JP2004252421A - Photosensitive resin composition, photosensitive image forming material using the same and photosensitive image forming material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having excellent safelight property under a yellow lamp and high sensitivity and high resolution in a blue-violet region. <P>SOLUTION: The photosensitive resin composition contains a sensitizer and an active compound which generates at least one of radicals, acids and bases by the interaction with the exposed sensitizer. The sensitizer is a compound expressed by general formula (I), wherein each of R<SP>1</SP>and R<SP>2</SP>independently represents a hydrogen atom or an optional substituent and R<SP>3</SP>represents an optional substituent. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to a photosensitive resin composition capable of forming a resist image by exposure to blue-violet laser light, and development, and a photosensitive image forming material and a photosensitive image forming material using the photosensitive resin composition. In particular, a photosensitive material that is useful for forming fine electronic circuits such as printed wiring boards, wiring boards for plasma displays, wiring boards for liquid crystal displays, large-scale integrated circuits, thin transistors, and semiconductor packages by direct drawing using blue-violet laser light. The present invention relates to a photosensitive resin composition, a photosensitive image forming material using the photosensitive resin composition, and a photosensitive image forming material.

  2. Description of the Related Art Conventionally, for forming fine electronic circuits such as printed wiring boards, wiring boards for plasma displays, wiring boards for liquid crystal displays, large-scale integrated circuits, thin transistors, and semiconductor packages, for example, a photosensitive resist material is formed on a substrate to be processed. Using an image forming material having a layer and, if necessary, a protective layer provided thereon, exposing the photosensitive resist material layer to ultraviolet light through a mask film and exposing the mask film, and then peeling off the mask film for further protection If a protective layer is provided, the protective layer is peeled off, and a pattern layer is formed by developing using a difference in solubility of the exposed part and the non-exposed part in a developing solution. A lithography method of forming a circuit pattern on a substrate to be processed by etching or the like is widely used.

Furthermore, in recent years, a laser direct drawing method for forming an image directly from digital information of a computer or the like without using a mask film by using a laser beam as an exposure light source has been used not only for productivity but also for resolution and positional accuracy. The use of laser light has also been actively studied in the lithography method.
Various light sources from the ultraviolet to the infrared region are known as laser light, but the laser light that can be used for image exposure includes an argon ion laser in terms of output, stability, photosensitivity, cost, and the like. , Helium neon laser, YAG laser, semiconductor laser, etc. that emit light in the visible to infrared region are considered promising. For example, lithography using an argon ion laser with a wavelength of 488 nm and an FD-YAG laser with a wavelength of 532 nm The law has already reached practical use. Under such technical requirements, a photosensitive resin composition capable of forming an image with visible light has been studied, and a photosensitive resin composition containing a resin, a photoacid generator, and a pyrone-based sensitizer. Is known (for example, see Patent Document 1).

However, since the photosensitive resin composition proposed in Patent Document 1 is a photosensitive resin composition suitable for image formation using visible laser light, it is inferior in safelight property under yellow light and red light illumination. There is a restriction that work in a dark room environment is required.
On the other hand, a remarkable advance in laser technology in recent years has made it possible to use a semiconductor laser capable of operating in a bright room environment such as yellow lamp illumination and capable of stably oscillating in a blue-violet region. However, because the output is lower than that of other visible laser light, the sensitivity of the photosensitive resist material is not always sufficient, and it can be used not only in direct writing but also in lithography. At present.

For these reasons, a photosensitive resin composition having high sensitivity and high resolution in a blue-violet region has been demanded.
On the other hand, the chemically amplified photosensitive resin composition conventionally used in the manufacture of semiconductor integrated circuits has the feature of having high resolution, but is a composition sensitive to ultraviolet and far ultraviolet, and has a blue-violet region. Has no absorption, so that image formation with a blue-violet laser is impossible. Further, as a photosensitive resin composition containing a dye having an absorption in the blue-violet region, for example, a photopolymerization composition containing a coumarin-based compound is known, but this has absorption at a wavelength of about 480 nm. It has poor sensitivity to a violet laser having a wavelength of 350 to 450 nm, and is inferior in safelight property under yellow light (see Non-Patent Document 1).
JP-A-2002-258478 Polymer Engineering and Science (1983) Vol.23 No.18 P.1022

  An object of the present invention is to solve the above-mentioned conventional problems and to provide a photosensitive resin composition having excellent safelight properties under yellow light, and having excellent sensitivity and resolution in a blue-violet region.

As a result of intensive studies, the present inventors have found that the above object can be achieved by using an iminosulfone compound as a sensitizer, and have reached the present invention.
The gist of the present invention is to provide a photosensitive resin composition containing a sensitizer and an active compound that generates at least one of a radical, an acid and a base by an interaction between the sensitizer and the exposed sensitizer. And the sensitizer is a compound represented by the following general formula (I).

(Here, R ¹ and R ² each independently represent a hydrogen atom or an arbitrary substituent, and R 3 represents an arbitrary substituent.)
In the present invention, a specific sensitizing dye represented by the above general formula (I) and an active compound which undergoes a chemical change by the light absorption energy of the sensitizing dye to generate at least one of a radical, an acid and a base In combination, the present invention provides a photosensitive resin composition which exhibits high sensitivity even in a specific wavelength region where the active compound cannot function.

The photosensitive image forming material of the present invention is characterized in that a layer of such a photosensitive resin composition is formed on a temporary support film.
The photosensitive image forming material of the present invention is characterized in that such a photosensitive image forming material is laminated on a substrate to be processed on the side of the photosensitive resin composition layer.

  As described in detail above, according to the present invention, there is provided a photosensitive resin composition having excellent safelight properties under yellow light, high sensitivity and high resolution in a blue-violet region. Therefore, the photosensitive resin composition of the present invention can be obtained by direct drawing using a blue-violet laser beam, by using a printed wiring board, a wiring board for a plasma display, a wiring board for a liquid crystal display, a large-scale integrated circuit, a thin transistor, a semiconductor package, and the like. Industrially extremely useful for the formation of fine electronic circuits.

Hereinafter, embodiments of the photosensitive resin composition of the present invention will be described.
First, the sensitizer contained in the photosensitive resin composition of the present invention will be described.
The sensitizer used in the present invention contains the compound represented by the general formula (I), and preferably comprises 32
It absorbs light having a wavelength of 0 to 450 nm and has a molar extinction coefficient (ε) at a wavelength of 405 nm of 100 or more and 100,000 or less, efficiently absorbs light having a wavelength in the blue-violet region, and interacts with an active compound described later. Is a light absorbing dye having a function of generating at least one of a radical, an acid and a base from an active compound. The molar extinction coefficient is preferably at least 1,000, more preferably at least 10,000.
In formula (I), preferred groups as R ¹ and R ² include a hydrogen atom; methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, and n-butyl. A linear or branched alkyl group having 1 to 18 carbon atoms such as a heptyl group; a cycloalkyl group having 3 to 18 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group; a vinyl group, a propenyl group, and a hexenyl group A straight-chain or branched alkenyl group having 2 to 18 carbon atoms, such as cyclopentenyl group, cyclohexenyl group, etc .; a cycloalkenyl group having 3 to 18 carbon atoms; 1-phenylvinyl group, 2-phenylvinyl group, 2-phenyl Propenyl group, 1- (α-naphthyl) vinyl group, 2- (α-naphthyl) vinyl group, 1- (β-naphthyl) vinyl group, 2- (β-na Cyl) an arylalkenyl group having 8 to 18 carbon atoms such as a vinyl group; a saturated group such as a 2-thienyl group, a 2-pyridyl group, a furyl group, a thiazolyl group, a benzothiazolyl group, a morpholino group, a pyrrolidinyl group, and a tetrahydrothiophenedioxide group. Unsaturated heterocyclic group; aryl group having 6 to 18 carbon atoms such as phenyl group, tolyl group, xylyl group and mesityl group; aralkyl group having 7 to 20 carbon atoms such as benzyl group and phenethyl group; acetyl group and propionyl group , A butyryl group, an isobutyryl group, a valeryl group, a linear or branched acyl group having 2 to 18 carbon atoms such as an isovaleryl group; a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a sec- A linear or branched alkoxy group having 1 to 18 carbon atoms such as a butoxy group and a tert-butoxy group; A linear or branched alkenyloxy group having 3 to 18 carbon atoms such as an oxy group, a butenyloxy group, a pentenyloxy group, etc .: methylthio group, ethylthio group, n-propylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group Table with -NR ⁵ R ^6; acyloxy group represented by -OCOR ^4; linear or branched alkylthio group having 1 to 18 carbon atoms group or the like; a cyano group; a hydroxyl group; a formyl group; a sulfonic group; a carboxyl group carboxylic acid ester group represented by -COOR ^10;; sulfonamide group represented by -NHSOOR ^9; carbamate group represented by -NHCOOR ^8; acylamino group represented by -NHCOR ^7; amino group -CONR a carbamoyl group represented by ¹¹ R ^12; -SOONR ¹³ sulfamoyl group represented by R ^14; -SO ₂ OR ₁₅
And the like.

Preferred groups for R ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group,
a linear or branched alkyl group having 1 to 18 carbon atoms such as n-butyl group, sec-butyl group, tert-butyl group, n-heptyl group; carbon such as cyclopropyl group, cyclopentyl group, cyclohexyl group and adamantyl group A cycloalkyl group having 3 to 18 carbon atoms; a linear or branched alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group, and a hexenyl group; a cycloalkenyl having 3 to 18 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group Groups: 1-phenylvinyl group, 2-phenylvinyl group, 2-phenylpropenyl group, 1- (α-naphthyl) vinyl group, 2- (α-naphthyl) vinyl group, 1- (β-naphthyl) vinyl group, An arylalkenyl group having 8 to 18 carbon atoms such as a 2- (β-naphthyl) vinyl group; a 2-thienyl group, a 2-pyridyl group, a furyl group, a thiazolyl group, A saturated or unsaturated heterocyclic group such as a zothiazolyl group, a morpholino group, a pyrrolidinyl group, and a tetrahydrothiophenedoxide group; an aryl group having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, and a mesityl group; An aralkyl group having 7 to 20 carbon atoms such as a phenethyl group; a linear or branched acyl group having 2 to 18 carbon atoms such as an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group; a methoxy group, an ethoxy group A linear or branched alkoxy group having 1 to 18 carbon atoms such as a group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group; propenyloxy group, butenyloxy group, pentenyloxy A linear or branched alkenyloxy group having 3 to 18 carbon atoms such as a group: a methylthio group; C1-C18 linear or branched alkylthio groups such as tylthio group, n-propylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group; cyano group; hydroxy group; formyl group; in -NHSOOR ^21;; carbamate group represented by -NHCOOR ^20; carboxyl group; an acyloxy group represented by -OCOR ^16; acylamino group represented by -NHCOR ^19; amino group represented by -NR ¹⁷ R ¹⁸ Table with -SO ₂ OR ^27; sulfamoyl group represented by -SOONR ²⁵ R ^26; carbamoyl groups represented by -CONR ²³ R ^24; carboxylic acid ester group represented by -COOR ^22; sulfonamide group represented A sulfonate group to be used;
Imino group represented by -N = CR ²⁸ R ²⁹ can be mentioned.

