived from a monomer having an unsaturated double bond and R ¹⁵ is a group represented by the formula (I) and the following formulas (IV-1) to IV-4):

-R ⁴ -OR ¹⁶ (IV-1)

_{^{- (R 5 -O) m -R}} 16 ... (IV-2)

-R ⁴ -OR ¹³ -C (= O) -OR ¹⁶ - (IV-3)

- (R ⁵ -O) _m -R ¹⁴ -C (= O) -OR ¹⁶ (IV-4)

And R &lt; 2 &gt;

In the formulas (IV-1) to (IV-4), R ⁴ , R ⁵ , R ¹³ and R ¹⁴ are as defined above, and -OR ¹⁶ in the terminal partial structure is a group represented by formula (I)

(B-1) copolymer containing a structural unit represented by the following formula (1).

In the copolymer (B-1), the amount of the unit represented by the formula (III-1) is preferably 1 to 70% by weight, and more preferably 5 to 40% by weight. Of these polymers, the amount of the unit of the formula (III-2) is preferably 10 to 90% by weight, and more preferably 30 to 70% by weight. The copolymer (B-1) is preferably composed of a unit represented by the formula (III-1) and a unit represented by the formula (III-2). Hereinafter, the unit represented by the formula (III-1) and the unit represented by the formula (III-2) will be described.

(Unit represented by the formula (III-1)

The unit represented by the formula (III-1) is a unit for imparting a hydrophilic group represented by the above-mentioned formulas (II-1) to (II-3) to the exposed (B-1) copolymer.

(II-1) to (II-3) and the following formula (II-1) as the functional group R ¹⁰ to be bonded to X ^{1 which} is a trivalent organic group derived from an unsaturated double bond, 4) to (II-7):

-R ⁴ -OR ¹¹ ... (II-4)

_{^{- (R 5 -O) m -R}} 12 ... (II-5)

-R ⁴ -OR ¹³ -C (= O) -OR ¹¹ (II-6)

- (R ⁵ -O) _m -R ¹⁴ -C (= O) -OR ¹² (II-7)

And a group selected from the group consisting of

In the formulas (II-4) to (II-7), R ⁴ , R ⁵ and m are as defined above. R ¹³ and R ¹⁴ are the same as R ⁹ described above. R ¹¹ is a protecting group which can be deprotected when the photosensitive resin composition is exposed.

Such a protecting group is a group which has been conventionally employed as a protecting group for a group containing an active hydrogen such as a hydroxyl group of a resin component contained in a photosensitive resin composition and includes a group represented by the following formula Can be appropriately selected from groups other than groups. Such a group includes a group represented by the following formula (b1), which is a protective group which is deprotected by the action of an acid.

[Chemical Formula 18]

[Chemical Formula 19]

(In the formula (b1), R ^b1 represents a linear, branched or cyclic alkyl group of 1 to 6 carbon atoms, and o represents 0 or 1.)

Suitable examples of R ^b1 in the case of a linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert- Pentyl group and the like. Further, suitable examples of the case where R ^b1 is a cyclic alkyl group include a cyclopentyl group and a cyclohexyl group. Specific examples of the acid dissociable, dissolution inhibiting group represented by formula (b1) include a tert-butoxycarbonyl group and a tert-butoxycarbonylmethyl group.

Examples of the trivalent organic group derived from a monomer having an unsaturated double bond represented by X &lt; ¹ &gt; include the following (x-1) to (x-22). R ^b2 represents a hydrogen atom or a methyl group. * Is the combined number (hand). Further, among the bonds in the trivalent organic group, the two bonds to be bonded to the main chain of the copolymer (B-1) are omitted from the symbol &quot; * &quot;.

[Chemical Formula 20]

As the unit represented by the formula (III-1), a unit derived from a (meth) acrylic acid ester or a styrene derivative is preferable.

With respect to the unit represented by the formula (III-1), the units derived from the (meth) acrylic acid ester include units represented by the following formulas (b2) to (b8).

[Chemical Formula 21]

(Wherein (b2) ~ (b8) of, R ^b2 is a hydrogen atom or a methyl ^{group. R 4, R 5, R} 6, R 11, R 12, R 13, R 14, m and n are the same as described above Do.)

Among the units represented by the formulas (b2) to (b8), a unit represented by the formula (b2) or (b3) is preferable and a unit represented by the formula (b2) is particularly preferable.

With respect to the unit represented by the formula (III-1), the units derived from the styrene derivative include units represented by the following formulas (b9) to (b15).

[Chemical Formula 22]

(In the formulas (b9) to (b15), R ⁴ , R ⁵ , R ⁶ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , m and n are as defined above and p is 0 or 1.)

In the formulas (b9) to (b15), p is 0 or 1, preferably 1. Among the units represented by the formulas (b9) to (b15), a unit represented by the formula (b9) or (b10) is preferable and a unit represented by the formula (b9) is more preferable. In the units represented by formulas (b9) to (b15), the substituent on the benzene ring is preferably bonded to the para position relative to the position at which the benzene ring bonds to the main chain of the (B-1) copolymer.

(Unit represented by the formula (III-2)

The unit represented by the formula (III-2) essentially includes a group represented by the formula (I) which is the aforementioned water-repellent protecting group. Therefore, when the (B-1) copolymer containing the unit represented by the formula (III-2) is blended in the photosensitive resin composition, the unexposed photosensitive resin composition is not miscible with the alkali developing solution, The resin composition is well mixed with an alkali developing solution.

The unit represented by the formula (III-2) is preferably a group represented by the formula (I) described above as the functional group R ¹⁵ to be bonded to X ^{2 which} is a trivalent organic group derived from an unsaturated double bond, (IV-4):

-R ⁴ -OR ¹⁶ (IV-1)

_{^{- (R 5 -O) m -R}} 16 ... (IV-2)

-R ⁴ -OR ¹³ -C (= O) -OR ¹⁶ - (IV-3)

- (R ⁵ -O) _m -R ¹⁴ -C (= O) -OR ¹⁶ (IV-4)

Lt; 2 &gt;

In the formulas (IV-1) to (IV-4), R ⁴ , R ⁵ , R ¹³ and R ¹⁴ have the same meanings as described above, and -OR ¹⁶ in the terminal partial structure is a group represented by formula (I).

Examples of the trivalent organic group derived from a monomer having an unsaturated double bond of X ² include the above-mentioned formulas (x-1) to (x-22).

As the unit represented by the formula (III-2), a unit derived from a (meth) acrylic acid ester or a styrene derivative is preferable.

With respect to the unit represented by the formula (III-2), the units derived from the (meth) acrylic acid ester include units represented by the following formulas (b16) to (b20).

(23)

(In the formulas (b16) to (b20), R ^b2 , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ¹³ , R ¹⁴ and m are as defined above.)

Among the units represented by the formulas (b16) to (b20), a unit represented by the formula (b16) or (b17) is preferable and a unit represented by the formula (b16) is particularly preferable.

With respect to the unit represented by the formula (III-2), the units derived from the styrene derivative include units represented by the following formulas (b21) to (b25).

&Lt; EMI ID =

(In the formulas (b21) to (b25), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ¹³ , R ¹⁴ and m are as defined above.)

Among the units represented by the formulas (b21) to (b25), a unit represented by the formula (b21) or (b22) is preferable and a unit represented by the formula (b21) is more preferable. In the units represented by the formulas (b21) to (b25), the substituent on the benzene ring is preferably bonded to the para position relative to the position at which the benzene ring binds to the main chain of the (B-1) copolymer.

When the (B-1) copolymer contains units other than the units represented by the formula (III-1) and the units represented by the formula (III-2), the units may be those derived from a monomer having an unsaturated double bond Is not particularly limited as long as it does not impair the object of the present invention. The unit other than the unit represented by the formula (III-1) and the unit represented by the formula (III-2) can be obtained from a large number of units conventionally employed as the constitutional unit for various resins incorporated in the photosensitive resin composition It can be selected appropriately.

