WO2001022165A1 - Photosensitive resin compositions, photosensitive element containing the same, process for producing resist pattern, and process for producing printed circuit board - Google Patents

Abstract

A photosensitive resin composition comprising (A) a binder polymer, (B1) a photopolymerizable compound having at least one polymerizable cyclic ether group per molecule, and (C1) a photo-acid generator; a photosensitive resin composition comprising (A) a binder polymer, (B2) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group per molecule, and (C1) a photo-acid generator; and a photosensitive resin composition comprising (A) a binder polymer, (B1) a photopolymerizable compound having at least one polymerizable cyclic ether group per molecule, (B2) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group per molecule, and (C2) a free-radical polymerization initiator.

Description

 Five

Description Photosensitive resin composition, photosensitive element using the same, method for producing resist pattern, and method for producing printed wiring board

 The present invention relates to a photosensitive resin composition, a photosensitive element using the same, a method for producing a resist pattern, and a method for producing a printed wiring board. Background technology

 Conventionally, in the field of manufacturing printed wiring boards, photosensitive resin compositions and photosensitive elements obtained using a support and a protective film have been widely used as resist materials for etching, plating, and the like. I have.

 The printed wiring board is formed by laminating the photosensitive element on a copper substrate, exposing it to a pattern, removing the cured part with a developing solution, performing etching or plating, forming a pattern, and then curing. It is manufactured by a method that removes the part from the substrate.

 With regard to photosensitive elements, demands for higher resolution and higher adhesion than ever have been increasing as the density of printed wiring boards has increased in recent years.

 On the other hand, from the viewpoint of improving workability, a photosensitive resin composition having a high sensitivity and a low bathing stain is desired, and these characteristics depend on the type and amount of the photoinitiator used. Is what you do.

High-sensitivity photoinitiators are described in German Patent No. 2,027,467, European Patent Publication No. 11,787, European Patent Publication No. 220, Although described in Patent Publication No. 5889 and Japanese Patent Application Laid-Open No. 6-69631, these tend to have plating bath contaminating properties. In addition, a highly sensitive photosensitive resin composition obtained by combining 2,4,5-triene diimidazo monomer, a photoinitiator with low plating bath contamination, and a hydrogen-donating compound is disclosed in US Pat. Although it is described in the specification of No. 3,479,185, if the required sensitivity is adjusted, increasing the amount of 2,4,5-triphenylimidazol-l-mer will increase the resist. When the amount of the hydrogen donor compound used is increased, the adhesion to copper and the storage stability are deteriorated. It is also conceivable to use a compound having a highly reactive ethylenically unsaturated group (for example, polyethylene glycol dimethacrylate) with 2,4,5-triphenylimidazomoni dimer. The properties are extremely poor. Disclosure of the invention

Then, an object of the present invention is to provide a photosensitive resin composition which is excellent in resolution, adhesion, sensitivity, peeling properties and the like, and has low plating bath contamination. Another object is resolution, adhesion, sensitivity, release properties, low with bath fouling is to provide an excellent photosensitive element workability and productivity and the _like: Another object is resolved An object of the present invention is to provide a method for producing a resist pattern excellent in properties, adhesion, sensitivity, peeling properties, low-contamination bath contamination, workability, and productivity. Still another object is to provide a method for producing a printed wiring board which is excellent in resolution, adhesion, sensitivity, peeling properties, low plating bath contamination, workability, and productivity.

 According to a first aspect of the present invention, it comprises (A) a binder polymer, (B 1) a photopolymerizable compound having at least one polymerizable cyclic ether group in a molecule, and (C 1) a photoacid generator. A photosensitive resin composition is provided.

According to a second aspect of the present invention, (A) a binder polymer, (B 2) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in a molecule, and (C 1) a photoacid generator Resin composition containing Things are provided.

 According to a third aspect of the present invention, (A) a binder polymer, (B 1) a photopolymerizable compound having at least one polymerizable cyclic ether group in a molecule, (B 2) at least one polymerizable compound in a molecule A photosensitive resin composition comprising a photopolymerizable compound having a polymerizable ethylenically unsaturated group and (C 2) a radical polymerization initiator is provided.

 According to another aspect of the present invention, there is provided a photosensitive element in which a resist layer comprising the photosensitive resin composition according to the present invention is formed on a support.

 According to still another aspect of the present invention, there is provided a method for manufacturing a resist pattern, comprising the following steps:

 i) A photosensitive element formed by forming a resist layer comprising the photosensitive resin composition according to the present invention on a support, on a circuit-forming substrate, the resist layer being in close contact with the surface of the circuit-forming substrate. Laminating in such a manner that:

 i i) a step of irradiating with an actinic ray through a mask pattern or directly drawing and exposing a laser, and photo-curing the resist layer in an exposed portion;

 iii) a step of forming a resist pattern by selectively removing the unexposed portion of the resist layer by development.

 According to still another aspect of the present invention, there is provided a method for manufacturing a printed wiring board, comprising the following steps:

 i) a photosensitive element having a resist layer comprising the photosensitive resin composition according to the present invention formed on a support, a circuit element having a layer to be processed on a surface, a circuit forming substrate; Laminating so as to be in close contact with the surface of the layer to be processed of the forming substrate;

 i i) a step of irradiating with an actinic ray through a mask pattern or directly drawing and exposing a laser, and photo-curing the resist layer in an exposed portion;

iii) forming a resist pattern by selectively removing the unexposed resist layer by development. iv) a step of etching or selectively plating the layer to be processed of the circuit-forming substrate using the resist pattern as a mask; BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1 is a schematic view showing one embodiment of a photosensitive element.

FIG. 2 is a schematic view showing steps of a method for manufacturing a resist pattern. 3 and 4 are schematic views showing steps of a method for manufacturing a printed wiring board. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail. In the following description, (meth) acrylic acid means acrylic acid and its corresponding methacrylic acid, (meth) acrylate means acrylate and its corresponding methacrylate, and (meth) acryloyl group means It means an acryloyl group and its corresponding methacryloyl group. The photosensitive resin composition according to the present invention has three independent features. That is, the first feature is that it comprises (A) a binder polymer, (B 1) a photopolymerizable compound having at least one polymerizable cyclic ether group in a molecule, and (C 1) a photoacid generator. It is to become. The second feature is that it contains (A) a binder polymer, (B 2) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in a molecule, and (C 1) a photoacid generator. It is becoming. The third feature is that (A) a binder polymer, (B 1) a photopolymerizable compound having at least one polymerizable cyclic ether group in a molecule, and (B 2) at least one polymerizable compound in a molecule. A photopolymerizable compound having an ethylenically unsaturated group and a (C 2) radical polymerization initiator. According to the first feature, it is possible to provide a photosensitive resin composition having excellent resolution, adhesion, sensitivity, and peeling properties, and having low plating bath contamination. According to the second feature, adhesion, sensitivity, A photosensitive resin composition having excellent chemical resistance and flexibility and low plating bath contamination can be provided. According to the third feature, a photosensitive resin composition having excellent resolution, sensitivity, pattern shape, and release characteristics can be provided.

 Compared to a conventional radical polymerization system containing a binder polymer, a radical polymerizable compound and a radical polymerization initiator, a photopolymerizable compound having at least one polymerizable cyclic ether group in the molecule of the component (B 1) By using this, the component (B 1) functions as a plasticizer for radical polymerization and softens the system, resulting in a resin composition having a particularly good shape, and promotes radical polymerization. Since the crosslink density does not increase, the effect of shortening the stripping time of the cured product is obtained. On the other hand, by using the photoacid generator of the (C 1) component with respect to the conventional radical polymerization system, the radical generated from the (C 1) component contributes to the radical polymerization. A resin composition is obtained. Further, by using the component (B 1) and the component (C 1) with respect to the conventional radical polymerization system, cationic polymerization occurs together with radical polymerization, and a resin composition having particularly excellent sensitivity can be obtained. .

 Examples of the binder polymer as the component (A) include an acrylic resin, a styrene resin, an epoxy resin, an amide resin, an amide epoxy resin, an alkyd resin, and a phenol resin. Acrylic resins are preferred from the viewpoint that they can be developed with an alkaline aqueous solution. These can be used alone or in combination of two or more. Further, if necessary, these binder polymers may have a photosensitive group.

 The binder polymer can be produced, for example, by radically polymerizing a polymerizable monomer.

