JP4325392B2 - Photosensitive resin composition, photosensitive image forming material and photosensitive image forming material using the same - Google Patents

Description

  The present invention relates to a photosensitive resin composition capable of forming a resist image by exposure with blue-violet laser light and development processing, a photosensitive image forming material and a photosensitive image forming material using the photosensitive resin composition, In particular, photosensitivity useful for forming fine electronic circuits such as printed wiring boards, plasma display wiring boards, liquid crystal display wiring boards, 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.

  Conventionally, for forming fine electronic circuits such as printed wiring boards, plasma display wiring boards, liquid crystal display wiring boards, large-scale integrated circuits, thin transistors, semiconductor packages, etc., for example, a photosensitive resist material on a substrate to be processed Using an image-forming material that has a layer and, if necessary, a protective layer provided thereon, the photosensitive resist material layer is exposed to ultraviolet rays through the mask film, and then the mask film is peeled off and further protected. In the case of having a layer, the protective layer is peeled off, and a pattern layer is formed by developing using the difference in solubility between the exposed portion and the unexposed portion in the developer, and the substrate to be processed using this pattern layer as a mask A lithography method for forming a circuit pattern on a substrate to be processed by etching or the like is widely used.

Furthermore, in recent years, the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask film by using a laser beam as an exposure light source is not only productive, but also resolution and positional accuracy. As a result, the use of laser light has been actively studied in the lithography method.
Various light sources from the ultraviolet to the infrared region are known as laser light, but as laser light that can be used for image exposure, an argon ion laser is used from the viewpoint of output, stability, photosensitive ability, and cost. , Helium neon lasers, YAG lasers, semiconductor lasers, etc. that emit light in the visible to infrared region are 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 been put into 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 (see, for example, 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 safe light property under a yellow lamp, and is illuminated with a red lamp. There is a restriction that it is necessary to work in a dark room environment.
On the other hand, a remarkable progress in laser technology in recent years has made it possible to use a semiconductor laser that can operate in a bright room environment such as yellow light illumination and can stably oscillate in a blue-violet region. However, because the output is low compared to other visible laser beams, the sensitivity of the photosensitive resist material is not necessarily sufficient, and it can be put to practical use not only in the direct drawing method but also in the lithography method. It is the current situation that has not reached.

For these reasons, a photosensitive resin composition having high sensitivity and high resolution in the blue-violet region is demanded.
On the other hand, the chemically amplified photosensitive resin composition conventionally used in the manufacture of semiconductor integrated circuits has a feature of high resolution, but is a composition sensitive to ultraviolet and far ultraviolet, and has a blue-violet region. Has no absorption, it is impossible to form an image with a blue-violet laser. In addition, as a photosensitive resin composition containing a dye having 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. The sensitivity to violet laser with a wavelength of 350 to 450 nm is poor, and the safelight property under yellow light is poor (see Non-Patent Document 1).
JP 2002-258478 A 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 which is excellent in safe light property under yellow light and excellent in 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 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 the interaction of the exposed sensitizer. The photosensitive resin composition is characterized in that the sensitizer is a compound of the following general formula (I).

(Here, R ¹ and R ² each independently represents a hydrogen atom or an arbitrary substituent, and R 3 represents an arbitrary substituent.)
In the present invention, the 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 and generates at least one of radical, acid and base Is used in combination to provide a photosensitive resin composition exhibiting highly sensitive photosensitivity 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 the substrate to be processed on the photosensitive resin composition layer side.

  As described above in detail, according to the present invention, there is provided a photosensitive resin composition that is excellent in safe light property under a yellow light, has high sensitivity and high resolution in a blue-violet region. Therefore, the photosensitive resin composition of the present invention is a printed wiring board, a wiring board for plasma display, a wiring board for liquid crystal display, a large scale integrated circuit, a thin transistor, a semiconductor package, etc. by direct drawing using blue-violet laser light. It is extremely useful industrially for forming fine electronic circuits.

Embodiments of the photosensitive resin composition of the present invention will be described below.
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), preferably 32.
Absorbs light with a wavelength of 0 to 450 nm, has a molar extinction coefficient (ε) at a wavelength of 405 nm of 100 or more and 100000 or less, efficiently absorbs light with 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 the active compound. The molar extinction coefficient is preferably 1000 or more, more preferably 10,000 or more.
In general formula (I), preferred groups as R ¹ and R ² are hydrogen atom; methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n- C1-C18 linear or branched alkyl group such as heptyl group; C3-C18 cycloalkyl group such as cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group; vinyl group, propenyl group, hexenyl group Straight chain or branched alkenyl group having 2 to 18 carbon atoms such as cycloalkenyl group having 3 to 18 carbon atoms such as cyclopentenyl group and cyclohexenyl group; 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-naphthal) Til) vinyl alkenyl group having 8 to 18 carbon atoms; saturated or 2-thienyl group, 2-pyridyl group, furyl group, thiazolyl group, benzothiazolyl group, morpholino group, pyrrolidinyl group, tetrahydrothiophene dioxide group, etc. 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 , Butyryl group, isobutyryl group, valeryl group, isovaleryl group, etc., linear or branched acyl group having 2 to 18 carbon atoms; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec- A linear or branched alkoxy group having 1 to 18 carbon atoms such as butoxy group and tert-butoxy group; C3-C18 linear or branched alkenyloxy groups such as oxy group, butenyloxy group, pentenyloxy group: 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 An amino group represented by —NHCOR ⁷ ; a carbamate group represented by —NHCOOR ⁸ ; a sulfonamide group represented by —NHSOOR ⁹ ; a carboxylic acid ester group represented by —COOR ¹⁰ ; A carbamoyl group represented by ¹¹ R ¹² ; a sulfamoyl group represented by —SOONR ¹³ R ¹⁴ ; —SO ₂ OR ₁₅
The sulfonic acid ester group etc. which are represented by these are mentioned.

Preferred groups as R ³ include methyl group, ethyl group, propyl group, isopropyl group,
C1-C18 linear or branched alkyl group such as n-butyl group, sec-butyl group, tert-butyl group, n-heptyl group; carbon such as cyclopropyl group, cyclopentyl group, cyclohexyl group, 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 group having 3 to 18 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group Group: 1-phenylvinyl group, 2-phenylvinyl group, 2-phenylpropenyl group, 1- (α-naphthyl) vinyl group, 2- (α-naphthyl) vinyl group, 1- (β-naphthyl) vinyl group, Arylalkenyl groups having 8 to 18 carbon atoms such as 2- (β-naphthyl) vinyl group; 2-thienyl group, 2-pyridyl group, furyl group, thiazolyl group, Saturated or unsaturated heterocyclic group such as zothiazolyl group, morpholino group, pyrrolidinyl group, tetrahydrothiophene dioxide group; aryl group having 6 to 18 carbon atoms such as phenyl group, tolyl group, xylyl group, mesityl group; benzyl group, Aralkyl groups having 7 to 20 carbon atoms such as phenethyl group; linear or branched acyl groups having 2 to 18 carbon atoms such as acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group and isovaleryl group; methoxy group, 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 straight-chain or branched alkenyloxy group having 3 to 18 carbon atoms such as a methylthio group, A linear or branched alkylthio group having 1 to 18 carbon atoms such as a tilthio group, n-propylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group; cyano group; hydroxy group; formyl group; sulfonic acid group A carboxyl group; an acyloxy group represented by —OCOR ¹⁶ ; an amino group represented by —NR ¹⁷ R ¹⁸ ; an acylamino group represented by —NHCOR ¹⁹ ; a carbamate group represented by —NHCOOR ²⁰ ; and —NHSOOR ²¹ . A sulfonamido group represented by —COOR ²² represented by —COOR ²² ; a carbamoyl group represented by —CONR ²³ R ²⁴ ; a sulfamoyl group represented by —SOONR ²⁵ R ²⁶ ; a table represented by —SO ₂ OR ²⁷ Sulfonic acid ester groups;
An imino group represented by —N═CR ²⁸ R ²⁹ and the like can be mentioned.