The homopolymer (B-2) described below may also be suitably used as the (B) non-alkali-soluble resin. Suitable examples of the homopolymer (B-2) include homopolymers composed of any one of the units represented by the following formulas (b17) to (b18) and (b22) to (b25).

(25)

(In the formulas (b17) to (b20), R ^b2 , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ¹³ , R ¹⁴ and m are as defined above.)

(26)

(In the formulas (b22) to (b25), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ¹³ , R ¹⁴ and m are as defined above.)

As the homopolymer (B-2), a homopolymer composed of only the units represented by the above-mentioned formulas (b17), (b18), (b22), or (b23) is more preferable.

As the homopolymer (B-2), it is preferable to include at least one of the groups represented by the following formulas as the unit represented by the above-mentioned formula (I).

(27)

When the alkali-soluble resin (A) and / or the alkali-soluble resin (A ') described above are used in combination with the alkali-soluble resin (B), when the photosensitive resin composition is baked at a predetermined temperature after exposure and development, A resin having an acidic group such as a carboxyl group or a phenolic hydroxyl group is included. Therefore, when a pattern is formed by a predetermined method using the photosensitive resin composition comprising the alkali-soluble resin (A) and / or the alkali-soluble resin (A ') and the alkali-soluble resin (B) , A crosslinking reaction involving a carboxyl group and a phenolic hydroxyl group proceeds and a pattern having excellent chemical resistance is formed.

The content of the (B) non-alkali-soluble resin in the photosensitive resin composition suitably used in the present invention is not particularly limited within the range not hindering the object of the present invention. The weight of the alkali-soluble resin (A) and / or the alkali-soluble resin (A ') in the photosensitive resin composition, the weight of the non-alkali-soluble resin (B) Alkali-soluble resin is preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 1 to 50% by weight based on the total amount of the non-alkali-soluble resin (B).

<(B ') Other non-alkali-soluble resin>

The photosensitive resin composition suitably used in the present invention may contain (B) other non-alkali-soluble resin (B '), which is a non-alkali-soluble resin other than the non-alkali-soluble resin, within the range not hindering the object of the present invention .

(B ') The other non-alkali-soluble resin is not particularly limited as long as it is a resin other than the alkali-soluble resin (A) which does not correspond to the (B) non-alkali-soluble resin. (B ') Other non-alkali-soluble resins include structural units derived from various (meth) acrylic acid derivatives and hydroxystyrene derivatives described above, unsaturated carboxylic acids other than (meth) acrylic acid, (meth) acrylic acid, (Meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes and epoxy group-containing unsaturated compounds having no alicyclic group .

The other non-alkali-soluble resin (B ') preferably contains a structural unit having an epoxy group. As the monomer giving the epoxy group-containing monomer, an alicyclic epoxy group-containing unsaturated compound having a structure represented by the above-mentioned formulas (a3-1) to (a3-16) or glycidyl (meth) acrylate is preferable.

Further, from the viewpoint of easily obtaining a photosensitive resin composition which gives good developability and gives a pattern having excellent chemical resistance, it is preferable that the other non-alkali soluble resin (B ') has high solubility in an alkaline developer by exposure Do. That is, the (B ') other non-alkali-soluble resin preferably has an alkali-soluble group such as a carboxyl group or a phenolic hydroxyl group protected by a protecting group which can be deprotected by exposure. Deprotection may occur by the action of a compound which generates an acid or a radical by the action of (C) light described later.

The content of the other non-alkali-soluble resin (B ') in the photosensitive resin composition is not particularly limited within the range not hindering the object of the present invention. (B ') relative to the total of the weight of the alkali-soluble resin (A), the weight of the non-alkali-soluble resin (B) and the weight of the other non-alkali- The proportion of the alkali-soluble resin is preferably 70% by weight or less, more preferably 50% by weight or less, further preferably 1 to 50% by weight, particularly preferably 10 to 50% by weight, % Is most preferable.

&Lt; (C) Compound which generates an acid or a radical by the action of light &gt;

The photosensitive resin composition suitably used in the present invention preferably contains (C) a compound which generates an acid or a radical by the action of light. When the photosensitive resin composition does not contain a compound which generates an acid or a radical by the action of light (C), the protective group of (A) the alkali-soluble resin and (B) the non-alkali- The type of light source used for exposure is limited. However, when the photosensitive resin composition contains (C) a compound which generates an acid or a radical by the action of light, the alkali-soluble resin (A), the non-alkali (B) The protecting group of the soluble resin can be satisfactorily deprotected.

Therefore, when the photosensitive resin composition contains (C) a compound which generates an acid or a radical by the action of light, it is easy to form a pattern having a good shape at a low exposure amount.

(C) The compound which generates an acid or a radical by the action of light may be a nonionic organic compound or an ionic organic compound. Examples of the nonionic organic compound include halide compounds, diazo ketones, sulfon compounds and sulfonic acid compounds. Examples of the nonionic organic compound include onium salts and the like. As the compound (C) which generates an acid or a radical by the action of light, two or more compounds may be used in combination. (C) a compound which generates an acid or a radical by the action of light, when a combination of two or more kinds is used, a nonionic organic compound and an ionic organic compound may be used in combination.

[Nonionic organic compound]

Examples of the nonionic organic compound that can be used as the compound (C) that generates an acid or a radical by the action of light include compounds represented by the following formulas (C1), (C2), (C3), and .

(28)

(In the formula (C1), R ^c1 represents an aliphatic hydrocarbon group of 1 to 10 carbon atoms which may have a substituent, a perfluoroalkyl group of 1 to 8 carbon atoms which may have a substituent, a carbon which may have a substituent An aromatic hydrocarbon group having 6 to 16 atoms.

[Chemical Formula 29]

(In the formula (C2), A represents -O- or -S-, ^Rc2 represents a perfluoroalkyl group having 1 to 8 carbon atoms, two ^Rc3s may be the same or different and each independently A hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

(30)

R ^c4 represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkyl group of 1 to 10 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, or an acyl group, and R ^c5 represents a carbon atom A hydrocarbon group of 1 to 20 carbon atoms or a halogenated hydrocarbon group of 1 to 20 carbon atoms, and the hydrocarbon group or the halogenated hydrocarbon group may contain -O-, -S-, or a carbonyl group. The hydrocarbon group or When the halogenated hydrocarbon group contains a carbonyl group, the number of carbon atoms contained in the carbonyl group is not included in the number of carbon atoms of the hydrocarbon group or the halogenated hydrocarbon group.)

(31)

(In the formula (C4), R ^c6 is the same as R ^c5 in the formula (C3).)

Hereinafter, the compounds represented by the formulas (C1) to (C4) will be described in order.

(A compound represented by the formula (C1)

In the formula (C1), when R ^c1 is an aliphatic hydrocarbon group, the aliphatic hydrocarbon group may have an oxo group (= O). When R ^c1 is a perfluoroalkyl group, the perfluoroalkyl group preferably has no substituent. When R ^c1 is an aromatic hydrocarbon group, examples of the substituent which the aromatic hydrocarbon group may have include a halogen atom and an alkyl group having 1 to 4 carbon atoms.

Specific examples of the compound represented by the formula (C1) include the following compounds.

(32)

(Compound represented by the formula (C2)

Specific examples of the compound represented by the formula (C2) include compounds represented by the following formulas.

(33)

(Compound represented by the formula (C3)

Specific examples of the compound represented by the formula (C3) include compounds represented by the following formulas.

(34)

(Compound represented by the formula (C4)

Preferable examples of the compound represented by the formula (C4) include compounds described in the following formulas, and compounds described in JP 2007-328090 A and JP 2007-328234 A.