Examples of the polymerizable monomer include, for example, a polymerizable styrene derivative having a substituted mono- or aromatic ring such as styrene, vinyltoluene and hexamethylstyrene, acrylamide such as diacetone acrylamide, acrylonitrile, and vinyl. — Vinyl alcohols such as n-butyl ether Ester of coal, alkyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, getylaminoethyl (meth) acrylate, (meth) acrylic acid Glycidyl ester, 2,2,2-Trifluoroethyl (meth) acrylate, 2,2,3,3-Tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, α-bromo (meth) acrylic acid, (Meth) acrylic acid, / 3-furyl (meth) acrylic acid, 3-styrylyl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, etc. Acid monoester, fumaric acid, cinnamate, α- Examples include anookeic acid, itaconic acid, crotonic acid, and propiolic acid. These can be used alone or in combination of two or more.

Examples of the alkyl (meth) acrylate include those represented by the general formula (3):

(Wherein, R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ represents an alkyl group having 1 to 12 carbon atoms)

And compounds in which an alkyl group of these compounds is substituted with a hydroxyl group, an epoxy group, a halogen group, or the like.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ⁷ in the general formula (3) include a methyl group, an ethyl group, a propyl group, a butyl group, a benzyl group, a hexyl group, a heptyl group, Examples thereof include an octyl group, a nonyl group, a decyl group, a pendecyl group, a dodecyl group, and structural isomers thereof. Examples of the monomer represented by the general formula (3) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, Pentyl (meth) acrylate, hexyl (meth) acrylate Steryl, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl ester (meth) acrylate, (meta) And the like.) Decenyl acrylate, dodecyl (meth) acrylate, and the like.

 The binder polymer as the component (A) in the present invention preferably contains a carboxyl group from the viewpoint that it can be developed with an alkaline aqueous solution, that is, it can be developed with an alkaline solution. For example, a polymerizable monomer having a carboxyl group And other polymerizable monomers by radical polymerization.

 Further, from the viewpoint of resolution and flexibility, the binder polymer of the component (A) preferably contains styrene and Z or a styrene derivative as a polymerizable monomer. When styrene and a styrene or styrene derivative are contained as a copolymer component, it is preferable to contain 0.1 to 30% by weight, and 1 to 28% by weight, in order to improve both adhesion and peeling properties. %, More preferably 1.5 to 27% by weight. If this content is less than 0.1% by weight, the adhesion tends to be poor, and if it exceeds 30% by weight, the peeled pieces tend to be large and the peeling time tends to be long.

 It is preferable that the binder polymer of the component (A) is alkali-developable, and from that viewpoint, the acid value is preferably 30 to 50 OmgKOH / g, and 100 to 50 OmgKOH / g. g, more preferably 100 to 400 mgKOH / g, and most preferably 100 to 200 mgKOH / g. When the acid value is less than 30 mgKOH / g, the development time tends to be long, and when it exceeds 50 OmgKOH / g, the developer resistance of the photocured resist tends to decrease.

The weight average molecular weight of the binder polymer (A) (measured by gel permeation chromatography (GPC) and converted by a calibration curve using standard polystyrene) is 20.000 to 300.000. , 0 0 0 It is preferably 30, 00 00-: L 50, 00 0, and more preferably 40, 00 0-: L 0 0, 00 0. New When the weight average molecular weight is less than 200,000, the developer resistance tends to decrease, and when it exceeds 300,000, the development time tends to be long.

 When two or more of these binder polymers are used in combination, examples of the combination include two or more binder polymers composed of different copolymer components, two or more binder polymers having different weight average molecular weights, Examples include two or more types of binder polymers having different dispersities. Further, a polymer having a multimode molecular weight distribution described in Japanese Patent Application Laid-Open No. 11-327137, the disclosure of which is incorporated by reference, can also be used.

 Next, the component (B 1) will be described. This component (B 1) is used in the photosensitive resin composition of the present invention having the first feature and the third feature. By including this component, the sensitivity, pattern shape, and the like of the resin composition can be improved.

 The photopolymerizable compound having at least one polymerizable cyclic ether group in the molecule (B 1) is not particularly limited as long as it has at least one polymerizable cyclic ether group in the molecule. Compounds having a cationically polymerizable cyclic ether group in the molecule can be used. Specific examples include an oxetane compound and an epoxy compound. By using these, the sensitivity, release characteristics, and pattern shape of the photosensitive resin composition are further improved. These are used alone or in combination of two or more.

The oxetane compound is not particularly limited as long as it has an oxetane ring in the molecule, a compound having one oxetane ring, a compound having two oxetane rings, a compound having three oxetane rings, Examples include compounds having four oxetane rings. These are used alone or in combination of two or more. Examples of the compound having one oxetane ring include alkyloxane, such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane; Methyl-3-methoxymethyloxetane, 3,3-di (trifluoromethyl) perfluoroxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, and the general formula (1) :

(In the formula, R ′ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and an aryl having 6 to 18 carbon atoms. Group, (meth) acryloyl group, phenacyl group, amino group, C1-C10 alkylamino group, C2-C20 alkylamino group, nitro group, cyano group, carbonyl group, mercapto group, Alkyl mercapto group having 1 to 10 carbon atoms, aryl group, hydroxyl group, hydroxyalkyl group having 1 to 20 carbon atoms, carboxyl group, carboxyalkyl group having 1 to 10 carbon atoms of alkyl group, carbon number of alkyl group Is an alkoxy group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms. N-Alkyi with 2 to 10 carbon atoms Lukabamoyl group or a group containing a heterocyclic ring, or an aryl group substituted with one or more of these substituents)

And the like. Further, the hydrogen atom of the oxetane ring may be substituted with a halogen atom such as fluorine. These are used alone or in combination of two or more.

In the substituents in the above general formula (1), hydrogen atoms in these substituents may be substituted by the above substituents such as halogen atoms, etc. In the general formula (1), R ′ is hydrogen It is preferably an atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a 6 to 18 carbon atom aryl group or a group containing a heterocyclic ring. More preferably, it is an alkyl group having 1 to 5 carbon atoms.

In the general formula (1), R ² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms, and a carbon atom having 1 to 20 carbon atoms. Is preferably an alkoxycarbonyl group or an N-alkyl group having 2 to 10 carbon atoms, and more preferably a hydrogen atom.

 Examples of the halogen atom in the general formula (1) include fluorine, chlorine, bromine, iodine, and astatine.

 Examples of the alkyl group having 1 to 20 carbon atoms in the general formula (1) 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, and a tert-butyl group. Group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, pendecyl group, dodecyl group, tridecyl group, tetradecyl group, pendecyl group, hexadecyl group, heptyl group Examples thereof include a decyl group, an octadecyl group, a nonadecyl group, an icosyl group, and structural isomers thereof.

 Examples of the cycloalkyl group having 3 to 10 carbon atoms in the general formula (1) include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. . Examples of the aryl group having 6 to 18 carbon atoms in the general formula (1) include a phenyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthryl group and a phenanthryl group. May be substituted with a halogen atom, an amino group, a nitro group, a cyano group, a mercapto group, an aryl group, an alkyl group having 1 to 20 carbon atoms, or the like.

 Examples of the alkylamino group having 1 to 10 carbon atoms in the general formula (1) include a methylamino group, an ethylamino group, a propylamino group, and an isopropylamino group.

Examples of the dialkylamino group having 2 to 20 carbon atoms in the general formula (1) include, for example, dimethylamino, getylamino, dipropylamino, And a diisopropylamino group.

 Examples of the alkyl mercapto group having 1 to 10 carbon atoms in the general formula (1) include a methyl mercapto group, an ethyl mercapto group, and a propyl mercapto group.

 Examples of the hydroxyalkyl group having 1 to 20 carbon atoms in the general formula (1) include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxyisopropyl group, and a hydroxybutyl group.

 Examples of the carboxyalkyl group having 1 to 10 carbon atoms in the alkyl group in the general formula (1) include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, and a carboxybutyl group.

 Examples of the acryl group having 1 to 10 carbon atoms in the alkyl group in the general formula (1) include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isoptyryl group, a valeryl group, an isovaleryl group, and a vivaloyl group. Are listed.

 Examples of the alkoxy group having 1 to 20 carbon atoms in the general formula (1) include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the alkoxycarbonyl group having 1 to 20 carbon atoms in the general formula (1) include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group.