R ^{4 to} R ²⁹ are arbitrary substituents, and are preferably carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group and n-heptyl group. A linear or branched alkyl group of formulas 1 to 18; a cycloalkyl group having 3 to 18 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group and adamantyl group; and 2 carbon atoms such as vinyl group, propenyl group and hexenyl group A linear or branched alkenyl group having from 18 to 18; a cycloalkenyl group having 3 to 18 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group; 2-thienyl group, 2-pyridyl group, furyl group, thiazolyl group, benzothiazolyl group, morpholino Or unsaturated heterocyclic groups such as a group, a pyrrolidinyl group, a tetrahydrothiophene dioxide group; a phenyl group, a tolyl , Xylyl group, and an aryl group having 6 to 18 carbon atoms such as a mesityl group.

Further, the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, and heterocyclic group contained in the groups represented by R ^{1 to} R ²⁹ may be further substituted. Examples of the substituent in this case include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group and other alkoxy groups having 1 to 10 carbon atoms; methoxymethoxy An alkoxyalkoxy group having 2 to 12 carbon atoms such as a group, ethoxymethoxy group, propoxymethoxy group, ethoxyethoxy group, propoxyethoxy group, methoxybutoxy group; methoxymethoxymethoxy group, methoxymethoxyethoxy group, methoxyethoxymethoxy group, methoxymethoxy An alkoxyalkoxyalkoxy group having 3 to 15 carbon atoms such as an ethoxy group and an ethoxyethoxymethoxy group; an allyloxy group; an aryl group having 6 to 12 carbon atoms such as a phenyl group, a tolyl group, and an xylyl group (these are further substituted with a substituent Pheno) An alkenyloxy group having 2 to 12 carbon atoms such as a silyl group, a tolyloxy group, a xylyloxy group, and a naphthyloxy group; an acyl group such as an acetyl group and a propionyl group; a cyano group; a nitro group; a hydroxyl group; a tetrahydrofuryl group; An alkylamino group having 1 to 10 carbon atoms such as an N, N-dimethylamino group and an N, N-diethylamino group; an alkylamino group having 1 to 6 carbon atoms such as a methylsulfonylamino group, an ethylsulfonylamino group and an n-propylsulfonylamino group Alkylsulfonylamino group; halogen atom such as fluorine atom, chlorine atom and bromine atom; alkoxycarbonyl group having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and n-butoxycarbonyl group; methylcarbonyloxy group and ethylcarbonyl An oxy group, an n-propylcarbonyloxy group, An alkylcarbonyloxy group having 2 to 7 carbon atoms such as a propylcarbonyloxy group and an n-butylcarbonyloxy group; a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propoxycarbonyloxy group, an isopropoxycarbonyloxy group, and an n-butoxy group Examples thereof include an alkoxycarbonyloxy group having 2 to 7 carbon atoms such as a carbonyloxy group. When R ^{1 to} R ²¹ are an alkyl group, a cycloalkyl group, or a cycloalkenyl group, a preferred substituent is an alkoxy group or an alkoxyalkoxy group, and R ^{1 to} R ²⁹ are preferably an alkenyl group, an aryl group, or a heterocyclic group. The substituent is an alkoxy group, an alkoxyalkoxy group, an aryl group, an amino group, an alkylamino group, a cyano group or a hydroxy group.

More preferably, at ^{least one} of R ^{1 to} R ³ is a linear or branched alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group or a hexenyl group; a cyclopentenyl group or a cyclohexenyl group A cycloalkenyl group having 3 to 18 carbon atoms, such as 1-phenylvinyl group, 2-phenylvinyl group, 2-phenylpropenyl group, 1- (α-naphthyl) vinyl group, 2- (α-naphthyl) vinyl group, An arylalkenyl group having 8 to 18 carbon atoms such as a 1- (β-naphthyl) vinyl group or a 2- (β-naphthyl) vinyl group; a 2-thienyl group, a 2-pyridyl group, a furyl group, a thiazolyl group, a benzothiazolyl group, and the like An aryl group having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xylyl group and a mesityl group; an acetyl group, a propionyl group, a butyryl group and an isobutyryl This is the case of a linear or branched acyl group having 2 to 18 carbon atoms such as a group, a valeryl group, an isovaleryl group and the like. In particular, an unsaturated heterocyclic group which may be independently substituted with at least one of R ^{1 to} R ³ or an aryl group which may be substituted is preferred. Most preferably, R ¹ is a hydrogen atom, and R ² and R ³ are each independently an optionally substituted unsaturated heterocyclic group and / or an optionally substituted aryl group.

The molecular weight of the compound represented by the general formula [I] is preferably 2,000 or less, more preferably 1,000 or less, and usually 200 or more.
Specific examples of the compound represented by the general formula [I] include the following, but are not limited thereto.

  In the present invention, as the sensitizer, one kind of the compound represented by the general formula (I) may be used alone, or two or more kinds may be used in combination. As the sensitizer, a known sensitizer other than the compound represented by the general formula (I) may be used in combination, and a sensitizer other than the compound represented by the general formula (I) may be used. When used in combination, the content of the compound represented by formula (I) in the sensitizer is preferably 1% by weight or more, particularly preferably 10% by weight or more, in order to surely obtain the effects of the present invention. .

The photosensitive resin composition of the present invention comprises such a sensitizer and, when exposed to light, interacts with the sensitizer to produce at least one of a radical, an acid and a base. And the photosensitive composition itself may be any of a chemically amplified type and a photopolymerized type, or a negative type and a positive type.
As the chemically amplified negative photosensitive resin composition, the sensitizer, an acid generator as an active compound, a film-forming resin that is alkali-soluble and a crosslinking agent that acts on an alkali-soluble resin under acidic conditions. Containing.

Examples of the chemically amplified positive photosensitive resin composition include those containing the sensitizer, an acid generator as an active compound, and an acid-decomposable group-containing polymer as a film-forming resin.
Examples of the photopolymerizable photosensitive resin composition include those containing the sensitizer, a photopolymerization initiator as an active compound, and an ethylenically unsaturated compound.
Hereinafter, components and compositions other than the sensitizer of the photosensitive resin composition of the present invention will be described. [Acid generator as active compound of chemically amplified negative and positive photosensitive resin compositions]
The acid generator of the chemically amplified photosensitive resin composition is a compound that generates an acid when actinic rays are received, and is not particularly limited as long as it is a known acid generator as a resist composition. It does not generate acid at the wavelength. Examples include halogen-containing compounds such as halogen-substituted alkanes, halomethylated s-triazine derivatives, onium salts, and sulfone compounds.In particular, in the present invention, sulfonic acid is converted to sulfonic acid by light irradiation. Generated sulfone compounds are particularly preferred.

Among the acid generators, specific examples of the halogen-substituted alkane among the halogen-containing compounds include dichloromethane, trichloromethane, 1,2-dichloroethane, and 1,2-dibromoethane.
Further, as the halomethylated s-triazine derivative, specifically, 2,4,6-tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,2 4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s- Triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- ( p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine , 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl ) -S-Triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine , 2- (p-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- Phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris Dibromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4, 6-bis (tribromomethyl) -s-triazine and the like, among which bis (trihalomethyl) -s-triazine is preferable, and 2-methyl-4,6-bis (trichloromethyl) -s-triazine, -Phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine and the like are particularly preferred.

Further, among the acid generators, onium salts include ammonium salts such as tetramethylammonium bromide and tetraethylammonium bromide, diphenyliodonium hexafluoroarsenate, diphenyliodonium tetrafluoroborate, diphenyliodonium p-toluenesulfonate, and diphenyliodonium camphorsulfonate. Iodonium salts such as dicyclohexyliodonium hexafluoroarsenate, dicyclohexyliodonium tetrafluoroborate, dicyclohexyliodonium p-toluenesulfonate, dicyclohexyliodonium camphorsulfonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium tetrafluoroborate, triphenylene Sulfonium p- toluenesulfonate, triphenylsulfonium camphorsulfonate, tri-cyclohexyl hexafluoroarsenate, tri-cyclohexyl sulfonium tetrafluoroborate, tri-cyclohexyl sulfonium p- toluenesulfonate, sulfonium salts such as tri-cyclohexyl sulfonium camphorsulfonate, and the like.

  Further, among the acid generators, specific examples of the sulfone compounds include bis (phenylsulfonyl) methane, bis (p-hydroxyphenylsulfonyl) methane, bis (p-methoxyphenylsulfonyl) methane, and bis (α- Bis (sulfonyl) methane compounds such as naphthylsulfonyl) methane, bis (β-naphthylsulfonyl) methane, bis (cyclohexylsulfonyl) methane, bis (t-butylsulfonyl) methane, phenylsulfonyl (cyclohexylsulfonyl) methane, and phenylcarbonyl (phenyl) Sulfonyl) methane, naphthylcarbonyl (phenylsulfonyl) methane, phenylcarbonyl (naphthylsulfonyl) methane, cyclohexylcarbonyl (phenylsulfonyl) methane, t-butylcarbonyl (phenylsulfonyl) Carbonyl (sulfonyl) methane compounds such as methane, phenylcarbonyl (cyclohexylsulfonyl) methane, phenylcarbonyl (t-butylcarbonyl) methane, bis (phenylsulfonyl) diazomethane, bis (p-hydroxyphenylsulfonyl) diazomethane, bis (p-methoxy) Phenylsulfonyl) diazomethane, bis (α-naphthylsulfonyl) diazomethane, bis (β-naphthylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, phenylsulfonyl (cyclohexylsulfonyl) diazomethane, bis (sulfonyl) ) Diazomethane compound, phenylcarbonyl (phenylsulfonyl) diazomethane, naphthylcarbonyl (phenylsulfonyl) di Carbonyl (sulfonyl) such as azomethane, phenylcarbonyl (naphthylsulfonyl) diazomethane, cyclohexylcarbonyl (phenylsulfonyl) diazomethane, t-butylcarbonyl (phenylsulfonyl) diazomethane, phenylcarbonyl (cyclohexylsulfonyl) diazomethane, and phenylcarbonyl (t-butylcarbonyl) diazomethane ) Diazomethane compounds, particularly those represented by the following general formulas (A) and (B).

In the above general formulas (A) and (B), examples of the substituent represented by Ra, Rd and Re are as follows. A hydrogen atom; a linear or branched alkyl group having 1 to 18 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and an n-heptyl group; C3-18 cycloalkyl groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group and adamantyl group; C2-18 linear or branched alkenyl groups such as vinyl group, propenyl group and hexenyl group; cyclopentenyl A cycloalkenyl group having 3 to 18 carbon atoms, such as a cyclohexenyl group or a cyclohexenyl group; 2-thienyl group, 2
-A saturated or unsaturated heterocyclic group such as a pyridyl group, a furyl group, a thiazolyl group, a benzothiazolyl group, a morpholino group, a pyrrolidinyl group, a tetrahydrothiophenedoxide group; a carbon number of a phenyl group, a tolyl group, a xylyl group, a mesityl group; An aryl group having 6 to 18; an aralkyl group having 7 to 20 carbon atoms such as a benzyl group or a phenethyl group; a linear chain having 2 to 18 carbon atoms such as an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group; Or a branched acyl group; a linear or branched alkoxy group having 1 to 18 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group and a tert-butoxy group. A straight chain having 3 to 18 carbon atoms such as a propenyloxy group, a butenyloxy group, and a pentenyloxy group; A branched alkenyloxy group; a linear or branched alkylthio group having 1 to 18 carbon atoms such as a methylthio group, an ethylthio group, an n-propylthio group, an n-butylthio group, a sec-butylthio group, a tert-butylthio group; A halogen atom such as a chlorine atom or a bromine atom; a nitro group; a cyano group; a hydroxyl group; a formyl group; a sulfonic acid group; a carboxyl group; an acyloxy group represented by -OCOR '; An acylamino group represented by -NHCOR '; a carbamate group represented by -NHCOOR'; a sulfonamide group represented by -NHSOOR '; a carboxylic acid ester group represented by -COOR';'carbamoyl group represented by; -SOONR'R' sulfamoyl group represented by '; sulfonic acid ester represented by -SO ₂ OR' Group and the like (R ', R''is an alkyl group.).