(35)

[Ionic Organic Compound]

Examples of the ionic organic compound which can be used as the compound (C) for generating an acid or a radical by the action of light include compounds represented by the following formulas (C5), (C6), (C7) and (C8).

(36)

(In the formula (C5), R ^c7 , R ^c8 and R ^c9 each independently represent a hydroxyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, a, b and c each independently , R ^c7 , R ^c8, or R ^c9 may be the same or different when one of a, b, and c is 2 or more, and Z ^- represents an organic double ion.

(37)

(C6), ^Rc10 and ^Rc11 each independently represent a hydroxyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, d and e each independently represent 0 or 1 Z ^- represents an organic double ion.)

(38)

(In the formula (C7), R ^c12 and R ^c13 each independently represent an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, or R ^c12 and R ^c13 are bonded to each other May form a ring having 3 to 7 carbon atoms with the sulfur atom to which they are bonded The methylene group constituting the ring may be substituted with a carbonyl group, -O- or -S- R ^c14 represents a hydrogen atom, and R ^c15 is a ring indicate an alkyl group of carbon atoms 1 to 6, carbon atoms, 3 to 10 cycloalkyl group, or an aromatic hydrocarbon group which may be substituted, or R ¹⁴ and R ^c15 are bonded to each other together with the carbon atom to which they are bonded And Z &lt; ^- &gt; represents an organic double ion.

[Chemical Formula 39]

(In the formula (C8), A represents -O- or -S-, each of two R ^c16 independently represents a methyl group or a phenyl group, R ^c17 represents a perfluoroalkyl group of 1 to 8 carbon atoms .)

The compounds represented by the following formulas (C5) to (C8) will be described in order.

(Compound represented by the formula (C5)

Preferable examples of the organic cation constituting the compound represented by the formula (C5) include the following organic cations.

(40)

The organic double ion (Z ^- ), which is an anion constituting the compound represented by the formula (C5), is preferably an organic acid anion, more preferably an organic sulfonic acid anion. Preferable examples of the organic double ion (Z &lt; ^- &gt;) include anions represented by the following formula (C9).

(41)

(C9), R ^c18 to R ^c22 each independently represent a hydrogen atom, a halogen atom, a formyl group, an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, a carbon atom number of 1 A halogenated alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a cyano group, an alkylthio group having 1 to 4 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms , A hydroxyl group, a nitro group or a group represented by the following formula (C10):

- (C = O) -OR ^c23- R ^c24 (C10)

. In formula (C10), R ^c23 represents a straight chain aliphatic alkylene group having 1 to 16 carbon atoms which may be partially substituted with -O- or -S-, and R ^c24 represents a straight chain aliphatic alkylene group having 3 to 20 carbon atoms An alicyclic hydrocarbon group.

Preferable examples of R ^c18 to R ^c22 in the case of a halogenated alkyl group having 1 to 8 carbon atoms include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl and perfluorobutyl groups .

When R ^c18 to R ^c22 are aryl groups having 6 to 12 carbon atoms, the aryl group may be substituted with an alkyl group or an alkoxy group. Preferable examples of the aryl group include a phenyl group, a tolyl group, a methoxyphenyl group and a naphthyl group.

Preferable examples of R ^c18 to R ^c22 in the case of an aralkyl group having 7 to 12 carbon atoms include a benzyl group, a chlorobenzyl group and a methoxybenzyl group.

Preferable examples of R ^c18 to R ^c22 in the case of an alkylthio group having 1 to 4 carbon atoms include methylthio group, ethylthio group, n-propylthio group, isopropylthio group and n-butylthio group.

Preferable examples of R ^c18 to R ^c22 in the case of an alkylsulfonyl group having 1 to 4 carbon atoms include a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, an isopropylsulfonyl group and an n-butylsulfonyl group .

When two or more of R ^c18 to R ^c22 in the formula (C9) are groups represented by the formula (C10), the groups represented by a plurality of the formula (C10) may be the same or different.

R ^c23 is a straight chain aliphatic alkylene group having 1 to 16 carbon atoms which may be partially substituted with -O- or -S-. Preferred examples of the group include alkyleneoxy groups having 1 to 15 carbon atoms, alkyleneoxyalkylene groups having 2 to 14 carbon atoms, alkylene thio groups having 1 to 15 carbon atoms, and alkylene thioalkylene groups having 2 to 14 carbon atoms. .

Preferable examples of R ^c23 include groups represented by the following formulas (C10-1) to (C10-15).

-CH ₂ - (C 10-1)

-CH ₂ CH ₂ - (C 10-2)

-CH ₂ CH ₂ CH ₂ - (C 10-3)

-CH ₂ CH ₂ CH ₂ CH ₂ - (C 10-4)

-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ - (C 10-5)

-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ - (C ₁₀ -6)

-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ - (C 10-7)

-CH ₂ -O- (C10-8)

-CH ₂ -O-CH ₂ - (C 10-9)

-CH ₂ -O-CH ₂ CH ₂ - (C ₁₀ - 10)

-CH ₂ CH ₂ -O-CH ₂ CH ₂ - (C 10-11)

-CH ₂ -S- (C10-12)

-CH ₂ -S-CH ₂ - (C 10-13)

-CH ₂ -S-CH ₂ CH ₂ - (C 10-14)

-CH ₂ CH ₂ -S-CH ₂ CH ₂ - (C 10-15)

Among R ^c23 , a straight chain alkylene group of 1 to 8 carbon atoms unsubstituted (for example, groups represented by formulas (C10-1) to (C10-7)) is preferable.

The group represented by R ^c24 is preferably a group represented by the following formula:

(42)

Among the above groups, R ^c24 is more preferably a group of the following formula.

(43)

Specific examples of the anion represented by the formula (C9) include the following.

(44)

[Chemical Formula 45]

(46)

(47)

(48)

(49)

(50)

(51)

(52)

(53)

(54)

(55)

(56)

(57)

(58)

The anion represented by the following formula (C11) is also a preferable example of the organic double ion (Z &lt; ^- &gt;).

R ^c25 -SO ₃ ^- (C11)

(In the formula (C11), R ^c25 represents a perfluoroalkyl group having 1 to 25 carbon atoms, a naphthyl group which may have a substituent, or an anthryl group which may have a substituent.)

Examples of the substituent which the naphthyl group or the anthryl group may have include an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms.

Preferable examples of the anion represented by the formula (C11) include the following.

[Chemical Formula 59]

(60)

The anion represented by the following formula (C12) is also a preferable example of the organic double ion (Z ^- ).

^{_{R c26 -SO 2 -N - -SO 2}} -R c27 (C12)

(Formula (C12) of, R ^c26 and R ^c27 are each independently, a carbon atom number of 1-20 perfluoroalkyl group, or the number of carbon atoms from 1 to 4 carbon atoms, 6 to 20 which may have the alkyl group of the aryl Lt; / RTI &gt;

R ^c26 and R ^c27 is a group or different, and may be the same group, preferably the same group.

Preferable examples of the anion represented by the formula (C12) include the following.

^{_{CF 3 -SO 2 -N - -SO 2}} -CF 3

^{_{C 2 F 5 -SO 2 -N -}} -SO 2 -C 2 F 5

^{_{CF 3 -SO 2 -N - -SO 2}} -C 2 F 5

^{_{nC 4 F 9 -SO 2 -N -}} -SO 2 -nC 4 F 9

^{_{nC 8 F 17 -SO 2 -N -}} -SO 2 -nC 8 F 17

^{_{nC 10 F 21 -SO 2 -N -}} -SO 2 -nC 10 F 21

^{_{nC 12 F 25 -SO 2 -N -}} -SO 2 -nC 12 F 25

^{_{nC 16 F 33 -SO 2 -N -}} -SO 2 -nC 16 F 33

^{_{nC 20 F 41 -SO 2 -N -}} -SO 2 -nC 20 F 41

(61)

(Compound represented by the formula (C6)

Preferable examples of the organic cation constituting the compound represented by the formula (C6) include the following organic cations.