 Examples of the alkylcarbonyl group having 2 to 10 carbon atoms in the general formula (1) include an ethylcarbonyl group, a propylcarbonyl group, a butylcarbonyl group and the like.

 The alkenyl group having 2 to 10 carbon atoms in the general formula (1) includes, for example, 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 2-methyl_2 —Propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group and the like.

In the general formula (1), examples of the N-alkyl group having 2 to 10 carbon atoms include an ethylcarbamoyl group, a propyl group, and a propyl group. And a butylcarbamoyl group and a pentylcarbamoyl group. Examples of the group containing a heterocyclic ring in the general formula (1), that is, a group derived from a heterocyclic compound include a furyl group, a phenyl group, a pyrrolyl group, a thiazolyl group, an indolyl group, and a quinolyl group.

More specifically, in the general formula (1), a compound in which R ^{1 is an} ethyl group and R ^{2 is a} hydrogen atom (manufactured by Toagosei Co., Ltd., product name: OXT—101):

Compound in which R ¹ methyl group and R ² = phenyl group (manufactured by Toagosei Co., Ltd., product name: O XT—2 1 1):

Compounds with R ¹ ^ methyl group and R ² = 2-ethylhexyl group (manufactured by Toagosei Co., Ltd., product name OXT-212):

R ^] = ethyl group, R ² == methacryloyl group compound (manufactured by Toagosei Co., Ltd., product name: OXT—MA):

等が好ましく挙げられる。

And the like.

Examples of the compound having two oxetane rings include a compound represented by the following general formula (2):

(Wherein, R ³ represents a divalent organic group, and R ⁴ and R ⁵ each independently have the same meaning as R ′ in the general formula (1))

A compound represented by the general formula (2a):

(Wherein two R ³ are defined agree with R ³ each independently in the general formula (2), R ⁴及beauty R ⁵ in R ⁴ and R ⁵ are each independently the general formula (2) Is equivalent to

And the like.

 In the general formula (2), examples of the divalent organic group include a linear or branched alkylene group having 120 carbon atoms, and a linear or branched poly (alkylene group having 16 carbon atoms in the alkylene group). An xylene group, a linear or branched unsaturated hydrocarbon group, a carbonyl group, an alkylene group including a carbonyl group having an alkylene group of 120, and a carboxyl group having an alkylene group of 120 carbon atoms. And an alkylene group including a carbamoyl group having 120 carbon atoms in the alkylene group.

 In the above, examples of the linear or branched alkylene group having 120 carbon atoms include an ethylene group, a propylene group, and a butylene group. Examples of the linear or branched poly (alkylenoxy) group having 16 carbon atoms in the alkylene group include a poly (ethyleneoxy) group and a poly (propylenoxy) group. Examples of the linear or branched unsaturated hydrocarbon group include an ethenylene group, a propenylene group, a methyl probenylene group, a butenylene group and the like.

Furthermore, examples of the divalent organic group in the general formula (2) include groups represented by the following general formulas or formulas (4) and (16). (Four)

(Wherein, R ^s has the same meaning as R ′ in the general formula (1))

(Five)

(Where m is a natural number from 1 to 10 and may be a mixture of compounds having different values of m)

 (Wherein R9 is an oxygen atom, a sulfur atom, an alkylene having 1 to 6 carbon atoms, or

CF, CH ₃ II ³

—— 丽 一一 so— — so ₂ — — c— — C—

を示す）

, CF ₃ CH ₃

Indicates)

(Wherein, R ′ ^e has the same meaning as R ′ in the general formula (1))

(Wherein, R ^u is the same as R ⁹ in general formula (6))

(In the formula, R ′ ² has the same meaning as R ′ in general formula (1), and 2 to 4 naphthalene rings may be substituted.)

(Wherein, R ¹³ has the same meaning as R ′ in formula (1), and may have 2 to 4 substituents on the naphthalene ring)

 (Where n is a natural number from 1 to 10 and may be a mixture of compounds having different values of n)

Indicates)

 Preferred compounds among the compounds having two oxetane rings include, for example, compounds represented by the following formulas (17) to (21).

(R ¹⁴ is a methyl group or an ethyl group)

Examples of available compounds having two oxetane rings include, for example, the following formula:

A compound represented by the following formula (manufactured by Toagosei Co., Ltd., product name: OXT-2211), having the following formula

で表される化合物 （宇部興産 （株） 製、 製品名 OXT— BD〇E)、 下 式：

で表される化合物 （宇部興産 （株） 製、 製品名〇XT— DD〇E)、 下 記式： (Product name: OXT-BTOE, manufactured by Ube Industries, Ltd.)

(Product name: OXT—BD〇E, manufactured by Ube Industries, Ltd.)

A compound represented by the following formula (manufactured by Ube Industries, Ltd., product name 産 XT—DD〇E).

(Hitachi Chemical Industry Co., Ltd., sample name HM-20), Formula F:

(Sample name HM-23, manufactured by Hitachi Chemical Co., Ltd.), Feci formula:

(Sample name: HM-24, manufactured by Hitachi Chemical Co., Ltd.). The compound having three or four oxetane rings includes, for example, a compound represented by the general formula (22):

(Wherein, R ′ has the same meaning as R ′ in the general formula (1), and R ¹⁵ represents a branched alkylene group having 1 to 12 carbon atoms or a branched poly (alkyleneoxy) group. J is 3 or 4)

A compound represented by the general formula (22a):

(Wherein, R ¹ is as defined as R ¹ in the general formula (1), R ³ is as defined the R ³ in the formula (2), R ¹⁵ is the one general formula Is the same as R ¹⁵ in (22), and j is the same as j in the general formula (22).

A compound represented by the general formula (22b):

(Wherein, R ¹ is as defined as R ¹ in the general formula (1), R ³ is as defined the R ³ in the formula (2), R ¹⁵ is the one general formula Is the same as R ¹⁵ in (22), and ji and j ₂ are each independently 1, 2, or 3, and are selected so that ji + j ₂ = 3 or 4. No.

In the above general formula (22), a branched alkylene group having 1 to 12 carbon atoms For example, general formula (23):

 (Wherein R '"' is an alkyl group having 16 carbon atoms)

A group represented by the following formula (24) and the following formula (25)

 twenty four)

_{-? CH 2 -CH 2 -CH- CH} 2 -CH- CH ~ CH 2 ( group represented by 25 and the like.

 Examples of the branched poly (alkyleneoxy) group in the above general formula (22) include the general formula (26):

 (Where ρ is independently an integer of 110)

And the like.

 Preferred compounds among the compounds having 3 or 4 oxetane rings include, for example, the following formula (27):

で表される化合物、 下記式：

A compound represented by the following formula:

(Sample name: HM-16, manufactured by Hitachi Chemical Co., Ltd.).

Further, the aromatic ring in the above oxetane compound may have a substituent, and examples of such a substituent include those exemplified for R ¹ in the general formula (1). When there are a plurality of these substituents, each of the plurality of substituents may be the same or different.

 In addition to the above-mentioned oxetane compound, for example, a compound having 1 to 4 oxenine rings having a high molecular weight of about 1,000 to 5,000 can be used.

 Further, as a polymer containing oxetane, a polymer having an oxetane ring in a side chain described in K. Sato, A. Kameyama and T. Nishikubo, Macromolecules, 25, 1198 (1992), the disclosure of which is incorporated by reference. Can be used as well.

The epoxy compound preferably used as the component (B1) is not particularly limited as long as it has an epoxy group in the molecule, and examples thereof include compounds represented by the following formula. These are used alone or in combination of two or more.

\ ノ CH ^ ~ rO- "CH2― CH2 ~~ O— CH ^

〇 O

^ — CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -0-CH _2- /

 O O Also available epoxy compounds include the following formula:

(Manufactured by Kyoeisha Chemical Co., Ltd., product name: Kokuyo Poli 4000) represented by the following formula:

(Manufactured by Kyoeisha Chemical Co., Ltd., product name Kotori 3002).