Rd and Re may form a ring, and the ring may be further condensed with another ring. Examples of the other ring include a saturated or unsaturated hydrocarbon ring or heterocyclic ring.
In the general formula (A), Rb is an optional substituent, and is a hydrogen atom, an optionally substituted straight-chain, branched or cyclic alkyl group, an optionally substituted straight-chain, branched or cyclic alkenyl group, Aryl group which may be substituted, aralkyl group which may be substituted, carboxyl group, cyano group, nitro group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, acyloxy group and the like, preferably a cyano group, Examples include an alkyloxycarbonyl group, a nitro group, and an acyl group. These groups may further have a substituent. Particularly preferred are a cyano group and an alkyloxycarbonyl group.

  Rc and Rf in the general formulas (A) and (B) are optional substituents, and each may be a substituted linear, branched or cyclic alkyl group, an optionally substituted linear, branched or cyclic alkyl group. Represents an alkenyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, or an optionally substituted camphor group. Further, hydrogen atoms in these substituents may be replaced by fluorine atoms. Further, the alkyl group, alkenyl group, aryl group, and heterocyclic group contained in the groups represented by Rc and Rf may be further substituted.

When the ring formed by Rb, Rc, Rf, and Rd and Re has a substituent, examples of the substituent include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a sec-butoxy group. A C1-C10 alkoxy group such as a tert-butoxy group; a C2-C12 alkoxyalkoxy such as a methoxymethoxy group, an ethoxymethoxy group, a propoxymethoxy group, an ethoxyethoxy group, a propoxyethoxy group, a methoxybutoxy group; A methoxymethoxymethoxy group, a methoxymethoxyethoxy group, a methoxyethoxymethoxy group, a methoxymethoxyethoxy group, an ethoxyethoxymethoxy group and the like; an alkoxyalkoxyalkoxy group having 3 to 15 carbon atoms; an allyloxy group; a phenyl group, a tolyl group, and a xylyl group Aryl groups having 6 to 12 carbon atoms such as These may be further substituted with a substituent); an alkenyloxy group having 2 to 12 carbon atoms such as a phenoxy group, a tolyloxy group, a xylyloxy group, and a naphthyloxy group; an acyl group such as an acetyl group and a propionyl group; Nitro group; hydroxyl group; tetrahydrofuryl group; amino group; alkylamino group having 1 to 10 carbon atoms such as N, N-dimethylamino group, N, N-diethylamino group; methylsulfonylamino group, ethylsulfonylamino group , An n-propylsulfonylamino group or other alkylsulfonylamino group having 1 to 6 carbon atoms; a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; a carbon number such as a methoxycarbonyl group, an ethoxycarbonyl group, or an n-butoxycarbonyl group. 2-7 alkoxycarbonyl groups; methylcarbonyloxy group, ethylcarbo C2-C7 alkylcarbonyloxy groups such as nyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group; methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group And an alkoxycarbonyloxy group having 2 to 7 carbon atoms such as an isopropoxycarbonyloxy group and an n-butoxycarbonyloxy group. Further, hydrogen atoms in these substituents may be replaced by fluorine atoms.

  Among the sulfone compounds represented by the general formula (B), specific examples of the case where Rd and Re form a ring include the following, but are not limited thereto. .

The acid generator that does not generate an acid at the wavelength of the exposure light source is, for example, when the light source is a blue-violet laser, a wavelength of 405 nm is added to 5 ml of a 2.0 mmol / dm ³ acetonitrile solution of the acid generator.
No acid is generated when 250 mJ of laser is irradiated. Here, for detection of acid, CVL (crystal violet lactone) {3,3-bis [4- (dimethylamino) phenyl] -6- (dimethylamino) -1 (3H) isobenzofuranone} was used as an indicator. After the laser irradiation, an equal amount of a 2.0 mL / dm ³ acetonitrile solution of CVL is added, and if the absorption at a wavelength of 610 nm is 0.01 or less, it is determined that no acid is generated.
[Alkali-Soluble Resin and Crosslinking Agent in Chemically Amplified Negative-Type Photosensitive Resin Composition] As the alkali-soluble resin in the chemically amplified negative-type photosensitive resin composition, an unexposed portion becomes alkali-soluble during development, and is used in an alkali developer. Although it is not particularly limited as long as it elutes, usually, novolak resin, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, and acrylic acid, vinyl alcohol or vinyl phenol as a monomer unit Polymers or derivatives thereof are used. Among these, those containing a polymerized unit having a phenolic hydroxyl group are particularly preferable, and novolak resins and polyvinyl phenols are preferable.

  Novolak resins include m-cresol, o-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, resorcinol, pyrogallol, bisphenol, bisphenol-A, trisphenol, o-ethylphenol, m-ethyl At least one kind of aromatic hydrocarbons such as phenol, p-ethylphenol, propylphenol, n-butylphenol, t-butylphenol, 1-naphthol and 2-naphthol are subjected to formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde under an acidic catalyst. And aldehydes such as furfural and those obtained by polycondensation with at least one aldehyde or ketone selected from ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone.Note that paraformaldehyde and paraaldehyde may be used instead of formaldehyde and acetaldehyde, respectively.

The novolak resin has a polystyrene-equivalent weight average molecular weight (hereinafter, referred to as "weight average molecular weight Mw by GPC measurement") of 1,000 to 15 as measured by gel permeation chromatography (hereinafter, abbreviated as "GPC"). , Preferably 1,500 to 10,000.
The novolak resin is more preferably at least one phenol selected from o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, and resorcinol in formaldehyde, acetaldehyde, and propion. Novolak resins polycondensed with at least one selected from aldehydes such as aldehydes are exemplified. Above all, the mixing ratio of m-cresol: p-cresol: 2,5-xylenol: 3,5-xylenol: resorcinol is 70 to 100: 0 to 30: 0 to 20: 0 to 20: 0 to 20 in a molar ratio. Novolak resins, which are polycondensates of phenols and aldehydes, are preferred. Here, among the aldehydes, formaldehyde is particularly preferred.

  Examples of polyvinylphenols include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2- (o-hydroxyphenyl) propylene, 2- (m-hydroxyphenyl) propylene, and 2- (p-hydroxyphenyl) propylene Or a polymer of two or more hydroxystyrenes. Hydroxystyrenes may be substituted on the aromatic ring with a halogen such as chlorine, bromine, iodine or fluorine or a substituent such as an alkyl group having 1 to 4 carbon atoms. Examples thereof include polyvinyl phenol which may have a substituent of an alkyl group having 1 to 4 carbon atoms.

  Polyvinyl phenols are usually obtained by polymerizing hydroxystyrenes which may have a substituent alone or in combination of two or more in the presence of a radical polymerization initiator or a cationic polymerization initiator. Such polyvinylphenols may be partially hydrogenated to reduce the absorbance of the resin. Further, a resin in which some OH groups of polyvinylphenols are protected by a t-butoxycarbonyl group, a pyranyl group, a furanyl group, or the like may be used.

As the polyvinylphenols, those having a weight average molecular weight Mw of 1,000 to 100,000, preferably 1,500 to 50,000 as measured by GPC are used.
More preferably, polyvinyl phenols include polyvinyl phenols in which the aromatic ring may be substituted by an alkyl group having 1 to 4 carbon atoms, and unsubstituted polyvinyl phenol is particularly preferable.

When the molecular weight of such an alkali-soluble resin is smaller than the above range, a sufficient coating film as a resist cannot be obtained, and when the molecular weight is larger than the above range, the solubility of an unexposed portion in an alkali developing solution decreases, and the resist pattern Tend not to be obtained. Among the above alkali-soluble resins, unsubstituted polyvinylphenol and novolak resins are particularly preferable.
The crosslinking agent is not particularly limited as long as it is a compound that undergoes a crosslinking reaction with an alkali-soluble resin under acidic conditions.Examples of the crosslinking agent include melamine, benzoguanamine, a compound obtained by reacting formalin with glycoluril or urea, or an alkyl-modified compound thereof. , Epoxy compounds, resole compounds and the like.

  Specifically, Cymel (registered trademark) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327, 703, 701, 266, 267, 285, 232, 235, 238 of Mitsui Cyanamid Co., Ltd. 1141, 272, 254, 202, 1156, 1158, Niwalac (registered trademark) E-2151, MW-100LM, MX-750LM of Sanwa Chemical Co., Ltd., and a compound obtained by reacting melamine with formalin or an alkyl-modified product thereof As

  In addition, Cymel (registered trademark) 1123, 1125, and 1128 can be mentioned as examples of a compound obtained by allowing benzoguanamine to act on formalin or an alkyl-modified product thereof. Cymel (registered trademark) 1170, 1171, 1174, 1172, and Nicalac (registered trademark) MX-270 can be mentioned as examples of a compound obtained by reacting glycoluril with formalin or an alkyl-modified product thereof. Examples of the compound obtained by reacting urea with formalin or an alkyl-modified product thereof include UFR (registered trademark) 65, 300 and Nikalac (registered trademark) MX-290 manufactured by Mitsui Syamide.

  Examples of epoxy compounds include novolak epoxy resins (YDP N-638, 701, 702, 703, 704, etc., manufactured by Toto Kasei), amine epoxy resins (YH-434, manufactured by Toto Kasei), bisphenol A epoxy resin (Epcoat 825, 826, 827, 828, 1001, 1002, 1003, 1055, 1004, 1007, 1009, 1010, etc., manufactured by Japan Epoxy Resin), sorbitol (poly) glycidyl ether, (poly) glycerol (poly) glycidyl ether , Pentaerythritol (poly) glycidyl ether, triglycidyl trishydroxyethyl isocyanurate, allyl glycidyl ether, ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol glycidyl ether, Uryl alcohol glycidyl ether, adipic acid glycidyl ether, phthalic acid glycidyl ether, dibromophenyl glycidyl ether, dibromoneopentyl glycol diglycidyl ether, glycidyl phthalimide, (poly) ethylene glycol glycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl Examples thereof include ether, glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, and butyl glycidyl ether.