(62)

Preferable examples of the organic double ion (Z &lt; ^- &gt;) constituting the compound represented by the formula (C6) are as described for the formula (C5).

(Compound represented by the formula (C7)

Preferable examples of the organic cation constituting the compound represented by the formula (C7) include the following organic cations.

(63)

Preferable examples of the organic double ion (Z &lt; ^- &gt;) constituting the compound represented by the formula (C7) are as described for the formula (C5).

(Compound represented by the formula (C8)

Preferable examples of the organic cation constituting the compound represented by the formula (C8) include the following organic cations.

&Lt; EMI ID =

The organic double ion (Z ^- ) constituting the compound represented by the formula (C8) is a perfluoroalkanesulfonic acid ion having 1 to 8 carbon atoms.

The content of the (C) compound capable of generating an acid or a radical by the action of light in the photosensitive resin composition suitably used in the present invention is not particularly limited within the range not hindering the object of the present invention. The content of the acid or radical-generating compound (C) in the photosensitive resin composition by the action of light is preferably 0.1 to 20% by weight, more preferably 3 to 10% by weight based on the weight of the solid content of the photosensitive resin composition desirable.

&Lt; (D) Compound generating imidazole compound by heating &gt;

The photosensitive resin composition suitably used in the present invention is obtained by heating (D)

(65)

(Wherein R ^d1 , R ^d2 and R ^d3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, , A phosphino group, a phosphinyl group, a phosphonate group or an organic group.

(Hereinafter also referred to as a component (D)) which generates an imidazole compound represented by the following formula (1).

By including the compound (D) which generates an imidazole compound by heating, the crosslinking reaction involving the acid group of the resin contained in the photosensitive resin composition proceeds in the baking step, and a pattern having excellent chemical resistance Can be formed.

Examples of the organic group in R ^d1 , R ^d2 and R ^d3 include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group and an aralkyl group. This organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be any of linear, branched and cyclic. This organic group is usually monovalent, but in the case of forming a cyclic structure, it may be a divalent or higher-valent organic group.

R ^d1 and R ^d2 may be bonded to form a cyclic structure or may further contain a heteroatom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and condensed rings may be used.

The bond included in the organic group of R ^d1 , R ^d2 and R ^d3 is not particularly limited as long as the effect of the present invention is not impaired and the organic group is preferably a bond including a hetero atom such as an oxygen atom, . Specific examples of the bond containing a hetero atom include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond (-N═C (-R) C (= NR) -: R represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond and an azo bond.

^Examples of the bond containing a hetero atom which the organic group of R ^d1 , R ^d2 and R ^d3 may have include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, (-N═C (-R) -, -C (═NR) -: R represents a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond .

When the organic group of R ^d1 , R ^d2 and R ^d3 is a substituent other than the hydrocarbon group, R ^d1 , R ^d2 and R ^d3 are not particularly limited as long as the effect of the present invention is not impaired. Specific examples of R ^d1 , R ^d2 and R ^d3 include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyanato group, a cyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, An alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a thiocarbamoyl group, a nitro group, a nitroso group, a carboxylate group, an acyl group, an acyloxy group, a sulfino group, a sulfonate group, a phosphino group, An alkyl ether group, an alkenyl ether group, an alkylthioether group, an alkenylthioether group, an arylether group, and an arylthioether group. The hydrogen atom contained in the substituent may be substituted by a hydrocarbon group. The hydrocarbon group contained in the substituent may be any of straight chain, branched chain and cyclic.

As R ^d1 , R ^d2 and R ^d3 , a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a halogen atom are preferable and a hydrogen atom is more preferable.

The component (D) is not particularly limited as long as it is a compound capable of generating an imidazole compound represented by the formula (D1) by heating. (Skeleton) derived from an amine generated at the time of heat treatment with respect to a compound (thermobase generator) which has been conventionally compounded in various compositions and generates amines by the action of heat is referred to as imidazole Substituted compound to the skeleton derived from the compound, a compound used as the component (D1) can be obtained.

Preferred examples of the component (D) include compounds represented by the following formula (D2):

(66)

(Wherein R ^d1 , R ^d2 and R ^d3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, R ^d4 and R ^d5 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group R ^d6 , R ^d7 , R ^d8 , R ^d9, and R 8 are the same or different and each represents a hydrogen atom, a nitro group, a sulfo group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, ^d10 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, A phosphono group, a phosphonate group, an amino group, an ammonium group or an organic group, R ^d6 , R ^d7 , R ^d8 , R ^d9 and R ^d10 may form a cyclic structure by combining two or more thereof, and may contain a bond of a hetero atom.

And the like.

In the formula (D2), R ^d1, R ^d2 and R ^d3 are the same as those described about the formula (D1).

R ^d4 and R ^d5 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, A sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, or an organic group.

Examples of the organic group at R ^d4 and R ^d5 are those exemplified for R ^d1 , R ^d2 and R ^d3 . This organic group may contain a hetero atom in the organic group as in the case of R ^d1 , R ^d2 and R ^d3 . The organic group may be any of linear, branched and cyclic.

R ^d4 and R ^d5 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, an aryloxyalkyl group having 7 to 16 carbon atoms, An alkyl group having 2 to 11 carbon atoms having a cyano group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amide group having 2 to 11 carbon atoms, an alkyl group having 1 to 10 carbon atoms An alkyl group having 1 to 10 carbon atoms, an ester group having 2 to 11 carbon atoms (-COOR, -OCOR: R represents a hydrocarbon group), an aryl group having 6 to 20 carbon atoms, an electron donating group and / Is preferably a substituted C6-C20 aryl group, an electron-donating group and / or a benzyl group substituted with an electron-withdrawing group, a cyano group or a methylthio group. More preferably, both of R ^d4 and R ^d5 are hydrogen atoms, or R ^d4 is a methyl group, and R ^d5 is a hydrogen atom.

In the formula (D2), R ^d6 , R ^d7 , R ^d8 , R ^d9 and R ^d10 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, A sulfo group, a sulfone group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonium group or an organic group.

Examples of the organic group at R ^d6 , R ^d7 , R ^d8 , R ^d9 and R ^d10 include those exemplified for R ^d1 , R ^d2 and R ^d3 . The organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group as in the case of R ^d1 and R ^d2 . The organic group may be any of linear, branched and cyclic.

R ^d6 , R ^d7 , R ^d8 , R ^d9 and R ^d10 may combine with each other to form a cyclic structure, or may contain a heteroatom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and condensed rings may be used. For example, R ^d6 , R ^d7 , R ^d8 , R ^d9, and R ^d10 share two or more of them and share atoms of a benzene ring bonded to R ^d6 , R ^d7 , R ^d8 , R ^d9, and R ^d10 , , Condensed rings such as anthracene, phenanthrene, and indene may be formed.

R ^d6 , R ^d7 , R ^d8 , R ^d9 and R ^d10 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, An aryloxyalkyl group having 7 to 16 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms having a cyano group, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, , An amide group of 1 to 10 carbon atoms, an acyl group of 1 to 10 carbon atoms, an ester group of 2 to 11 carbon atoms, an aryl group of 6 to 20 carbon atoms, an electron donating group and / A cyano group, a methylthio group, or a nitro group substituted with an aryl group having 6 to 20 carbon atoms, an electron donating group and / or an electron withdrawing group.