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

In addition, 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. In this case, examples of the substituent include alkoxy groups having 1 to 10 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; Group, ethoxymethoxy group, propoxymethoxy group, ethoxyethoxy group, propoxyethoxy group, methoxybutoxy group, etc., alkoxyalkoxy group having 2 to 12 carbon atoms; methoxymethoxymethoxy group, methoxymethoxyethoxy group, methoxyethoxymethoxy group, methoxymethoxy An alkoxyalkoxyalkoxy group having 3 to 15 carbon atoms such as ethoxy group and ethoxyethoxymethoxy group; an aryloxy group; an aryl group having 6 to 12 carbon atoms such as phenyl group, tolyl group and xylyl group (these are further substituted with a substituent) Feno C2-C12 alkenyloxy groups such as silyl group, tolyloxy group, xylyloxy group, naphthyloxy group; acyl groups such as acetyl group, propionyl group; cyano group; nitro group; hydroxyl group; tetrahydrofuryl group; amino group; C1-C10 alkylamino groups such as N, N-dimethylamino group and N, N-diethylamino group; C1-C6 such as methylsulfonylamino group, ethylsulfonylamino group and 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, ethylcarbonyl Oxy group, n-propylcarbonyloxy group, a C2-C7 alkylcarbonyloxy groups such as propylcarbonyloxy group and n-butylcarbonyloxy group; methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, isopropoxycarbonyloxy group, n-butoxy Examples thereof include C2-C7 alkoxycarbonyloxy groups such as carbonyloxy group. A preferable substituent when R ^{1 to} R ²¹ are an alkyl group, a cycloalkyl group, or a cycloalkenyl group 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, any one or more of R ^{1 to} R ³ is a linear or branched alkenyl group having 2 to 18 carbon atoms such as vinyl group, propenyl group, hexenyl group; cyclopentenyl group, cyclohexenyl group. A C3-C18 cycloalkenyl group such as 1-phenylvinyl group, 2-phenylvinyl group, 2-phenylpropenyl group, 1- (α-naphthyl) vinyl group, 2- (α-naphthyl) vinyl group, C8-18 arylalkenyl groups such as 1- (β-naphthyl) vinyl group and 2- (β-naphthyl) vinyl group; 2-thienyl group, 2-pyridyl group, furyl group, thiazolyl group, benzothiazolyl group, etc. An unsaturated heterocyclic group; an aryl group having 6 to 18 carbon atoms such as phenyl group, tolyl group, xylyl group, mesityl group; acetyl group, propionyl group, butyryl group, isobutyryl This is the case of a linear or branched acyl group having 2 to 18 carbon atoms such as a group, valeryl group, and isovaleryl group. In particular, an unsaturated heterocyclic group or an optionally substituted aryl group in which any one or more of R ^{1 to} R ³ may be independently substituted is preferable. 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 type of the compound represented by the general formula (I) may be used alone, or two or more types 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 the general 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 is an active compound that generates such a sensitizer and at least one of a radical, an acid, and a base by interaction with the sensitizer when exposed to light. The photosensitive composition itself may be either chemically amplified or photopolymerized, or negative or positive.
The chemically amplified negative photosensitive resin composition includes the above sensitizer, an acid generator as an active compound, a film-forming resin that is alkali-soluble, and a crosslinking agent that acts on the alkali-soluble resin under acidic conditions. The thing to contain is mentioned.

Examples of the chemically amplified positive photosensitive resin composition include those containing the above sensitizer, an acid generator as an active compound, and an acid-decomposable group-containing polymer as a film-forming resin.
Moreover, as a photopolymerization type photosensitive resin composition, the thing containing the said sensitizer, the photoinitiator as an active compound, and an ethylenically unsaturated compound is mentioned.
The components and composition other than the sensitizer of the photosensitive resin composition of the present invention will be described below. [Acid generator as an active compound in chemically amplified negative and positive photosensitive resin compositions]
The acid generator of the chemically amplified photosensitive resin composition is not particularly limited as long as it is a compound that generates an acid when receiving actinic rays and is a known acid generator as a resist composition. The one that does not generate acid at the wavelength of. Examples include halogen-containing alkanes, halogen-containing compounds such as halomethylated s-triazine derivatives, onium salts, sulfone compounds, and the like. Among them, in the present invention, sulfonic acid is added by light irradiation. The generated sulfone compound is particularly preferred.

Among the acid generators, the halogen-substituted alkanes among the halogen-containing compounds specifically include dichloromethane, trichloromethane, 1,2-dichloroethane, 1,2-dibromoethane and the like.
Specific examples of halomethylated s-triazine derivatives include 2,4,6-tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 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-triazi 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 are mentioned, among which bis (trihalomethyl) -s-triazine is preferable, and 2-methyl-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) Particularly preferred is -4,6-bis (trichloromethyl) -s-triazine.

Of the acid generators, onium salts include ammonium salts such as tetramethylammonium bromide and tetraethylammonium bromide, diphenyliodonium hexafluoroarsenate, diphenyliodonium tetrafluoroborate, diphenyliodonium p-toluenesulfonate, diphenyliodonium camphorsulfonate , Icyclohexyl salts such as dicyclohexyliodonium hexafluoroarsenate, dicyclohexyliodonium tetrafluoroborate, dicyclohexyliodonium p-toluenesulfonate, dicyclohexyliodonium camphorsulfonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium tetrafluoroborate, triphenyl 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.

  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, 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 compounds, phenylcarbonyl (phenylsulfonyl) diazomethane, naphthylcarbonyl (phenylsulfonyl) di Carbonyl (sulfonyl) such as azomethane, phenylcarbonyl (naphthylsulfonyl) diazomethane, cyclohexylcarbonyl (phenylsulfonyl) diazomethane, t-butylcarbonyl (phenylsulfonyl) diazomethane, phenylcarbonyl (cyclohexylsulfonyl) diazomethane, 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 include the following. A hydrogen atom; a linear or branched alkyl group having 1 to 18 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-heptyl group; A cycloalkyl group having 3 to 18 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group and an adamantyl group; a linear or branched alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group and a hexenyl group; cyclopentenyl Group, cycloalkenyl group having 3 to 18 carbon atoms such as cyclohexenyl group; 2-thienyl group, 2
-Saturated or unsaturated heterocyclic group such as pyridyl group, furyl group, thiazolyl group, benzothiazolyl group, morpholino group, pyrrolidinyl group, tetrahydrothiophene dioxide group; carbon number such as phenyl group, tolyl group, xylyl group, mesityl group Aryl group having 6 to 18 carbon atoms; aralkyl group having 7 to 20 carbon atoms such as benzyl group and phenethyl group; straight chain having 2 to 18 carbon atoms such as acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group and 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, or a tert-butoxy group. Straight chain having 3 to 18 carbon atoms such as propenyloxy group, butenyloxy group, pentenyloxy group, or the like; Cross-linked alkenyloxy groups; straight chain or branched alkylthio groups having 1 to 18 carbon atoms such as methylthio group, ethylthio group, n-propylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group; fluorine atom, Halogen atoms such as chlorine atom and bromine atom; nitro group; cyano group; hydroxyl group; formyl group; sulfonic acid group; carboxyl group; acyloxy group represented by —OCOR ′; amino represented by —NR′R ″ 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';-CONR'R''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 other rings include saturated or unsaturated hydrocarbon rings or heterocyclic rings.
In the general formula (A), Rb is an arbitrary substituent, a hydrogen atom, an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted linear, branched or cyclic alkenyl group, An aryl group that may be substituted, an aralkyl group that may be substituted, a carboxyl group, a cyano group, a nitro group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, and the like, preferably a cyano group, Examples thereof 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, each of which may be substituted, a linear, branched or cyclic alkyl group, an optionally substituted linear, branched or cyclic group. An alkenyl group, an aryl group that may be substituted, an aralkyl group that may be substituted, or a camphor group that may be substituted is represented. Moreover, the hydrogen atom in these substituents may be replaced with a fluorine atom. 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 sec-butoxy. Group, alkoxy group having 1 to 10 carbon atoms such as tert-butoxy group; alkoxyalkoxy having 2 to 12 carbon atoms such as methoxymethoxy group, ethoxymethoxy group, propoxymethoxy group, ethoxyethoxy group, propoxyethoxy group and methoxybutoxy group Group: C3-C15 alkoxyalkoxyalkoxy group such as methoxymethoxymethoxy group, methoxymethoxyethoxy group, methoxyethoxymethoxy group, methoxymethoxyethoxy group, ethoxyethoxymethoxy group; allyloxy group; phenyl group, tolyl group, xylyl group An aryl group having 6 to 12 carbon atoms such as They may be further substituted with a substituent); C2-C12 alkenyloxy groups such as phenoxy group, tolyloxy group, xylyloxy group, naphthyloxy group; acyl groups such as acetyl group and propionyl group; Group; nitro group; hydroxyl group; tetrahydrofuryl group; amino group; alkylamino group having 1 to 10 carbon atoms such as N, N-dimethylamino group and N, N-diethylamino group; methylsulfonylamino group, ethylsulfonylamino group Alkylsulfonylamino groups having 1 to 6 carbon atoms such as n-propylsulfonylamino group; halogen atoms such as fluorine atom, chlorine atom and bromine atom; carbon numbers such as methoxycarbonyl group, ethoxycarbonyl group and 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. Moreover, the hydrogen atom in these substituents may be replaced with a fluorine atom.