Among these, particularly preferred compounds include compounds having a —N (CH ₂ OR) ₂ group (wherein R represents an alkyl group or a hydrogen atom) in the molecule. The compound which has been acted or an alkyl-modified product thereof is preferred.
[Composition of chemically amplified negative photosensitive resin composition]
In the chemically amplified negative photosensitive resin composition, the crosslinking agent is usually 1 to 80 parts by weight, preferably 5 to 60 parts by weight, and the acid generator is usually 0.001 to 100 parts by weight based on 100 parts by weight of the alkali-soluble resin. 30 parts by weight, preferably 0.005 to 10 parts by weight, and the sensitizer 0.01 to 30 parts by weight, preferably 0.1 to 20 parts by weight. The ratio of the crosslinking agent to the acid generator is usually 0.05 to 30,000 parts by weight, preferably 0.5 to 10,000 parts by weight, and the ratio of the sensitizer to the acid generator is usually 0.001 to 30,000 parts by weight, preferably 0 to 0,000 parts by weight. 0.01 to 4000 parts by weight.

If the amount of the crosslinking agent is less than the above range, a sufficient crosslinking effect cannot be obtained, and the resist pattern tends to be defective. On the other hand, when the amount of the cross-linking agent is larger than this range, the coating properties of the resist tend to decrease. If the amount of the sensitizer is less than this range, the sensitivity tends to be low. When the amount of the sensitizer is larger than the above range, the transparency of the resist film is reduced by the sensitizer, so that the resist pattern tends to have an inverted trapezoidal shape, causing a reduction in resolution.
[Acid-decomposable group-containing polymer in chemically amplified positive photosensitive resin composition]
The acid-decomposable group-containing polymer constituting the chemically amplified positive photosensitive resin composition is formed by an acid generated as an acid compound as an active compound when the photosensitive resin composition is irradiated with actinic rays. The polymer is not particularly limited as long as it is a polymer containing an acid-decomposable group that decomposes and imparts alkali solubility to the polymer itself.

  Specific examples of the acid-decomposable group include an alkoxy group having 1 to 15 carbon atoms such as a methoxy group, an ethoxy group, an i-propoxy group and a t-butoxy group, a methoxymethoxy group, a dimethoxymethoxy group, and an ethoxymethoxy group. An alkoxyalkoxy group having 2 to 15 carbon atoms such as 1-methoxyethoxy group, 1-ethoxyethoxy group, 1-propoxyethoxy group, 1-t-butoxyethoxy group, 1-cyclohexyloxyethoxy group, 1-ethoxypropoxy group, etc. 2 to 15 alkoxycarbonyloxy groups such as methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyloxy group, t-butoxycarbonyloxy group, and ethoxy. Carbonyloxymethoxy group, n-propyl An alkoxy group having at least a terminal such as an alkoxycarbonyloxyalkoxy group having 2 to 15 carbon atoms such as a oxycarbonyloxymethoxy group, an i-propoxycarbonyloxymethoxy group, an n-butoxycarbonyloxymethoxy group, and a t-butoxycarbonyloxymethoxy group. Groups.

  As the polymer containing an acid-decomposable group, for example, a phenolic resin such as a novolak resin and a resol resin, and at least a part of a phenolic hydroxyl group of a phenolic hydroxyl group-containing resin such as a polyvinyl phenol resin are etherified or A resin to which the acid-decomposable group is introduced by esterification is preferable. Among them, in the present invention, a resin in which the acid-decomposable group is introduced into a polyvinylphenol resin or a novolak resin is preferable, and a resin in which the acid-decomposable group is introduced into a polyvinylphenol resin is particularly preferable.

  Here, the novolak resin is, for example, phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, o-ethylphenol, m-ethylphenol, p-cresol, as described above. -Ethylphenol, propylphenol, n-butylphenol, t-butylphenol, 1-naphthol, 2-naphthol, pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol, phloroglucinol, 4,4'- At least one phenol such as biphenyldiol and 2,2-bis (4′-hydroxyphenyl) propane is converted into an aldehyde such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and furfural under an acid catalyst. , Paraformaldehyde may be used in place of formaldehyde, and paraaldehyde may be used in place of acetaldehyde.) Or ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. The resole resin is a resin that has been polycondensed in the same manner except that an alkali catalyst is used instead of the acid catalyst in the polycondensation of the novolak resin.

These novolak resins and resol resins preferably have a weight average molecular weight Mw of 1,000 to 15,000, and particularly preferably 1,500 to 10,000, as measured by GPC.
Examples of the polyvinyl phenol resin include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene, trihydroxystyrene, tetrahydroxystyrene, pentahydroxystyrene, 2- (o-hydroxyphenyl) propylene, Hydroxystyrenes such as-(m-hydroxyphenyl) propylene and 2- (p-hydroxyphenyl) propylene (these include halogen atoms such as chlorine, bromine, iodine and fluorine on the benzene ring, or carbon atoms having 1 to 4 carbon atoms). ) May be used as a substituent.) Or a combination thereof in the presence of a radical polymerization initiator or a cationic polymerization initiator. These polyvinyl phenol resins preferably have a weight average molecular weight Mw of 1,000 to 100,000 as measured by GPC, and particularly preferably 1,500 to 50,000.

Further, as the polymer containing an acid-decomposable group, for example, a resin in which at least a part of a carboxyl group of a carboxyl group-containing vinyl resin is esterified to introduce the acid-decomposable group can also be mentioned as a preferable resin. . Examples of the carboxyl group-containing vinyl resin include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, and citraconic acid, and styrene and α-methylstyrene. , Hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- (meth) acrylate ) Vinyl compounds such as acryloylmorpholine, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide and vinyl acetate These carboxyl group-containing vinyl resins preferably have a weight average molecular weight Mw of 1,000 to 300,000 as measured by GPC (in the present specification, "( “Meth) acryl” means “acryl and / or methacryl. The same applies to“ (meth) acrylo ”and“ (meth) acrylate ”.)
[Composition of chemically amplified positive photosensitive resin composition]
In the above-mentioned chemically amplified positive photosensitive resin composition, the acid generator as an active compound is usually 0.001 to 30 parts by weight, preferably 0.1 to 100 parts by weight, based on 100 parts by weight of the acid-decomposable group-containing polymer. 005 to 10 parts by weight and a sensitizer of 0.01 to 30 parts by weight, preferably 0.1 to 20 parts by weight. The ratio of the sensitizer to the acid generator is usually 0.001 to 30,000 parts by weight, preferably 0.01 to 4000 parts by weight.

If the amount of the sensitizer is less than this range, the sensitivity tends to be low.If the amount of the sensitizer is more than this range, the resist pattern is reduced due to a decrease in the transparency of the resist film due to the sensitizer. It tends to be an inverted trapezoid, causing a reduction in resolution.
[Photopolymerization initiator as active compound in photopolymerizable photosensitive resin composition]
The photopolymerization initiator as an active compound constituting the photopolymerization-type photosensitive resin composition, when irradiated with light in the presence of the sensitizer or the like, receives the photoexcitation energy of the sensitizer and generates an active radical. It is a radical generator that is generated and leads to the polymerization of an ethylenically unsaturated compound described below, for example, a hexaarylbiimidazole compound, a titanocene compound, a halogenated hydrocarbon derivative, a diaryliodonium salt, and an organic peroxide. Objects and the like. Among them, hexaarylbiimidazole-based compounds and titanocene-based compounds are preferable, and hexaarylbiimidazole-based compounds are particularly preferable, in view of sensitivity as a photosensitive resin composition, adhesion to a substrate, and storage stability.

Specific examples of the hexaarylbiimidazole compound include 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (o -Chlorophenyl) -4,4 ', 5,5'-tetra (p-methylphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p- Methoxyphenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-ethoxycarbonylphenyl) biimidazole, 2,2 ′
-Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-chlorophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (O, p-dichlorophenyl) biimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazole, 2,2′- Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-fluorophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (O, p-dibromophenyl) biimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazole, 2,2′- Bis (o-bromophenyl) -4,4 ', 5,5' Tetra (p-iodophenyl) biimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (o-chloro-p-methoxyphenyl) biimidazole, 2,2 '-Bis (o-chlorophenyl) -4,4', 5,5'-tetra (p-chloronaphthyl) biimidazole and the like. Among them, a hexaphenylbiimidazole compound is preferable, and a compound in which the o-position of a benzene ring bonded to the 2,2′-position on the imidazole ring is substituted with a halogen atom is more preferable. Those in which the benzene ring bonded to the ', 5,5'-position is unsubstituted or substituted with a halogen atom or an alkoxycarbonyl group are particularly preferred. These hexaarylbiimidazole compounds are synthesized by the method disclosed in, for example, Bull.Chem.Soc.Japan; 33,565 (1960), J. Org.Chem .; 36,2262 (1971). May be used in combination with a biimidazole compound.

Specific examples of the titanocene-based compound include dicyclopentadienyltitanium dichloride, dicyclopentadienyltitanium bisphenyl, dicyclopentadienyltitanium bis (2,4-difluorophenyl), and dicyclopentane. Dienyl titanium bis (2,6-difluorophenyl), dicyclopentadienyl titanium bis (2,4,6-trifluorophenyl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluoro Phenyl), dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluorophenyl), di (methylcyclopentadienyl) titanium bis (2,6-difluorophenyl), di (methylcyclopenta Dienyl) titanium bis (2,3,4,5,6-pen Fluorophenyl) dicyclopentadienyl titanium bis [2,6-difluoro-3- (1-pyrrolyl) phenyl], and the like. Among them, a titanocene compound having a dicyclopentadienyl structure and a biphenyl structure is preferable, and a compound in which the o-position of the biphenyl ring is substituted with a halogen atom is particularly preferable.
[Ethylenically unsaturated compound in photopolymerizable photosensitive resin composition]
The ethylenically unsaturated compound constituting the photopolymerizable photosensitive resin composition is added by the action of the photopolymerization initiation system including the above photopolymerization initiator when the photosensitive resin composition is irradiated with actinic rays. It is a compound having at least one radically polymerizable ethylenically unsaturated bond in a molecule which is polymerized and optionally crosslinked and cured.

  As such an ethylenically unsaturated compound, a compound having one ethylenically unsaturated bond in the molecule, specifically, (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid And the like, and its alkyl esters, (meth) acrylonitrile, (meth) acrylamide, and styrene. From the viewpoint that the difference can be enlarged, a compound having two or more ethylenic unsaturated bonds in the molecule is preferable, and an acrylate compound in which the unsaturated bond is derived from a (meth) acryloyloxy group is particularly preferable. .

Typical examples of the compound having two or more ethylenically unsaturated bonds in the molecule include esters of an unsaturated carboxylic acid and a polyhydroxy compound, (meth) acryloyloxy group-containing phosphates, and hydroxy (meth) acrylate Examples thereof include urethane (meth) acrylates of a compound and a polyisocyanate compound, and epoxy (meth) acrylates of a (meth) acrylic acid or hydroxy (meth) acrylate compound and a polyepoxy compound.

  As the esters, specifically, the unsaturated carboxylic acids as described above, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, tripropylene glycol, trimethylene glycol, tetramethylene glycol, neopentyl Glycol, hexamethylene glycol, nonamethylene glycol, trimethylolethane, tetramethylolethane, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, sorbitol, and their ethylene oxide adducts, propylene oxide adducts, diethanolamine, triethanol Reaction products with aliphatic polyhydroxy compounds such as amines, specifically, ethylene glycol di (meth) Rate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetramethylene glycol di (meth) ) Acrylate, neopentyl glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, nonamethylene glycol di (meth) acrylate, trimethylolethanetri (meth) acrylate, tetramethylolethanetri (meth) acrylate, trimethylol Propane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide-added tri ( (T) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide added tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri ( Meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol Examples thereof include hexa (meth) acrylate and the like, and similar crotonates, isocrotonates, maleates, itaconates, citraconates, and the like.