Next, the component (II) will be described. This component (II) is used in the photosensitive resin composition of the present invention having the second and third characteristics, and is also preferably used in the photosensitive resin composition of the present invention having the first characteristic. Can be. By including this component, the sensitivity of the photosensitive resin composition according to the present invention can be further increased. As the photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule of the component (B 2), for example, a radical polymerizable compound is preferably used. G, a compound obtained by reacting a / 3-unsaturated carboxylic acid, 2,2-bis (4-((methyl) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-1 (( Bisphenol A (meta) acrylate compounds such as (meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, glycidyl Compounds obtained by reacting α, / 3-unsaturated carboxylic acids with group-containing compounds, urethane monomers such as (meth) acrylate compounds having urethane bonds , Nonylphenyldioxylene (meth) acrylate, archloro-1 / 3-hydroxypropyl-1-β '— (meth) acryloyloxetyl-ο-phthalate,) 3-hydroxyethyl-1) 3' — (meta) ) Acryloyloxyshethyl-o-phthalate, β-hydroxypropyl-13 '-(meth) acryloyloxechyl-o-phthalate, alkyl (meth) acrylate, and the like. Above all, from the viewpoints of sensitivity, resolution, and fine wire adhesion of the photosensitive resin composition, a bisphenol-based (meth) acrylate compound or a (meth) acrylate compound having a urethane bond may be contained as an essential component. preferable. These are used alone or in combination of two or more.

Examples of the compound obtained by reacting the above polyhydric alcohol with β-unsaturated carboxylic acid include polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and the number of propylene groups. Is 2 to 14, polypropylene glycol di (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolpropanetri (meth) acrylate, trimethylolpropaneethoxylate (meth) acrylate, Trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropanetriethoxytri (meth) Acrylate, trimethylolpropane tetraethoxytri (meth) acrylate, trimethylolpropanepentaethoxytri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, dipentyl erythritol pen (Meth) acrylate, dipentyl erythritol hexa (meth) acrylate, and the like.

 Examples of the α, 3-unsaturated carboxylic acid include (meth) acrylic acid.

 Examples of the 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include, for example, 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane , 2,2-bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxypheneethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-(((meth) acryloxyheptae) Toloxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyctaethoxy) phenyl) propane, 2,2-bis (4-(((meth) acryloxynonaethoxy)) Nyl) propane, 2,2-bis (4-((meth) acryloxydeoxyethoxy) phenyl) and the like, and 2,2-bis (4- (methacryloxypentylethoxy) phenyl) propane are: 5—500 (Shin-Nakamura Chemical Co., Ltd., product name), F 製品 -321 、 (Hitachi Chemical Co., Ltd., trade name), etc. are commercially available.

Examples of the 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include, for example, 2,2-bis (4-1 ((meth) acryloxydiethoxyoctapropoxy). ) Phenyl) pu bread, 2,2-bis (4-((meth) acryloxytetraethoxyte trapropoxy) phenyl) propane, 2,2-bis (4-((meta) Acryloxyhexaethoxyhexapropoxy) phenyl) propane and the like. These are used alone or in combination of two or more.

 As the glycidyl group-containing compound, for example, trimethylolpropane triglycidyl ether tertri (meth) acrylate, 2,2-bis (4- (meth) acryloxy-2-hydroxypropyloxy) phenyl and the like can be mentioned. Can be

 Examples of the urethane monomer include, for example, an acrylic monomer having an OH group at the i3 position (mean), isophorone diisocyanate, 2,6-toluenediisocyanate, 2,4-toluenediisocyanate, 1,6 Addition reaction product with diisocyanate compounds such as hexamethylene diisocyanate, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, E〇modified urethane resin (Meth) acrylate, P〇 modified urethane (meth) acrylate, E〇, P〇 modified urethane (meth) acrylate, and the like. E O denotes ethylene oxide, and the compound modified with E O has a block structure of an ethylene oxide group. P O represents propylene oxide, and the compound modified with P O has a block structure of a propylene oxide group.

 As the above-mentioned E O-modified urethane (meth) acrylate, P ウ -modified urethane (meth) acrylate and E O, PO-modified urethane (meth) acrylate, for example, the general formula (28):

(In the formula, R ′ ⁷ and R ^IS each independently represent a hydrogen atom or a methyl group, X ¹ and X ² each independently represent an ethylene oxide group or a propylene oxide group, and Z has 2 to 2 carbon atoms. Represents a hydrocarbon group of 16 and s and t are each independently an integer of 2 to 30) And the like.

When s and t are each 2 or more, two or more X ′ and two or more X ² may be the same or different, and X ¹ and X ² are two alkylene oxide groups (ethylene Oxoxide group and propylene oxide group), two kinds of X ¹ and two kinds of X ² may exist at random or may exist in blocks.

 Examples of the EO-modified urethane (meth) acrylate represented by the general formula (28) include Shin Nakamura Chemical Co., Ltd. product name U A-11.

 Examples of E〇, P〇 modified urethane (meth) acrylate include Shin Nakamura Chemical Co., Ltd. product name U A-13. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, methyl (meth) acrylate, butyl (meth) acrylate, and 2-methylhexyl (meth) acrylate. No.

 Next, the component (C 1) will be described. This component (C 1) is used in the photosensitive resin composition of the present invention having the first feature and the second feature. By including this component, the sensitivity and resolution of the photosensitive resin composition according to the present invention can be further increased.

The photoacid generator of the component (C1) is not particularly limited as long as it is a compound that generates an acid (electron pair acceptor) by light. For example, a cation that generates a carbocation by light or heat What is used as a polymerization initiator can be used. Specifically, for example, a rhododium salt compound, a sulfonium salt compound, an ammonium salt compound, a phosphonium salt compound, an arsonium salt compound, a stibonium salt compound, an oxonium chloride compound, a selenodium salt compound, a stannonium salt compound And the like, and preferably a rhododium salt compound, a sulfonium salt compound or an ammonium chloride compound. These are used alone or in combination of two or more. Examples of the above-mentioned sodium salts include, but are not limited to, diphenyl pentafluorobenzene, difluorohexafluorophosphinate, diphenyl pentafluorohexaphosphate, and 4′-butyl phenylphenyl. ) Edmium hexafluorophosphate, bis (4,4 'overnight butylphenyl) Odonium hexafluorophosphine, bis (4,4' overnight butylphenyl) (Jaributylphenyl) odonium hexafluoroarsenate, diphenyl odonium triflate, bis (4,4 'overnight carbyl phenyl) benzodiamine triflate and the like. These may be used alone or in combination of two or more.

 Examples of the sulfonium salt include triphenylsulfonium tetrafluoroporate, triphenylsulfoniumhexafluorophosphinate, triphenylsulfoniumhexafluoroantimonate, and triphenylsulfoniumhexafluorate. Loarsenate, triphenylsulfonium triflate and the like. These are used alone or in combination of two or more.

 Next, the component (C 2) will be described. This component (C 2) is used in the photosensitive resin composition of the present invention having the third feature. It is also preferably used for the photosensitive resin composition of the present invention having the first feature and the second feature. That is, the photosensitive resin composition of the present invention having the first feature and the second feature includes a photoacid generator as an essential component as the component (C 1), and a radical polymerization initiator as the component (C 2). It is preferable to use an initiator that generates cations and radicals by light or heat. By including this component, the sensitivity of the photosensitive resin composition according to the present invention can be further increased.

 Examples of the (C 2) radical polymerization initiator include benzophenone,

N, N'—tetramethyl-1,4,4—diaminobenzophenone (Mich Laketone), Ν, Ν '—tetraethyl-4,4' diaminobenzophenone, 4-methoxy-1 4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-11- (4-morpholinophenyl) -one 1,2-Methyl-1-1 [4- (Methylthio) phenyl]-2-Morphorinopropanone-11, Aromatic ketone such as 1, 2-ethylanthraquinone, phenanthrenequinone, 2-iert-butylanthraquin Non, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-mono-anthraquinone, 2-methylanthraquinone , 1, 4-naphthoquinone, 9, 10 — phenanthine raquinone, 2 — methyl 1, 4-naphthoquinone, 2, 3- dimethyl Quinones such as en Torakinon, benzoin methyl ether, Benzoine Chirueteru, Benzoine one ether compounds such as benzoin phenylpropyl ether, benzoin, methyl benzoin, Ben Zoin compounds such as E chill benzoin, benzyl derivatives such as benzyl dimethyl ketal, 2,

Acridine derivatives such as 4,5-triarylimidazole dimer, 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane, N-phenylglycine, N-phenyldaricin derivatives, and coumarin derivatives And the like. Further, the substituents of the aryl groups of the two 2,4,5-triarylimidazoles constituting the dimer may be the same to give a target compound, or a different asymmetric compound may be given. From the viewpoints of adhesion and sensitivity, 2,4,5-triarylimidazole dimer is more preferable. These are used alone or in combination of two or more.