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

The acid generator that does not generate acid at the wavelength of the exposure light source is, for example, a wavelength of 405 nm in 5 ml of a 2.0 mmol / dm ³ acetonitrile solution of the acid generator when the light source is a blue-violet laser.
This means that 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} is used as an indicator. After the laser irradiation, an equivalent amount of CVL 2.0 mmol / dm ³ acetonitrile solution is added, and if the absorption at a wavelength of 610 nm is 0.01 or less, no acid is generated.
[Alkali-Soluble Resin and Crosslinking Agent in Chemically Amplified Negative Photosensitive Resin Composition] As the alkali-soluble resin in the chemically amplified negative photosensitive resin composition, the unexposed area becomes alkali-soluble during development, and the alkali developer contains Although it is not particularly limited as long as it elutes, it is usually a novolak resin, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, and acrylic acid, vinyl alcohol or vinylphenol as monomer units. Polymers containing these or derivatives thereof are used. Among these, those containing a polymer unit having a phenolic hydroxyl group are particularly preferred, and novolak resins or polyvinylphenols are preferred.

  As novolak resins, m-cresol, o-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, resorcin, 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, 2-naphthol, etc., in the presence of an acidic catalyst, formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde And aldehydes such as furfural and those obtained by polycondensation with at least one aldehyde selected from ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.Paraformaldehyde and paraaldehyde may be used in place of formaldehyde and acetaldehyde, respectively.

The novolak resin has a polystyrene-reduced weight average molecular weight (hereinafter referred to as “weight average molecular weight Mw by GPC measurement”) measured by gel permeation chromatography (hereinafter abbreviated as “GPC”) of 1,000 to 15. 1,000, preferably 1,500 to 10,000 are used.
As the novolak resin, more preferably, at least one phenol selected from o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, and resorcin is formaldehyde, acetaldehyde, propion. Examples thereof include novolak resins polycondensed with at least one selected from aldehydes such as aldehydes. Among them, the mixing ratio of m-cresol: p-cresol: 2,5-xylenol: 3,5-xylenol: resorcin is 70 to 100: 0 to 30: 0 to 20: 0 to 20: 0 to 20 in molar ratio. A novolak resin which is a polycondensate of phenols and aldehydes is preferred. Among the aldehydes, formaldehyde is particularly preferable.

  Polyvinylphenols include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2- (o-hydroxyphenyl) propylene, 2- (m-hydroxyphenyl) propylene, 2- (p-hydroxyphenyl) propylene Examples thereof include hydroxystyrenes alone or two or more polymers. 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. Therefore, as polyvinylphenols, The polyvinylphenol which may have a substituent of a C1-C4 alkyl group is mentioned.

  Polyvinylphenols are usually obtained by polymerizing hydroxystyrenes which may have a substituent alone or 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 a part of OH groups of the polyvinylphenols is protected with 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 by GPC measurement of 1,000 to 100,000, preferably 1,500 to 50,000 are used.
More preferably, examples of the polyvinylphenol include polyvinylphenol in which the aromatic ring may be substituted with an alkyl group having 1 to 4 carbon atoms, and unsubstituted polyvinylphenol is particularly preferable.

If 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. If the molecular weight is larger than the above range, the solubility of the unexposed portion in the alkaline developer is reduced, and the resist pattern Tend not to be obtained. Of the alkali-soluble resins described above, unsubstituted polyvinylphenol and novolac 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 thereof include compounds in which formalin is allowed to act on melamine, benzoguanamine, glycoluril or urea, or alkyl-modified compounds thereof. , Epoxy compounds, resol compounds and the like.

  Specifically, Mitsui Cyanamid's Cymel (registered trademark) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141,272,254,202,1156,1158, Sanka Chemical's Nicarak (registered trademark) E-2151, MW-100LM, MX-750LM, a compound in which formalin is allowed to act on melamine, or an example of an alkyl modified product thereof As mentioned.

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

  Examples of epoxy compounds include novolak epoxy resins (manufactured by Toto Kasei Co., Ltd., YDP N-638, 701, 702, 703, 704, etc.), amine epoxy resins (manufactured by Toto Kasei Co., Ltd., YH-434, etc.), and bisphenol A epoxy resins. (Japan Epoxy Resin, Epicoat 825, 826, 827, 828, 1001, 1002, 1003, 1055, 1004, 1007, 1009, 1010, etc.), 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 include ether, glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, and butyl glycidyl ether.

Among these, particularly preferred compounds include compounds having —N (CH ₂ OR) ₂ group in the molecule (wherein R represents an alkyl group or a hydrogen atom), and in particular, formalin is added to urea or melamine. Preferred is an acted compound or an alkyl-modified product thereof.
[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 of the alkali-soluble resin. 30 parts by weight, preferably 0.005 to 10 parts by weight, and 0.01 to 30 parts by weight, preferably 0.1 to 20 parts by weight of a sensitizer are used. The ratio of the crosslinking agent to the acid generator is usually 0.05 to 30000 parts by weight, preferably 0.5 to 10000 parts by weight, and the ratio of the sensitizer to the acid generator is usually 0.001 to 30000 parts by weight, preferably 0. 0.01 to 4000 parts by weight.

When 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 crosslinking agent is larger than this range, the coating characteristics of the resist tend to be lowered. Further, when 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 this range, the resist pattern becomes an inverted trapezoid due to a decrease in transparency of the resist film due to the sensitizer, and the resolution tends to decrease.
[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 by an acid generator as an active compound when the photosensitive resin composition is irradiated with actinic rays. Any polymer containing an acid-decomposable group that decomposes and imparts alkali solubility to the polymer itself is not particularly limited.

