KR102397614B1 - Method of forming pattern - Google Patents

Abstract

[assignment]
To provide a pattern forming method using a positive photosensitive resin composition, which can form a resist pattern having a desired cross-sectional shape with a low exposure dose and can form a pattern excellent in chemical resistance.
[Solution]
As the photosensitive resin composition, (D) using a substance containing a compound that generates an imidazole compound by heating, and a state in which a component having an acidic group is contained in a coating film composed of a photosensitive resin composition patterned by exposure and development In this, the patterned coating film is heated to a predetermined temperature to form a pattern.

Description

Pattern formation method {METHOD OF FORMING PATTERN}

The present invention relates to a method for forming a pattern.

In the lithography technique, for example, a resist film made of a resist material is formed on a substrate, and the resist film is selectively exposed to radiation such as light or an electron beam through a mask on which a predetermined pattern is formed. The process of forming a resist pattern of a predetermined|prescribed shape by giving a developing process to a resist film is made|formed.

A resist material in which the exposed portion changes in a characteristic which dissolves in a developer is called a positive type, and a resist material in which the exposed portion changes in a characteristic in which the characteristic does not dissolve in a developer is referred to as a negative type.

In recent years, in the manufacture of a semiconductor element and a liquid crystal display element, the refinement|miniaturization of a pattern is progressing rapidly with advance in lithography technology.

As a method of miniaturization, generally, the wavelength reduction of an exposure light source is made|formed. Specifically, conventionally, ultraviolet rays typified by g-rays and i-rays have been used, but mass production of semiconductor devices using KrF excimer lasers and ArF excimer lasers is now being started. Moreover, examination is made also about the F2 excimer laser of a shorter wavelength than these excimer lasers, an electron beam, EUV (extreme ultraviolet rays), X-rays, etc. are made|formed.

The resist material is required to have lithographic properties such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with fine dimensions.

As a resist material that satisfies these requirements, a chemically amplified resist containing a base resin whose alkali solubility changes due to the action of an acid and an acid generator that generates an acid upon exposure is used. For example, a positive-type chemically amplified resist contains, as a base resin, a resin whose alkali solubility increases due to 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. When it does, an exposed part will become alkali-soluble.

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

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

However, when a pattern is formed using a positive resist composition, since polymerization reaction or crosslinking reaction does not occur in the pattern, the chemical resistance of the pattern formed inevitably tends to be inferior to that of a pattern formed using a negative resist composition. There is this.

In addition, when a pattern is formed using a positive resist composition as described in Patent Documents 1 and 2, when post-exposure heating (PEB) is not performed, or in the case of a low-temperature PEB process, the pattern at a low exposure dose In some cases, it is difficult to form or to form a pattern having a desired cross-sectional shape. If a good pattern can be formed by not performing PEB or by low-temperature PEB processing, the throughput of various products or semi-finished products having a resist pattern can be improved by shortening the pattern formation time.

The present invention has been made in view of the above problems, and it is possible to form a resist pattern having a desired cross-sectional shape with a low exposure dose, and to form a pattern using a positive photosensitive resin composition that can form a pattern excellent in chemical resistance. The purpose is to provide a method.

The present inventors, using (D) a substance containing a compound that generates an imidazole compound upon heating, as a photosensitive resin composition, in a coating film comprising a photosensitive resin composition patterned by exposure and development, having an acidic group By heating the patterned coating film to a predetermined temperature to form a pattern in a state in which the component is included, it was found that the above problems could be solved, and the present invention was completed. Specifically, the present invention provides the following.

The aspect of this invention apply|coats the positive photosensitive resin composition whose solubility with respect to an alkali developing solution increases by exposure on a support body, The coating film formation process of forming a coating film;

exposure process of exposing the coating film positionally,

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

Bake process which bakes the patterned coating film by image development

As a pattern forming method comprising a,

A positive photosensitive resin composition is a following formula (D1) by (D) heating:

[Formula 1]

(in formula (D1), R ^d1 , R ^d2 and R ^d3 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 nitro group, a nitroso group, a phosphino group , a sulfonate group, a phosphinyl group, a phosphonate group or an organic group.)

contains a compound that generates an imidazole compound represented by

The baking temperature of the coating film in the baking step is equal to or higher than the temperature at which the compound that generates the imidazole compound represented by (D1) by heating (D) generates the imidazole compound represented by the formula (D1) by thermal decomposition,

The coating film in the baking process is a pattern formation method characterized by containing the component which has an acidic group.

According to the present invention, it is possible to provide a pattern forming method using a positive photosensitive resin composition that can form a resist pattern having a desired cross-sectional shape with a low exposure dose and can form a pattern excellent in chemical resistance. .

≪Pattern Forming Method≫

The pattern forming method according to the present invention comprises:

A coating film forming step of applying, on a support, a positive photosensitive resin composition whose solubility in an alkali developer increases by exposure to light to form a coating film;

an exposure step of exposing the coating film positionally;

A developing step of developing the exposed coating film with an alkali developer;

Bake process which bakes the patterned coating film by image development

A pattern forming method comprising a.

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

Hereinafter, each process included in the pattern forming method which concerns on this invention is demonstrated in order.

[coating film forming process]

The method of apply|coating the photosensitive resin composition on a support body is not specifically limited, For example, a spinner is used suitably. With respect to the formed photosensitive resin film, prebaking is performed as needed. A prebaking is performed for 40 to 120 second at 80-120 degreeC, for example.

The support is not particularly limited as long as it is conventionally used for forming a resist pattern. As a preferable support body, the board|substrate for electronic components, the thing in which the predetermined|prescribed wiring pattern was formed in this, etc. can be illustrated, for example. More specifically, a silicon wafer, a metal substrate, such as copper, chromium, iron, and aluminum, a glass substrate, etc. are mentioned. As a material of a wiring pattern, copper, aluminum, nickel, gold|metal|money, etc. can be used, for example.

As the support, an inorganic and/or organic film may be provided on the same substrate as described above. Examples of the inorganic film include an inorganic antireflection film (inorganic BARC). Examples of the organic film include an organic antireflection film (organic BARC).

[Photosensitive resin composition]

Hereinafter, the photosensitive resin composition is demonstrated. As mentioned above, the photosensitive resin composition contains the compound which generate|occur|produces the imidazole compound of a specific structure by (D) heating essentially. The coating film of the photosensitive resin composition patterned by exposure and image development is baked at predetermined temperature in the state containing the component which has an acidic group.

A carboxyl group and a phenolic hydroxyl group are mentioned as a suitable example of the acidic group contained in the coating film which consists of the photosensitive resin composition baked at predetermined temperature. In addition, what arose on resin during baking may be sufficient as an acidic group. These acidic groups cause a condensation reaction by the action of the imidazole compound generated in the baking step to be described later, and improve chemical resistance and the like of the pattern baked at a predetermined temperature.

Examples of the photosensitive resin composition satisfying these conditions include a photosensitive resin composition containing a component having an acidic group protected by a protecting group capable of being detached by exposure or heating, or an alkali-soluble component having an acidic group, and exposed to an alkali developer by exposure. The photosensitive resin composition which solubility with respect to increases is mentioned. Here, as a component which has an acidic group, resin which has an acidic group, or the compound which has an acidic group (a non-polymer and a non-polymer type may be mentioned) is mentioned here. As an alkali-soluble component, (A) alkali-soluble resin or (A') alkali-soluble compound is mentioned.

As a thing suitable as such a photosensitive resin composition, (A) alkali-soluble resin and/or (A') alkali-soluble compound, and the thing containing (B) non-alkali-soluble resin which has the specific functional group mentioned later is mentioned. As such a photosensitive resin composition, it is preferable that (A) alkali-soluble resin and (B) non-alkali-soluble resin which has the specific functional group mentioned later are included. The photosensitive resin composition (C) may contain the compound which generate|occur|produces an acid or radical by the action of light. The photosensitive resin composition may further contain the (S) solvent. Hereinafter, the component containing said suitable photosensitive resin composition is demonstrated in order.

<(A) alkali-soluble resin>

The photosensitive resin composition contains (A) alkali-soluble resin. Here, the alkali-soluble resin refers to a resin film having a thickness of 1 µm formed on a substrate with a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20 wt%, and dissolved in a 2.38 wt% TMAH aqueous solution. When immersed for minutes, it means to melt|dissolve 0.01 micrometer or more.

(A) As alkali-soluble resin, it is preferable that it is at least 1 sort(s) of resin selected from the group which consists of (A1) novolak resin, (A2) polyhydroxystyrene resin, (A3) acrylic resin, and (A4) cardo resin. Do.

Moreover, it is preferable that alkali-soluble resin has an unsaturated double bond and/or an epoxy group. Alkali-soluble resin has an alkali-soluble group like a phenolic hydroxyl group and a carboxyl group normally. 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, or epichlorohydrin, and etherifying or acylating the phenolic hydroxyl group, phenol An unsaturated double bond or an epoxy group can be introduce|transduced into alkali-soluble resin which has an acidic hydroxyl group. In addition, when the alkali-soluble resin is a resin having a carboxyl group, by reacting a compound having an epoxy group with an unsaturated double bond such as (meth)acrylic acid ester containing this carboxyl group and an epoxy group, to the resin having a carboxyl group, an unsaturated double bond can be introduced

(A) Alkali-soluble groups, such as a phenolic hydroxyl group and a carboxyl group which alkali-soluble resin has, the one part or all may be protected with the protecting group deprotected by exposure. In this case, as a protecting group, the group represented by Formula (I) mentioned later which is a water-repellent protecting group which (B) non-alkali-soluble resin essentially has is preferable.

(A) The unit which may be contained in alkali-soluble resin and has a protected alkali-soluble group, for example, a unit derived from (meth)acrylic acid in which a carboxyl group is protected by a group represented by formula (I), and formula ( and units derived from hydroxystyrene in which a phenolic hydroxyl group is protected by the group represented by I).

(A) When some or all of the alkali-soluble groups of the alkali-soluble resin are protected by a protecting group, in order to promote deprotection during exposure, the photosensitive resin composition is acidified by the action of (C) light, which will be described later. Or it is preferable to contain the compound which generate|occur|produces a radical.

[(A1) novolac resin]

(A1) The novolak resin is obtained by, for example, addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as "phenols") and aldehydes in the presence of an acid catalyst.

Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butyl phenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, resolucinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, chloroglycinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol, and the like.

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

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

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

(A1) Although the weight average molecular weight of a novolak resin is not specifically limited in the range which does not impair the objective of this invention, It is preferable that it is 1000-50000.

