JP4581387B2 - Photosensitive resin composition, and 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, and a photosensitive image forming material and a photosensitive image forming material using the photosensitive resin composition.

  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, and semiconductor packages, 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. 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, and the like 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. For example, JP-A-2002-258478 discloses a resin, a photoacid generator and a sensitizer. A photosensitive resin composition is disclosed.

  However, the photosensitive resin composition proposed in Japanese Patent Application Laid-Open No. 2002-258478 is a photosensitive resin composition suitable for image formation using visible laser light. Inferior, there is a restriction that work in a dark room environment such as red light illumination is necessary.

  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 always 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, so image formation with a blue-violet laser is impossible. Further, as a photosensitive resin composition containing a dye having absorption in the blue-violet region, for example, as shown in Polymer Engineering and Science (1983) Vol.23 No.18 P.1022, a coumarin-based light is used. Although a polymerization system is known, since this has absorption at a wavelength of about 480 nm, it is insensitive to a violet laser having a wavelength of 350 to 450 nm and is inferior in safe light property under a yellow light.

JP-A-59-208541 discloses a photopolymerizable composition containing a sensitizing dye having a nitrogen-containing 6-membered ring structure condensed with a benzene ring and an ethylenically unsaturated compound. Although the dye is sensitive to exposure to light in the blue-violet region, its solubility in the solvent is low, so for example, the solvent when applying the photopolymerizable composition to the support is limited, or the solubility is low. Since it is low, the sensitizing dye is crystallized at the time of application, and there is a problem that a uniform coating film cannot be obtained.
JP 2002-258478 A JP 59-208541 A Polymer Engineering and Science (1983) Vol.23 No.18 P.1022

  The present invention solves the above-mentioned conventional problems, and provides a photosensitive resin composition having good solubility in a solvent, excellent safelight under a yellow light, and excellent sensitivity and resolution in a blue-violet region. The purpose is to provide.

The negative photosensitive resin composition of the present invention comprises a sensitizer and an active compound that generates at least one of a radical, an acid, and a base by interaction with the sensitizer when exposed to light. The negative photosensitive resin composition to be contained is characterized in that the sensitizer contains a compound represented by the following general formula [I].

（一般式［Ｉ］中、Ｒ⁷は下記一般式［II］

（一般式［II］中、Ｒ¹⁰は水素原子又は任意の置換基を表し、Ｘは２価の任意の原子又は置換基を表す。但し、Ｒ⁶とＲ¹⁰、又は、Ｒ⁸とＲ¹⁰が互いに結合して、置換基を有していても良い環を形成していても良い。）で表される置換基を表し、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁸及びＲ⁹は、それぞれ独立して水素原子又は任意の置換基を表す。但し、Ｒ¹〜Ｒ ⁶ 、Ｒ ⁸ 及びＲ⁹のうち隣り合う置換基同士、Ｒ¹とＲ⁹、及びＲ⁵とＲ⁶、のうちの１又は２以上の組み合せでそれぞれ互いに結合して、置換基を有していても良い環を形成していても良い。）

(In the general formula [I], R ⁷ represents the following general formula [II].

(In the general formula [II], R ¹⁰ represents a hydrogen atom or an arbitrary substituent, and X represents an arbitrary divalent atom or substituent. However, R ⁶ and R ¹⁰ , or R ⁸ and R ^{10. May} be bonded to each other to form a ring which may have a substituent.), And R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ and R ⁹ each independently represents a hydrogen atom or an arbitrary substituent. However, adjacent substituents among R ¹ to R ⁶ , R ⁸ and R ⁹ , R ¹ and R ⁹ , and one or a combination of two or more of R ⁵ and R ⁶ are bonded to each other, A ring which may have a substituent may be formed. )

  In the present invention, the specific sensitizing dye represented by the above general formula [I] and an active compound that 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 high photosensitivity even in a specific wavelength region where the active compound cannot function.

The negative photosensitive image forming material of the present invention is characterized in that such a layer of the negative photosensitive resin composition of the present invention is formed on a temporary support film.