  Further, as an ester thereof, a reaction product of the above unsaturated carboxylic acid with an aromatic polyhydroxy compound such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, specifically, hydroquinone di (meth) acrylate , Resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate and the like; a reaction product of the unsaturated carboxylic acid as described above with a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, specifically Di (meth) acrylate and tri (meth) acrylate of tris (2-hydroxyethyl) isocyanurate; a reaction product of an unsaturated carboxylic acid, a polyvalent carboxylic acid, and a polyhydroxy compound, specifically, (meth) Condensates of acrylic acid, phthalic acid and ethylene glycol, Condensates of (meth) acrylic acid, maleic acid and diethylene glycol, condensates of (meth) acrylic acid, terephthalic acid and pentaerythritol, condensates of (meth) acrylic acid, adipic acid, butanediol and glycerin, etc. Can be

  The (meth) acryloyloxy group-containing phosphates are not particularly limited as long as they are (meth) acryloyloxy group-containing phosphate compounds. Among them, they are represented by the following general formula (Ia) or (Ib) Are preferred.

(In the general formulas (Ia) and (Ib), R ²¹ represents a hydrogen atom or a methyl group, n is an integer of 1 to 25, and m is 1, 2, or 3.)
Here, n is preferably 1 to 10, particularly preferably 1 to 4. Specific examples of such (meth) acryloyloxy group-containing phosphates include, for example, (meth) acryloyloxyethyl phosphate, bis [( (Meth) acryloyloxyethyl] phosphate, (meth) acryloyloxyethylene glycol phosphate, and the like, each of which may be used alone or as a mixture.

  Specific examples of the urethane (meth) acrylates include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and tetramethylolethane triacrylate. Hydroxy (meth) acrylate compounds such as (meth) acrylate and hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine methyl ester diisocyanate, lysine methyl ester triisocyanate, dimer acid diisocyanate, 1,6,11- Aliphatic polyisomers such as undecatriisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane Alicyclic polyisocyanates such as anate, cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptane triisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,2 6-tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tolidine diisocyanate, 1,5-naphthalene diisocyanate, tris (isocyanate phenyl methane), tris (isocyanate phenyl) thiophosphate, etc. Heterocyclic polyisocyanes such as aromatic polyisocyanates and isocyanurates DOO, reaction products of the polyisocyanate compounds and the like.

Above all, as the urethane (meth) acrylates, a compound having four or more urethane bonds [—NH—CO—O—] and four or more (meth) acryloyloxy groups in one molecule is preferable. For example, a compound having four or more hydroxyl groups in one molecule such as pentaerythritol and polyglycerin is reacted with a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, and tolylene diisocyanate. Compound (i-1); or compounds having two or more hydroxyl groups in one molecule such as ethylene glycol and the like, "Duranate 24A-100", "Duranate 22A-75PX" and "Duranate 21S" manufactured by Asahi Kasei Corporation. -75E "and" Durane 18H-70B, etc .; and adduct types such as "Duranate P-301-75E", "Duranate E-402-90T", and "Duranate E-405-80T". A compound (i-2) obtained by reacting a compound having two or more isocyanate groups; or a compound (i-3) obtained by polymerizing or copolymerizing isocyanate ethyl (meth) acrylate or the like. Compound (i) having four or more, preferably six or more isocyanate groups in one molecule, such as "Duranate ME20-100" manufactured by Asahi Kasei Corporation, pentaerythritol di (meth) acrylate, pentane Erythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol One or more hydroxyl groups and two or more, preferably three or more, (meth) acryloyls in one molecule such as rutri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate It can be obtained by reacting with a compound (ii) having an oxy group.

  Here, the molecular weight of the compound (i) is preferably from 500 to 200,000, and particularly preferably from 1,000 to 150,000. The urethane (meth) acrylates preferably have a molecular weight of 600 to 150,000. Further, as the urethane (meth) acrylates, those having 6 or more urethane bonds are preferable, those having 8 or more urethane bonds are particularly preferable, those having 6 or more (meth) acryloyloxy groups are preferable, and 8 or more are preferable. Is particularly preferred.

  In addition, such urethane (meth) acrylates are obtained, for example, by reacting the compound (i) and the compound (ii) with an organic solvent such as toluene or ethyl acetate by forming the former isocyanate group and the latter hydroxyl group. The reaction can be carried out at a molar ratio of 1/10 to 10/1 and a reaction at 10 to 150 ° C. for about 5 minutes to 3 hours using a catalyst such as n-butyltin dilaurate, if necessary. it can.

  As such urethane (meth) acrylates, those represented by the following general formula (II) are particularly preferred.

(In the general formula (II), R ²² has a repeating structure of the alkylene group or arylene group, and showed a 4-20 a group having oxy group capable of binding with R ^23, R ²³ and R ²⁴ Each independently represents an alkylene group having 1 to 10 carbon atoms, R ²⁵ represents an organic residue having 1 to 10 (meth) acryloyloxy groups, and R ²² , R ²³ , R ²⁴ and R ²⁵ represent (It may have a substituent, x is an integer of 4 to 20, y is an integer of 0 to 15, and z is an integer of 1 to 15.)
Here, as the repeating structure of the alkyleneoxy group of R ²² in the general formula (II), for example, those derived from propylene triol, glycerin, pentaerythritol and the like, and as the repeating structure of the aryleneoxy group, for example, , Pyrogallol, 1,3,5-benzenetriol and the like. The number of carbon atoms of the alkylene group R ²³ and R ²⁴ is preferably 1 to 5 each independently also preferably (meth) acryloyloxy group in R ²⁵ is 1 to 7. Further, it is preferable that x is 4 to 15, y is 1 to 10, and z is 1 to 10, respectively.

Further, R ²² is represented by the following formula (where k is an integer of 2 to 10), and R ²³ and R ²⁴ are each independently a dimethylene group or a monomethyl group. Particularly preferably, they are a dimethylene group or a trimethylene group, and R ²⁵ is represented by the following formula.

In addition, specific examples of the epoxy (meth) acrylates include (meth) acrylic acid or the hydroxy (meth) acrylate compound as described above, (poly) ethylene glycol polyglycidyl ether, and (poly) propylene glycol poly. Glycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) trimethylolpropane poly Aliphatic polyepoxy compounds such as glycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether, and phenol novolak polyepoxy compound Aromatic polyepoxy compounds such as brominated phenol novolak polyepoxy compounds, (o-, m-, p-) cresol novolak polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds, sorbitan polyglycidyl ether, Reaction products with polyepoxy compounds such as heterocyclic polyepoxy compounds such as glycidyl isocyanurate and triglycidyl tris (2-hydroxyethyl) isocyanurate, and the like.

Other ethylenically unsaturated compounds other than the above include, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, and vinyl group-containing compounds such as divinyl phthalate. Is mentioned.
The above ethylenically unsaturated compounds may be used alone or in combination of two or more.

In particular, as the ethylenically unsaturated compound, ester (meth) acrylates, (meth) acryloyloxy group-containing phosphates, or urethane (meth) acrylates are preferable, and (meth) acryloyloxy group-containing phosphates, or Urethane (meth) acrylates are particularly preferred. The proportion of the (meth) acryloyloxy group-containing phosphate relative to the whole ethylenically unsaturated compound is preferably from 1 to 60% by weight, particularly preferably from 2 to 40% by weight, Urethane (meth) acrylates preferably account for 0.5 to 50% by weight, and more preferably 2 to 40% by weight.
[Composition of photopolymerizable negative photosensitive resin composition]
The content of each of the ethylenically unsaturated compound, the sensitizer, and the photopolymerization initiator as the active compound in the photopolymerizable negative-type photosensitive resin composition is sensitized with respect to 100 parts by weight of the ethylenically unsaturated compound. The amount of the agent is usually 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, and the amount of the photopolymerization initiator is usually 1 to 60 parts by weight, preferably 5 to 40 parts by weight.

  This negative photosensitive resin composition, in addition to a sensitizer, an ethylenically unsaturated compound and a photopolymerization initiator, for the purpose of improving the formability as a photosensitive resist material layer on a substrate, and improving the developability, etc. Further, those containing a polymer binder component are preferable. Examples of the polymer binder include (meth) acrylic acid, (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, and maleic acid. Homo- or copolymers such as styrene, vinyl acetate, vinylidene chloride, and maleimide; and polyamide, polyester, polyether, polyurethane, polyvinyl butyral, polyvinyl alcohol, polyvinyl pyrrolidone, and acetyl cellulose. From the viewpoint of properties and the like, a carboxyl group-containing vinyl resin is preferred.

Specific examples of the carboxyl group-containing vinyl resin include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid and citraconic acid, and styrene, α -Methylstyrene, hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- (Meth) acryloylmorpholine, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, vinyl such as vinyl acetate These carboxyl group-containing vinyl resins may have an acid value of 30 to 250 KOH-mg / g and a weight average molecular weight Mw of 1,000 to 300,000 as measured by GPC. preferable.

  Further, as the carboxyl group-containing vinyl resin, those having an ethylenically unsaturated bond in a side chain are preferable. Specifically, the carboxyl group-containing polymer may be allyl glycidyl ether, glycidyl (meth) acrylate, α Aliphatic epoxy such as ethyl glycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, monoalkyl monoglycidyl itaconate, monoalkyl monoglycidyl fumarate, and monoalkyl monoglycidyl maleate; Group-containing unsaturated compound, or 3,4-epoxycyclohexylmethyl (meth) acrylate, 2,3-epoxycyclopentylmethyl (meth) acrylate, 7,8-epoxy [tricyclo [5.2.1.0] decy An unsaturated compound containing an alicyclic epoxy group such as 2-yl] oxymethyl (meth) acrylate is reacted with 5 to 90 mol%, preferably about 30 to 70 mol% of the carboxyl group of the carboxyl group-containing polymer. Reaction product obtained, and allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate, methallyl (meth) acrylate, N, N Compounds having two or more unsaturated groups such as -diallyl (meth) acrylamide, or vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) ) Acrylate, vinyl crotonate, vinyl (meth) acrylic Ratio of a compound having two or more unsaturated groups such as amide and an unsaturated carboxylic acid such as (meth) acrylic acid or further unsaturated carboxylic acid ester to the total of the former compound having an unsaturated group And a reaction product obtained by copolymerizing so as to be about 10 to 90 mol%, preferably about 30 to 80 mol%.

The content ratio of such a polymer binder in the negative photosensitive resin composition is preferably 50 to 500 parts by weight, and more preferably 70 to 200 parts by weight, based on 100 parts by weight of the ethylenically unsaturated compound as the component. Is more preferable.
The negative photosensitive resin composition of the present invention preferably further contains a hydrogen-donating compound for the purpose of improving photopolymerization initiation ability and the like. -Mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, ethylene glycol dithiopropio , Dimethylolpropane tristhiopropionate, mercapto group-containing compounds such as pentaerythritol tetrakisthiopropionate, hexanedithiol, trimethylolpropane tristhioglyconate, and pentaerythritol tetrakisthiopropionate. Active thiol compounds, N, N-dialkylaminobenzoic acid esters, N-phenylglycine or salts thereof such as ammonium and sodium salts, derivatives thereof such as esters, phenylalanine or salts thereof such as ammonium and sodium salts, ibid. And amino acids having an aromatic ring, such as derivatives of esters, and derivatives thereof. Among them, in the present invention, mercapto group-containing compounds, N-phenylglycine, or salts thereof such as ammonium and sodium salts, and derivatives such as esters thereof are preferable.