(A1) Some of the hydroxyl groups which the novolak resin has may be converted into the group represented by Formula (I) contained in (B) non-alkali-soluble resin mentioned later. The group represented by the formula (I) described later generates a phenolic hydroxyl group by thermal decomposition at a temperature close to the temperature at which the compound that generates an imidazole compound by heating (D) generates an imidazole compound by thermal decomposition. Therefore, when the photosensitive resin composition containing such a novolak resin is heated in the baking process mentioned later, the phenolic hydroxyl group which is an acidic group will generate|occur|produce on the novolak resin.

[(A2) polyhydroxy styrene resin]

(A2) Examples of the hydroxystyrene-based compound constituting the polyhydroxystyrene resin include p-hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene.

Moreover, it is preferable to make (A2) polyhydroxy styrene resin into the copolymer of a hydroxy styrene type compound and a styrene type compound. Examples of the styrene-based compound constituting the styrene resin include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, and α-methylstyrene.

(A2) Although the weight average molecular weight of polyhydroxystyrene resin is not specifically limited in the range which does not impair the objective of this invention, It is preferable that it is 1000-50000.

(A2) A part of the hydroxyl groups which the polyhydroxystyrene resin has may also be converted into the group represented by Formula (I) mentioned later similarly to (A1) novolak resin.

[(A3) acrylic resin]

(A3) As an acrylic resin, resin obtained by copolymerizing (meth)acrylic acid and the monomer which has another unsaturated bond is preferable. Examples of the monomer copolymerizable with (meth)acrylic acid include unsaturated carboxylic acids other than (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes and The epoxy group containing unsaturated compound etc. which do not have an alicyclic group are mentioned.

As a preferable example of unsaturated carboxylic acids other than (meth)acrylic acid, Monocarboxylic acids, such as a crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; anhydrides of these dicarboxylic acids;

Examples of (meth)acrylic acid esters include linear or branched chain alkyl (meth)acrylate; Chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, Furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and phenyl (meth)acrylate;

Moreover, as (A) alkali-soluble resin, what has an epoxy group is preferable. For this reason, as (meth)acrylic acid ester, epoxy-group containing (meth)acrylic acid ester is also preferable. As a preferable example of epoxy-group containing (meth)acrylic acid ester, the alicyclic epoxy-group containing unsaturated compound of the structure shown, for example by following formula (a3-1) - (a3-16) is mentioned. Among these, compounds represented by the following formulas (a3-1) to (a3-6) are preferable, and compounds represented by the following formulas (a3-1) to (a3-4) are more preferable.

[Formula 2]

[Formula 3]

[Formula 4]

In the above formula, R ^a4 represents a hydrogen atom or a methyl group, R ^a5 represents a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, R ^a6 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and n is 0 to 10 represents the integer of As R ^a5 , a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group is preferable. As R ^a6 , for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, a cyclohexylene group, -CH ₂ -Ph-CH ₂ -( Ph represents a phenylene group) is preferable.

Moreover, the epoxy group containing unsaturated compound which does not have an alicyclic group is also used suitably as a monomer for introduce|transducing an epoxy group into (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, and 6,7-epoxyheptyl. (meth)acrylic acid epoxyalkyl esters such as (meth)acrylate; α-alkyl acrylic acid epoxy alkyl esters such as α-ethyl acrylate glycidyl, α-n-propyl glycidyl acrylate, α-n-butyl acrylate glycidyl, and α-ethyl acrylic acid 6,7-epoxyheptyl; and the like. Among these, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and 6,7-epoxyheptyl (meth)acrylate are preferable.

As (meth)acrylamides, (meth)acrylamide, N-alkyl (meth)acrylamide, N-aryl (meth)acrylamide, N,N-dialkyl (meth)acrylamide, N,N-aryl ( Meth)acrylamide, N-methyl-N-phenyl (meth)acrylamide, N-hydroxyethyl-N-methyl (meth)acrylamide, etc. are mentioned.

Examples of the allyl compound include allyl esters such as allyl acetate, allyl caproate, 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-dimethylpropyl vinyl. Ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether alkyl vinyl ethers such as; 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 trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloro acetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, and vinyl phenyl acetate. , vinylacetoacetate, vinyllactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like.

Examples of the styrenes include styrene; Methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene , alkyl styrenes such as acetoxymethyl styrene; Alkoxy styrene, such as methoxy styrene, 4-methoxy-3- methyl styrene, and dimethoxy styrene; Chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene , halo styrene such as 4-fluoro-3-trifluoromethyl styrene; and the like.

(A3) 5-70 weight% is preferable and, as for the ratio of the unit containing a carboxyl group in an acrylic resin, it is more preferable that it is 10-40 weight%.

(A3) A part of the carboxyl group which the acrylic resin has may also be converted into the group represented by Formula (I) mentioned later similarly to the hydroxyl group which (A1) novolak resin has.

[(A4) Cardo Resin]

(A4) Cardo resin is resin which has a cardo structure. (A) (A4) Cardo resin as alkali-soluble resin is not specifically limited, It can select suitably from what has conventionally mix|blended with the photosensitive composition. Especially, resin represented by the following formula (a-1) which is resin which has a (meth)acryloyl group is preferable.

[Formula 5]

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

[Formula 6]

In the formulas (a-2) and (a-2'), R ^a1 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ^a2 is each independently A hydrogen atom or a methyl group is represented, and W ^a represents the group represented by a following formula (a-3).

[Formula 7]

In addition, in said Formula ( ^a -1), Y<a> represents the residue which removed the acid anhydride group (-CO-O-CO-) from dicarboxylic acid anhydride. Examples of the dicarboxylic anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride , glutaric anhydride, etc. are mentioned.

In addition, in said Formula (a-1), Z ^a represents the residue which removed two acid anhydride groups from tetracarboxylic dianhydride. As an example of tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, etc. are mentioned.

In addition, in said formula (a-1), x represents the integer of 0-20.

1000-50000 are preferable and, as for the weight average molecular weight (Mw: The measured value by polystyrene conversion of gel permeation chromatography (GPC)) of (A) alkali-soluble resin demonstrated above, 3000-10000 are more preferable.

In addition, about the weight average molecular weight of (A4) cardo resin, 1000-40000 are preferable and 2000-30000 are more preferable.

Content of (A) alkali-soluble resin in the photosensitive resin composition is not specifically limited in the range which does not impair the objective of this invention. (A) alkali-soluble resin with respect to the sum total of the weight of (A) alkali-soluble resin in the photosensitive resin composition, the weight of (B) non-alkali-soluble resin, and the weight of (B') other non-alkali-soluble resin mentioned later 30 weight% or more is preferable, as for the ratio of the weight, 50 weight% or more is more preferable, 50 to 70 weight% is especially preferable.

Moreover, in the said photosensitive resin composition, when using (A') alkali-soluble compound instead of (A) alkali-soluble resin or simultaneously, as an alkali-soluble compound, the low molecular-weight compound which has the said acidic group is mentioned.

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

[Formula 8]

(In formula (A'1-1), R ^a1 is a hydrogen atom or a methyl group, R ^a2 is an organic group having a valence of (d+e+f), d is an integer of 1 to 3, and e is 0 to 3 is an integer, and f is an integer from 1 to 3.)

When R ^a2 is an organic group, the organic group may be an aliphatic group, an aromatic group, or a combination of an aliphatic group and an aromatic group. Moreover, the said organic group may contain hetero atoms, such as N, S, O, P, and 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 is not particularly limited, but 1 to 20 are preferable, and 1 to 12 is more preferable, and 1 to 8 are particularly preferable.

As a 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 formula (A'1-1), the compound represented by the following formula (A'1-2) is preferable.

[Formula 9]

(In formula (A'1-2), R ^a1 is a hydrogen atom or a methyl group, R ^a3 and R ^a4 are an alkylene group having 1 to 20 carbon atoms, and L is -O-, -CO-O- or - O-CO-, and g is an integer from 0 to 5.)

It is preferable that it is a C1-C10 alkylene group, and, as for R ^a3 and R ^a4 in a formula (A'1-2), it is more preferable that it is a C1-C6 alkylene group. Methylene group, 1,2-ethanediyl group, 1,3-propanediyl group, 1,2-propanediyl group, 1,4-butanediyl group, 1,5-pentanediyl group, 1,6-hexanediyl group can be heard

The integer of 0-3 is preferable and, as for g in Formula (A'1-2), 0 or 1 is preferable.

(A ') The compound having a non-polymeric acid group having a carboxyl group and a (meth)acryloyl group, which is suitably used as an alkali-soluble compound, each has at least one hydroxyl group and a carboxyl group All of the hydroxyl groups possessed by the compound, It is manufactured by acylating according to the acylating agent which gives the above-mentioned (meth)acryloyl group.

In addition, the compound having a non-polymeric acid group having a carboxyl group, a hydroxyl group, and a (meth)acryloyl group includes a part of the hydroxyl groups in the compound containing two or more hydroxyl groups and one or more carboxyl groups, as described above (meth)acryl It is prepared by acylating with an acylating agent that imparts a royl group.

In the compound which has a non-polymer type acidic group, the compound which has a non-polymer type acidic group which has a carboxyl group and a (meth)acryloyl group from the point which preparation and an acquisition are easy are preferable.

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

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

Content of the (A') alkali-soluble compound in the photosensitive resin composition is not specifically limited in the range which does not impair the objective of this invention. The ratio of the weight of (A') alkali-soluble compound to the sum total of the weight of (A') alkali-soluble compound and (B) non-alkali-soluble resin in the photosensitive resin composition is 30 weight% or more, and , more preferably 50% by weight or more, and particularly preferably 50 to 70% by weight.

<(B) non-alkali-soluble resin>

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

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

(B) As for non-alkali-soluble resin, in the exposed state, some or all of the above-mentioned water-repellent protective groups are deprotected. For this reason, when the photosensitive resin composition is exposed, it becomes easy to be miscible with an alkali developing solution.

Moreover, (B) non-alkali-soluble resin has the hydrophilic functional group of a specific structure in the deprotected state. Such a hydrophilic functional group contributes to the improvement of contrast, and accelerates|stimulates the dissolution of (A) alkali-soluble resin to an alkali developing solution. For this reason, (B) when the photosensitive resin composition containing the non-alkali-soluble resin is exposed, the alkali developer is well miscible with the photosensitive resin composition, and (A) the alkali-soluble resin dissolves favorably in the alkali developer. , the exposed portion in the photosensitive resin composition is favorably removed with an alkaline developer.