  Specific examples of the acid-decomposable group include a methoxy group, an ethoxy group, an i-propoxy group, a t-butoxy group and the like, an alkoxy group having 1 to 15 carbon atoms, a methoxymethoxy group, a dimethoxymethoxy group, and an ethoxymethoxy group. 1-methoxyethoxy group, 1-ethoxyethoxy group, 1-propoxyethoxy group, 1-t-butoxyethoxy group, 1-cyclohexyloxyethoxy group, 1-ethoxypropoxy group, etc. 2-15 alkoxycarbonyloxy groups such as methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyloxy group, t-butoxycarbonyloxy group, ethoxy Carbonyloxymethoxy group, n-propyl An alkoxy group at least at the end, such as a C2-C15 alkoxycarbonyloxyalkoxy group such as a poxycarbonyloxymethoxy group, i-propoxycarbonyloxymethoxy group, n-butoxycarbonyloxymethoxy group, t-butoxycarbonyloxymethoxy group, etc. Group which has.

  Examples of the polymer containing the acid-decomposable group include etherification or at least part of the phenolic hydroxyl group of a phenolic hydroxyl group-containing resin such as a phenolic resin such as a novolak resin or a resol resin, and a polyvinylphenol resin. A resin in 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 novolac 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 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 kind of phenols such as biphenyldiol and 2,2-bis (4′-hydroxyphenyl) propane is reacted with an aldehyde such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and furfural under an acid catalyst (N In addition, paraformaldehyde may be used instead of formaldehyde, and paraaldehyde may be used instead of acetaldehyde.) Or a resin obtained by polycondensation with at least one of acetone, methyl ethyl ketone, methyl isobutyl ketone and other ketones. The resol 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 by GPC measurement of 1,000 to 15,000, particularly preferably 1,500 to 10,000.
Polyvinylphenol resins include, for example, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene, trihydroxystyrene, tetrahydroxystyrene, pentahydroxystyrene, 2- (o-hydroxyphenyl) propylene, 2 Hydroxystyrenes such as-(m-hydroxyphenyl) propylene and 2- (p-hydroxyphenyl) propylene (note that these are halogen atoms such as chlorine, bromine, iodine and fluorine on the benzene ring, or carbon numbers 1 to 4 Or an alkyl group may be used as a substituent.) A resin obtained by polymerizing one or more of them 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 by GPC measurement of 1,000 to 100,000, particularly preferably 1,500 to 50,000.

Moreover, as a polymer containing the said acid-decomposable group, the resin which introduce | transduced the said acid-decomposable group by esterifying at least one part of the carboxyl group of carboxyl group-containing vinyl resin can also be mentioned as a preferable thing, for example. . As the carboxyl group-containing vinyl resin, for example, (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and other unsaturated carboxylic acids, 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) ) Vinyl compounds such as acryloylmorpholine, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, vinyl acetate These carboxyl group-containing vinyl resins are preferably those having a weight average molecular weight Mw of 1,000 to 300,000 by GPC measurement (in this specification, “( The term “(meth) acryl” means “acryl or / and methacryl.” The same applies to “(meth) acrylo” and “(meth) acrylate”.
[Composition of chemically amplified positive photosensitive resin composition]
In the above-mentioned chemical amplification type positive photosensitive resin composition, the acid generator as the active compound is usually 0.001 to 30 parts by weight, preferably 0. 0 parts by weight per 100 parts by weight of the acid-decomposable group-containing polymer. 005 to 10 parts by weight, and a sensitizer is used in an amount 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 30000 parts by weight, preferably 0.01 to 4000 parts by weight.

If the amount of the sensitizer is smaller than this range, the sensitivity tends to be low.If the amount of the sensitizer is larger than this range, the resist pattern may be deteriorated due to a decrease in transparency of the resist film by the sensitizer. It tends to be an inverted trapezoid and cause a decrease in resolution.
[Photopolymerization initiator as active compound in photopolymerizable photosensitive resin composition]
The photopolymerization initiator as an active compound constituting the photopolymerizable photosensitive resin composition receives the photoexcitation energy of the sensitizer and emits active radicals when irradiated with light in the presence of the sensitizer. A radical generator that generates an ethylenically unsaturated compound, which will be described later, for polymerization, for example, a hexaarylbiimidazole compound, a titanocene compound, a halogenated hydrocarbon derivative, a diaryliodonium salt, and an organic peroxide Thing etc. are mentioned. Of these, hexaarylbiimidazole compounds and titanocene compounds are preferable, and hexaarylbiimidazole compounds are particularly preferable from the viewpoints of sensitivity as a photosensitive resin composition, adhesion to a substrate, storage stability, and the like.

Specific examples of the hexaarylbiimidazole compound include 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 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 Examples include '-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p-chloronaphthyl) biimidazole. Among them, hexaphenylbiimidazole compounds are preferable, and those in which the o-position of the benzene ring bonded to the 2,2′-position on the imidazole ring is substituted with a halogen atom are more preferable. It is particularly preferred that the benzene ring bonded to the ', 5,5'-position is unsubstituted or substituted with a halogen atom or an alkoxycarbonyl group. These hexaarylbiimidazole compounds are synthesized by a method disclosed in, for example, Bull. Chem. Soc. Japan; 33,565 (1960), J. Org. Chem .; 36, 2262 (1971), etc. May be used in combination with a biimidazole compound.

Specific examples of the titanocene compound include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,4-difluorophenyl), and dicyclopenta. 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 these, 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 containing the above-mentioned photopolymerization initiator when the photosensitive resin composition is irradiated with actinic rays. It is a compound that has at least one radically polymerizable ethylenically unsaturated bond in the molecule that polymerizes and optionally crosslinks and cures.

  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 Unsaturated carboxylic acids such as, and alkyl esters thereof, (meth) acrylonitrile, (meth) acrylamide, styrene, etc., are polymerizable, crosslinkable, and the solubility of the developer in the exposed and unexposed areas associated therewith. From the viewpoint that the difference can be expanded, a compound having two or more ethylenically 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. .

The compounds having two or more ethylenically unsaturated bonds are typically esters of unsaturated carboxylic acids and polyhydroxy compounds, (meth) acryloyloxy group-containing phosphates, hydroxy (meth) acrylates. Examples 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.

  Specific examples of the esters include 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) acrylate 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, trimethylolethane tri (meth) acrylate, tetramethylolethane tri (meth) acrylate, trimethylol Propane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide added tri ( Acrylate), glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition 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 include hexa (meth) acrylate and the like, and similar crotonate, isocrotonate, maleate, itaconate, citraconate and the like.

  Further, as esters thereof, a reaction product of an unsaturated carboxylic acid as described above 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, etc .; a reaction product of an unsaturated carboxylic acid as described above with a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, specifically , Tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tri (meth) acrylate, etc .; reaction product of unsaturated carboxylic acid, polyvalent carboxylic acid and polyhydroxy compound, specifically (meth) A condensate of acrylic acid, phthalic acid and ethylene glycol, Examples include 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. It is done.

  In addition, the (meth) acryloyloxy group-containing phosphates are not particularly limited as long as they are phosphate compounds containing a (meth) acryloyloxy group, but are represented by the following general formula (Ia) or (Ib). Those 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 1 to 4, and 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. These may be used alone or as a mixture.

  Specific examples of urethane (meth) acrylates include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and tetramethylolethanetri. Hydroxy (meth) acrylate compounds such as (meth) acrylate, hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine methyl ester diisocyanate, lysine methyl ester triisocyanate, dimer acid diisocyanate, 1,6,11- Aliphatic polyisoses such as undecatriisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane Cycloaliphatic 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, 6-tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, tolidine diisocyanate, 1,5-naphthalene diisocyanate, tris (isocyanate phenylmethane), tris (isocyanate phenyl) thiophosphate, etc. Heterocyclic polyisocyanates such as aromatic polyisocyanates and isocyanurates DOO, reaction products of the polyisocyanate compounds and the like.