The content ratio of such a hydrogen donating compound in the negative photosensitive resin composition is preferably 0.01 to 50 parts by weight, preferably 0.1 to 40 parts by weight, based on 100 parts by weight of the ethylenically unsaturated compound. More preferably, it is part by weight.
Further, the negative photosensitive resin composition of the present invention preferably contains an amine compound for the purpose of improving storage stability and the like as the photosensitive resin composition, and the amine compound includes an aliphatic compound, It may be any of alicyclic or aromatic amines, and is not limited to monoamines, but may be polyamines such as diamines and triamines, and may be any of primary, secondary and tertiary amines. However, those having a pKb of 7 or less are preferred.

  Specific examples of the amine compound include butylamine, dibutylamine, tributylamine, amylamine, diamylamine, triamylamine, hexylamine, dihexylamine, trihexylamine, allylamine, diallylamine, triallylamine, triethanolamine, and benzylamine. And aliphatic amines which may be substituted with a hydroxyl group or a phenyl group, such as dibenzylamine and tribenzylamine. Among them, tribenzylamine is preferred in the present invention.

The content ratio of such an amine compound in the negative photosensitive resin composition is preferably 1 to 20 parts by weight, and more preferably 5 to 10 parts by weight based on 100 parts by weight of the ethylenically unsaturated compound. More preferred.
Further, the negative photosensitive resin composition of the present invention has a nonionic property, an anionic property, for the purpose of improving applicability at the time of forming a photosensitive resist material layer on a substrate, and improving developability of the photosensitive resist material layer. It is preferable to contain a surfactant such as a cationic, amphoteric, and fluorine-based surfactant. As such a surfactant, specifically, as a nonionic surfactant, polyoxyethylene alkyl ethers, Polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythritol fatty acid esters , Polyoxyethylene pentaerythri Fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbite fatty acid esters, polyoxyethylene sorbite fatty acid esters, etc., and as anionic surfactants, alkyl sulfonates, alkyl benzene sulfones Acid salts, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfates, higher alcohol sulfates, aliphatic alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxy Ethylene alkyl phenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether Phosphates, etc., as cationic surfactants, quaternary ammonium salts, imidazoline derivatives, amine salts, etc., and as amphoteric surfactants, betaine-type compounds, imidazolium salts, imidazolines, etc. , Amino acids and the like.

The content of such a surfactant in the negative photosensitive resin composition is preferably 0.1 to 10 parts by weight, and more preferably 1 to 5 parts by weight based on 100 parts by weight of the ethylenically unsaturated compound. More preferably, it is.
Further, the negative photosensitive resin composition of the present invention may contain a silane coupling agent for improving adhesion to a substrate. Specific examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltrichlorosilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-methacryloyloxypropyltrisilane. Ethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3
-Glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- [N- (2-aminoethyl) amino] propyltrimethoxysilane, 3- [N- (2-aminoethyl) amino] propyltriethoxysilane, 3- [N- (2-aminoethyl) amino] propylmethyldimethoxysilane, 3- [N- (2-aminoethyl) amino] propylmethyldiethoxysilane, 3- (N-allyl-N-glycidylamino) propyl Trimethoxysilane, 3- (N-allyl-N Glycidylamino) propyltriethoxysilane, 3- (N, N-diglycidylamino) propyltrimethoxysilane, 3- (N, N-diglycidylamino) propyltriethoxysilane, 3- (N-phenylamino) propyltri Methoxysilane, 3- (N-phenylamino) propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, and the like, and N-glycidyl-N, N-bis [3- (trimethoxysilyl) propyl] amine, N-glycidyl-N, N-bis [3- (triethoxysilyl) propyl] amine, N-glycidyl-N, N -Bis [3- (methyldimethoxysilyl) propyl] Min, N- glycidyl -N, N- bis silane compounds such as [3- (methyl-diethoxy silyl) propyl] amine.

The content ratio of such a silane coupling agent in the negative photosensitive resin composition is preferably 20 parts by weight or less based on 100 parts by weight of the ethylenically unsaturated compound, and is preferably 0.1 to 10 parts by weight. More preferably, it is.
Each type of the photosensitive resin composition of the present invention contains various additives, for example, a dye, a pigment, a coating improver, a development improver, and an adhesion improver, as long as the performance is not impaired. It is also possible.

  The photosensitive resin composition of the present invention is usually used for forming a photosensitive resist layer by dissolving in a solvent. In this case, the solvent used is not sufficient for each component of the above-described photosensitive resin composition. There is no particular limitation as long as it has a solubility and a solvent that gives good coating properties.For example, cellosolve solvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monoethyl ether, propylene glycol mono Propylene glycol solvents such as butyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol dimethyl ether, propylene glycol monoethyl ether acetate, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, Ester solvents such as ethyl acid, ethyl-2-hydroxybutyrate, 2-methylacetoacetate, methyl lactate and ethyl lactate, alcohol solvents such as heptanol, hexanol, diacetone alcohol and furfuryl alcohol, cyclohexanone, methyl amyl ketone Such as ketone solvents, ether solvents such as methylphenyl ether and diethylene glycol dimethyl ether, highly polar solvents such as dimethylformamide and N-methylpyrrolidone, or a mixed solvent thereof, or a mixed solvent further containing an aromatic hydrocarbon. Is mentioned.

The ratio of the solvent used is preferably in the range of 1 to 20 times by weight based on the total amount of solids in the photosensitive resin composition.
The photosensitive resin composition of the present invention composed of the above components preferably has a maximum spectral sensitivity peak in a wavelength region of 320 to 450 nm, and has a maximum spectral sensitivity peak in a wavelength region of 390 to 430 nm. Is more preferred. When having the maximum peak of spectral sensitivity in a wavelength range less than the above range, the sensitivity to laser light having a wavelength of 320 to 450 nm as a photosensitive resin composition tends to be inferior, while, when having a wavelength range exceeding the above range. Tends to have poor safelight properties under yellow light.

  In the present invention, the maximum peak of the spectral sensitivity refers to, for example, as described in detail in "Photopolymer Technology" (Ao Yamaoka, published by Nikkan Kogyo Shimbun in 1988, p. 262) and the like. A photosensitive image forming material sample having a photosensitive resin composition layer formed on the substrate surface was subjected to spectral sensitivity measurement using a spectral sensitivity measuring device. In addition, the exposure intensity is set to change logarithmically in the direction of the vertical axis, and after irradiating and exposing, an image corresponding to the sensitivity of each exposure wavelength is obtained by developing, and from the image height, Exposure energy at which an image can be formed is calculated, and the maximum peak in a spectral sensitivity curve obtained by plotting the wavelength on the horizontal axis and the reciprocal of the exposure energy on the vertical axis is shown.

The photosensitive resin composition of the present invention is more preferably the image forming minimum exposure amount capable of wavelength 410nm is [S _410] is preferably 50 mJ / cm ² or less, 30 mJ / cm ² or less, It is particularly preferred that it is 20 mJ / cm ² or less. If the minimum exposure amount [ _S410 ] exceeds the above range, the exposure time becomes longer, and the practicability tends to decrease, depending on the exposure intensity of the laser light source. The lower limit of the minimum exposure amount [S ₄₁₀ ] is preferably as small as possible, but is usually 1 mJ / cm ² or more.

The photosensitive resin composition of the present invention has a ratio [S ₄₁₀ ] / [S ₄₅₀ ] to the minimum exposure amount [S ₄₅₀ ] (mJ / cm ² ) at which the image can be formed at the wavelength of 450 nm of the above [S ₄₁₀ ]. It is preferably 0.1 or less, more preferably 0.05 or less. This ratio [ _S410 ]
When / [S ₄₅₀ ] is outside the above range, it tends to be difficult to achieve both the blue-violet laser sensitivity and the safelight property under yellow light.

In addition, the photosensitive resin composition of the present invention has a minimum exposure amount [S _450-650 ] (mJ / cm ² ) at which the image can be formed at a wavelength of 450 nm and a wavelength of 450 nm or less and 650 nm or less. it is preferred that the amount [S _450] (mJ / cm ²⁾ the ratio [S _450-650) / (S _450] is 1 exceeded. The ratio [S _450-650] / with [S _450] is less than the range, the blue-violet laser photosensitive and difficult tendency is possible to achieve both a safe light of a yellow light.

The minimum exposure amount at which the image can be formed at the wavelength of 410 nm [S ₄₁₀ ] and the wavelength of 450 nm
minimum exposure amount [S ₄₅₀ ] at which image formation can be performed in nm, and a wavelength exceeding 450 nm and 650 n
The minimum exposure amount [S _450-650 ] at which an image can be formed at each wavelength of not more than m is the image calculated from the image height obtained in the measurement of the maximum peak of the spectral sensitivity using the above-described spectral sensitivity measuring device. Determined as exposure energy that can be formed, in that case, the type of developer, the development temperature, the minimum exposure amount that can form an image under optimal development conditions determined by changing the development conditions such as development time, As the optimum developing condition, usually, a condition of immersing in an alkaline developer having a pH of 11 to 14 at a temperature of 25 ° C. for 0.5 to 3 minutes is adopted.

  Further, when the photosensitive resin composition of the present invention has an exposure sensitivity of a minimum exposure amount capable of producing an image having a line width of 10 μm in the same manner as described above, a photosensitive film having a dry film thickness of 10 μm is formed. The ratio (S2 / S1) of the exposure sensitivity (S2) of the photosensitive resin composition layer formed to a dry film thickness of 20 μm to the exposure sensitivity (S1) of the resin composition layer is preferably 5 or less, particularly preferably 3 or less. . When the exposure sensitivity ratio (S2 / S1) is within this range, a change in sensitivity due to a change in film thickness is small, and a good image can be formed even when there is a step on the substrate to be processed.

The minimum reproducible line width (μm) of the photosensitive resin composition of the present invention varies depending on the thickness of the photosensitive resist layer of the image forming material. That is, the maximum value of film thickness (μm) / line width (μm) is obtained by changing the film thickness and obtaining the minimum line width. The value determined in this manner is preferably 1 or more, and more preferably 1.2 or more. The higher the value, the better.
The photosensitive resin composition of the present invention generally includes a step of forming a photosensitive resist layer on a conductive substrate to be processed, a step of exposing the photosensitive resist layer to actinic rays, and a step of developing with an alkali developer. As a result, an image is formed. Then, a circuit pattern is formed on the surface by performing etching, plating and the like using the obtained resist pattern layer as a mask.