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

[Formula 10]

(in 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-, and R ² and R ³ are each independently -O- or A hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by -S-, 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 formula (I), R< ¹ >, R< ² > and R< ³ > are a C1-C20 hydrocarbon group. 1-10 are preferable, as for carbon atom number of this hydrocarbon group, 1-8 are more preferable, and 1-6 are especially preferable. An aliphatic hydrocarbon group or an aromatic hydrocarbon group may be sufficient as this hydrocarbon group, and what combined an aliphatic hydrocarbon group and an aromatic hydrocarbon group may be sufficient as it.

When R ¹ , R ² , and R ³ are an aliphatic hydrocarbon group, the aliphatic hydrocarbon group may be linear or cyclic, and may include a chain structure and a cyclic structure. The aliphatic hydrocarbon group may have an unsaturated bond. As the aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable.

When R ¹ , R ² and R ³ are a chain aliphatic hydrocarbon group, specific examples thereof include a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- Butyl group, n-pentyl group, isopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethyl-n-hexyl group, n-nonyl group, n-decyl group , n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nona and a decyl group and an n-icosyl group.

R ¹ , R ² and R ³ are a cyclic aliphatic hydrocarbon group, and specific examples in the case where the cyclic aliphatic hydrocarbon group is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. , a cyclononyl group, a cyclodecyl group, a cycloundecyl group and a cyclododecyl group.

R ¹ , R ² and R ³ are a cyclic aliphatic hydrocarbon group, and specific examples of the case where the cyclic aliphatic hydrocarbon group is a polycyclic group include a group obtained by removing one hydrogen atom from the following polycyclic aliphatic hydrocarbon group.

[Formula 11]

When R ¹ , R ² and R ³ are an aromatic hydrocarbon group, 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 a group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are combined, an aralkyl group is exemplified as such a group. Specific examples of the aralkyl group include benzyl group, phenethyl group, 3-phenyl-n-propyl group, 4-phenyl-n-butyl group, α-naphthylmethyl group, β-naphthylmethyl group, 2-(α-naphthyl) an ethyl group and a 2-(β-naphthyl)ethyl group.

When R ¹ , R ² and R ³ are a hydrocarbon group containing an aromatic ring, the aromatic ring is a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 2 carbon atoms. It may be substituted with one or more substituents selected from the group which consists of a -10 alkanoyl group and a C2-C10 alkanoyloxy group. When a plurality of substituents exist on an aromatic ring, the plurality of substituents may be the same or different.

In formula (I), a hydrogen atom is preferable as R ¹ . As R ² , a methyl group is preferable. 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 heterocycle containing an oxygen atom bonded to R ³ . With respect to the heterocyclic ring containing an oxygen atom, 3-7 are preferable and, as for the carbon atom number, 4-6 are more preferable. The heterocycle may further contain a hetero atom other than the oxygen atom bonded to R ³ . As a hetero atom in that case, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned.

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

[Formula 12]

A suitable example of the group represented by Formula (I) is shown below.

[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. Therefore, as group represented by Formula (I), the following group is preferable among said group.

[Formula 14]

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

[Formula 15]

When the photosensitive resin composition is exposed, (B) non-alkali-soluble resin is following formula (II-1) - (II-3):

-R ⁴ -OH... (II-1)

-(R ⁵ -O) _m -R ⁶ ... (II-2)

-(R ⁷ -SO ₂ ) _n -R ⁸ ... (II-3)

(In formula (II-1), R ⁴ is an alkylene group having 1 to 20 carbon atoms. In formula (II-2), R ⁵ is an alkylene group having 2 to 4 carbon atoms, and 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], and m is an integer from 2 to 20. In 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 from 1 to 20. A plurality of R ⁵ in formula (II-2) is , may be the same or different. In formula (II-3), when n is an integer of 2 to 20, a plurality of R ⁷ in formula (II-3) may be the same or different.)

It has at least 1 type of group represented by

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

When the terminal of the group represented by the above formula (II-1) or (II-2) is an OH group, the (B) non-alkali-soluble resin before exposure is the formula (II-1) or the formula (II) in which the terminal is an OH group You may have group represented by -2).

In addition, (B) non-alkali-soluble containing a group represented by formula (II-1) or formula (II-2) in which the terminal is an OH group in a state protected by a protecting group in which the terminal OH group can be deprotected by exposure You may use resin. In this case, when (B) non-alkali-soluble resin is exposed, group represented by Formula (II-1) or Formula (II-2) whose terminal is an OH group produces|generates.

In formula (II-1), R ⁴ is an alkylene group having 1 to 20 carbon atoms. This alkylene group may be linear or branched. As this alkylene group, a linear alkylene group is preferable. Specific examples of the linear alkylene group having 1 to 20 carbon atoms include a methylene group, ethane-1,2-diyl group, n-propane-1,3-diyl group, n-butane-1,4-diyl group, n-pentane-1,5-diyl group, n-hexane 1,6-diyl group, n-heptane-1,7-diyl group, n-octane-1,8-diyl group, n-nonane-1,9 -diyl group, n-decane-1,10-diyl group, n-undecane-1,11-diyl group, n-dodecane-1,12-diyl group, n-tridecane-1,13-diyl group , n-tetradecane-1,14-diyl group, 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-nonadecan-1,19-diyl group and n-icosane-1,20-diyl group are mentioned.

Preferred examples of the group represented by formula (II-1) include 2-hydroxyethyl group, 3-hydroxy-n-propyl group, 4-hydroxy-n-butyl group, 5-hydroxy-n-pentyl group, 6 -hydroxy-n-hexyl group, 7-hydroxy-n-heptyl group, 8-hydroxy-n-octyl group, 9-hydroxy-n-nonyl group and 10-hydroxy-n-decyl group. can Among them, 2-hydroxyethyl group, 3-hydroxy-n-propyl group, 4-hydroxy-n-butyl group, 5-hydroxy-n-pentyl group and 6-hydroxy-n-hexyl group more preferably.

In 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].

R ⁵ is preferably an ethane-1,2-diyl group, n-propane-1,2-diyl group, n-propane-1,3-diyl group and n-butane-1,4-diyl group, and ethane -1,2-diyl group and n-propane-1,2-diyl group are more preferable.

When R< ⁶ > in Formula (II-2) is a hydrocarbon group, carbon atom number of this hydrocarbon group is 1-50, 1-12 are preferable and 1-8 are more preferable. In addition, an aliphatic hydrocarbon group or an aromatic hydrocarbon group may be sufficient as this hydrocarbon group, and what combined an aliphatic hydrocarbon group and an aromatic hydrocarbon group may be sufficient as it.

When R ⁶ is an aliphatic hydrocarbon group, the aliphatic hydrocarbon group may be linear or cyclic, and may contain a chain structure and a cyclic structure. The aliphatic hydrocarbon group may have an unsaturated bond. As the aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable. Suitable examples as the hydrocarbon group for R ⁶ are the same as those suitable for the hydrocarbon group for R ¹ , R ² and R ³ .

R ⁹ in formula (II-2) is a divalent organic group. This organic group may contain hetero atoms, such as N, S, O, and a halogen atom. This organic group may contain a chain|strand structure and a cyclic structure also as a chain|strand shape or a cyclic|annular form. 1-50 are preferable and, as for carbon atom number of this organic group, 1-12 are more preferable. As this organic group, the hydrocarbon group which does not contain 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, and more preferably a linear alkylene group. Suitable examples in the case where R ⁹ is a linear alkylene group are the same as those of R ⁴ described above. When R< ⁹ > is a linear alkylene group, a C1-C6 linear alkylene group is especially preferable.

In 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. Suitable examples of R ⁷ are the same as those of R ⁵ in formula (II-2). Suitable examples of R ⁸ are the same as those of R ⁶ in formula (II-2).

(B) Non-alkali-soluble resin has group represented by formula (I), and if it has at least one of group represented by formula (II-1) - (II-3) in the exposed state, the main skeleton is specifically limited doesn't happen For example, a linear shape may be sufficient as a main skeleton, the shape may be sufficient as it, and a water phase (brush shape) may be sufficient as it.

As a preferable main skeleton, the main skeleton which consists of carbon-carbon bonds contained in the polymer of the monomer which has an unsaturated bond, and the skeleton of an acetylenediol derivative are mentioned.

Among these, the main skeleton which consists of carbon-carbon bonds contained in the polymer of the monomer which has 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 (meth)acrylic acid ester, a polymer of an unsaturated alicyclic compound such as (poly)cycloolefin, and a polymer of a maleimide derivative. and a copolymer of the unsaturated alicyclic compound and the maleimide derivative. In addition, when it becomes a copolymer, you may copolymerize with maleic anhydride.

As the (B) non-alkali-soluble resin, which is a polymer of a monomer having such an unsaturated bond, a linear polymer that can be produced by polymerization of a monomer having an unsaturated double bond by a reaction between unsaturated double bonds, or a chemical modification of the linear polymer A linear polymer comprising:

Formula (III-1):

[Formula 16]

(In formula (III-1), X ¹ is a trivalent organic group derived from a monomer having an unsaturated double bond, R ¹⁰ is the above formulas (II-1) to (II-3), and the following formulas ( 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)

is a group selected from the groups represented by

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

In formulas (II-5) and (II-7), R ⁵ is an alkylene group having 2 to 4 carbon atoms, a plurality of R ⁵ may be the same or different, and 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.)

A structural unit represented by and the following formula (III-2):

[Formula 17]

(In 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 formula (I) and a group represented by the following formulas (IV-1) to the following formulas ( 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)

is a group selected from the groups represented by

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

The copolymer (B-1) containing the structural unit represented by

Among these copolymers (B-1), the amount of the unit represented by the formula (III-1) is preferably 1 to 70% by weight, more preferably 5 to 40% by weight. Among these polymers, 10-90 weight% is preferable and, as for the quantity of the group which consists of said Formula (III-2), 30-70 weight% is more preferable. Moreover, it is preferable that the copolymer (B-1) consists of the unit represented by the said Formula (III-1), and the unit represented by the said Formula (III-2). Hereinafter, the unit represented by Formula (III-1) and the unit represented by Formula (III-2) are demonstrated.

(unit represented by formula (III-1))

The unit represented by the formula (III-1) is a unit that imparts a hydrophilic group represented by the aforementioned formulas (II-1) to (II-3) to the exposed copolymer (B-1).