Among these, as urethane (meth) acrylates, compounds having 4 or more urethane bonds [—NH—CO—O—] and 4 or more (meth) acryloyloxy groups in one molecule are preferable. For example, obtained by reacting a compound having four or more hydroxyl groups in one molecule such as pentaerythritol and polyglycerol with a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, and tolylene diisocyanate. Compound (i-1); or a compound having two or more hydroxyl groups in one molecule such as ethylene glycol, “Duranate 24A-100”, “Duranate 22A-75PX”, “Duranate 21S” manufactured by Asahi Kasei Kogyo Co., Ltd. -75E "," Durane " 3 in one molecule such as biuret type such as “18H-70B”, adduct type such as “Duranate P-301-75E”, “Duranate E-402-90T”, “Duranate E-405-80T”, etc. A compound (i-2) obtained by reacting a compound having one or more isocyanate groups; or a compound (i-3) obtained by polymerizing or copolymerizing isocyanate ethyl (meth) acrylate or the like, Compound (i) having 4 or more, preferably 6 or more isocyanate groups in one molecule, such as “Duranate ME20-100” manufactured by Asahi Kasei Kogyo Co., Ltd., pentaerythritol di (meth) acrylate, penta Erythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol Lutri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc., one or more hydroxyl groups and two or more, preferably three or more (meth) acryloyl per molecule. It can be obtained by reacting the compound (ii) having an oxy group.

  Here, the molecular weight of the compound (i) is preferably 500 to 200,000, particularly preferably 1,000 to 150,000. The molecular weight of the urethane (meth) acrylates as described above is preferably 600 to 150,000. Further, as the urethane (meth) acrylates, those having 6 or more urethane bonds are preferable, those having 8 or more are particularly preferable, those having 6 or more (meth) acryloyloxy groups are preferable, and 8 or more What has is especially preferable.

  In addition, such urethane (meth) acrylates include, for example, the compound (i) and the compound (ii) between the former isocyanate group and the latter hydroxyl group in an organic solvent such as toluene or ethyl acetate. It can be produced by a method of reacting at a molar ratio of 1/10 to 10/1 at 10 to 150 ° C. for about 5 minutes to 3 hours using a catalyst such as n-butyltin dilaurate as 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, etc., and the repeating structure of the aryleneoxy group include, 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, x is preferably 4 to 15, y is 1 to 10, and z is 1 to 10.

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

In addition, as the epoxy (meth) acrylates, specifically, (meth) acrylic acid or the hydroxy (meth) acrylate compound as described above, (poly) ethylene glycol polyglycidyl ether, (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 novolac polyepoxy compounds , Aromatic polyepoxy compounds such as brominated phenol novolac polyepoxy compounds, (o-, m-, p-) cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds, sorbitan polyglycidyl ether, tri Examples thereof include reactants with polyepoxy compounds such as heterocyclic polyepoxy compounds such as glycidyl isocyanurate and triglycidyl tris (2-hydroxyethyl) isocyanurate.

In addition to the above, other ethylenically unsaturated compounds 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, (meth) acryloyloxy group-containing phosphates, or Urethane (meth) acrylates are particularly preferred. The proportion of the (meth) acryloyloxy group-containing phosphates with respect to the entire ethylenically unsaturated compound is preferably 1 to 60% by weight, particularly preferably 2 to 40% by weight, The proportion of urethane (meth) acrylates is preferably 0.5 to 50% by weight, particularly preferably 2 to 40% by weight.
[Composition of photopolymerization type negative photosensitive resin composition]
Each content ratio of the ethylenically unsaturated compound, the sensitizer, and the photopolymerization initiator as the active compound in the photopolymerizable negative photosensitive resin composition is sensitized with respect to 100 parts by weight of the ethylenically unsaturated compound. The agent is usually 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, and the photopolymerization initiator is usually 1 to 60 parts by weight, preferably 5 to 40 parts by weight.

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

Specific examples of the carboxyl group-containing vinyl resin include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and other unsaturated carboxylic acids, 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- Vinyl such as (meth) acryloylmorpholine, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, vinyl acetate Examples of the carboxyl group-containing vinyl resin include an acid value of 30 to 250 KOH-mg / g, and a weight average molecular weight Mw by GPC measurement of 1,000 to 300,000. preferable.

  Furthermore, as the carboxyl group-containing vinyl resin, those having an ethylenically unsaturated bond in the side chain are suitable. Specifically, the carboxyl group-containing polymer may be allyl glycidyl ether, glycidyl (meth) acrylate, α -Aliphatic epoxies such as ethyl glycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, itaconic acid monoalkyl monoglycidyl ester, fumaric acid monoalkyl monoglycidyl ester, maleic acid monoalkyl monoglycidyl ester Group-containing unsaturated compound, or 3,4-epoxycyclohexylmethyl (meth) acrylate, 2,3-epoxycyclopentylmethyl (meth) acrylate, 7,8-epoxy [tricyclo [5.2.1.0] deci 2-yl] an alicyclic epoxy group-containing unsaturated compound such as 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 products obtained in this manner, 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 (meta ) Acrylate, vinyl crotonate, vinyl (meth) acrylic A ratio of the compound having two or more unsaturated groups such as imide and unsaturated carboxylic acid such as (meth) acrylic acid, or further unsaturated carboxylic acid ester to the whole compound having the unsaturated group. The reaction product etc. which were copolymerized so that it may become 10-90 mol%, preferably about 30-80 mol% are mentioned.

The content ratio of such a polymer binder in the negative photosensitive resin composition is preferably 50 to 500 parts by weight, and 70 to 200 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated compound as the component. More preferably, it is part.
In addition, the negative photosensitive resin composition in the present invention preferably further contains a hydrogen donating compound for the purpose of improving the photopolymerization initiating 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 Mercapto group-containing compounds such as acrylate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, hexanedithiol, trimethylolpropane tristhioglyconate, pentaerythritol tetrakisthiopropionate, etc. Active thiol compounds, N, N-dialkylaminobenzoic acid ester, N-phenylglycine, or a salt thereof such as ammonium or sodium salt thereof, a derivative such as the above ester, phenylalanine or a salt thereof such as ammonium or sodium salt, the same as above An amino acid having an aromatic ring, such as a derivative such as an ester, or a derivative thereof. Among these, in the present invention, mercapto group-containing compounds and N-phenylglycine, or salts thereof such as ammonium and sodium salts, and derivatives such as the above-described esters are preferred.

It is preferable that the content rate of such a hydrogen donor compound in a negative photosensitive resin composition is 0.01-50 weight part with respect to 100 weight part of said ethylenically unsaturated compounds, 0.1-40 More preferably, it is part by weight.
Moreover, the negative photosensitive resin composition in the present invention preferably contains an amine compound for the purpose of improving the storage stability as the photosensitive resin composition, and the amine compound is aliphatic, Either an alicyclic or aromatic amine may be used, and the amine is not limited to a monoamine, and may be a polyamine such as diamine or triamine, and may be any of primary amine, secondary amine, and tertiary amine. However, it is preferable that pKb is 7 or less.