Examples of the 2,4,5—triarylimidazole dimers include, for example, 2,2′-bis (2-chlorophenyl) -1,4,4 ′, 5,5′—tetraphenylbisimidazole, 2,2'-bis (2,4-dichloromouth phenyl) 1-4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,3-dichloromouth phenyl) 1-4, 4 ', 5, 5'-tetraphenylbisimidazole, 2, 2'-bis (2-cyclophenyl) -1,4 ', 5,5'-tetrakis (m-methoxy) phenylbisimidazole, 2,2' —Bis (2,3-dichloromouth phenol) 1-4,4 ′, 5,5 ′ —Tetrakis (m-methoxy) phenirubiimidazole, 2,2′-Bis (2,4-dichloro) Phenyl) one 4,

4'.5,5'-tetrakis (m-methoxy) phenylbisimidazole, 2,2'-bis (2,6-dichlorophenyl) -1,4,4 ', 5,

5'-tetrakis (m-methoxy) phenylbisimidazole, 2,2'-bis (2-fluorophenyl) 1,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,4-difluorophenyl) 1-4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,3-difluorophenyl) 1,4,4', 5,5'-tetra Phenylbisimidazole, 2,2'-bis (2-fluorophenyl) -1,4 ', 5,5'-tetrakis (m-methoxy) phenylbisimidazole, 2,2'-bis (2,3— 1,4 ', 5,5'-tetrakis (m-methoxy) phenylbisimidazole, 2,2'-bis (2,4-difluorophenyl) 1-4,4', 5,5 ' -Tetrakis (m-methoxy) phenylbisimidazole, 2,2 ' Scan (2, 6-1-difluorophenyl) _ 4, 4 ', 5, 5' - tetrakis (m-methoxyphenyl) phenylalanine bis imidazo Ichiru,

2,2'-bis (2-bromophenyl) _4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5 ' —Tetraphenylbisimidazole, 2,2′-bis (2,3-dibromophenyl) —4,4 ′, 5,5′-tetraphenylbisimidazole and the like. These may be used alone or in combination of two or more.

The (C 2) radical polymerization initiator includes, as sensitizers, for example, 7-amino-14-methylcoumarin, 7-dimethylamino-14-methylcoumarin, 7-ethylamino-4-methylcoumarin, and 7-methylamido. No 4-methylcoumarin, 7-ethylamino-1 4-methylcoumarin, 7-dimethylaminocyclopentene [c] coumarin, 7-aminocyclopentene [c] coumarin, 7-getylaminocyclopentene [c] coumarin, 4,6-dimethyl-7-ethylaminocoumarin, 4,6-dimethyl-7-ethylaminocoumarin, 4,6-dimethyl-7-ethylaminocoumarin, 4,6-dimethyl-7-dimethylaminocoumarin, 4, , 6-Jetyl-7-Jetylaminocoumarin, 4,6-Detyl-1-7-dimethylaminocoumarin, 4,6-Dimethyl-7-ethylaminocoumarin and the like can be used in combination. These are used alone or in combination of two or more.

 Further, in the (C 1) photoacid generator, for example, a thioxanthone derivative such as methyl thioxanthone and isopropyl thioxanthone, anthracene, pyrene and phenothiazine can be used in combination as a sensitizer. These are used alone or in combination of two or more.

 The amount of the component (A) is 100 parts by weight of the total of the components (A) and (B) ((B1) component + (B2) component), When used as a photosensitive element, it is at least 40 parts by weight from the viewpoint of coating properties, preferably at most 80 parts by weight, more preferably at least 45 to 60 parts by weight from the viewpoint of sensitivity.

 The amount of the component (B) (the component (B1) + the component (B2)) is, for the same reason as described above, based on 100 parts by weight of the total amount of the components (A) and (B). It is preferably 20 to 60 parts by weight, more preferably 40 to 55 parts by weight.

 In the component (B), the component (B1) is at least 5% by weight from the viewpoint of the peeling time, preferably 95% by weight or less, and more preferably 5 to 80% by weight from the viewpoint of sensitivity. More preferably, it is particularly preferably from 10 to 50% by weight.

The component (B 2) is present in the component (B) in an amount of 5% by weight or more from the viewpoint of sensitivity. Yes, it is preferably 95% by weight or less, more preferably 20 to 95% by weight, and particularly preferably 50 to 90% by weight from the viewpoint of the peeling time.

 The amount of component (C) (component (C 1) + component (C 2)) should be at least 1 part by weight from the viewpoint of sensitivity, based on 100 parts by weight of the total of components (A) and (B). From the viewpoint of resolution, the amount is preferably 10 parts by weight or less, more preferably 2 to 6 parts by weight.

 The component (C 1) in the component (C) is preferably at least 10% by weight from the viewpoint of resolution and release characteristics, and is preferably at most 80% by weight from the viewpoint of sensitivity, and is preferably from 10 to 50% by weight. Is more preferable, and particularly preferably 10 to 40% by weight.

 The component (C 2) in the component (C) is preferably at least 20% by weight from the viewpoint of fine wire adhesion, and preferably at most 90% by weight from the viewpoint of resolution and sensitivity, and 50 to 90% by weight. %, More preferably 60 to 90% by weight.

 If necessary, the photosensitive resin composition containing the above components may contain a dye such as malachite green, a photochromic agent such as tribromophenylsulfone or leucocrystalline violet, a thermochromic inhibitor, Plasticizers such as toluenesulfone amide, pigments, fillers, defoamers, flame retardants, stabilizers, adhesion promoters, leveling agents, release accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking An agent or the like can be contained in an amount of about 0.01 to 20 parts by weight each based on 100 parts by weight of the total of the components (A) and (B). These are used alone or in combination of two or more.

The photosensitive resin composition according to the present invention may contain, as necessary, methanol, ethanol, acetone, methyl ethyl ketone, methyl sorb, ethyl sorb, toluene, N, N-dimethylformamide, propylene. It can be dissolved in a solvent such as glycol monomethyl ether or a mixed solvent thereof and applied as a solution having a solid content of about 30 to 60% by weight. Its use is not particularly limited, but copper, copper-based alloy, iron, iron-based alloy, etc. It is preferable to apply it as a liquid resist on the metal surface and dry it, and then use a protective film if necessary, or use it in the form of a photosensitive element.

 The thickness of the photosensitive resin composition layer to be applied varies depending on the application, but is preferably about 1 to 100 m in thickness after drying. When applied as a liquid resist and then covered with a protective film, the protective film may be a polymer film such as polyethylene or polypropylene.

 Next, a photosensitive element according to the present invention, that is, a resist layer comprising a photosensitive resin composition having any one of the first, second, and third features of the present invention described above is formed on a support. The resulting photosensitive element will be described with reference to the drawings.

 FIG. 1 schematically shows an embodiment of the photosensitive element. The photosensitive element 1 includes a support 11 and a resist layer (photosensitive resin composition layer) formed thereon. 1) and 2 are included. As the support 11, for example, a polymer film of polyethylene terephthalate, polypropylene, polyethylene, polyester, or the like can be preferably used. The method for forming the resist layer 12 on the support 11 is not particularly limited, but it can be preferably obtained by applying and drying a photosensitive resin composition. The application can be performed by a known method such as, for example, one night in the mouth, one night in the comma, one night in the graviaco, one night in the air, one night in the die, one night in the barco, and the like. Drying can be performed at about 70 to 150 ° (: about 5 to 30 minutes. The amount of the remaining organic solvent in the resist layer 12 is determined by the amount of the organic solvent diffusion in a later step. From the viewpoint of prevention, the content is preferably 2% by weight or less.

The thickness of the polymer film of the support 11 is preferably 1 to 100 m. One of these polymer films may serve as a support for the resist layer, and the other may serve as a protective film for the resist layer, and may be laminated on both sides of the resist layer. As a protective film, a resist layer and a support It is preferable to select a film having a smaller adhesive force between the resist layer and the protective film than the adhesive force of the film, and a film having a low fish eye is preferable.

 Although not shown in the figure, the photosensitive element has an intermediate layer and a protective layer such as a cushion layer, an adhesive layer, a light absorbing layer, and a gas barrier layer in addition to the resist layer, the support, and the protective film. May be.