The unit represented by the formula (III-1) is a functional group R ¹⁰ bonded to X ¹ which is a trivalent organic group derived from an unsaturated double bond, and the above formulas (II-1) to (II-3) and the following formulas (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)

It has a group selected from the group consisting of.

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

Such a protecting group is a group conventionally employed as a protecting group of a group containing an active hydrogen such as a hydroxyl group in the resin component contained in the photosensitive resin composition, and contained in the group represented by the above formula (I), represented by the following formula It can select suitably from groups other than group. Examples of such a group include a group represented by the following formula (b1), which is a protecting group deprotected by the action of an acid.

[Formula 18]

[Formula 19]

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

Suitable examples when R ^b1 is a linear or branched alkyl group include a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neo A pentyl group etc. are mentioned. In addition, suitable examples in 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 the formula (b1) include a tert-butoxycarbonyl group and a tert-butoxycarbonylmethyl group.

As a trivalent organic group derived from the monomer which has an unsaturated double bond of X< ¹ >, the following (x-1) - (x-22) are mentioned, for example. R ^b2 represents a hydrogen atom or a methyl group. * is a combined number. In addition, the sign of "*" is abbreviate|omitted for the two bond numbers couple|bonded with the main chain of (B-1) copolymer among the number of bonds which a trivalent organic group has.

[Formula 20]

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

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

[Formula 21]

(In formulas (b2) to (b8), R ^b2 represents 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), the unit represented by the formula (b2) or (b3) is preferable, and the unit represented by the formula (b2) is particularly preferable.

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

[Formula 22]

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

In formulas (b9) - (b15), p is 0 or 1, and it is preferable that it is 1. Among the units represented by the formulas (b9) to (b15), the unit represented by the formula (b9) or (b10) is preferable, and the 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 with respect to the position where the benzene ring is bonded to the main chain of the copolymer (B-1).

(unit represented by formula (III-2))

The unit represented by the formula (III-2) essentially contains the group represented by the formula (I) which is the aforementioned water-repellent protecting group. For this reason, when the (B-1) copolymer containing the unit represented by Formula (III-2) is mix|blended with the photosensitive resin composition, the exposed photosensitivity compared with the unexposed photosensitive resin composition not being miscible with an alkaline developing solution. The resin composition is well miscible with an alkaline developer.

The unit represented by formula (III-2) is a functional group R ¹⁵ bonded to X ² , which is a trivalent organic group derived from an unsaturated double bond, a group represented by the aforementioned formula (I) and a group represented by the above formula (I) and the following formulas (IV-1) to the following formulas (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)

has a group selected from the groups represented by

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

As a trivalent organic group derived from the monomer which has an unsaturated double bond of X< ² >, said Formula (x-1) - (x-22) is mentioned, for example.

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

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

[Formula 23]

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

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

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

[Formula 24]

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

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

(B-1) When the copolymer contains a unit other than the unit represented by the formula (III-1) and the unit represented by the formula (III-2), this unit is derived from a monomer having an unsaturated double bond. As a unit, it will not specifically limit, if it does not impair the objective of this invention. The unit represented by the formula (III-1) and the unit other than the unit represented by the formula (III-2) are from a number of units employed as such structural units for various resins conventionally blended in the photosensitive resin composition. can be appropriately selected.

Moreover, the (B-2) homopolymer demonstrated below can also be used suitably as (B) non-alkali-soluble resin. (B-2) As a suitable example of a homopolymer, the homopolymer comprised by any one of the units represented by the following formulas (b17)-(b18) and (b22)-(b25) is mentioned.

[Formula 25]

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

[Formula 26]

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

(B-2) As a homopolymer, the homopolymer which consists only of the unit represented by said formula (b17), (b18), (b22), or (b23) is more preferable.

(B-2) As a homopolymer, it is preferable to contain 1 or more types of groups represented by the following formula as a unit represented by the above-mentioned formula (I).

[Formula 27]

When using the above-described (A) alkali-soluble resin and/or (A') alkali-soluble compound and (B) non-alkali-soluble resin in combination, the photosensitive resin composition is exposed and developed and then baked at a predetermined temperature, Resin which has a carboxyl group or phenolic hydroxyl group which is necessarily an acidic group is contained. Therefore, when forming a pattern by a predetermined method using the photosensitive resin composition containing said (A) alkali-soluble resin and/or (A') alkali-soluble compound, and (B) non-alkali-soluble resin, a baking process In this, a crosslinking reaction involving a carboxyl group and a phenolic hydroxyl group proceeds, and a pattern excellent in chemical resistance is formed.

Content of (B) non-alkali-soluble resin in the photosensitive resin composition used suitably in this invention is not specifically limited in the range which does not impair the objective of this invention. The weight of (A) alkali-soluble resin and/or (A') alkali-soluble compound in the photosensitive resin composition, (B) the weight of non-alkali-soluble resin, and the weight of (B') other non-alkali-soluble resin mentioned later, and 70 weight% or less is preferable, as for the ratio of the weight of (B) non-alkali-soluble resin with respect to the sum total, 50 weight% or less is more preferable, 1-50 weight% is especially preferable.

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

The photosensitive resin composition used suitably in this invention contains (B') other non-alkali-soluble resin which is non-alkali-soluble resin other than (B) non-alkali-soluble resin in the range which does not impair the objective of this invention, there may be

(B') Other non-alkali-soluble resin will not be specifically limited if it is resin other than (A) alkali-soluble resin which does not correspond to (B) non-alkali-soluble resin. (B') Other non-alkali-soluble resins include structural units derived from the various (meth)acrylic acid derivatives and hydroxystyrene derivatives described above, and unsaturated carboxylic acids other than (meth)acrylic acid and (meth)acrylic acid, ( Consists of structural units derived from monomers selected from the group consisting of meth)acrylic acid esters, (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and epoxy group-containing unsaturated compounds having no alicyclic group. It is preferable to be

Moreover, it is preferable that (B') other non-alkali-soluble resin contains the structural unit which has an epoxy group. As a monomer which provides the structural unit which has an epoxy group, the alicyclic epoxy group containing unsaturated compound and glycidyl (meth)acrylate of the structure shown by the above-mentioned formula (a3-1) - (a3-16) are preferable.

Moreover, since it is easy to obtain the photosensitive resin composition which has favorable developability and provides the pattern excellent in chemical resistance, (B') It is preferable that the solubility with respect to an alkaline developing solution increases as for (B') other non-alkali-soluble resin by exposure. Do. That is, it is preferable that (B') other non-alkali-soluble resin has alkali-soluble groups, such as a carboxyl group and phenolic hydroxyl group, protected by the protecting group which can be deprotected by exposure. The deprotection may occur by the action of a compound that generates an acid or a radical by the action of (C) light, which will be described later.

Content of (B') other non-alkali-soluble resin in the photosensitive resin composition is not specifically limited in the range which does not impair the objective of this invention. (B') other ratio with respect to the sum total of the weight of (A) alkali-soluble resin in the photosensitive resin composition, the weight of (B) non-alkali-soluble resin, and the weight of (B') other non-alkali-soluble resin mentioned later As for the ratio of the weight of alkali-soluble resin, 70 weight% or less is preferable, 50 weight% or less is more preferable, 1-50 weight% is still more preferable, 10-50 weight% is especially preferable, 20-40 weight% % is most preferred.

<(C) A compound that generates an acid or a radical by the action of light>

It is preferable that the photosensitive resin composition used suitably in this invention contains (C) the compound which generate|occur|produces an acid or a radical by the action of light. When the photosensitive resin composition (C) does not contain a compound that generates an acid or a radical by the action of light, the protecting group of (A) alkali-soluble resin or (B) non-alkali-soluble resin is not favorably deprotected For this purpose, the kind of light source used at the time of exposure is limited. However, when the photosensitive resin composition contains (C) a compound that generates an acid or a radical by the action of light, regardless of the type of light source used at the time of exposure, (A) alkali-soluble resin or (B) non-alkali The protecting group which the soluble resin has can be deprotected favorably.

For this reason, when the photosensitive resin composition contains the compound which generate|occur|produces an acid or radical by the action of (C) light, it is easy to form a favorable pattern with a low exposure dose.

(C) A nonionic organic compound may be sufficient as the compound which generate|occur|produces an acid or a radical by the action of light, and an ionic organic compound may be sufficient as it. Examples of the nonionic organic compound include halogen-containing compounds, diazoketones, sulfone compounds, and sulfonic acid compounds. As a nonionic organic compound, an onium salt etc. are mentioned. (C) As a compound which generate|occur|produces an acid or a radical by the action of light, you may use in combination of 2 or more type. (C) When using in combination of 2 or more types as a compound which generate|occur|produces an acid or radical by the action of light, you may use combining a nonionic organic compound and an ionic organic compound.

[Nonionic organic compound]

(C) Examples of the nonionic organic compound that can be used as a compound that generates an acid or a radical by the action of light include compounds represented by the following formulas (C1), (C2), (C3) and (C4). .

[Formula 28]

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

[Formula 29]

(In formula (C2), A represents -O- or -S-, R ^c2 represents a perfluoroalkyl group having 1 to 8 carbon atoms, two R ^c3 may be the same or different, and each independently It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

[Formula 30]

(In formula (C3), R ^c4 represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an acyl group, and R ^c5 is a carbon atom represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, wherein the hydrocarbon group or the halogenated hydrocarbon group may contain -O-, -S-, or a carbonyl group. When the halogenated hydrocarbon group includes a carbonyl group, the number of carbon atoms included in the carbonyl group is not included in the number of carbon atoms in the hydrocarbon group or the halogenated hydrocarbon group.)

[Formula 31]

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

The compounds represented by formulas (C1) to (C4) below will be described in order.

(Compound represented by formula (C1))

In 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, it is preferable that the perfluoroalkyl group 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, an alkyl group having 1 to 4 carbon atoms, and the like.

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

[Formula 32]

(Compound represented by formula (C2))

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

[Formula 33]

(Compound represented by formula (C3))

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

[Formula 34]

(Compound represented by formula (C4))

As a preferable example of the compound represented by Formula (C4), the compound of the following formula, and the compound described in Unexamined-Japanese-Patent No. 2007-328090 and 2007-328234 are mentioned.

[Formula 35]

[ionic organic compounds]

(C) As an ionic organic compound which can be used as a compound which generate|occur|produces an acid or a radical by the action of light, the compound represented by following formula (C5), (C6), (C7) and (C8) is mentioned.

[Formula 36]

(In 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 are each independently represents an integer of 0 to 3, and when any one of a, b and c is 2 or more, a plurality of R ^c7 , R ^c8 or R ^c9 may be different or the same, respectively. Z ^- represents an organic counterion.)