R ^d6 , R ^d7 , R ^d8 , R ^d9 and R ^d10 are bonded to each other by two or more of them and share atoms of a benzene ring bonded to R ^d6 , R ^d7 , R ^d8 , R ^d9 and R ^d10 , The condensed rings such as anthracene, phenanthrene, indene and the like are also preferably formed because the absorption wavelength becomes long.

Among the compounds represented by the formula (D2), a compound represented by the following formula (D3):

(67)

(Formula (D3) of, R ^d1, R ^d2 and R ^d3 are the same as in formula (D1) and ^{(D2). R d4 ~ R} d9 is the same as that of formula (D2). R ^d11 is a hydrogen atom or It represents an organic group. R ^d6 and R ^d7 is no case where the hydroxyl group. R ^d6, R ^d7, R ^d8 and R ^d9 is may form a cyclic structure it is bonded over their second, and includes a combination of heteroatoms It may be.)

Are preferred.

The compound represented by the formula (D3) has a substituent group -OR ^d11 and is thus excellent in solubility in an organic solvent.

In the formula (D3), R ^d11 is a hydrogen atom or an organic group. When R ^d11 is an organic group, those exemplified as R ^d1 , R ^d2 and R ^d3 can be given as organic groups. The organic group may contain a hetero atom in the organic group. The organic group may be any of linear, branched and cyclic. As R ^d11 , a hydrogen atom or an alkyl group having 1 to 12 carbon atoms is preferable, and a methyl group is more preferable.

Specific examples of the compound particularly preferable as the component (D) are shown below.

(68)

The imidazole compound represented by the following formula (D4) is also suitable as the compound which generates the imidazole compound by heating (D).

(69)

(Wherein R ^d12 is a hydrogen atom or an alkyl group, R ^d13 is an aromatic group which may have a substituent, R ^d14 is an alkylene group which may have a substituent, R ^d1 , R ^d2 and R ^d3 , Equation (D1))

In the formula (D4), R ^d12 is a hydrogen atom or an alkyl group. When R ^d12 is an alkyl group, the alkyl group may be a straight chain alkyl group or a branched chain alkyl group. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably from 1 to 20, more preferably from 1 to 10, and still more preferably from 1 to 5.

Specific examples of the preferable alkyl group as R ^d12 include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec- n-pentyl group, n-pentyl group, n-hexyl group, n-heptyl group, N-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group and n-icosyl group.

In the formula (D4), R ^d13 is an aromatic group which may have a substituent. The aromatic group which may have a substituent may be an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent.

The kind of the aromatic hydrocarbon group is not particularly limited within the range not hindering the object of the present invention. The aromatic hydrocarbon group may be a monocyclic aromatic group, may be formed by condensation of two or more aromatic hydrocarbon groups, or may be formed by combining two or more aromatic hydrocarbon groups by a single bond. As the aromatic hydrocarbon group, a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthrenyl group are preferable.

The kind of the aromatic heterocyclic group is not particularly limited within the range not hindering the object of the present invention. The aromatic heterocyclic group may be a monocyclic group or a polycyclic group. Examples of the aromatic heterocyclic group include pyridyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, benzoxazolyl, benzothiazolyl And a benzimidazolyl group are preferable.

Examples of the substituent which the phenyl group, polycyclic aromatic hydrocarbon group or aromatic heterocyclic group may have include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, , A phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonia group and an organic group. When the phenyl group, polycyclic aromatic hydrocarbon group, or aromatic heterocyclic group has a plurality of substituents, the plurality of substituents may be the same or different.

When the substituent of the aromatic group is an organic group, examples of the organic group include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group and an aralkyl group. This organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be any of linear, branched and cyclic. This organic group is usually monovalent, but in the case of forming a cyclic structure, it may be a divalent or higher-valent organic group.

When the aromatic group has a substituent on the adjacent carbon atom, the two substituents bonded to adjacent carbon atoms may combine to form a cyclic structure. Examples of the cyclic structure include an aliphatic hydrocarbon ring and an aliphatic ring containing a hetero atom.

When the substituent of the aromatic group is an organic group, the bond included in the organic group is not particularly limited as long as the effect of the present invention is not impaired. The organic group is a bond including a hetero atom such as an oxygen atom, a nitrogen atom, . Specific examples of the bond containing a hetero atom include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond (-N═C (-R) C (= NR) -: R represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond and an azo bond.

Examples of the bond containing a hetero atom which the organic group may have include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, (-N═C (-R) -, -C (═NR) -: R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, A carbonate group, a sulfonyl group or a sulfinyl group.

When the organic group is a substituent other than the hydrocarbon group, the kind of the substituent other than the hydrocarbon group is not particularly limited within the range not hindering the object of the present invention. Specific examples of the substituent other than the hydrocarbon group include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyanato group, a cyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, An amino group, a monoalkylamino group, a dialkylamino group, a monoarylamino group, a diarylamino group, a carbamoyl group, a thiocarbamoyl group, a nitro group, a nitroso group, a carboxylate group, an acyl group, an acyl group An alkoxy group, an oxy group, a sulfino group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, an alkyl ether group, an alkenyl ether group, an alkylthioether group, an alkenylthioether group, And the like. The hydrogen atom contained in the substituent may be substituted by a hydrocarbon group. The hydrocarbon group contained in the substituent may be any of straight chain, branched chain and cyclic.

Examples of the substituent of the phenyl group, polycyclic aromatic hydrocarbon group, or aromatic heterocyclic group include an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, An aryloxy group having 1 to 12 carbon atoms, an arylamino group having 1 to 12 carbon atoms, and a halogen atom.

As R ^d13 , an imidazole compound represented by the formula (D4) can be easily synthesized at a low cost. From the viewpoint that the imidazole compound is excellent in solubility in water and an organic solvent, , And a thienyl group is preferable.

In the formula (D4), R ^d14 is an alkylene group which may have a substituent. The substituent which the alkylene group may have is not particularly limited within the scope of not impairing the object of the present invention. Specific examples of the substituent which the alkylene group may have include a hydroxyl group, an alkoxy group, an amino group, a cyano group and a halogen atom. The alkylene group may be a straight chain alkylene group, a branched chain alkylene group or a straight chain alkylene group. The number of carbon atoms of the alkylene group is not particularly limited, but is preferably from 1 to 20, more preferably from 1 to 10, and still more preferably from 1 to 5. The number of carbon atoms of the alkylene group does not include the carbon atom of the substituent bonded to the alkylene group.

The alkoxy group as a substituent bonded to the alkylene group may be either a straight chain alkoxy group or a branched chain alkoxy group. The number of carbon atoms of the alkoxy group as a substituent is not particularly limited, but is preferably from 1 to 10, more preferably from 1 to 6, and particularly preferably from 1 to 3.

The amino group as a substituent bonded to the alkylene group may be a monoalkylamino group or a dialkylamino group. The alkyl group contained in the monoalkylamino group or the dialkylamino group may be either a straight chain alkyl group or a branched chain alkyl group. The number of carbon atoms of the alkyl group contained in the monoalkylamino group or dialkylamino group is not particularly limited, but is preferably from 1 to 10, more preferably from 1 to 6, and particularly preferably from 1 to 3.

Specific examples of the alkylene group suitable as R ^d14 include a methylene group, an ethane-1,2-diyl group, an n-propane-1,3-diyl group, N-pentane-1,5-diyl group, n-hexane-1,6-diyl group, n-heptane-1,7-diyl group, N-decane-1,10-diyl group, n-decane-1,11-diyl group, n-dodecane-1,12-diyl group, n-tridecane- N-pentadecane-1,15-diyl group, n-hexadecane-1,16-diyl group, n-heptadecane-1, An n-octadecane-1,18-diyl group, an n-nonadecane-1,19-diyl group and an n-icoic acid-1,20-diyl group.