  Specific examples of the amine compound include butylamine, dibutylamine, tributylamine, amylamine, diamylamine, triamylamine, hexylamine, dihexylamine, trihexylamine, allylamine, diallylamine, triallylamine, triethanolamine, benzylamine. And aliphatic amines optionally substituted with a hydroxyl group or a phenyl group, such as dibenzylamine and tribenzylamine. Of these, 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 preferably 5 to 10 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated compound. Further preferred.
In addition, the negative photosensitive resin composition in the present invention is nonionic, anionic for the purpose of improving the coating property when forming the photosensitive resist material layer on the substrate and the developability of the photosensitive resist material layer. , Cationic, amphoteric, and fluorine-containing surfactants are preferable, and as such surfactants, specifically, as nonionic surfactants, 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 sorbit fatty acid esters, and the like, and anionic surfactants include alkyl sulfonates, alkyl benzene sulfones. Acid salts, alkylnaphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate esters, 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 Examples of the phosphates include quaternary ammonium salts, imidazoline derivatives, amine salts and the like, and examples of the amphoteric surfactants include betaine-type compounds, imidazolium salts, imidazolines. , 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 with respect to 100 parts by weight of the ethylenically unsaturated compound, and 1 to 5 parts by weight. More preferably it is.
Furthermore, the negative photosensitive resin composition in the present invention may contain a silane coupling agent in order to improve adhesion to the substrate. Specific examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltrichlorosilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-methacryloyloxypropyltri 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 of such a silane coupling agent in the negative photosensitive resin composition is preferably 20 parts by weight or less with respect to 100 parts by weight of the ethylenically unsaturated compound, and is 0.1 to 10 parts by weight. More preferably it is.
In addition, each type of the photosensitive resin composition of the present invention described above contains various additives such as dyes, pigments, coatability improvers, development improvers, adhesion improvers and the like as long as the performance is not impaired. It is also possible to do.

  The photosensitive resin composition of the present invention is usually dissolved in a solvent and used to form a photosensitive resist layer. In this case, the solvent used is sufficient for each component of the photosensitive resin composition described above. The solvent is not particularly limited as long as it has a solubility and gives good coating properties. For example, cellosolv 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, pyrubi Ester solvents such as ethyl acid, ethyl-2-hydroxybutyrate, 2-methylacetoacetate, methyl lactate, ethyl lactate, alcohol solvents such as heptanol, hexanol, diacetone alcohol, 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 mixed solvents thereof, and further mixed solvents including aromatic hydrocarbons, etc. Is mentioned.

The use ratio of the solvent is preferably in the range of 1 to 20 times as a weight ratio with respect to 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 the wavelength region of 320 to 450 nm, and has a maximum spectral sensitivity peak in the wavelength region of 390 to 430 nm. Is more preferable. In the case where the spectral sensitivity has a maximum peak in a wavelength region less than the above range, the sensitivity to the laser beam having a wavelength of 320 to 450 nm tends to be inferior as the photosensitive resin composition, while on the other hand, in the wavelength region exceeding the above range. Tends to be inferior in safe light under yellow light.

  In the present invention, the maximum peak of spectral sensitivity is, for example, as described in detail in “Photopolymer Technology” (Akio Yamaoka, published by Nikkan Kogyo Shimbun, 1988, page 262), etc. The exposure wavelength is linear in the horizontal axis direction when the light-sensitive image forming material sample having a photosensitive resin composition layer formed on the substrate surface is spectrally separated from a light source such as a xenon lamp or a tungsten lamp using a spectral sensitivity measuring device. The exposure intensity is set to logarithmically change in the vertical axis direction, and after irradiation and exposure, an image corresponding to the sensitivity of each exposure wavelength is obtained by developing, and from the image height It indicates the maximum peak in the spectral sensitivity curve obtained by calculating the exposure energy capable of forming an image and plotting the wavelength on the horizontal axis and the reciprocal of the exposure energy on the vertical axis.

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 preferably 20 mJ / cm ² or less. When the minimum exposure amount [S ₄₁₀ ] exceeds the above range, although depending on the exposure intensity of the laser light source, the exposure time becomes longer and the practicality tends to be lowered. 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, the minimum exposure amount capable of forming an image at the wavelength 450nm of [S _410] [S _450] (mJ / cm ²⁾ the ratio [S _410] / [S _450] is It is preferably 0.1 or less, and more preferably 0.05 or less. This ratio [S ₄₁₀ ]
If [S ₄₅₀ ] exceeds the above range, it tends to be difficult to achieve both the blue-violet laser sensitivity and the safe light property under a yellow lamp.

Further, the photosensitive resin composition of the present invention has a minimum exposure capable of forming an image at a wavelength of 450 nm with a minimum exposure amount [S _450-650 ] (mJ / cm ² ) capable of forming an image at each wavelength of 450 nm to 650 nm. The ratio [S _450-650 ] / [S ₄₅₀ ] to the amount [S ₄₅₀ ] (mJ / cm ² ) is preferably more than 1. When the ratio [S _450-650 ] / [S ₄₅₀ ] is less than the above range, it tends to be difficult to achieve both the blue-violet laser sensitivity and the safe light property under a yellow light.

Incidentally, the minimum exposure amount [S ₄₁₀ ] capable of forming an image at the wavelength of 410 nm, the wavelength of 450
minimum exposure amount [S ₄₅₀ ] capable of forming an image at nm, and wavelength exceeding 450 nm 650 n
The minimum exposure amount [S _450-650 ] capable of forming an image at each wavelength of m or less is an image calculated from the image height obtained in the measurement of the maximum peak of spectral sensitivity using the above-described spectral sensitivity measuring apparatus. It is calculated as the exposure energy that can be formed, and means the minimum exposure amount that can form an image under the optimum development conditions determined by changing the development conditions such as the type of developer, development temperature, development time, etc. As the optimum development conditions, usually, conditions 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 are employed.

  Further, the photosensitive resin composition of the present invention is a photosensitive resin formed to have a dry film thickness of 10 μm when exposure sensitivity is defined as the minimum exposure amount at which a 10 μm line width image can appear in the same manner as described above. The ratio (S2 / S1) of the exposure sensitivity (S2) of the photosensitive resin composition layer formed to a dry film thickness of 20 μm with respect to the exposure sensitivity (S1) of the resin composition layer is preferably 5 or less, particularly preferably 3 or less. . When the ratio of exposure sensitivity (S2 / S1) is within this range, the change in sensitivity due to film thickness variation is reduced, and favorable image formation is possible 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 film 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 thus determined is preferably 1 or more, and more preferably 1.2 or more. The higher this value, the better.
The photosensitive resin composition of the present invention usually comprises a step of forming a photosensitive resist layer on a conductive substrate to be processed, a step of exposing the photosensitive resist layer with active rays, and a step of developing with an alkaline developer. After that, an image is formed. Then, a circuit pattern is formed on the surface by etching, plating, or the like using the obtained resist pattern layer as a mask.

  Here, as the conductive substrate, copper, aluminum, gold, silver, chromium, zinc, tin, lead, nickel, etc. metal plate; 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, resin such as thermoplastic resin, paper, glass And inorganic materials such as alumina, silica, barium sulfate, calcium carbonate, or composite materials such as glass cloth base epoxy resin, glass nonwoven base epoxy resin, paper base epoxy resin, paper base phenol resin, etc. , The surface of the insulating support having a thickness of about 0.02 to 10 mm, The metal foil such as metal oxide such as genus or indium oxide, tin oxide, indium oxide doped tin oxide (ITO) is heated, pressure-laminated, or the metal is sputtered, vapor-deposited, plated, etc. A metal-clad laminate having a conductive layer of about 1 to 100 μm; a wafer in 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; 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 coating method of 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 that time is such an amount 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, the photosensitive resin composition layer is used from the point of use as an etching resist or a plating resist. 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 seconds to 60 minutes, preferably about 10 seconds to 30 minutes. Is adopted.

  The photosensitive resin composition of the present invention is a photosensitive resin formed as necessary by applying and drying on a temporary support film as a coating solution in which the above components are dissolved or dispersed in the appropriate solvent described above. By covering the surface of the composition layer with a coating film, the photosensitive image forming material of the present invention as a so-called dry film resist material is formed, and the photosensitive resin composition layer side of the image forming material is covered with the coating film. In the case where the photosensitive resin composition is peeled off and laminated on the substrate to be processed, the layer of the photosensitive resin composition of the present invention is formed on the substrate to be processed. Suitable for use as an image forming method in which a photosensitive resin composition layer of the image forming material is scanned and exposed, for example, with a laser beam having a wavelength of 390 to 430 nm and developed to display a negative image. Used.