[Formula 37]

(in formula (C6), R ^c10 and R ^c11 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, and d and e are each independently 0 or 1 Z ^- represents an organic counterion.)

[Formula 38]

(in 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 Together with the sulfur atom to which they bind, may form a ring having 3 to 7 carbon atoms. The methylene group constituting this ring may be substituted with a carbonyl group, -O- or -S-. R ^c14 represents a hydrogen atom, and R ^c15 represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an optionally substituted aromatic hydrocarbon group, or R ¹⁴ and R ^c15 are bonded to each other to form a ring together with the carbon atom to which they are bonded may be formed. Z ^- represents an organic counterion.)

[Formula 39]

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

The compounds represented by formulas (C5) to (C8) are described below in order.

(Compound represented by formula (C5))

The following organic cations are mentioned as a preferable example of the organic cation which comprises the compound represented by Formula (C5).

[Formula 40]

The organic counterion (Z ⁻ ) which is an anion constituting the compound represented by the formula (C5) is preferably an organic acid anion, and more preferably an organic sulfonic acid anion. Preferred examples of the organic counterion (Z ⁻ ) include an anion represented by the following formula (C9).

[Formula 41]

(in formula (C9), R ^c18 to R ^c22 are each independently 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, or 1 carbon atom Halogenated alkyl group of ~8, aryl group of 6~12 carbon atoms, aralkyl group of 7~12 carbon atoms, cyano group, alkylthio group of 1~4 carbon atoms, alkylsulfonyl group of 1~4 carbon atoms , a hydroxyl group, a nitro group or a formula (C10):

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

is a group represented by In the formula (C10), R ^c23 represents a straight-chain aliphatic alkylene group having 1 to 16 carbon atoms in which a part of the methylene group may be substituted with -O- or -S-, and R ^c24 represents 3 to 20 carbon atoms It represents an alicyclic hydrocarbon group.)

Preferred examples when R ^c18 to R ^c22 are halogenated alkyl groups having 1 to 8 carbon atoms include a trifluoromethyl group, perfluoroethyl, perfluoropropyl group, perfluoroisopropyl group and perfluorobutyl group. can be heard

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

Preferred examples of when R ^c18 to R ^c22 are an aralkyl group having 7 to 12 carbon atoms include a benzyl group, a chlorobenzyl group and a methoxybenzyl group.

Preferred examples of when R ^c18 to R ^c22 are an alkylthio group having 1 to 4 carbon atoms include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group and an n-butylthio group.

Preferred examples when R ^c18 to R ^c22 are 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. .

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

R ^c23 is a linear aliphatic alkylene group having 1 to 16 carbon atoms in which a part of the methylene group may be substituted with -O- or -S-. Preferred examples of the group include an alkyleneoxy group having 1 to 15 carbon atoms, an alkyleneoxyalkylene group having 2 to 14 carbon atoms, an alkylene thio group having 1 to 15 carbon atoms, and an alkylenethioalkylene group having 2 to 14 carbon atoms. can

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

-CH ₂ - (C10-1)

-CH ₂ CH ₂ - (C10-2)

-CH ₂ CH ₂ CH ₂ - (C10-3)

-CH ₂ CH ₂ CH ₂ CH ₂ - (C10-4)

-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ - (C10-5)

-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ - (C10-6)

-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ - (C10-7)

-CH ₂ -O- (C10-8)

-CH ₂ -O-CH ₂ - (C10-9)

-CH ₂ -O-CH ₂ CH ₂ - (C10-10)

-CH ₂ CH ₂ -O-CH ₂ CH ₂ - (C10-11)

-CH ₂ -S- (C10-12)

-CH ₂ -S-CH ₂ - (C10-13)

-CH ₂ -S-CH ₂ CH ₂ - (C10-14)

-CH ₂ CH ₂ -S-CH ₂ CH ₂ - (C10-15)

Among R ^c23 , an unsubstituted straight-chain alkylene group having 1 to 8 carbon atoms (eg, a group represented by formulas (C10-1) to (C10-7)) is preferable.

As a group preferable as R ^c24 , the following formula is mentioned.

[Formula 42]

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

[Formula 43]

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

[Formula 44]

[Formula 45]

[Formula 46]

[Formula 47]

[Formula 48]

[Formula 49]

[Formula 50]

[Formula 51]

[Formula 52]

[Formula 53]

[Formula 54]

[Formula 55]

[Formula 56]

[Formula 57]

[Formula 58]

The anion represented by the following formula (C11) is also exemplified as a preferable example of the organic counterion (Z ⁻ ).

R ^c25 -SO ₃ ^- (C11)

(In formula (C11), R ^c25 represents a perfluoroalkyl group having 1 to 25 carbon atoms, an optionally substituted naphthyl group, or an optionally substituted anthryl group.)

As a substituent which the naphthyl group or an anthryl group may have, a C1-C4 alkyl group and a C1-C4 alkoxy group are mentioned.

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

[Formula 59]

[Formula 60]

In addition, the anion represented by a following formula (C12) is also mentioned as a preferable example of an organic counterion (Z- ⁾ .

R ^c26 -SO ₂ -N ^- -SO ₂ -R ^c27 (C12)

(In formula (C12), R ^c26 and R ^c27 are each independently a perfluoroalkyl group having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms which may have an alkyl group having 1 to 4 carbon atoms represents the flag.)

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

Preferred 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

[Formula 61]

(Compound represented by formula (C6))

The following organic cations are mentioned as a preferable example of the organic cation which comprises the compound represented by Formula (C6).

[Formula 62]

Preferred examples of the organic counterion (Z ⁻ ) constituting the compound represented by the formula (C6) are the same as those described for the formula (C5).

(Compound represented by formula (C7))

The following organic cations are mentioned as a preferable example of the organic cation which comprises the compound represented by Formula (C7).

[Formula 63]

Preferred examples of the organic counterion (Z ⁻ ) constituting the compound represented by the formula (C7) are the same as those described for the formula (C5).

(Compound represented by formula (C8))

The following organic cations are mentioned as a preferable example of the organic cation which comprises the compound represented by Formula (C8).

[Formula 64]

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

Content of the compound which generate|occur|produces an acid or a radical by the action|action of (C) light in the photosensitive resin composition used suitably in this invention is not specifically limited in the range which does not impair the objective of this invention. In the photosensitive resin composition, as for content of the compound which generates an acid or radical by the action of (C) light, 0.1 to 20 weight% is preferable with respect to the weight of solid content of the photosensitive resin composition, and 3 to 10 weight% is more desirable.

<(D) A compound which generates an imidazole compound by heating>

The photosensitive resin composition used suitably in this invention is following formula (D1) by (D) heating:

[Formula 65]

(in formula (D1), R ^d1 , R ^d2 and R ^d3 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 nitro group, a nitroso group, and a sulfonate group , a phosphino group, a phosphinyl group, a phosphonate group or an organic group.)

It contains a compound (hereinafter also referred to as component (D)) that generates an imidazole compound represented by .

When the photosensitive resin composition contains (D) a compound that generates an imidazole compound by heating, a crosslinking reaction involving an acidic group of the resin contained in the photosensitive resin composition in the baking step proceeds, and a pattern excellent in chemical resistance can form.

Examples of the organic group for 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. The organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. In addition, linear, branched, or cyclic any may be sufficient as this organic group. This organic group is usually monovalent, but in the case of forming a cyclic structure, it may be a divalent or higher organic group.

R ^d1 and R ^d2 may be bonded to each other to form a cyclic structure, or may further include a hetero atom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and may be a condensed ring.

The bond contained in the organic group of R ^d1 , R ^d2 and R ^d3 is not particularly limited as long as the effects of the present invention are not impaired, and the organic group is a bond containing a hetero atom such as an oxygen atom, a nitrogen atom, or a silicon atom. may be included. 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, an azo bond, etc. are mentioned.

As the bond containing a hetero atom which the organic group of R ^d1 , R ^d2 and R ^d3 may have, from the viewpoint of heat resistance of the imidazole compound, an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, Amide bond, urethane bond, imino bond (-N=C(-R)-, -C(=NR)-: R represents a hydrogen atom or a monovalent organic group), carbonate bond, sulfonyl bond, sulfinyl bond This is preferable.

When the organic group of R ^d1 , R ^d2 and R ^d3 is a substituent other than a hydrocarbon group, R ^d1 , R ^d2 and R ^d3 are not particularly limited as long as the effects of the present invention are 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 isocyano group, a cyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, and a silyl group. group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfonate group, phosphino group, phospho a phinyl group, a phosphonate group, an alkyl ether group, an alkenyl ether group, an alkyl thioether group, an alkenyl thioether group, an aryl ether group, an aryl thioether group, etc. are mentioned. The hydrogen atom contained in the said substituent may be substituted by the hydrocarbon group. In addition, linear, branched and cyclic any may be sufficient as the hydrocarbon group contained in the said substituent.

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.

(D) A component will not be specifically limited if it is a compound which can generate|occur|produce the imidazole compound represented by said Formula (D1) by heating. With respect to a compound (thermal base generator) that generates an amine by the action of heat, which has been conventionally blended in various compositions, imidazole in which a skeleton derived from an amine generated during heating is represented by the formula (D1) By substituting for the skeleton derived from the compound, the compound used as the component (D1) can be obtained.

As a preferable component (D), following formula (D2):

[Formula 66]

(in formula (D2), R ^d1 , R ^d2 and R ^d3 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 nitro group, a nitroso group, a sulfonate group; represents a phosphino 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, a silanol group, or a nitro group. group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group or organic group R ^d6 , R ^d7 , R ^d8 , R ^d9 and R ^d10 is each independently 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 phosphinyl group, represents a phosphono group, a phosphonate group, an amino group, an ammonia group or an organic group.R ^d6 , R ^d7 , R ^d8 , R ^d9 and R ^d10 may combine two or more of them to form a cyclic structure, It may contain a bond.)

and compounds represented by

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

In formula (D2), R ^d4 and R ^d5 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 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, or an organic group is represented.

Examples of the organic group in R ^d4 and R ^d5 include those exemplified for R ^d1 , R ^d2 and R ^d3 . This organic group may contain a hetero atom in the said organic group similarly to the case of R ^d1 , R ^d2 and R ^d3 . In addition, linear, branched, or cyclic any may be sufficient as this organic group.