Of the imidazole compounds represented by the formula (D4), compounds represented by the following formula (D4-1) are preferable because they are low cost and can be easily synthesized and are excellent in solubility in water or an organic solvent. (D4-1), and R ^d14 is a methylene group.

(70)

R ^d12 and R ^d14 are the same as in the formula (D4), and R ^d1 , R ^d2 and R ^d3 are as shown in the formula (D1). R ^d15 , R ^d16 , R ^d17 , R ^d18 And R ^d19 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, , Phosphino group, phosphono group, phosphonate group, amino group, ammonia group or organic group, provided that at least one of R ^d15 , R ^d16 , R ^d17 , R ^d18 and R ^d19 is a group other than a hydrogen atom .)

When R ^d15 , R ^d16 , R ^d17 , R ^d18 and R ^d19 are organic groups, this organic group is the same as the organic group R ^d13 in formula (D4). R ^d15 , R ^d16 , R ^d17 and R ^d18 are preferably hydrogen atoms from the viewpoint of the solubility of the imidazole compound in a solvent.

Among them, at least one of R ^d15 , R ^d16 , R ^d17 , R ^d18 and R ^d19 is preferably the following substituent, and it is particularly preferable that R ^d19 is the following substituent. When R ^d19 is a substituent shown below, R ^d15 , R ^d16 , R ^d17 and R ^d18 are preferably hydrogen atoms.

-OR ^d20

(R ^d20 is a hydrogen atom or an organic group)

When R ^d20 is an organic group, this organic group is the same as the organic group having R ^d13 in the formula (D4) as a substituent. R ^d20 is preferably an alkyl group, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.

Among the compounds represented by the above formula (D4-1), the compounds represented by the following formula (D4-1-1) are preferable.

(71)

In the (expression (D4-1-1), R ^d12 is equal to the expression (D4). R ^d21, R ^d22, R ^d23, R ^d24 and R ^d25 are each independently a hydrogen atom, a hydroxyl group, a mercapto group, A silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, , Provided that at least one of R ^d21 , R ^d22 , R ^d23 , R ^d24 and R ^d25 is a group other than a hydrogen atom.

Among the compounds represented by formula (D4-1-1), R ^d21, R ^d22, R ^d23, R ^d24 and R ^d25 at least one of, preferably a group represented by -OR ^d20 of the above and, R is -OR ^{d25 d20} Is particularly preferable. When R ^d25 is a group represented by -OR ^d20 , R ^d21 , R ^d22 , R ^d23 and R ^d24 are preferably hydrogen atoms.

The method of synthesizing the imidazole compound represented by the formula (D4) is not particularly limited. For example, a halogen-containing carboxylic acid derivative represented by the following formula (D5) and an imidazole compound represented by the above formula (D1) are reacted in accordance with a conventional method to carry out imidazolylation, 1) can be synthesized.

(72)

(In the formula (D5), R ^d12 , R ^d13 and R ^d14 are the same as in the formula (D4), and Hal is a halogen atom.)

When the imidazole compound is a compound represented by the formula (D4) and R ^d14 is a methylene group, that is, when the imidazole compound is a compound represented by the following formula (D6), the following Michael addition reaction , An imidazole compound can also be synthesized.

(73)

(In the formula (D6), R ^d12 and R ^d13 are as in the formula (1), and R ^d1 , R ^d2 and R ^d3 are as in the formula (D1).)

Specifically, for example, a 3-substituted acrylic acid derivative represented by the following formula (D7) and an imidazole compound represented by the above formula (D1) are mixed in a solvent to cause a Michael addition reaction, Lt; / RTI &gt;

&Lt; EMI ID =

(In the formula (D7), R ^d12 and R ^d13 are as shown in the formula (D4).)

An imidazole compound represented by the following formula (D9) can be obtained by adding a 3-substituted acrylic acid derivative represented by the following formula (D8) containing an imidazolyl group to a solvent containing water.

(75)

(, R ^d13 of formula (D8) and formula (D9) is equal to the expression ^{(D4), R d1, R} d2 and R ^d3 is equal to the expression (D1).)

In this case, the imidazole compound represented by the formula (D1) and the 3-substituted acrylic acid represented by the following formula (D10) are produced by hydrolysis of the 3-substituted acrylic acid derivative represented by the formula (D8). Then, a Michael addition reaction takes place between the 3-substituted acrylic acid represented by the following formula (D10) and the imidazole compound represented by the formula (D1) to produce an imidazole compound represented by the formula (D9).

[Formula 76]

(In the formula (D10), R ^d13 is the same as the formula (D4).)

Suitable specific examples of the imidazole compound represented by the formula (D4) include the followings.

[Formula 77]

The content of the compound (D) which generates an imidazole compound by heating in the photosensitive resin composition suitably used in the present invention is not particularly limited within the range not hindering the object of the present invention. The content of the compound capable of generating an imidazole compound by heating (D) in the photosensitive resin composition is preferably 0.1 to 20% by weight, more preferably 0.1 to 5% by weight based on the weight of the solid content of the photosensitive resin composition .

<(S) Solvent>

The photosensitive resin composition may contain a solvent (S), if necessary, for the purpose of adjusting the coating property and the viscosity. As the component (S), any component that can dissolve each component to be used to form a homogeneous solution can be used. Any one or more kinds of solvents selected from known solvents used in the photosensitive resin composition can be used as the (S) solvent.

Specific examples of the (S) solvent include lactones such as? -Butyrolactone; Ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone and 2-heptanone; Polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; Ethylene glycol monoacetate, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, ethylene glycol monopropionate, diethylene glycol monopropionate, propylene glycol monopropionate or dipropylene glycol monopropionate A compound having an ester bond such as a nate; Monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether, dimethyl ether, diethyl ether, dipropyl ether, or dibutyl ether of these polyhydric alcohols [among these, propylene glycol monomethyl ether (PGME) is preferred; Monoalkyl ethers or monophenyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether and the like of the compound having ester bond (among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl Ether (PGME) is preferred; Cyclic ethers such as dioxane, esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate; Benzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene and the like in the presence of a base such as anisole, ethylbenzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, Aromatic organic solvents; N, N, N'-tetramethylurea, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetoamide, hexamethylphosphoramide, Dimethyl-2-imidazolidinone, N, N, 2-trimethylpropionamide, and other nitrogen-containing polar solvents. These organic solvents may be used alone or in combination of two or more.

Examples of the solvent (S) include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), EL,? -Butyrolactone, N, N, N ', N'-tetramethylurea, N, N -Dimethylacetamide, N, N, 2-trimethylpropionamide are preferable. These organic solvents may be used alone or in combination of two or more. A mixed solvent obtained by mixing PGMEA with a polar solvent other than the PEGMEA is also preferable. The compounding ratio (weight ratio) may be suitably determined in consideration of the compatibility of the PGMEA with the polar solvent and the like, but is preferably within the range of 1: 9 to 9: 1, more preferably 2: 8 to 8: 2 desirable.

More specifically, when EL is mixed as a polar solvent, the weight ratio of PGMEA: EL is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. When PGME is blended as a polar solvent, the weight ratio of PGMEA: PGME is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, still more preferably 3: 7: 3.

As the (S) solvent, a mixed solvent of γ-butyrolactone and at least one selected from PGMEA and EL is also preferable. In this case, as the mixing ratio, the weight ratio of the former to the latter is preferably 70:30 to 95: 5.

The amount of the (S) solvent to be used is not particularly limited and is appropriately set in accordance with the thickness of the coating film at a concentration that can be applied to a substrate or the like. In general, the solid concentration of the photosensitive resin composition is used in the range of 1 to 40% by weight, preferably 2 to 39% by weight, and more preferably 3 to 25% by weight.