  Here, as the conductive substrate to be processed, a metal plate of copper, aluminum, gold, silver, chromium, zinc, tin, lead, nickel, etc .; epoxy resin, polyimide resin, bismaleimide resin, unsaturated polyester resin, phenol resin, Thermosetting resin such as melamine resin, saturated polyester resin, polycarbonate resin, polysulfone resin, acrylic resin, polyamide resin, polystyrene resin, polyvinyl chloride resin, polyolefin resin, thermoplastic resin such as fluororesin, paper, glass And inorganic materials such as alumina, silica, barium sulfate, and calcium carbonate, or composite materials such as glass cloth-based epoxy resin, glass nonwoven fabric-based epoxy resin, paper-based epoxy resin, and paper-based phenolic resin. The thickness of which is about 0.02 to 10 mm on the surface of the insulating support, Metal foils such as metal oxides such as metals or indium oxide, tin oxide, indium oxide-doped tin oxide (ITO) and the like are heated and pressure-bonded or laminated by sputtering, vapor-depositing or plating metal. A metal-clad laminate on which a conductive layer of about 1 to 100 μm is formed; a wafer on which an electronic circuit element and / or an insulating layer is formed on a silicon wafer and a metal layer such as copper, aluminum, or gold is formed; a glass substrate A substrate on which an ITO film is formed is used. Of these, metal-clad laminates and wafers are preferably used.

  As a method for applying the photosensitive resin composition when forming the photosensitive resist layer on such a substrate to be processed, conventionally known methods, for example, spin coating, wire bar coating, spray coating, dip coating, air knife Coating, roll coating, blade coating, screen coating, curtain coating, and the like can be used. The coating amount at this time is such that a photosensitive resist layer having a dry film thickness of usually 0.1 to 100 μm, preferably 0.5 to 70 μm, more preferably 5 to 70 μm is formed. In particular, in the photosensitive image forming material of the present invention in which the photosensitive resin composition layer of the present invention is laminated on a substrate to be processed, in terms of use as an etching resist or a plating resist, the photosensitive resin composition layer The thickness is preferably 10 μm or more as a dry film thickness, and the upper limit of the film thickness is preferably about 100 μm from the viewpoint of sensitivity and the like. The drying temperature at that time is, for example, about 30 to 150 ° C., preferably about 40 to 110 ° C., and the drying time is, for example, about 5 to 60 minutes, preferably about 10 to 30 minutes. Is adopted.

  The photosensitive resin composition of the present invention is a coating solution obtained by dissolving or dispersing each of the above-mentioned components in the above-mentioned appropriate solvent, applied on a temporary support film and dried, and if necessary, the formed photosensitive resin. By covering the surface of the composition layer with a covering film, the photosensitive image forming material of the present invention as a so-called dry film resist material or the like is obtained. The photosensitive resin composition layer side of the image forming material is covered with a covering film. When the coating film is peeled off and laminated on a substrate to be processed, the photosensitive resin composition of the present invention in which a layer of the photosensitive resin composition of the present invention is formed on the substrate to be processed The photosensitive resin composition layer of the image forming material is, for example, scan-exposed with a laser beam having a wavelength of 390 to 430 nm, and is subjected to a developing process to be suitable for use as an image forming method for producing a negative image. Used.

As the temporary support film when used as an image forming material as the dry film resist material or the like, for example, a conventionally known film such as a polyethylene terephthalate film, a polyimide film, a polyamideimide film, a polypropylene film, and a polystyrene film is used. At that time, when those films have solvent resistance, heat resistance, and the like necessary for producing the image forming material, the coating solution of the photosensitive resin composition is directly applied to those temporary support films. It can be applied and dried to produce the image forming material of the present invention, and even if those films have low solvent resistance or heat resistance, for example, a polytetrafluoroethylene film or a mold release After first forming a photosensitive resin composition layer on a film having a release property such as a film, a temporary support film having low solvent resistance and heat resistance is laminated on the layer, and then the release property is improved. The image forming material of the present invention can be produced by peeling the film having the resin.

The solvent used for coating and the coating method are the same as described above.
When used as an image forming material such as a dry film resist material, the surface of the formed photosensitive resin composition layer may be covered with a covering film until the image forming material is laminated on a substrate to be processed. Preferably, a conventionally known film such as a polyethylene film, a polypropylene film, a polytetrafluoroethylene film or the like is used as the coating film.

  In addition, when the photosensitive resin composition layer side of such an image forming material is covered with a covering film, the covering film is peeled off and laminated on a substrate to be processed by heating, pressing, or the like. The photosensitive image forming material of the present invention formed as described above, or, as described above, a coating solution of the photosensitive resin composition of the present invention directly applied and dried to form a photosensitive resin composition layer-formed workpiece The substrate has a negative image that appears by scanning and exposing the photosensitive resin composition layer formed thereon on it with a laser beam and developing it as a resist. Patterns such as circuits and electrodes are formed.

  Light having a wavelength of 320 to 450 nm is usually used for exposure. This light may be monochromatic light or broad light. For example, light with a wavelength of 366 nm or 436 nm of a high-pressure mercury lamp can be used. However, in terms of output, stability, photosensitivity, cost, and the like, blue light from an argon ion laser, a helium neon laser, a YAG laser, Among those that emit light in the violet to infrared range, a light source that emits laser light in the blue-violet range in the wavelength range of 390 to 430 nm is particularly preferable. The exposure light source is not particularly limited, but specific examples thereof include an indium gallium nitride semiconductor laser that emits light having a wavelength of 405 nm. It is also possible to perform exposure with DeepUV light having a wavelength of 320 nm or less.

When heating (PEB) is performed after exposure, a hot plate or an oven is preferably used at 90 to 140 ° C. for about 1 to 30 minutes. When an oven is used instead of a hot plate, a longer heating time is usually required than when a hot plate is used.
Examples of the developing solution used for development include inorganic alkalis such as potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, and di-n-. Alkaline developers comprising aqueous solutions of secondary amines such as propylamine, tertiary amines such as triethylamine and trimethylamine, and quaternary ammonium salts such as tetramethylammonium hydroxide and trimethylhydroxyethylammonium hydroxide are preferably used. Is done. If necessary, an alcohol, a surfactant or the like may be added to the developing solution before use.

The development is usually performed by immersing the image forming material having the photosensitive resist layer formed in the developing solution or by contacting the developing solution with the photosensitive resist layer of the image forming material by a spray method, a paddle method, or the like. At about 10 to 50 ° C., more preferably about 15 to 45 ° C., for about 5 seconds to about 10 minutes.
In the present invention, in the photopolymerizable negative image forming material, a blue-violet laser photosensitive material comprising the photosensitive resin composition of the present invention formed on the substrate to be processed as described above. On the resist layer, such as an oxygen blocking layer for preventing the polymerization inhibiting action of the photopolymerizable photosensitive resin composition due to oxygen, or a light transmittance adjusting layer for adjusting the wavelength region of the maximum peak of spectral sensitivity. A protective layer may be formed.

  As the constituent material of the oxygen barrier layer, water or a water-soluble polymer soluble in a mixed solvent of water and a water-miscible organic solvent such as alcohol or tetrahydrofuran, or a water-insoluble polymer such as polyethylene terephthalate is used. Specifically, specifically, derivatives such as polyvinyl alcohol and its partially acetalized product, its cation-modified product such as quaternary ammonium salt, its anion-modified product such as sodium sulfonate, polypinylpyrrolidone, polyethylene oxide, methylcellulose , Carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like.

  Among them, polyvinyl alcohol and its derivatives are preferable from the viewpoint of oxygen barrier properties and the like, and vinyl pyrrolidone and vinyl pyrrolidone-vinyl acetate copolymer and the like from the viewpoint of adhesion to the photosensitive resist layer. Pyrrolidone polymers are preferred, and as the oxygen barrier layer according to the present invention, the polyvinylpyrrolidone polymer is preferably used in an amount of preferably 1 to 20 parts by weight, more preferably 3 to 100 parts by weight, based on 100 parts by weight of polyvinyl alcohol or a derivative thereof. It is preferably used as a mixture obtained by mixing 15 parts by weight.

  Further, the oxygen barrier layer preferably contains an organic acid such as succinic acid or an organic acid salt such as ethylenediaminetetraacetic acid from the viewpoint of preservation and the like, and further, a nonionic such as polyoxyethylene alkylphenyl ether. Surfactant, anionic such as sodium dodecylbenzenesulfonate, cationic such as alkyltrimethylammonium chloride, defoamer, pigment, plasticizer, pH adjuster, etc. The total content of these components is preferably 10% by weight or less, more preferably 5% by weight or less.

The oxygen barrier layer is formed as a solution of water or a mixed solvent of water and a water-miscible organic solvent by a coating method similar to that of the above-described photosensitive resist layer. is preferably in the range of 10 g / m ^2, more preferably in the range of 1.5~7g / m ^2.
Further, as a material constituting the light transmittance adjusting layer, a polymer binder containing, for example, a light-absorbing dye in the visible region such as a coumarin-based dye may be used. Is a polyvinyl alcohol or a derivative thereof, or a polyvinylpyrrolidone-based polymer mentioned in the oxygen barrier layer, whereby a protective layer having an oxygen barrier ability and a light transmittance adjusting ability can be obtained.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded.
In the following, each evaluation of the obtained photosensitive resin composition and photosensitive image forming material was performed according to the following methods.
<Absorbance>
With respect to the photosensitive resist layer having a dry film thickness of 10 μm formed on the glass substrate, the absorbance at a wavelength of 405 nm was measured using a spectrophotometer (“UV-3100PC” manufactured by Shimadzu Corporation), and the measured value was divided by the film thickness. By doing so, the absorbance per 1 μm was calculated.

<Maximum spectral sensitivity peak>
A sample obtained by cutting out the image forming material to a size of 50 × 60 mm was subjected to a xenon lamp (“US-501C” manufactured by USHIO Inc.) using a diffraction spectroscopic irradiation apparatus (“RM-23” manufactured by Narumi).
) Is used as a light source, and is irradiated for 10 seconds by irradiating light separated in a wavelength range of 320 to 650 nm by setting such that the exposure wavelength changes linearly in the horizontal axis direction and the exposure intensity logarithmically changes in the vertical axis direction. Then, by performing development processing under the development conditions described in each example, to obtain an image corresponding to the sensitivity of each exposure wavelength, calculate the exposure energy that can form an image from the image height, wavelength on the horizontal axis, The maximum peak in the spectral sensitivity curve obtained by plotting the reciprocal of the exposure energy on the vertical axis was read.

<[S _410] / [S _450], [S _450-650] / [S _450]>
In the same manner as described in the above <maximum spectral sensitivity>, when the exposure is performed by changing the wavelength in the wavelength range of 320 to 650 nm, and the image is developed, the minimum exposure amount at which the image can be formed at the wavelength of 410 nm [ _S410] ] (MJ / cm ² ) and the minimum exposure amount at which the image can be formed at a wavelength of 450 nm [S ₄₅₀ ] (mJ / cm ² ), and the minimum exposure amount at which the image can be formed at a wavelength exceeding 450 nm and at most 650 nm [S _450- calculated _650] (mJ / cm ²⁾ for each of the ratio [S _410] / [S _450], and to calculate the [S _450-650) / (S _450], and evaluated according to the following criteria.

<Evaluation criteria for [ _S410 ] / [ _S450 ]>
A: [ _S410 ] / [ _S450 ] is 0.03 or less.
B: [ _S410 ] / [ _S450 ] is more than 0.03 and 0.05 or less.
C: [ _S410 ] / [ _S450 ] exceeds 0.05 and 0.1 or less.
D: [ _S410 ] / [ _S450 ] exceeded 0.1.