As a temporary support film in the case of being used as an image forming material as the dry film resist material, a conventionally known film such as a polyethylene terephthalate film, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is used. At that time, when those films have the solvent resistance and heat resistance necessary for the production of the image forming material, the photosensitive resin composition coating solution is directly applied on the temporary support film. The image forming material of the present invention can be prepared by applying and drying, and even if those films have low solvent resistance or heat resistance, for example, polytetrafluoroethylene film or mold release First, a photosensitive resin composition layer is formed on a film having releasability such as a film, and then a temporary support film having low solvent resistance or heat resistance is laminated on the layer, and then the releasability is increased. The image-forming material of the present invention can also be produced by peeling off the film it has.

The solvent and coating method used for coating are the same as described above.
When used as an image forming material as a dry film resist material or the like, the surface of the formed photosensitive resin composition layer may be covered with a coating 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, or a polytetrafluoroethylene film is used as the covering film.

  Further, when the photosensitive resin composition layer side of such an image forming material is covered with a coating film, the coating film is peeled off and laminated on the substrate to be processed by heating, pressing, or the like. The photosensitive image forming material of the present invention formed by the above process, or as described above, a coating liquid of the photosensitive resin composition of the present invention is directly applied and dried to form a photosensitive resin composition layer. The substrate is subjected to etching processing or plating processing on the surface thereof by using a negative image that appears by scanning exposure with a laser beam and developing the photosensitive resin composition layer formed thereon as a resist. Patterns such as circuits and electrodes are formed.

  For exposure, light having a wavelength of 320 to 450 nm is usually used. This light may be monochromatic light or broad light. For example, light having a wavelength of 366 nm, 436 nm or the like of a high-pressure mercury lamp can be used. From the viewpoint of output, stability, photosensitivity, cost, etc., blue of argon ion laser, helium neon laser, YAG laser, semiconductor laser, etc. Of those emitting light in the violet to infrared region, a light source that generates laser light in the blue-violet region having a wavelength range of 390 to 430 nm is particularly preferable. The exposure light source is not particularly limited, and specific examples include an indium gallium nitride semiconductor laser that oscillates light having a wavelength of 405 nm. It is also possible to expose with Deep UV light having a wavelength of 320 nm or less.

When performing heating (PEB) after exposure, a condition of about 90 to 140 ° C. and about 1 to 30 minutes is preferably used using a hot plate or an oven. When an oven is used instead of a hot plate, a longer heating time is usually required than when a hot plate is used.
Developers 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- An alkaline developer comprising an aqueous solution of a secondary amine such as propylamine, a tertiary amine such as triethylamine or trimethylamine, or a quaternary ammonium salt such as tetramethylammonium hydroxide or trimethylhydroxyethylammonium hydroxide is preferably used. Is done. In some cases, an alcohol, a surfactant or the like is added to the developer as necessary.

Development is usually performed by immersing an image forming material in which a photosensitive resist layer is formed in the developer, or by bringing the developer into contact with the photosensitive resist layer of the image forming material by a spray method, a paddle method, or the like. Is preferably carried out at a temperature of about 10 to 50 ° C., more preferably about 15 to 45 ° C. for a time of about 5 seconds to 10 minutes.
In the present invention, the photopolymerizable negative-type image forming material has a blue-violet laser photosensitivity comprising the photosensitive resin composition of the present invention formed on the substrate to be processed as described above. On the resist layer, an oxygen blocking layer for preventing polymerization-inhibiting action due to oxygen of the photopolymerizable photosensitive resin composition, or a light transmission adjusting layer for adjusting the wavelength range of the maximum peak of spectral sensitivity, etc. A protective layer may be formed.

  The oxygen barrier layer is composed of 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. Specifically, polyvinyl alcohol, its partially acetalized product, its cation-modified product with quaternary ammonium salt, etc., its anion-modified product with sodium sulfonate, etc., polypinylpyrrolidone, polyethylene oxide, methylcellulose , Carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and the like.

  Among them, polyvinyl alcohol and derivatives thereof are preferable from the viewpoint of oxygen barrier properties, and vinyl such as polyvinylpyrrolidone and vinylpyrrolidone-vinyl acetate copolymer from the viewpoint of adhesion to the photosensitive resist layer. Pyrrolidone polymers are preferred, and the oxygen barrier layer according to the present invention is preferably 1-20 parts by weight, more preferably 3-20 parts by weight of polyvinyl pyrrolidone polymer, particularly with respect to 100 parts by weight of polyvinyl alcohol or a derivative thereof. It is preferable to use it as a mixture of 15 parts by weight.

  Further, the oxygen barrier layer preferably contains an organic acid such as oxalic acid or an organic acid salt such as ethylenediaminetetraacetic acid from the viewpoint of imparting preservability, and further nonionic such as polyoxyethylene alkylphenyl ether. Oxygen barrier layer, may contain surfactants such as anionic properties such as sodium dodecylbenzenesulfonate, cationic properties such as alkyltrimethylammonium chloride, antifoaming agents, dyes, plasticizers, pH adjusters, etc. The total content of these components is preferably 10% by weight or less, and more preferably 5% by weight or less.

The oxygen-blocking layer is formed as a solution of water or a mixed solvent of water and a water-miscible organic solvent by the same coating method as 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.
Moreover, as what constitutes a light transmittance adjusting layer, for example, a polymer binder that contains a light-absorbing dye in the visible region such as a coumarin-based dye can be mentioned. Can be used as a protective layer having an oxygen blocking ability and a light transmittance adjusting ability.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
In addition, in the following, each evaluation of the obtained photosensitive resin composition and the photosensitive image forming material followed the following method.
<Absorbance>
For a photosensitive resist layer having a dry film thickness of 10 μm formed on a 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. As a result, the absorbance per 1 μm was calculated.

<Maximum peak of spectral sensitivity>
A sample obtained by cutting the image forming material into a size of 50 × 60 mm was used with a diffraction spectroscopic irradiation device (“RM-23” manufactured by Narumi), and a xenon lamp (“UI-501C” manufactured by USHIO INC.).
) And irradiating with light for 10 seconds, setting the exposure wavelength linearly in the horizontal axis direction and logarithmically changing the exposure intensity in the vertical axis direction. Then, by performing development processing under the development conditions described in each example, an image corresponding to the sensitivity of each exposure wavelength is obtained, and the exposure energy capable of image formation is calculated from the image height, the 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]>
Above in the same manner as described in <maximum peak of spectral sensitivity> exposure is conducted by changing the wavelength in a wavelength region of 320～650Nm, the minimum exposure dose capable of forming an image of, at a wavelength of 410nm when developed [S ₄₁₀ ] (MJ / cm ² ) and the minimum exposure amount capable of forming an image at a wavelength of 450 nm [S ₄₅₀ ] (mJ / cm ² ), and the minimum exposure amount capable of forming an image at each wavelength of more than 450 nm and not more than 650 nm [S _{450- 650} ] (mJ / cm ² ) was obtained, and the ratios [S ₄₁₀ ] / [S ₄₅₀ ] and [S _450-650 ] / [S ₄₅₀ ] were calculated and evaluated according to the following criteria.

<Evaluation criteria of [ _S410 ] / [ _S450 ]>
A: [ _S410 ] / [ _S450 ] is 0.03 or less.
B: [ _S410 ] / [ _S450 ] exceeds 0.03 and is 0.05 or less.
C: [S ₄₁₀ ] / [S ₄₅₀ ] is more than 0.05 and 0.1 or less.
D: [ _S410 ] / [ _S450 ] exceeds 0.1.