&Lt; (E) Other components &gt;

The photosensitive resin composition may further contain other components as required. For example, it is possible to use various additives such as a dissolving agent, a dissolution inhibitor, a basic compound, a surfactant, a dye, a pigment, a plasticizer, a photosensitizer, a light absorbent, a halation inhibitor, a storage stabilizer, a defoaming agent, .

[Exposure step]

The coating film formed of the photosensitive resin composition formed in the coating film forming step is exposed using an exposure apparatus having a desired light source. The wavelength used for exposure is not particularly limited. (Ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray (electron beam), and the like, for example, g, h, i line, ArF excimer laser (wavelength 193 nm), KrF excimer laser (wavelength 248 nm), F2 excimer laser, EUV , Soft X-ray, or the like. Among these, g, h, i line, ArF excimer laser, KrF excimer laser, EUV and EB are preferable. In the case of using a photosensitive resin composition that does not contain an acid or radical generating compound (C) by the action of light, an ArF excimer laser (wavelength: 193 nm) and EB ).

After the exposure step, the post-exposure heating step may be performed before or after the following development step. In the present invention, it is possible to form a resist pattern having a desired cross-sectional shape at a low exposure dose, without performing post-exposure heating step. In the case of carrying out the post-exposure heating step, it is carried out at a temperature lower than the temperature of the baking step described later, that is, at a temperature lower than the temperature for generating the imidazole compound represented by the above-mentioned formula (D1) At 120 ° C for 40 to 120 seconds.

[Development process]

In the exposure step, the coating film selectively exposed to a desired pattern is developed using an alkali developing solution. The alkali developing solution is suitably selected from those conventionally used in photolithography. A preferable example of the alkaline developer is an aqueous solution of tetramethylammonium hydroxide in an amount of 0.1 to 10% by weight. The developing solution is preferably rinsed with water and dried using pure water.

[Bake process]

In the baking process, the patterned coating film is baked by development. The baking temperature of the coating film in the baking step is not lower than a temperature at which the compound generating the imidazole compound by heating (D) generates an imidazole compound represented by the above formula (D1) by pyrolysis. (D) The temperature at which a compound generating an imidazole compound by heating generates an imidazole compound represented by the above formula (D1) by thermal decomposition can be measured by TG-DTA (thermogravimetric-differential thermal analysis) have. More specifically, the TG curve obtained by the TG-DTA analysis of a compound which generates an imidazole compound by heating (D) shows the start of weight reduction by pyrolysis and the temperature of the inflection point on the lowermost side on the baseline is , And a temperature at which an imidazole compound represented by formula (D1) is generated by pyrolysis may be used. The upper limit of the bake temperature is not particularly limited as long as it does not hinder the object of the present invention. The bake is typically carried out at a temperature of 300 DEG C or less. Typically at a temperature in the range of 150 deg. C to 300 deg. C (or above the temperature at which an imidazole compound represented by the formula (D1) is generated).

The baking time is not particularly limited, but is preferably 1 to 60 minutes, more preferably 1 to 30 minutes.

According to the above method, a resist pattern having a desired cross-sectional shape can be formed at a low exposure dose by forming a pattern using a predetermined positive photosensitive resin composition, and a pattern having excellent chemical resistance can be formed.

[ Example ]

Hereinafter, the embodiments of the present invention will be described, but the scope of the present invention is not limited to these embodiments.

[Examples 1 to 45 and Comparative Examples 1 to 3]

In Examples and Comparative Examples, a copolymer resin or a cardboard resin comprising at least one of the following units A1 to A10 was used as the alkali-soluble resin component (A). The weight ratios of the respective constituent units in the resin used as the component (A) are shown in Tables 1 and 2.

When the component (A) contains a copolymer resin composed of at least one unit selected from the following A1 to A10 and a cardo resin, the component ratio to the column of &quot; cardo resin &quot; The constituent ratios of the respective constituent units are shown in Tables 1 and 2 so that the total of the constituent ratios of the respective constituent units contained in the resin is 100. [

In this case, when preparing the photosensitive resin composition, a copolymer resin and a cardo resin were used as a copolymer resin: cardo resin at a weight ratio of 30:60.

(78)

In the Examples and Comparative Examples, a resin having a tetrahydro-2H-pyran-2-yl-oxy group as a group represented by the formula (I) was used as the component (B).

As the component (B), a resin comprising at least one of the following B1 to B5 is used. The weight ratios of the respective structural units in the resin used as the component (B) are shown in Tables 1 and 2.

(79)

In the examples, as the other (B ') other non-alkali soluble resin ((B') component) other than the component (B), a resin comprising at least one of the following units selected from B'1 to B'5 was used . The weight ratios of the respective structural units in the resin used as the component (B ') are shown in Tables 1 and 2.

(80)

In the examples and the comparative examples, a compound of the following formula was used as a compound which generates an acid or a radical by the action of light, which is the component (C).

[Formula 81]

In Examples and Comparative Examples, compounds IG1 to IG8 of the following formulas, which are compounds which generate an imidazole compound by heating as the component (D), and compound IG9 of the following formula, which is a compound generating piperidine by heating, Respectively. The temperature at which imidazole or piperidine is generated by pyrolysis for any of IG1 to IG9 is less than 230 占 폚.

(82)

(Preparation of photosensitive resin composition)

The components (A), (B), (B '), (C) and (D) of the weight parts shown in Tables 3 and 4 were dissolved in PGMEA so as to have a solid content concentration of 25% Thereby obtaining photosensitive resin compositions used in Examples and Comparative Examples. A pattern was formed using the photosensitive resin compositions of each of the Examples and Comparative Examples, and the sensitivity, pattern shape, and chemical resistance of the pattern were evaluated by the following methods. The evaluation results are shown in Tables 5 and 6.

<Sensitivity evaluation>

The photosensitive resin composition of each of the examples and the comparative examples was coated on a silicon wafer at a film thickness capable of forming a pattern having a thickness of 3 mu m to form a photosensitive resin film. The formed photosensitive resin film was subjected to prebaking under the conditions of 100 캜 for 120 seconds. After pre-baking, the photosensitive resin film was exposed with a light beam of the kind described in Table 3 while varying the exposure amount step by step through a mask for forming a hole pattern having a diameter of 10 mu m. Subsequently, the photosensitive resin film was developed using a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution at 23 DEG C for 30 seconds. The developed photosensitive resin film was washed with water, and then heated at 230 캜 for 20 minutes to obtain a hole pattern. In Comparative Examples 1 and 2, no baking was performed at 230 占 폚.

Then, the minimum exposure amount necessary for forming the hole pattern was determined to be an index of sensitivity. The results are shown in Tables 5 and 6 below.

?: 50 mJ / cm ² or less

?: 50 mJ / cm ² 300 mJ / cm ² or less

×: 300 mJ / cm ² More than

&Lt; Pattern shape evaluation &

In pattern shape evaluation, the photosensitive resin film was exposed at the lowest exposure amount measured in the sensitivity evaluation, and a hole pattern having holes with a diameter of 10 mu m was formed in the same manner as in the sensitivity evaluation.

From the electron microscope observation image of the cross section of the hole formed, a taper angle was obtained at an acute angle in the corner between the silicon wafer surface and the side surface of the hole pattern. The closer the taper angle is to 90 DEG, the better the rectangular sectional shape of the hole and the better the pattern shape.

Using the obtained taper angle, both sides of the pattern shape were judged according to the following criteria.

?: 80 ° or more

○: 70 ° or more and less than 80 °

×: less than 70 °

&Lt; Evaluation of chemical resistance in pattern &

A hole pattern having holes with a diameter of 10 mu m was formed in the same manner as in the pattern shape evaluation.

After the formed pattern was immersed in PGMEA at room temperature for 1 minute, the peeling of the pattern on the silicon wafer was observed. The chemical resistance in the pattern was determined according to the following criteria by using the observation result of the pattern peeling.