 The photosensitive element is stored, for example, as it is or by further laminating a protective film on the surface of the resist layer and winding it around a cylindrical core. In this case, it is preferable that the support is wound so that the support is on the outside. On the end surface of the roll-shaped photosensitive element roll, it is preferable to install an end separation from the viewpoint of protection of the end surface, and it is preferable to install a moisture-proof end surface separation from the viewpoint of edge-proof fusion. As a packing method, it is preferable to wrap in a black sheet having small moisture permeability.

 Examples of the core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).

Next, a method of manufacturing a resist pattern according to the present invention will be described with reference to FIG. 2, which schematically shows the steps as an embodiment. First, in step (i), as shown in FIG. 2 (A), the above-described photosensitive element 1 is placed on the circuit forming substrate 2 and the resist layer 12 is brought into close contact with the surface of the circuit forming substrate 2. Are stacked as described above. Prior to lamination, if a protective film is present on the resist layer 12 of the photosensitive element 1, the protective film is removed. As a lamination method, for example, while the resist layer 12 is heated to about 70 to 130 ° C., the circuit forming substrate 2 is coated with about 0.1 to 1 MPa (1 to: L 0 kgf / cm 2). ⁽ Approximately ² ). The method of laminating by pressure bonding at a pressure of about ² ) can be mentioned, and lamination can be performed under reduced pressure. In general, the substrate 2 for circuit formation A layer provided with a metal layer (not shown), which is a metal layer, is used. The surface of the substrate 2 on which the photosensitive element 1 is laminated is usually a metal surface, but there is no particular limitation.

 After the lamination of the photosensitive elements is completed, as shown in FIG. 2 (B), as shown in FIG. 2 (B), actinic rays are radiated imagewise onto the resist layer 12 through the mask pattern 3, and the resist in the exposed area is exposed. Layer 12 is light cured. The mask pattern 3 may be a negative type or a positive type, and a commonly used mask pattern can be used. As the light source of the actinic ray, a known light source, for example, a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, a xenon lamp, or the like that effectively emits ultraviolet light or visible light is used. Further, direct laser exposure can be performed without using a mask pattern. After the exposure, as a step (H i), the resist layer in the unexposed portion is selectively removed by development to form a resist pattern 121 as shown in FIG. 2 (C). The exposure in the step (ii) can be performed in the presence of the support 11 as long as light irradiation on the resist layer 12 is not hindered. In this case, the support 1 Remove one. The development is performed by removing unexposed portions by jet development using a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent, or dry development. The above-mentioned alkaline aqueous solution can be preferably used, for example, a dilute solution of 0.1 to 5% by weight of sodium carbonate, a dilute solution of 0.1 to 5% by weight of potassium carbonate, and a dilute solution of 0.1 to 5% by weight of sodium hydroxide. Dilute solutions are examples. The pH of this alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. Further, a surfactant, an antifoaming agent, an organic solvent and the like may be mixed in the alkaline aqueous solution. Examples of the development method include a dive method, a spray method, brushing, and slapping.

As a post-development treatment, the laser formed by heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 J / cm ² as necessary. The distaste pattern may be further cured.

 Next, a method for manufacturing a printed wiring board according to the present invention will be described with reference to FIGS. 3 and 4, which schematically show the steps as an embodiment.

 The steps up to the formation of the resist pattern include a step (i) of laminating the photosensitive element 1 on the circuit forming substrate 2, an exposure step (ii), and a development step (ih). This is the same as described in. However, in the method of manufacturing a printed wiring board, as shown in FIGS. 3 (A) and 4 (A), a circuit forming substrate 2 having a thin work layer 21 made of copper or the like on its surface is used. Use FIG. 3 shows a circuit forming process by a subtractive method using etching, and FIG. 4 shows a circuit forming process by a semi-additive method using plating.

 After the resist pattern 121 is formed, as shown in FIG. 3B, the process target layer of the circuit forming substrate 2 is formed by using the formed resist pattern 121 as a mask, as shown in FIG. 3B. Etching 21 or selectively plating the work layer 21 as shown in FIG. 4 (B) to form a plating layer (22) made of copper or the like. For example, a cupric chloride solution, a ferric chloride solution, an alkali etching solution, or the like can be used for etching the work layer 21 made of a metal surface. Examples of plating methods include copper plating, solder plating, nickel plating, and gold plating.

Finally, as shown in FIGS. 3 (C) and 4 (C), the resist pattern 121 remaining on the substrate 2 is peeled off with, for example, a more alkaline aqueous solution than the alkaline aqueous solution used for development. Thus, the printed wiring board 4 on which the circuit 211 is formed is obtained. In the case of the semi-additive method, as shown in FIG. 4 (D), after the resist pattern is stripped, the processed layer 21 is also removed by, for example, a quick etching method. Examples of the strong alkaline aqueous solution include 1 to 10% by weight water An aqueous solution of sodium oxide, an aqueous solution of 1 to 10% by weight of potassium hydroxide, and the like are used. Examples of the peeling method include an immersion method and a spray method. Further, the printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board or may have a small diameter through hole. Next, the present invention will be described in more detail with reference to examples. Examples 1-20 and Comparative Examples 1-3

 The components shown in Table 1 were blended to obtain a binder polymer solution.

次いで、 得られた溶液に、 表 2、 表 3、 表 4及び表 5に示す成分を 溶解させて、 感光性樹脂組成物の溶液を得た。

Next, the components shown in Table 2, Table 3, Table 4, and Table 5 were dissolved in the obtained solution to obtain a solution of the photosensitive resin composition.

Table 2 Amount / g

 Example 13 14 15 16 17 18

OXT-DDOE 10 0 0 0 0 0

OXT-MA 0 10 0 0 0 0

HM- 16 0 0 10 0 0 0

(B1)

 HM-20 0 0 0 10 0 0

HM-23 0 0 0 0 10 0

HM-24 0 0 0 0 0 10

(B2) FA-321M 35 35 35 35 35 35

(C1) BBI- 105 0.5 0.5 0.5 0.5 0.5 0.5 0.5

CI-HABI 3.0 3.0 3.0 3.0 3.0 3.0 3.0

(C2)

EAB 0.3 0.3 0.3 0.3 0.3 0.3 Table 5 Formulation

なお、 表 2〜 5において用いた化合物を以下に示す。 上記以外の表 中の化合物は、 既に製品名と共に前記されたものと同じ。

The compounds used in Tables 2 to 5 are shown below. The compounds in the tables other than the above are the same as those already described above together with the product names.

* 1 OXT—101: 3-ethyl-3-hydroxymethyloxane (a compound in which R ^{1 =} ethyl group and R ² = hydrogen atom in general formula (1), Toagosei Co., Ltd., product Name)

 * 2 O XT— 121: Xylylene dioxetane (1,4-bis (((3-ethyl-3-oxenyl) methoxy) methyl) benzene) (compound of the above formula (20)) (80 to 8 5% by weight) and R in the general formula (2)

¹ = R ⁵ = Ethyl group and R ³ = Mixture of compounds (10 to 15% by weight) in which m = 1 in the general formula (5), Toagosei Co., Ltd., product name

* 3 XDO: 1,4-bis (((3-ethyl-3-oxenyl) methoxy) methyl) benzene (compound of formula (20), Toagosei Co., Ltd., product name)

U UA—11: EO-modified urethane dimethacrylate (in the general formula (28), R ¹⁷ = R ′ ^s = methyl group, X ¹ = X ² = ethylene oxide group, Z = (CH ₂ ) ₆ and Compound where s = t = 5, Shin-Nakamura Kogyo Co., Ltd., product name)

 * 5 FA—3 2 1 M (2,2-bis (4-1 (methacryloxy pentyl ethoxy) phenyl) propane, Hitachi Chemical Co., Ltd., product name)

* 6 BBI — 105: 4-bis (t-butylphenyl) · Triflate

 * 7 SP—170: Bis [4- (2- (2-hydroxyethoxy) phenyl) sulfonio) -phenyl] sulfide bis-hexafluoroantinomate, 60% propiboner Solution (Asahi Denka Kogyo Co., Ltd., product name):

 * 8 C 1— HAB I: 2, 2'-bis (o-chloro phenyl) 4, 4 ', 5, 5'-tetraphenylbisimidazole

 * 9 E AB: Jetilamino Benzofuenonone

 * 10 NP-8 EA: Nonyl phenoxy oxyethylene acrylate (product name, manufactured by Kyoeisha Chemical Co., Ltd.)