<[S _450-650 ] / [S ₄₅₀ ] Evaluation Criteria>
A: [S _450-650 ] / [S ₄₅₀ ] is more than 10.
B: [S _450-650 ] / [S ₄₅₀ ] is more than 5 and 10 or less.
C: [S _450-650 ] / [S ₄₅₀ ] is more than 1 and 5 or less.
D: [S _450-650] / [S _450] is 1 or less.

<Exposure sensitivity>
Using a laser light source (“NLHV500C” manufactured by Nichia Corporation) with 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 surface illuminance of 2 μW and a beam spot diameter of 2.5 μm. The scanning exposure is performed while changing the interval and the scanning speed, and then development processing is performed under the development conditions described in each example to display an image. The minimum width required to reproduce a line width of 10 μm is obtained for the obtained image. The exposure amount was determined and used as the exposure sensitivity. As this exposure sensitivity, the exposure sensitivity (S1) when the film thickness of the photosensitive resist layer is 10 μm and the exposure sensitivity (S2) when the film thickness of the photosensitive resist layer is 20 μm are measured, and the ratio (S2 / S1). Was calculated.

<Resolution>
With respect to the obtained resist image, the reproducible line width and pattern shape in the film thicknesses shown in Table 1 were observed, and as a measure of resolution, “film thickness (μm) / reproducible line width (μm ) ”Was calculated.
<Safelight characteristics under yellow light>
After leaving the image forming material under yellow light illumination (conditions where light having a wavelength of about 470 nm or less was blocked) for 1 minute, 2 minutes, 5 minutes, 10 minutes, 20 minutes, 30 minutes, Scanning exposure and development processing were performed, and the standing time until the image changed compared to the above was obtained, and evaluated according to the following criteria.

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

A: No precipitate was observed at all, and the sensitivity and image before and after storage were unchanged.
B: No precipitate is observed, but the sensitivity after storage is slightly lowered.
C: A very small amount of precipitate was observed, and the sensitivity after storage decreased.
[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 hexamethoxymethylmelamine (“Nikarak E-2151” manufactured by Sanwa Chemical Co., Ltd.), represented by the above 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 to obtain a chemically amplified negative. Type photosensitive resin composition (N2) solution.

  The obtained photosensitive resin composition (N2) solution was spin-coated on a glass substrate so as to have a film 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 method for evaluating exposure sensitivity, followed by post-heating treatment in an oven at 100 ° C. for 10 minutes, and then a developer. Then, development processing was performed by dipping for 60 seconds at 20 ° C. using a 0.5 wt% aqueous solution of potassium hydroxide. The evaluation results of the obtained photosensitive resin composition and photosensitive image forming material are shown in Table 1.

[Example 2]
A chemically amplified negative photosensitive resin composition in the same manner as in Example 1 except that the acid generator is a 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 the resulting photosensitive resin composition solution was subjected to image formation in the same manner as in Example 1, and each evaluation result is shown in Table-1.

[Example 3], [Comparative Example 1], [Comparative Example 2]
Instead of the formula (7), the sensitizer is represented by the compound represented by the structural formula (1) (molar extinction coefficient 51,600 at a wavelength of 405 nm) or the following structural formula (51) as shown in Table 1 below. A chemically amplified negative photosensitive resin composition in the same manner as in Example 2 except that the compound (molar extinction coefficient 82,700 at a wavelength of 405 nm) was used (Comparative Example 1 did not use a sensitizer). A solution of (N2) was obtained. The resulting photosensitive resin composition solution was subjected to image formation 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 areas were dissolved in the developer, and no image was formed.
In Comparative Example 2, the safelight property was D and the unexposed part was not completely dissolved, and a good image was not formed. The results are shown in Table-1.
[Example 4]
As a 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, 55 parts by weight of a weight average molecular weight 68,000), 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 1.54Å, Bragg angle (2θ ± 0.2 °) having a maximum diffraction peak at 9.925 °) 12 parts by weight, N-phenylglycine dipolar compound 0.2 parts by weight, leuco crystal violet: 0.4 parts by weight, -0.2 part by weight of phenylacridine and 0.6 part by weight of the sensitizing dye (molar extinction coefficient / 405 nm = 7,320) represented by the structural formula (21) are methyl ethyl ketone / isopropanol (weight ratio 8/2). In addition to 100 parts by weight of the above mixed solvent, the coating liquid prepared by stirring at room temperature is formed on a polyethylene terephthalate film (thickness 19 μm) as a temporary support film, and the dry film thickness becomes 10 μm or 20 μm using an applicator. The film 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 laminate (thickness 1.5 mm, size 250 mm × 200 mm) bonded with a 35 μm thick copper foil is buffed with “Scotch Bright SF” manufactured by Sumitomo 3M, and washed with water. And drying the surface with an air stream, preheating it to 60 ° C. in an oven, and then applying the photosensitive image-forming material obtained above on the copper foil of the copper-clad laminate to the polyethylene film. A photosensitive composition on a copper-clad laminate is obtained by laminating at a peeling surface using a hand-type roll laminator at a roll temperature of 100 ° C., a roll pressure of 0.3 MPa, and a lamination speed of 1.5 m / min. 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 a 0.7 wt% sodium carbonate aqueous solution at 30 ° C. is sprayed as a developing solution to a pressure of 0.15 MPa, and spray development is performed for 1.5 times the minimum development time. The negative image was revealed. The results evaluated in the same manner as in Example 1 are shown in Table 1.

Comparative Example 3
In the photopolymerizable negative photosensitive resin composition (N1) of Example 4, 15 parts by weight of the compound of the structural formula (VIII) is used, and the following structure is 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 is used in the same manner as in Example 4 except that 30 parts by weight of the compound represented by the formula (XI) is used and no sensitizer is used. When it was prepared and subjected to development processing by scanning exposure, all the exposed portions were dissolved in the developer, and no image was formed. The results evaluated in the same manner as in Example 4 are shown in Table 1.

Comparative Example 4
In the photopolymerizable negative photosensitive resin composition (N1) of Example 4, 15 parts by weight of the compound of the structural formula (VIII) is used, and the following structure is used instead of the compounds of the structural formulas (IX) and (X). A photosensitive image was obtained 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 the sensitizer was changed to 1 part by weight of the compound represented by the structural formula (51). A forming material was produced to obtain a substrate to be processed on which a resist image was formed. When an image forming material having a photosensitive resist material layer having a thickness of 10 μm or 20 μm was subjected to scanning exposure and development processing, all the exposed portions were dissolved in the developer and no image was formed. The results evaluated in the same manner as in Example 4 are shown in Table 1.

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

The photosensitive resin composition of the present invention, the photosensitive image forming material using the photosensitive resin composition, and the photosensitive image forming material are printed wiring boards by direct drawing using blue-violet laser light,
It is industrially extremely useful for forming fine electronic circuits such as plasma display wiring boards, liquid crystal display wiring boards, 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 an exposed sensitizer,
A photosensitive resin composition, wherein the sensitizer is a compound of the following general formula (I).

(Here, R ¹ and R ² each independently represents a hydrogen atom or an arbitrary substituent, and R 3 represents an arbitrary substituent.)   The photosensitive resin composition according to claim 1, wherein the sensitizer has a molar extinction coefficient (ε) at 405 nm of 100 or more and 100,000 or less.   The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is a negative type containing an alkali-soluble resin and a crosslinking agent.   3. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is a positive type containing an acid-decomposable group-containing polymer.   3. The photosensitive resin composition according to claim 1, wherein the photosensitive resin 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, wherein the photosensitive image forming material according to claim 6 is laminated on a substrate to be processed such that the photosensitive resin composition layer side is the substrate side. The photosensitive image forming material according to claim 7, wherein the photosensitive resin composition layer laminated on the substrate to be processed has a thickness of 10 μm or more.