<Evaluation Criteria of [S _450-650] / [S _450]>
A: [S _450-650] / [S _450] is greater than 10.
B: [S _450-650) / (S _450] is 5 exceeds 10 or less.
C: [S _450-650) / (S _450] 1 exceeds 5 below.
D: [S _450-650] / [S _450] is 1 or less.

<Exposure sensitivity>
Using a laser light source ("NLHV500C" manufactured by Nichia Corporation) having a center wavelength of 405 nm and a laser output of 5 mW, the photosensitive resist layer of the image forming material is scanned with an image plane illuminance of 2 μW and a beam spot diameter of 2.5 μm. Scanning exposure is performed while changing the interval and the scanning speed, and then developed under the developing conditions described in each example to make an image appear. At this time, the minimum width required to reproduce a line width of 10 μm is obtained for the obtained image. The exposure amount was determined and defined as exposure sensitivity. As the exposure sensitivity, the exposure sensitivity (S1) when the photosensitive resist layer thickness is 10 μm and the exposure sensitivity (S2) when the photosensitive resist layer thickness is 20 μm are measured, and the ratio (S2 / S1) is obtained. Was calculated.

<Resolution>
With respect to the obtained resist image, the reproducible line width and the pattern shape at the film thickness shown in Table 1 were observed. Further, as a standard of resolution, "film thickness (μm) / reproducible line width (μm ) "Was calculated.
<Safe light under yellow light>
The image forming material was left for 1 minute, 2 minutes, 5 minutes, 10 minutes, 20 minutes, and 30 minutes under yellow light illumination (under the condition that light having a wavelength of about 470 nm or less was blocked). Scanning exposure and development processing were performed, and a standing time until an image was changed compared to the above was determined, and evaluated according to the following criteria.

A: Leaving time is 20 minutes or more B: Leaving time is 10 minutes or more and less than 20 minutes C: Leaving time is 1 minute or more and less than 10 minutes D: Leaving time is less than 1 minute <Storage stability of photosensitive resin composition coating liquid >
After the photosensitive resin composition coating solution was stored in a dark place at 25 ° C. for 7 days, a resist image was formed, and the resist image was observed for the presence of crystalline precipitates with a scanning electron microscope. Was evaluated.

A: No precipitate was observed at all, and there was no change in sensitivity and image before and after storage.
B: No precipitate was observed, but the sensitivity after storage was slightly lowered.
C: A trace amount of precipitate was observed, and the sensitivity after storage was lowered.
[Example 1]
100 parts by weight of poly-p-hydroxystyrene (weight average molecular weight Mw 5,000 by GPC measurement), 50 parts by weight of hexamethoxymethyl melamine (“Nikarac E-2151” manufactured by Sanwa Chemical Co., Ltd.), expressed by the structural formula (7) 1 part by weight of a sensitizer (molar extinction coefficient / 405 nm = 32,500) and 5 parts by weight of a compound represented by the following structural formula (VI) are dissolved in 290 parts by weight of propylene glycol monomethyl ether acetate, and the resultant is chemically amplified negative. And a solution of a photosensitive resin composition (N2).

  The obtained photosensitive resin composition (N2) solution was spin-coated on a glass substrate so as to have a thickness of 10 μm or 20 μm, and dried in an oven at 90 ° C. for 10 minutes to prepare a negative image forming material. The photosensitive resist layer of the obtained negative image forming material was subjected to scanning exposure under the conditions described in the above-described method for evaluating exposure sensitivity, and then subjected to a post-heating treatment in an oven at 100 ° C. for 10 minutes, followed by a developer. Was developed by immersing in a 0.5% by weight aqueous solution of potassium hydroxide at 20 ° C. for 60 seconds. Table 1 shows the evaluation results of the obtained photosensitive resin compositions and photosensitive image forming materials.

[Example 2]
Chemically amplified negative photosensitive resin composition in the same manner as in Example 1, except that the acid generator was changed to the compound represented by the following structural formula (VII) instead of the compound represented by the structural formula (VI). A solution of (N2) was prepared, and an image was formed on the obtained photosensitive resin composition solution in the same manner as in Example 1. Table 1 shows the results of each evaluation.

[Example 3], [Comparative Example 1], [Comparative Example 2]
The sensitizer may be replaced with a compound represented by the structural formula (1) (molar extinction coefficient at a wavelength of 405 nm of 51,600) or a compound represented by the following structural formula (51) as shown in Table 1 below instead of the formula (7). A chemically amplified negative photosensitive resin composition was prepared in the same manner as in Example 2 except that the compound represented (molar extinction coefficient at a wavelength of 405 nm, 82,700) was used (Comparative Example 1 did not use a sensitizer). (N2) solution. An image was formed from the obtained photosensitive resin composition solution in the same manner as in Example 2. Evaluation was performed in the same manner as in Example 2.

In Comparative Example 1, all the exposed portions were dissolved in the developer, and no image was formed.
In Comparative Example 2, the safelight property was D, and the unexposed portion did not completely dissolve, and a good image was not formed. The results are shown in Table 1.
[Example 4]
As the photopolymerizable negative photosensitive resin composition (N1), a styrene / methyl methacrylate / 2-hydroxyethyl methacrylate / methacrylic acid copolymer (molar ratio 10/50/20/20, acid value 129 KOH · mg / g, (Weight average molecular weight 68,000) 55 parts by weight, 11.5 parts by weight of a compound of the following structural formula (VIII), 10 parts by weight of a compound of the following structural formula (IX), 23.5 parts by weight of a compound of the following structural formula (X) , 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (melting point 196 ° C, X-ray diffraction spectrum at a wavelength of 1.54 °, Bragg angle (2θ ± 0.2 °) having a maximum diffraction peak at 9.925 °) 12 parts by weight, 0.2 parts by weight of a dipolar ion compound of N-phenylglycine, leuco crystal violet: 0.4 parts by weight, 0.2 parts by weight of phenylacridine and 0.6 parts by weight of a sensitizing dye represented by the structural formula (21) (molar extinction coefficient / 405 nm = 7,320) were added to methyl ethyl ketone / isopropanol (weight ratio: 8/2). A coating solution prepared by stirring at room temperature in addition to 100 parts by weight of a mixed solvent of above is coated on a polyethylene terephthalate film (19 μm thick) as a temporary support film to a dry film thickness of 10 μm or 20 μm using an applicator. It was dried in an oven at 90 ° C. for 10 minutes, and a polyethylene film (thickness: 25 μm) as a coating film was laminated on the formed photosensitive resin composition layer to obtain a photosensitive image forming material.

  Separately, the copper foil surface of a polyimide resin copper-clad laminated substrate (thickness: 1.5 mm, size: 250 mm × 200 mm) to which a copper foil having a thickness of 35 μm is attached is polished by baffle using “Scotch Bright SF” manufactured by Sumitomo 3M Limited, and washed with water. Then, after drying by air flow and surface conditioning, and then preheating this to 60 ° C. in an oven, the photosensitive image-forming material obtained above was placed on the copper foil of the copper-clad laminate substrate by the polyethylene film. The photosensitive composition is laminated on a copper-clad laminate substrate by laminating the peeled surface at a roll temperature of 100 ° C., a roll pressure of 0.3 MPa, and a laminating speed of 1.5 m / min using a hand-type roll laminator while peeling. A material layer was created.

  The obtained photosensitive composition layer was subjected to scanning exposure in the same manner as in Example 1 under the conditions described in the method for evaluating exposure sensitivity. After the exposure, the polyethylene terephthalate film is peeled off and sprayed with a 0.7% by weight aqueous solution of sodium carbonate at 30 ° C. as a developing solution to a pressure of 0.15 MPa, and spray-developed for 1.5 times the minimum developing time. The negative image appeared. Table 1 shows the results of the evaluation performed in the same manner as in Example 1.

Comparative Example 3
In the photopolymerizable negative photosensitive resin composition (N1) of Example 4, the compound of the structural formula (VIII) was 15 parts by weight, and the following structure was used instead of the compounds of the structural formulas (IX) and (X). A photosensitive resist material layer having a film thickness of 10 μm or 20 μm was prepared in the same manner as in Example 4 except that 30 parts by weight of the compound represented by the formula (XI) was used and no sensitizer was used. It was fabricated, scanned and exposed, and then subjected to a developing treatment. As a result, all the exposed portions were dissolved in the developing solution, and no image was formed. Table 1 shows the evaluation results in the same manner as in Example 4.

Comparative Example 4
In the photopolymerizable negative photosensitive resin composition (N1) of Example 4, the compound of the structural formula (VIII) was 15 parts by weight, and the following structure was used instead of the compounds of the structural formulas (IX) and (X). A photosensitive image was prepared in the same manner as in Example 4 except that the compound represented by the formula (XI) was used in an amount of 30 parts by weight, and the sensitizer was changed to 1 part by weight of the compound represented by the structural formula (51). A forming material was prepared, and a processed substrate having a resist image formed on the surface was obtained. The image forming material having a photosensitive resist material layer having a film thickness of 10 μm or 20 μm was subjected to a developing process by scanning exposure, and the exposed portions were all dissolved in the developing solution, and no image was formed. Table 1 shows the evaluation results in the same manner as in Example 4.

  From Table 1, it can be seen that the photosensitive resin composition of the present invention has excellent safelight properties under yellow light, and is a photosensitive resin composition having high sensitivity and high resolution in a blue-violet region.

The photosensitive resin composition of the present invention and a photosensitive image forming material and a photosensitive image forming material using the photosensitive resin composition are printed directly by using a blue-violet laser beam, a printed wiring board,
It is industrially extremely useful for forming fine electronic circuits such as wiring boards for plasma displays, wiring boards for liquid crystal displays, large-scale integrated circuits, thin transistors, and semiconductor packages.

Claims (8)

A sensitizer,
In a photosensitive resin composition containing an active compound that generates at least one of a radical, an acid, and a base by interaction with the exposed sensitizer,
The photosensitive resin composition, wherein the sensitizer is a compound represented by the following general formula (I).

(Here, R ¹ and R ² each independently represent a hydrogen atom or an arbitrary substituent, and R 3 represents an arbitrary substituent.)   2. The photosensitive resin composition according to claim 1, wherein the sensitizer has a molar absorption coefficient ([epsilon]) at 405 nm of 100 to 100,000.   The photosensitive resin composition according to claim 1, wherein the composition is a negative type containing an alkali-soluble resin and a crosslinking agent.   The photosensitive resin composition according to claim 1, wherein the composition is a positive type containing an acid-decomposable group-containing polymer.   3. The photosensitive resin composition according to claim 1, wherein the composition is a negative type containing an ethylenically unsaturated compound.   A photosensitive image forming material comprising a layer of the photosensitive resin composition according to any one of claims 1 to 5 formed on a temporary support film.   A photosensitive image forming material, comprising the photosensitive image forming material according to claim 6 laminated on a substrate to be processed such that the photosensitive resin composition layer side is on the substrate side. 8. The photosensitive image forming material according to claim 7, wherein the thickness of the photosensitive resin composition layer laminated on the substrate to be processed is 10 μm or more.