The photosensitive element was obtained by uniformly coating the film on a polyethylene terephthalate film and drying it in a hot air convection dryer at 100 ° C. for 10 minutes. The thickness of the photosensitive resin composition layer (resist layer) was 2.

 On the other hand, the copper surface of a copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E_61), which is a glass epoxy material with copper foil (thickness 35 ^ m) laminated on both sides, is equivalent to Polished using a polishing machine with a brush (made by Sankei Co., Ltd.), washed with water, dried in an air stream, and heated the obtained copper-clad laminate to 80 ° C. The photosensitive resin composition layer was laminated while being heated to 110 ° C.

Next, an exposure machine with a high-pressure mercury lamp (Oak Co., Ltd.) 590 As a negative, a stepr tablet of 41 steps was placed on the test piece as a negative, and exposed to 6 OmJ / cm ² .

 After the exposure, the polyethylene terephthalate film was peeled off, and unexposed portions were removed by spraying a 1% by weight aqueous solution of sodium carbonate at 30 ° C. for 20 seconds.

The photosensitivity of the photosensitive resin composition was evaluated by measuring the number of step tablets of the obtained resist pattern (that is, the photocured film formed on the copper-clad laminate). The light sensitivity is indicated by the number of steps on the step evening bullet, and the higher the number of steps on the step evening bullet, the higher the light sensitivity. Also, the pattern after development was observed, and the resolution (; m) was determined from the line width (m) remaining as line-and-space. Further, the film was cured at an exposure dose 6 0 mJ / cm ^z is impregnated with 3% N A_〇_H solution was measured the time required for peeling.

 Tables 6 to 9 show the above evaluation results. Table 6

表 7

Table 7

Example 6 7 8 9 10 11 12 Sensitivity (ST / 41) 27 26 26 26 26 25 25 Resolution (m) 25 20 20 20 18 20 22 Peeling time (sec) 37 18 32 26 36 40 47 Table 8

表 9

Table 9

実施例 2 1〜 24及び比較例 4

Examples 21 to 24 and Comparative Example 4

 The components shown in Table 10 were blended to obtain a solution of the photosensitive resin composition. Next, the components shown in Table 11 were dissolved in the obtained solution of the photosensitive resin composition to obtain a solution of the photosensitive resin composition.

 Table 10

 Material mix amount (g)

 Methacrylic acid / ethyl methacrylate / s 15 o0

(A) Ingredients Tylene (25/50/25 weight ratio, weight average content (solid molecular weight = 54,000), methyl sorbent / solvent 60) Rhen = 6/4 (weight ratio) solution, solid content = 40 Wt%, acid value = 75 mgKOH / g

 (B) Component FA-321M 40

(C) component C1-HABI * ⁷ 3-2

アセトン 10 溶剤 トルエン 7 EAB * ⁸ 0.1 Photochromic agent Leuco crystal violet 0.4 Dye Malachite green

Acetone 10 Solvent Toluene 7

Ν, Ν-dimethylformamide 3 methanol 3 00/0653

Table 11 Amount / g

次いで、 この感光性樹脂組成物の溶液を用い、 上記実施例と同様に •感光性エレメントを得た。 得られた感光性樹脂組成物層 （レジス ト層）の膜厚は、 30 /xmであった。 この感光性エレメントを用いて、 上記実施例と同様にして、 銅張り積層板 （上記と同じ） 上にラミネ一 卜した。

Next, a photosensitive element was obtained in the same manner as in the above example using this photosensitive resin composition solution. The thickness of the obtained photosensitive resin composition layer (resist layer) was 30 / xm. Using this photosensitive element, it was laminated on a copper-clad laminate (same as above) in the same manner as in the above example.

Next, using the same exposure apparatus as described above, strike one fur 41-step evening bullet placed on the test piece as a negative was exposed with an exposure amount of ^{30mJZcm 2, 60 mJZcm 2, 1} 20m J / cm 2 . Thereafter, unexposed portions were removed in the same manner as described above.

For the obtained resist pattern, the sensitivity of the photosensitive resin composition was evaluated by measuring the number of steps of the step resin bullet of the light-cured film formed on the copper-clad laminate, and the step resin bullet of 41 steps (OD = The exposure amount (mJ / cm ² ) necessary to cure the 21 step of 0.05) was taken as the sensitivity. The lower the number, the higher the sensitivity. The pattern after development was observed, and the resolution (im) was determined from the line width (/ m) remaining as line 'and' space. Furthermore, the pattern of a 30-zm-wide line was observed using SEM, and the pattern shape was evaluated. The resist pattern is preferably rectangular.

The peel time was measured as follows. The sample irradiated with an exposure amount (21 steps / 41) corresponding to each sensitivity was developed with a 1% by weight aqueous solution of sodium carbonate. After standing for 1 day and night, the 3 wt% sodium hydroxide solution was kept at 45 ° C and stirred with a stirrer to measure the time (sec) of immersion and the start of peeling. Note that the stripping time is preferably shorter. Table 12 shows the evaluation results of Examples 21 to 24 and Comparative Example 4. Table 12

The disclosure of the present application is disclosed in Japanese Patent Application No. 11-26, 863, filed on September 17, 1999, and in Japanese Patent Application No. It is related to the subject matter described in 1 1 1 3 1 3 1 0 0 8, the disclosure of which is incorporated by reference.

 It should be noted that various modifications and changes may be made to the above embodiments without departing from the novel and advantageous features of the invention, other than those already described. Accordingly, all such modifications and changes are intended to be included within the scope of the appended claims.

Claims

The scope of the claims  1. A photosensitive resin composition comprising (A) a binder polymer, (B 1) a photopolymerizable compound having at least one polymerizable cyclic ether group in a molecule, and (C 1) a photoacid generator.  2. The photosensitive resin composition according to claim 1, further comprising (B2) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in a molecule.  3. The photosensitive resin composition according to claim 1, further comprising (C2) a radical polymerization initiator.  4. The photosensitive resin composition according to claim 1, wherein the component (B1) is an oxetane compound.  5. The photosensitive resin composition according to claim 1, wherein the component (B1) is an epoxy compound. 6. The oxetane compound has the general formula (1):

(Wherein R ′ and are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, ( (Meth) acryloyl group, phenacyl group, amino group, alkylamino group having 1 to 10 carbon atoms, alkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, 1 to carbon atoms 10 alkylmercapto groups, aryl groups, hydroxyl groups, hydroxyalkyl groups having 1 to 20 carbon atoms, carboxyl groups, carboxyalkyl groups having 1 to 10 carbon atoms in alkyl groups, and 1 to 10 carbon atoms in alkyl groups. An alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 2 to 10 carbon atoms N-Alkylka A group containing a rubamoyl group or a heterocyclic ring, or one or more of these substituents Represents an aryl group substituted with) Or the general formula (2):