Among the above, R ^d4 and R ^d5 are each independently 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 having 2 to 11 carbon atoms, an amide group having 1 to 10 carbon atoms An alkylthio group, an acyl 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/or an electron withdrawing group It is preferable that it is a benzyl group, a cyano group, and a methylthio group substituted by the C6-C20 aryl group, the electron donating group, and/or the electron withdrawing group substituted by . More preferably, both R ^d4 and R ^d5 are hydrogen atoms, or R ^d4 is a methyl group and R ^d5 is a hydrogen atom.

In 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 nitro group, and a nitro group. A small 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, an ammonia group, or an organic group is represented.

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

Two or more of R ^d6 , R ^d7 , R ^d8 , R ^d9 and R ^d10 may be bonded to 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 may be a condensed ring. For example, R ^d6 , R ^d7 , R ^d8 , R ^d9 and R ^d10 are bonded to two or more of them, and R ^d6 , R ^d7 , R ^d8 , R ^d9 and R ^d10 share the benzene ring atom to which they are bonded, so that naphthalene , anthracene, phenanthrene, indene, etc. may be formed.

Among the above, R ^d6 , R ^d7 , R ^d8 , R ^d9 and R ^d10 are each independently 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, 2 to 11 carbon atoms The number of carbon atoms substituted by an amide group, an alkylthio group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, an ester group having 2 to 11 carbon atoms, an aryl group having 6 to 20 carbon atoms, an electron donating group and/or an electron withdrawing group of It is preferable that the benzyl group, cyano group, methylthio group, and nitro group are substituted by the aryl group of 6-20, the electron donating group and/or the electron withdrawing group.

In addition, as R ^d6 , R ^d7 , R ^d8 , R ^d9 and R ^d10 , two or more of them are bonded, and R ^d6 , R ^d7 , R ^d8 , R ^d9 and R ^d10 share an atom of the benzene ring to which they are bonded, naphthalene; Also in the case where condensed rings such as anthracene, phenanthrene, and indene are formed, the absorption wavelength is preferably longer.

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

[Formula 67]

(In formula (D3), R ^d1 , R ^d2 and R ^d3 are the same as in formulas (D1) and (D2). R ^d4 to R ^d9 are the same as in formula (D2). R ^d11 is a hydrogen atom or Represents an organic group.R ^d6 and R ^d7 do not form a hydroxyl group. R ^d6 , R ^d7 , R ^d8 and R ^d9 may be combined with two or more to form a cyclic structure, including a hetero atom bond; There may be.)

A compound represented by

Since the compound represented by formula (D3) has a substituent -OR ^d11 , it is excellent in solubility in an organic solvent.

In formula (D3), R ^d11 is a hydrogen atom or an organic group. When R ^d11 is an organic group, examples of the organic group include those exemplified for R ^d1 , R ^d2 and R ^d3 . This organic group may contain the hetero atom in the said organic group. In addition, linear, branched, or cyclic any may be sufficient as this organic group. 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.

(D) The specific example of the compound especially preferable as a component is shown below.

[Formula 68]

Moreover, the imidazole compound represented by following formula (D4) is also suitable as a compound which generate|occur|produces an imidazole compound by (D) heating.

[Formula 69]

(In formula (D4), R ^d12 is a hydrogen atom or an alkyl group, R ^d13 is an aromatic group which may have a substituent, and R ^d14 is an alkylene group which may have a substituent. R ^d1 , R ^d2 and R ^d3 are, Same as formula (D1).)

In 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. Although the number of carbon atoms of this alkyl group is not specifically limited, 1-20 are preferable, 1-10 are preferable, and 1-5 are more preferable.

Specific examples of the alkyl group preferable as R ^d12 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethyl-n-hexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n -tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group and n-icosyl group are mentioned.

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

The kind of aromatic hydrocarbon group is not specifically limited in the range which does not impair the objective of this invention. The aromatic hydrocarbon group may be a monocyclic aromatic group, may be formed by condensing two or more aromatic hydrocarbon groups, or may be formed by bonding two or more aromatic hydrocarbon groups by a single bond. As an aromatic hydrocarbon group, a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthrenyl group are preferable.

The kind of aromatic heterocyclic group is not specifically limited in the range which does not impair the objective of this invention. The aromatic heterocyclic group may be a monocyclic group or a polycyclic group. Examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, an isoxazolyl group, an isothiazolyl group, a benzoxazolyl group, and a benzothiazolyl group. and a benzimidazolyl group are preferred.

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 sulfo group, and a sulfonate 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, the polycyclic aromatic hydrocarbon group, or the aromatic heterocyclic group has a plurality of substituents, the plurality of substituents may be the same or different.

When the substituent which an aromatic group has is an organic group, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group, etc. are mentioned as this organic group. The organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. In addition, linear, branched, or cyclic any may be sufficient as this organic group. This organic group is usually monovalent, but in the case of forming a cyclic structure, it may be a divalent or higher organic group.

When the aromatic group has a substituent on an adjacent carbon atom, two substituents bonded on the adjacent carbon atom may be bonded to each other 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 effects of the present invention are not impaired, and the organic group is a bond containing a hetero atom such as an oxygen atom, a nitrogen atom, or a silicon atom. may contain 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, an azo bond, etc. are mentioned.

Examples of the bond containing a hetero atom that the organic group may have include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, amino bond (-NR-: R represents a hydrogen atom or a monovalent organic group), urethane bond, imino bond (-N=C(-R)-, -C(=NR)-: R is a hydrogen atom or 1 valent organic group), a carbonate bond, a sulfonyl bond, and a sulfinyl bond are preferable.

When an organic group is a substituent other than a hydrocarbon group, the kind of substituent other than a hydrocarbon group is not specifically limited in the range which does not impair the objective of this 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 isocyano group, a cyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a silyl group, and a sila group. Nol group, alkoxy group, alkoxycarbonyl group, amino group, monoalkylamino group, dialkylamino group, monoarylamino group, diarylamino group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxylate group, acyl group, acyl group Oxy group, sulfino group, sulfonate group, phosphino group, phosphinyl group, phosphonate group, alkylether group, alkenylether group, alkylthioether group, alkenylthioether group, arylether group, arylthioether and the like. The hydrogen atom contained in the said substituent may be substituted by the hydrocarbon group. In addition, linear, branched and cyclic any may be sufficient as the hydrocarbon group contained in the said substituent.

Examples of the substituent included in 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, and 1 to carbon atoms. An aryloxy group of 12, an arylamino group of 1 to 12 carbon atoms and a halogen atom are preferable.

As R ^d13 , the imidazole compound represented by the formula (D4) can be easily synthesized at low cost, and since the imidazole compound has good solubility in water and organic solvents, a phenyl group and a furyl group which may each have a substituent , a thienyl group is preferred.

In formula (D4), R ^d14 is an alkylene group which may have a substituent. The substituent which the alkylene group may have is not specifically limited in the range which does not impair the objective of this 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 or a branched-chain alkylene group, and a straight-chain alkylene group is preferable. Although carbon atom number of an alkylene group is not specifically limited, 1-20 are preferable, 1-10 are preferable, and 1-5 are more preferable. In addition, the carbon atom of the substituent couple|bonded with the alkylene group is not included in the carbon atom number of an alkylene group.

A straight-chain alkoxy group or a branched-chain alkoxy group may be sufficient as the alkoxy group as a substituent couple|bonded with the alkylene group. Although the number of carbon atoms of the alkoxy group as a substituent is not specifically limited, 1-10 are preferable, 1-6 are more preferable, and 1-3 are especially preferable.

A monoalkylamino group or a dialkylamino group may be sufficient as the amino group as a substituent couple|bonded with the alkylene group. The alkyl group contained in the monoalkylamino group or the dialkylamino group may be a straight-chain alkyl group or a branched-chain alkyl group. Although the number of carbon atoms of the alkyl group contained in a monoalkylamino group or a dialkylamino group is not specifically limited, 1-10 are preferable, 1-6 are more preferable, and 1-3 are especially preferable.

Specific examples of the alkylene group suitable as R ^d14 include methylene group, ethane-1,2-diyl group, n-propane-1,3-diyl group, n-propane-2,2-diyl group, n-butane-1, 4-diyl group, n-pentane-1,5-diyl group, n-hexane-1,6-diyl group, n-heptane-1,7-diyl group, n-octane-1,8-diyl group, n -nonane-1,9-diyl group, n-decane-1,10-diyl group, n-undecane-1,11-diyl group, n-dodecane-1,12-diyl group, n-tridecane- 1,13-diyl group, n-tetradecane-1,14-diyl group, 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-nonadecan-1,19-diyl group and n-icosan-1,20-diyl group are mentioned.

Among the imidazole compounds represented by the formula (D4), the compound represented by the following formula (D4-1) is preferable, from the viewpoint of being inexpensive and easily synthesizable, and having excellent solubility in water and organic solvents, A compound represented by (D4-1) and wherein R ^d14 is a methylene group is more preferable.

[Formula 70]

(In formula (D4-1), R ^d12 and R ^d14 are the same as in formula (D4), and R ^d1 , R ^d2 and R ^d3 are the same as in formula (D1). R ^d15 , R ^d16 , R ^d17 , R ^d18 and R ^d19 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 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, an ammonia group, or an 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, the organic group is the same as the organic group that R ^d13 in the formula (D4) has as a substituent. R ^d15 , R ^d16 , R ^d17 and R ^d18 are preferably a hydrogen atom from the viewpoint of solubility of the imidazole compound in a solvent.

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

-OR ^d20

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

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

Among the compounds represented by the formula (D4-1), a compound represented by the following formula (D4-1-1) is preferable.

[Formula 71]

(In formula (D4-1-1), R ^d12 is the same as in formula (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 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 phosphono group, a phosphonate group, an amino group, an ammonia group or an organic 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 the formula (D4-1-1), it is preferable that at least one of R ^d21 , R ^d22 , R ^d23 , R ^d24 and R ^d25 is a group represented by the above-mentioned -OR ^d20 , and R ^d25 is -OR ^d20 It is especially preferable that it is a group represented by When R ^d25 is a group represented by -OR ^d20 , R ^d21 , R ^d22 , R ^d23 and R ^d24 are preferably a hydrogen atom.

The synthesis method of the imidazole compound represented by the said Formula (D4) is not specifically limited. For example, by reacting a halogen-containing carboxylic acid derivative represented by the following formula (D5) with an imidazole compound represented by the aforementioned formula (D1) according to a conventional method to perform imidazolylation, the formula ( The imidazole compound represented by 1) can be synthesize|combined.