○: No pattern peeling

X: Peeling of the pattern

According to Examples 1 to 45, in the case of forming a pattern by using a positive photosensitive resin composition in which solubility in an alkali developer is increased by exposure, (D) a photosensitive composition containing a compound capable of generating an imidazole compound by heating A photosensitive resin composition is used, and in the state in which a component having an acidic group is present in a coating film of the exposed and developed photosensitive resin, a compound capable of generating an imidazole compound by heating (D) It can be seen that a pattern having a desired cross-sectional shape and excellent chemical resistance can be formed at a low exposure dose by heating at a temperature.

In particular, according to Example 15, it can be seen that even when a component having an acidic group is not contained in the exposed and developed coating film, a pattern having excellent chemical resistance can be formed when an acidic group is generated in the coating film during baking.

According to the comparative examples 1 and 2, it can be understood that when the exposed and developed coating film is not baked, a pattern having excellent chemical resistance can not be formed. Further, according to Comparative Example 3, when a photosensitive resin composition containing a compound which does not generate an imidazole compound by baking is used, it can be seen that even when the exposed and developed coating film is baked, a pattern having excellent chemical resistance can not be formed have.

Claims (6)

A coating film forming step of forming a coating film by applying a positive-working photosensitive resin composition which is exposed to increase solubility in an alkali developing solution on a support,
An exposure step of selectively exposing the coating film,
A developing step of developing the exposed coating film with an alkali developer,
A baking step of baking the coating film patterned by development,
A method for forming a pattern,
Wherein the positive photosensitive resin composition comprises (D) a compound represented by the following formula (D1):
[Chemical Formula 1]

(Wherein R ^d1 , R ^d2 and R ^d3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, , A sulfonate group, a phosphinyl group, a phosphonate group or an organic group.
Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;
The baking temperature of the coating film in the baking step is preferably such that the compound generating the imidazole compound represented by the formula (D1) by heating in the step (D) generates the imidazole compound represented by the formula (D1) Temperature,
Wherein the coating film in the baking step contains a component having an acidic group. The method according to claim 1,
Wherein the positive-working photosensitive resin composition contains (A) an alkali-soluble resin, (B) a non-alkali-soluble resin, and (D) a compound generating an imidazole compound represented by formula (D1)
The non-alkali-soluble resin (B)
(2)

(In the formula (I), R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by -O- or -S-; R ² and R ³ are each independently -O- or -O-; R ¹ and R ² may be bonded to each other to form a ring, and R ² and R ³ may be bonded to each other to form a ring.
, &Lt; / RTI &gt;
When the positive photosensitive resin composition is exposed, all or a part of the group represented by the formula (I) in the non-alkali-soluble resin (B) is deprotected and changed to an OH group,
(II-1) to (II-3): wherein the non-alkali-soluble resin (B)
-R ⁴ -OH ... (II-1)
_{^{- (R 5 -O) m -R}} 6 ... (II-2)
- (R ⁷ -SO ₂ ) _n -R ⁸ - (II-3)
(Wherein (II-1), R ⁴ is a carbon atom number of 1 to 20 alkyl group. In the formula (II-2) of, R ⁵ is a carbon atom number of 2 to 4 alkylene group, R ⁶ is a hydrogen atom And a hydrocarbon group having 1 to 50 carbon atoms and m is an integer of 2 to 20. In the formula (II-3), R ⁷ is an alkylene group having 1 to 4 carbon atoms and R ⁸ is a hydrocarbon group having 1 to 10 carbon atoms And n is an integer of 1 to 20. The plurality of R ⁵ in the formula (II-2) may be the same or different. When n is an integer of 2 to 20 in the formula (II-3) , And a plurality of R ⁷ in formula (II-3) may be the same or different.)
And at least one group represented by the formula:
Wherein at least one of the alkali-soluble resin (A) and the non-alkali-soluble resin (B) has a group in which an OH group in the acidic group or the acidic group is substituted with the formula (I). The method according to claim 1 or 2,
Wherein the compound generating the imidazole compound represented by the formula (D1) by heating (D) is represented by the following formula (D2):
(3)

(Wherein R ^d1 , R ^d2 and R ^d3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, , A sulfonate group, a phosphinyl group, a phosphonate group or an organic group R ^d4 and R ^d5 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, R ^d6 , R ^d7 , R ^d8 , R ^d9, and R ^{d10 are each independently a hydrogen} atom, an alkyl group, a nitro group, a sulfo group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, A halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, A phosphonate group, a phosphonate group, an amino group, an ammonia group or an organic group R ^{d 6} , R ^d7 , R ^d8 , R ^d9 and R ^d10 may combine with each other to form a cyclic structure or may contain a heteroatom bond.
&Lt; / RTI &gt; The method according to claim 1 or 2,
Wherein the compound generating the imidazole compound represented by the formula (D1) by heating (D) is represented by the following formula (D4):
[Chemical Formula 4]

(Wherein R ^d1 , R ^d2 and R ^d3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, , A sulfonate group, a phosphinyl group, a phosphonate group or an organic group, R ^d12 represents a hydrogen atom or an alkyl group, R ^d13 represents an aromatic group which may have a substituent, R ^d14 represents an alkylene Lt; / RTI &gt;
&Lt; / RTI &gt; The method according to claim 1 or 2,
Wherein the (B) non-alkali-soluble resin is a linear polymer capable of being produced by polymerizing a monomer having an unsaturated double bond by a reaction between unsaturated double bonds or a linear polymer chemically modified with the linear polymer,
(III-1): &lt; EMI ID =
[Chemical Formula 5]

(Formula (III-1) of, X ¹ is a trivalent organic group derived from a monomer having an unsaturated double bond, R ¹⁰ is the formula (II-1) ~ (II -3) and formula (II-4 ) To (II-7): &lt; EMI ID =
-R ⁴ -OR ¹¹ ... (II-4)
_{^{- (R 5 -O) m -R}} 12 ... (II-5)
-R ⁴ -OR ¹³ -C (= O) -OR ¹¹ (II-6)
- (R ⁵ -O) _m -R ¹⁴ -C (= O) -OR ¹² (II-7)
And R &lt; 2 &gt;
In the formula (II-4) and formula (II-6), R ⁴ is a carbon atom number of 1 to 20 alkylene group, R ¹¹ is a protecting group that can be de-protected in case that the photosensitive resin composition is exposed, R ¹³ Is a divalent organic group,
In the formulas (II-5) and (II-7), R ⁵ is an alkylene group having 2 to 4 carbon atoms, plural R ^{5 s} may be the same or different, m is an integer of 2 to 20, R ¹² is a protecting group which can be deprotected when the photosensitive resin composition is exposed, and R ¹⁴ is a divalent organic group.)
(III-2): &lt; EMI ID =
[Chemical Formula 6]

(Wherein, in the formula (III) -2, X ² is a trivalent organic group derived from a monomer having an unsaturated double bond and R ¹⁵ is a group represented by the formula (I) and a group represented by the following formulas (IV-1) IV-4):
-R ⁴ -OR ¹⁶ (IV-1)
_{^{- (R 5 -O) m -R}} 16 ... (IV-2)
-R ⁴ -OR ¹³ -C (= O) -OR ¹⁶ - (IV-3)
- (R ⁵ -O) _m -R ¹⁴ -C (= O) -OR ¹⁶ (IV-4)
And R &lt; 2 &gt;
In the formulas (IV-1) to (IV-4), R ⁴ , R ⁵ , R ¹³ and R ¹⁴ are as defined above and -OR ¹⁶ in the terminal partial structure is a group represented by the formula (I). )
&Lt; / RTI &gt; The method according to claim 1 or 2,
Wherein the positive photosensitive resin composition further comprises (C) a compound which generates an acid or a radical by the action of light.