(In the formula, represents a divalent organic group, and R ⁴ and R ⁵ are each independently the same as R ¹ in formula (1).) 5. The photosensitive resin composition according to claim 4, comprising a compound represented by the formula:  7. The photosensitive resin composition according to claim 2, wherein the component (B2) contains a bisphenol A-based (meth) acrylate compound.  8. The photosensitive resin composition according to claim 1, wherein the component (C1) contains one or more compounds selected from a oxidonium salt compound, a sulfonium chloride compound, and an ammonium salt compound.  9. The photosensitive resin composition according to claim 3, wherein the component (C2) contains a 2,4,5-triarylimidazonitrile monomer.  10. The photosensitive resin composition according to claim 1, wherein the component (A) contains styrene and / or a styrene derivative as a copolymer component.  1 1. The photosensitive resin composition according to claim 1, wherein the component (A) has an acid value of 30 to 500 mgKOH / g.  1 2. The photosensitive resin composition according to claim 1, wherein the component (A) is developable with an alkaline aqueous solution.  1 3. The photosensitive resin composition according to claim 1, wherein the component (A) has a weight average molecular weight of 20,000 to 300,000.  14. A photosensitive resin composition comprising (A) a binder polymer, (B 1) a photopolymerizable compound having at least one polymerizable cyclic ether group in a molecule, and (C 1) a photoacid generator. A photosensitive element formed by forming a resist layer comprising on a support.  1 5. Manufacturing method of resist pattern including the following steps: i) (A) binder polymer, (B 1) at least one in the molecule A photosensitive element comprising a resist layer comprising a photopolymerizable compound having two polymerizable cyclic ether groups and a photosensitive resin composition containing (C1) a photoacid generator is formed on a support. Stacking on the circuit-forming substrate such that the resist layer is in close contact with the surface of the circuit-forming substrate;  ii) irradiating with an actinic ray or directly drawing and exposing a laser through a mask pattern, and photo-curing the resist layer in the exposed portion;  iii) forming a resist pattern by selectively removing the unexposed portions of the resist layer by development.  1 6. Manufacturing method of printed wiring board including the following steps:  i) a photosensitive resin composition comprising (A) a binder polymer, (B 1) a photopolymerizable compound having at least one polymerizable cyclic ether group in the molecule, and (C 1) a photoacid generator. A photosensitive element having a resist layer formed on a support is provided on a circuit-forming substrate having a layer to be processed on the surface, and the resist layer is provided on the surface of the layer to be processed of the circuit-forming substrate. Laminating in close contact with the substrate;  ii) irradiating with an actinic ray or directly drawing and exposing with a laser through a mask pattern, and photo-curing the resist layer in the exposed portion;  iii) forming a resist pattern by selectively removing the unexposed portions of the resist layer by development.  iv) a step of etching or selectively plating the layer to be processed of the circuit-forming substrate using the resist pattern as a mask;  1 7. Photosensitivity comprising (A) a binder polymer, (B 2) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule, and (C 1) a photoacid generator. Resin composition.  18. The photosensitive resin composition according to claim 17, further comprising (C2) a radical polymerization initiator. 1 9. The component (B2) is bisphenol A-based (meth) acrylic 18. The photosensitive resin composition according to claim 17, further comprising a compound.  20. The photosensitive resin composition according to claim 17, wherein the component (C1) contains at least one compound selected from the group consisting of a rhododium salt compound, a sulfonyl chloride compound and an ammonium salt compound.  21. The photosensitive resin composition according to claim 18, wherein the component (C 2) contains a 2,4,5-triarylimidazole dimer.  22. The photosensitive resin composition according to claim 17, wherein the component (A) contains styrene and Z or a styrene derivative as a copolymer component. 23. The photosensitive resin composition according to claim 17, wherein the acid value of the component (A) is from 30 to 500 mgKOH /.  24. The photosensitive resin composition according to claim 17, wherein the component (A) is developable with an alkaline aqueous solution.  25. The photosensitive resin composition according to claim 17, wherein the component (A) has a weight average molecular weight of from 20,000 to 300,000.  26. A photosensitive composition comprising (A) a binder polymer, (B 2) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in a molecule, and (C 1) a photoacid generator. A photosensitive element in which a resist layer made of a photosensitive resin composition is formed on a support.  27. A method for producing a resist pattern comprising the following steps:  i) a photosensitive resin comprising (A) a binder polymer, (B 2) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in a molecule, and (C 1) a photoacid generator. Laminating a photosensitive element having a resist layer comprising a composition formed on a support on a circuit-forming substrate such that the resist layer is in close contact with the surface of the circuit-forming substrate;  i j) a step of irradiating with an actinic ray or direct laser beam drawing exposure through a mask panel and photo-curing the resist layer in the exposed portion; iii) forming a resist pattern by selectively removing the unexposed portions of the resist layer by development. 28. A method of manufacturing a printed wiring board including the following steps:  i) a photosensitive resin composition comprising (A) a binder polymer, (B 2) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule, and (C 1) a photoacid generator. A photosensitive element having a resist layer made of an object formed on a support is placed on a circuit forming substrate having a layer to be processed on the surface, and the resist layer is placed on the surface of the layer to be processed of the circuit forming substrate. Laminating in close contact;  i i) a step of irradiating with an actinic ray through a mask pattern or directly drawing and exposing a laser, and photo-curing the resist layer in an exposed portion;  iii) forming a resist pattern by selectively removing the unexposed portions of the resist layer by development.  iv) using the resist pattern as a mask, etching the process target layer of the circuit formation substrate or selectively attaching the process target layer on the process target layer.  29. (A) a binder polymer, (B 1) a photopolymerizable compound having at least one polymerizable cyclic ether group in the molecule, (B 2) at least one polymerizable ethylenically unsaturated group in the molecule A photosensitive resin composition comprising a photopolymerizable compound having the formula (I) and (C 2) a radical polymerization initiator. 30. The photosensitive resin composition according to claim 29, wherein the component (B1) is an oxetane compound. 3 1. The oxetane compound has the general formula (1):

(In the formula, R ′ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms. , A (meth) acryloyl group, a phenacyl group, an amino group, an alkylamino group having 1 to 10 carbon atoms, a diamine having 2 to 20 carbon atoms Alkylamino group, nitro group, cyano group, carbonyl group, mercapto group, alkyl mercapto group having 1 to 10 carbon atoms, aryl group, hydroxyl group, hydroxyalkyl group having 1 to 20 carbon atoms, carboxyl group, alkyl group having carbon number of A carboxyalkyl group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, and an alkylcarbonyl having 2 to 10 carbon atoms A alkenyl group having 2 to 10 carbon atoms, a group containing an N-alkylcarbamoyl group or a heterocyclic group having 2 to 10 carbon atoms, or an aryl group substituted with one or more of these substituents) Or the general formula (2):

(Wherein, R ³ represents a divalent organic group, and R ⁴ and R ⁵ each independently have the same meaning as R ¹ in the general formula (1)) 31. The photosensitive resin composition according to claim 30, comprising a compound represented by the following formula:  32. The photosensitive resin composition according to claim 29, wherein the component (B2) contains a bisphenol A-based (meth) acrylate compound. 33. The photosensitive resin composition according to claim 29, wherein the component (C 2) contains a 2,4,5-triarylimidazole dimer. 34. The photosensitive resin composition according to claim 29, wherein the component (A) contains styrene and / or a styrene derivative as a copolymer component. 35. The component (A) having an acid value of 30 to 500 mgKOH / g. 29. The photosensitive resin composition according to 29.  36. The photosensitive resin composition according to claim 29, wherein the component (A) is developable with an alkaline aqueous solution. 37. The photosensitive resin composition according to claim 29, wherein the component (A) has a weight average molecular weight of 20,000 to 300,000. 38. (A) a binder polymer, (B 1) a photopolymerizable compound having at least one polymerizable cyclic ether group in the molecule, (B 2) at least one polymerizable ethylenically unsaturated group in the molecule A photosensitive element in which a resist layer comprising a photopolymerizable compound having the formula (I) and a photosensitive resin composition containing a radical polymerization initiator (C2) is formed on a support.  3 9. Method of manufacturing resist pattern including the following steps:  i) (A) a binder polymer, (B1) a photopolymerizable compound having at least one polymerizable cyclic ether group in the molecule, and (B2) at least one polymerizable ethylenically unsaturated group in the molecule. A photosensitive element formed by forming a resist layer comprising a photosensitive resin composition containing a photopolymerizable compound and a (C 2) radical polymerization initiator on a support is placed on a circuit-forming substrate. Laminating the resist layer so as to be in close contact with the surface of the circuit forming substrate;  ii) irradiating with an actinic ray or directly drawing and exposing with a laser through a mask pattern, and photo-curing the resist layer in the exposed portion;  iii) forming a resist pattern by selectively removing the unexposed portions of the resist layer by development.  40. A method for manufacturing a printed wiring board that includes the following steps:  i) (A) a binder-polymer, (B 1) a photopolymerizable compound having at least one polymerizable cyclic ether group in the molecule, (B 2) at least one polymerizable ethylenically unsaturated group in the molecule A photosensitive element formed by forming a resist layer comprising a photopolymerizable compound having the formula (I) and a photosensitive resin composition containing a radical polymerization initiator (C2) on a support, and a layer to be processed on the surface. Stacking on the circuit forming substrate having the resist layer so as to be in close contact with the surface of the processed layer of the circuit forming substrate; ii) irradiating with an actinic ray or laser-drawing exposure through a mask pattern, and photo-curing the resist layer in the exposed portion; iii) forming a resist pattern by selectively removing the unexposed portions of the resist layer by development.  iv) a step of etching or selectively plating the layer to be processed of the circuit-forming substrate using the resist pattern as a mask;