[Formula 72]

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

In addition, when the imidazole compound is a compound represented by formula (D4) and R ^d14 is a methylene group, that is, when the imidazole compound is a compound represented by the following formula (D6), in the Michael addition reaction described below The imidazole compound can also be synthesized by the method according to

[Formula 73]

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

Specifically, for example, by mixing a 3-substituted acrylic acid derivative represented by the following formula (D7) and an imidazole compound represented by the formula (D1) in a solvent to cause a Michael addition reaction, the formula (D6) The imidazole compound shown can be obtained.

[Formula 74]

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

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

[Formula 75]

(In formulas (D8) and (D9), R ^d13 is the same as in formula (D4), and R ^d1 , R ^d2 and R ^d3 are the same as in formula (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 occurs between the 3-substituted acrylic acid represented by the following formula (D10) and the imidazole compound represented by the formula (D1) to produce the imidazole compound represented by the formula (D9).

[Formula 76]

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

The following are mentioned as a suitable specific example of the imidazole compound represented by Formula (D4).

[Formula 77]

Content of the compound which generate|occur|produces an imidazole compound by (D) heating in the photosensitive resin composition used suitably in this invention is not specifically limited in the range which does not impair the objective of this invention. 0.1 to 20 weight% is preferable with respect to the weight of solid content of the photosensitive resin composition, and, as for content of the compound which generate|occur|produces an imidazole compound by (D) heating in the photosensitive resin composition, 0.1 to 5 weight% is more preferable .

<(S) solvent>

The photosensitive resin composition may contain the (S) solvent as needed for the objective of applicability|paintability, adjustment of a viscosity, etc. (S) As a component, each component to be used can be melt|dissolved, and what is necessary is just what can be set as a uniform solution. Any 1 or more types of solvent chosen from the well-known solvent used for the photosensitive resin composition can be used as (S) solvent.

(S) Specific examples of the solvent include lactones such as γ-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, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, ethylene glycol monopropionate, diethylene glycol monopropionate, propylene glycol monopropionate or dipropylene glycol monopropionate compounds having an ester bond such as nate; Monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether, dimethyl ether, diethyl ether, dipropyl ether, or dibutyl ether of the polyhydric alcohols [among these, propylene glycol monomethyl ether (PGME) is preferred.]; Monoalkyl ethers or monophenyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether of the compound having an ester bond [among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferred]; cyclic ethers such as dioxane and esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; Anisole, ethylbenzyl ether, cresylmethyl ether, diphenyl ether, dibenzyl ether, phenetol, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene and mesitylene, etc. of aromatic organic solvents; N,N,N',N'-tetramethylurea, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetoamide, hexamethylphosphoamide, 1,3- and nitrogen-containing polar solvents such as dimethyl-2-imidazolidinone and N,N,2-trimethylpropionamide. These organic solvents may be used independently and may be used as 2 or more types of mixed solvent.

(S) As the solvent, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), EL, γ-butyrolactone, N,N,N',N'-tetramethylurea, N,N -Dimethylacetoamide and N,N,2-trimethylpropionamide are preferable. These organic solvents may be used independently and may be used as 2 or more types of mixed solvent. Moreover, the mixed solvent which mixed PGMEA and the polar solvent other than the said PEGMEA is also preferable. The compounding ratio (weight ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, etc., but it is preferably within the range of 1:9 to 9:1, more preferably 2:8 to 8:2. desirable.

More specifically, when EL is blended as a polar solvent, the weight ratio of PGMEA:EL is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. Moreover, when mix|blending PGME as a polar solvent, the weight ratio of PGMEA:PGME becomes like this. Preferably it is 1:9-9:1, More preferably, it is 2:8-8:2, More preferably, it is 3:7- 7:3.

(S) As the solvent, a mixed solvent of at least one selected from PGMEA and EL and γ-butyrolactone 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.

(S) The usage-amount of a solvent is not specifically limited, It is a density|concentration which can be apply|coated to a board|substrate etc., and it sets suitably according to the coating film thickness. Generally, solid content concentration of the photosensitive resin composition is 1 to 40 weight%, Preferably it is 2 to 39 weight%, It is used so that it may become in the range more preferably 3 to 25 weight%.

<(E) other ingredients>

The photosensitive resin composition may further contain other components as needed. For example, a dissolution control agent, a dissolution inhibitor, a basic compound, a surfactant, a dye, a pigment, a plasticizer, a light sensitizer, a light absorber, an antihalation agent, a storage stabilizer, an antifoaming agent, an adhesion aid, a phosphor, a magnetic material, etc. can

[Exposure process]

The coating film which consists of the photosensitive resin composition formed in the coating film formation process is exposed using the exposure apparatus provided with a desired light source. The wavelength used for exposure is not specifically limited. For example, g, h, i-rays, ArF excimer laser (wavelength 193 nm), KrF excimer laser (wavelength 248 nm), F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray , soft X-rays, etc. can be used, and exposure can be used. Among these, g, h, i-line, ArF excimer laser, KrF excimer laser, EUV, and EB are preferable. Further, (C) ArF excimer laser (wavelength 193 nm) and EB (electron beam) in that a pattern can be formed satisfactorily even when a photosensitive resin composition that does not contain a compound that generates acids or radicals by the action of light is used ) is preferred.

In addition, after an exposure process, before the following image development process, the post-exposure heating process may or does not need to be implemented. In the present invention, a resist pattern having a desired cross-sectional shape can be formed with a low exposure dose without performing a 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 at which the imidazole compound represented by the aforementioned formula (D1) is generated, for example, 80 to It is carried out at 120°C for 40 to 120 seconds.

[Development process]

In the exposure process, the coating film position-selectively exposed to a desired pattern is developed using an alkali developer. The alkali developer is appropriately selected from those conventionally used by the photolithography method. As a preferable alkaline developing solution, 0.1 to 10 weight% of tetramethylammonium hydroxide aqueous solution is mentioned, for example. The developer is preferably rinsed with water using pure water and dried.

[Bake process]

In a baking process, the coating film patterned by image development is baked. The baking temperature of the coating film in a baking process is more than the temperature at which the compound which generate|occur|produces the imidazole compound by said (D) heating generate|occur|produces the imidazole compound represented by the above-mentioned formula (D1) by thermal decomposition. (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) there is. Specifically, (D) the TG curve obtained by TG-DTA analysis of a compound that generates an imidazole compound by heating indicates the onset of weight loss due to thermal decomposition, and the temperature of the inflection point on the coldest side on the baseline What is necessary is just to set it as the temperature which generate|occur|produces the imidazole compound represented by Formula (D1) by thermal decomposition. The upper limit of the baking temperature is not particularly limited in a range that does not impair the object of the present invention. Baking is typically carried out at a temperature of 300° C. or lower. Typically, it is the range of 150 degreeC - 300 degreeC (or more than the temperature which generate|occur|produces the imidazole compound represented by Formula (D1) or more).

Although baking time is not specifically limited, 1 to 60 minutes are preferable and 1 to 30 minutes are more preferable.

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

[ Example ]

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

[Examples 1-45, and Comparative Examples 1-3]

In Examples and Comparative Examples, as component (A) which is alkali-soluble resin, a copolymer resin or cardo resin composed of one or more units selected from the following A1 to A10 was used. (A) Tables 1 and 2 show the weight ratio of each structural unit in the resin used as the component.

In addition, when the component (A) contains a cardo resin and a copolymer resin composed of one or more units selected from the following A1 to A10, copolymerization while describing the composition ratio as 100 in the column of "cardo resin" The structural ratio of each structural unit was described in Tables 1 and 2 so that the sum total of the structural ratio of each structural unit contained in resin might be 100.

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

[Formula 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 (B) component, resin which consists of 1 or more types of units selected from the following B1-B5 was used. (B) Tables 1 and 2 show the weight ratio of each structural unit in the resin used as the component.

[Formula 79]

In Examples, as (B') other non-alkali-soluble resin ((B') component) other than (B) component, resin which consists of 1 or more types of units selected from the following B'1 - B'5 was used. . Tables 1 and 2 show the weight ratio of each structural unit in the resin used as the component (B').

[Formula 80]

In Examples and Comparative Examples, the compound of the following formula was used as component (C), a compound that generates an acid or a radical by the action of light.

[Formula 81]

In Examples and Comparative Examples, as component (D), compounds IG1 to IG8 of the following formula, which are compounds that generate an imidazole compound by heating, and compounds IG9 of the following formulas, which are compounds that generate piperidine by heating was used. For any of IG1 to IG9, the temperature at which imidazole or piperidine is generated by thermal decomposition is less than 230°C.

[Formula 82]

(Preparation of photosensitive resin composition)

Component (A), component (B), component (B'), component (C) and component (D) in parts by weight described in Tables 3 and 4 were dissolved in PGMEA so that the solid content concentration was 25% by weight, and each The photosensitive resin composition used by the Example and the comparative example was obtained. A pattern was formed using the photosensitive resin composition of each Example and a comparative example, and the sensitivity, a pattern shape, and the chemical-resistance of a pattern were evaluated according to the following method. The evaluation results are shown in Tables 5 and 6.

<Sensitivity evaluation>

On a silicon wafer, the photosensitive resin composition of each Example and a comparative example was apply|coated to the film thickness which can form a pattern with a film thickness of 3 micrometers, and the photosensitive resin film was formed. About the formed photosensitive resin film, it prebaked on condition of 100 degreeC and 120 second. After the pre-baking, the photosensitive resin film was exposed to light of the type shown in Table 3 through a mask for forming a hole pattern having a diameter of 10 µm while changing the exposure amount stepwise. Next, the photosensitive resin film was developed using a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23°C for 30 seconds. After washing the developed photosensitive resin film with running water, it heated at 230 degreeC for 20 minutes, and obtained the hole pattern. In addition, in Comparative Examples 1 and 2, baking at 230 degreeC was not implemented.

Then, the minimum exposure amount required to form the hole pattern was obtained and used as an index of the sensitivity. The results are shown in Tables 5 and 6 below.

○: 50mJ/cm ² or less

△: 50mJ/cm ² More than 300mJ/cm ² or less

×: 300mJ/cm ² More than

<Pattern shape evaluation>

In the pattern shape evaluation, the photosensitive resin film was exposed at the lowest exposure dose measured in the sensitivity evaluation, and a hole pattern having a 10 µm diameter hole was formed in the same manner as in the sensitivity evaluation.

From the electron microscopic observation image of the cross section of the formed hole, an acute taper angle was determined among the corners formed by the surface of the silicon wafer and the side surface of the hole pattern. The closer the taper angle is to 90°, the better the cross-sectional shape of the hole is, and the better the pattern shape is.

Using the obtained taper angle, the quality of a pattern shape was judged according to the following criteria.

◎: 80° or more

○: 70° or more and less than 80°

×: less than 70°

<Pattern chemical resistance evaluation>

A hole pattern having a hole having a diameter of 10 µm 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 presence or absence of peeling of the pattern on the silicon wafer was observed. Pattern chemical resistance was judged according to the following criteria using the observation result of pattern peeling.

○: No pattern peeling

×: There is pattern peeling

According to Examples 1 to 45, in the case of forming a pattern using a positive photosensitive resin composition whose solubility in an alkali developer increases by exposure to light, (D) containing a compound that generates an imidazole compound by heating In a state where a component having an acidic group exists in the coating film of the photosensitive resin that is exposed and developed using the photosensitive resin composition, (D) the coating film is heated to a temperature higher than the temperature at which the compound that generates the imidazole compound generates imidazole. It can be seen that by heating to a temperature, a pattern having a desired cross-sectional shape and excellent chemical resistance can be formed with a low exposure dose.

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

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

Claims (7)

A coating film forming step in which a positive photosensitive resin composition having an increased solubility in an alkali developer by exposure is applied on a support to form a coating film;
An exposure process of exposing the coating film positionally,
a developing process of developing the exposed coating film with an alkali developer; and
Bake process of baking the patterned coating film by development
As a pattern forming method comprising a,
The said positive photosensitive resin composition is (A) alkali-soluble resin, (B) non-alkali-soluble resin, and (D) following formula (D1) by heating:
[Formula 1]

(in formula (D1), R ^d1 , R ^d2 and R ^d3 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 nitro group, a nitroso group, a phosphino group , a sulfonate group, a phosphinyl group, a phosphonate group or an organic group.)
contains a compound that generates an imidazole compound represented by
Said (B) non-alkali-soluble resin, the following formula (I):
[Formula 2]

(In 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-, and R ² and R ³ are each independently -O- or A hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by -S-, 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.)
has a group represented by
When the positive photosensitive resin composition is exposed, all or a part of the group represented by the formula (I) in the (B) non-alkali-soluble resin is deprotected to change to an OH group, and the deprotected (B) ) Non-alkali-soluble resin is the following formula (II-1) - (II-3):
-R ⁴ -OH ... (II-1)
-(R ⁵ -O) _m -R ⁶ ... (II-2)
-(R ⁷ -SO ₂ ) _n -R ⁸ ... (II-3)
(In formula (II-1), R ⁴ is an alkylene group having 1 to 20 carbon atoms. In formula (II-2), R ⁵ is an alkylene group having 2 to 4 carbon atoms, and R ⁶ is a hydrogen atom. , a hydrocarbon group having 1 to 50 carbon atoms, and m is an integer from 2 to 20. In formula (II-3), R ⁷ is an alkylene group having 1 to 4 carbon atoms, and R ⁸ is an integer of 2 to 20. a hydrocarbon group of -50, and n is an integer of 1-20. A plurality of R ⁵ in formula (II-2) may be the same or different.When n is an integer of 2-20 in formula (II-3) , a plurality of R ⁷ in formula (II-3) may be the same or different.)
has at least one group represented by
At least one of said (A) alkali-soluble resin and said (B) non-alkali-soluble resin has an acidic group or a group substituted by the OH group in the acidic group by the formula (I),
The baking temperature of the coating film in the said baking process is the said (D) compound which generate|occur|produces the imidazole compound represented by said Formula (D1) by heating, The imidazole compound represented by said Formula (D1) is generated by thermal decomposition. above the temperature,
The coating film in the said baking process contains the component which has an acidic group, The pattern formation method characterized by the above-mentioned. The method according to claim 1,
The compound which generates the imidazole compound represented by the said formula (D1) by said (D) heating is a following formula (D2):
[Formula 3]

(in formula (D2), R ^d1 , R ^d2 and R ^d3 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 nitro group, a nitroso group, a phosphino group , represents 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, a silanol group, or a nitro group. group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group or organic group 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 nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphine group Represents a phono group, a phosphonate group, an amino group, an ammonia group or an organic group R ^d6 , R ^d7 , R ^d8 , R ^d9 and R ^d10 may be combined with two or more to form a cyclic structure, or a hetero atom bond may be included.)
A method for forming a pattern, which is a compound represented by The method according to claim 1,
The compound that generates the imidazole compound represented by the formula (D1) by heating (D) has the following formula (D4):
[Formula 4]

(in formula (D4), R ^d1 , R ^d2 and R ^d3 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 nitro group, a nitroso group, a phosphino group , represents 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, and R ^d14 is an alkylene which may have a substituent represents the flag.)
A method for forming a pattern, which is a compound represented by A coating film forming step in which a positive photosensitive resin composition having an increased solubility in an alkali developer by exposure is applied on a support to form a coating film;
An exposure process of exposing the coating film positionally,
a developing process of developing the exposed coating film with an alkali developer; and
Bake process of baking the patterned coating film by development
As a pattern forming method comprising a,
The said positive photosensitive resin composition, following formula (D1) by (D) heating:
[Formula 1]

(in formula (D1), R ^d1 , R ^d2 and R ^d3 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 nitro group, a nitroso group, a phosphino group , a sulfonate group, a phosphinyl group, a phosphonate group or an organic group.)
contains a compound that generates an imidazole compound represented by
The compound which generates the imidazole compound represented by the above formula (D1) by heating (D) has the following formula (D4):
[Formula 4]

(in formula (D4), R ^d1 , R ^d2 and R ^d3 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 nitro group, a nitroso group, a phosphino group , represents 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, and R ^d14 is an alkylene which may have a substituent represents the flag.)
It includes a compound represented by
The baking temperature of the coating film in the said baking process is the said (D) compound which generate|occur|produces the imidazole compound represented by said Formula (D1) by heating, The imidazole compound represented by said Formula (D1) is generated by thermal decomposition. above the temperature,
The coating film in the said baking process contains the component which has an acidic group, The pattern formation method characterized by the above-mentioned. 5. The method according to claim 4,
The positive photosensitive resin composition contains (A) alkali-soluble resin, (B) non-alkali-soluble resin, and (D) a compound that generates an imidazole compound represented by formula (D1) by heating,
Said (B) non-alkali-soluble resin, the following formula (I):
[Formula 2]

(In 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-, and R ² and R ³ are each independently -O- or A hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by -S-, 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.)
has a group represented by
When the positive photosensitive resin composition is exposed, all or a part of the group represented by the formula (I) in the (B) non-alkali-soluble resin is deprotected to change to an OH group, and the deprotected (B) ) Non-alkali-soluble resin is the following formula (II-1) - (II-3):
-R ⁴ -OH ... (II-1)
-(R ⁵ -O) _m -R ⁶ ... (II-2)
-(R ⁷ -SO ₂ ) _n -R ⁸ ... (II-3)
(In formula (II-1), R ⁴ is an alkylene group having 1 to 20 carbon atoms. In formula (II-2), R ⁵ is an alkylene group having 2 to 4 carbon atoms, and R ⁶ is a hydrogen atom. , a hydrocarbon group having 1 to 50 carbon atoms, and m is an integer from 2 to 20. In formula (II-3), R ⁷ is an alkylene group having 1 to 4 carbon atoms, and R ⁸ is an integer of 2 to 20. a hydrocarbon group of -50, and n is an integer of 1-20. A plurality of R ⁵ in formula (II-2) may be the same or different.When n is an integer of 2-20 in formula (II-3) , a plurality of R ⁷ in formula (II-3) may be the same or different.)
has at least one group represented by
The pattern formation method in which at least one of said (A) alkali-soluble resin and said (B) non-alkali-soluble resin has an acidic group or group substituted by the OH group in an acidic group by the said Formula (I). 6. The method according to any one of claims 1 to 5,
The positive photosensitive resin composition contains (A) alkali-soluble resin, (B) non-alkali-soluble resin, and (D) a compound that generates an imidazole compound represented by formula (D1) by heating,
(B) the non-alkali-soluble resin is a linear polymer that can be produced by polymerization of a monomer having an unsaturated double bond by a reaction between unsaturated double bonds, or a linear polymer obtained by chemical modification of the linear polymer,
Formula (III-1):
[Formula 5]

(In the formula (III-1), X ¹ is a trivalent organic group derived from a monomer having an unsaturated double bond, and R ¹⁰ is the following formulas (II-1) to (II-3) and (II-4) ) to the following formula (II-7):
-R ⁴ -OH ... (II-1)
-(R ⁵ -O) _m -R ⁶ ... (II-2)
-(R ⁷ -SO ₂ ) _n -R ⁸ ... (II-3)
-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)
is a group selected from the groups represented by
In formula (II-1), R ⁴ is an alkylene group having 1 to 20 carbon atoms,
In formula (II-2), R ⁵ is an alkylene group having 2 to 4 carbon atoms, R ⁶ is a hydrogen atom or a hydrocarbon group having 1 to 50 carbon atoms, m is an integer of 2 to 20,
In 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, n is an integer of 1 to 20,
A plurality of R ⁵ in formula (II-2) may be the same or different,
In formula (II-3), when n is an integer of 2 to 20, a plurality of R ⁷ in formula (II-3) may be the same or different,
In formulas (II-4) and (II-6), R ⁴ is an alkylene group having 1 to 20 carbon atoms, R ¹¹ is a protecting group that can be deprotected when the photosensitive resin composition is exposed to light, and R ¹³ is a divalent organic group,
In formulas (II-5) and (II-7), R ⁵ is an alkylene group having 2 to 4 carbon atoms, a plurality of R ⁵ 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.)
A structural unit represented by and the following formula (III-2):
[Formula 6]

(In formula (III-2), X ² is a trivalent organic group derived from a monomer having an unsaturated double bond, and R ¹⁵ is a formula (I):
[Formula 2]

(In 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-, and R ² and R ³ are each independently -O- or A hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by -S-, 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.)
A group represented by 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)
is a group selected from the group represented by
In formulas (IV-1) to (IV-4), R ⁴ , R ⁵ , R ¹³ , and R ¹⁴ are the same as above, and -OR ¹⁶ in the terminal structure is a group represented by the formula (I). )
A pattern forming method comprising a structural unit represented by . 6. The method according to any one of claims 1 to 5,
The pattern forming method in which the said positive photosensitive resin composition further contains (C) the compound which generates an acid or a radical by the action of light.