The negative photosensitive image forming material of the present invention is obtained by laminating such a negative photosensitive image forming material of the present invention on the substrate to be processed on the negative photosensitive resin composition layer side. And

  According to the present invention, a photosensitive resin composition having good solubility in a solvent, excellent in safe light under yellow light, high sensitivity and high resolution in the blue-violet region, and this photosensitive resin composition A photosensitive image forming material and a photosensitive image forming material using the above are provided.

  Embodiments 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 absorbs light having a wavelength of 320 to 450 nm, and has a molar extinction coefficient (ε) at a wavelength of 405 nm of 100 or more and 100,000. Hereinafter, a light-absorbing dye having a function of efficiently absorbing light having a wavelength in the blue-violet region and generating at least one of a radical, an acid, and a base from an active compound by interaction with an active compound described below. is there.

The sensitizer is more preferably a compound in which R ⁷ in the general formula [I] is a substituent represented by the following general formula [II].

（一般式［II］中、Ｒ¹⁰は水素原子又は任意の置換基を表し、Ｘは２価の任意の原子又は置換基を表す。但し、Ｒ⁶とＲ¹⁰、又は、Ｒ⁸とＲ¹⁰が互いに結合して、置換基を有していても良い環を形成していても良い。）

(In the general formula [II], R ¹⁰ represents a hydrogen atom or an arbitrary substituent, and X represents an arbitrary divalent atom or substituent. However, R ⁶ and R ¹⁰ , or R ⁸ and R ^10. May be bonded to each other to form a ring which may have a substituent.

  The sensitizer is more preferably a compound represented by any one of the following general formulas [III] to [VII].

（一般式［III］〜［VII］中、Ｒ¹〜Ｒ⁹は前記一般式［Ｉ］におけると同義である。Ｙは酸素原子又はＮ−Ｒ¹⁶基を表し、Ｒ¹⁰〜Ｒ¹⁶は、それぞれ独立して水素原子又は任意の置換基を表す。但し、Ｒ⁶とＲ¹⁰、Ｒ⁸とＲ¹⁰、Ｒ¹⁰とＲ¹¹、Ｒ⁸とＲ¹²、Ｒ¹¹とＲ¹²、Ｒ¹⁰とＲ¹³、Ｒ⁸とＲ¹³、Ｒ¹⁰とＲ¹⁴、Ｒ¹⁰とＲ¹⁵、の組み合せでそれぞれ互いに結合して、置換基を有していても良い環を形成していても良い。）

(In the general formulas [III] to [VII], R ^{1 to} R ⁹ have the same meanings as in the general formula [I]. Y represents an oxygen atom or a N—R ¹⁶ group, and R ^{10 to} R ¹⁶ represent Each independently represents a hydrogen atom or an arbitrary substituent, provided that R ⁶ and R ¹⁰ , R ⁸ and R ¹⁰ , R ¹⁰ and R ¹¹ , R ⁸ and R ¹² , R ¹¹ and R ¹² , R ¹⁰ and R ¹³ , R ⁸ and R ¹³ , R ¹⁰ and R ¹⁴ , and R ¹⁰ and R ¹⁵ may be combined with each other to form a ring which may have a substituent.

In the general formula [I], R ² and / or R ³ are preferably not a hydrogen atom but an arbitrary substituent.

In the general formulas [I] to [VII], examples of the substituent represented by R ^{1 to} R ¹⁶ include the following.

A hydrogen atom; a linear or branched alkyl group having 1 to 18 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and an n-heptyl group; 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; C3-C18 cycloalkenyl groups such as pentenyl group and cyclohexenyl group; 2-thienyl group, 2-pyridyl group, furyl group, thiazolyl group, benzothiazolyl group, morpholino group, pyrrolidinyl group, tetrahydrothiophene dioxide group, etc. Saturated or unsaturated heterocyclic group; aryl group having 6 to 18 carbon atoms such as phenyl group, tolyl group, xylyl group and mesityl group Aralkyl groups having 7 to 20 carbon atoms such as benzyl group and 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; A linear or branched alkoxy group having 1 to 18 carbon atoms such as a group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group; propenyloxy group, butenyloxy group A straight or branched alkenyloxy group having 3 to 18 carbon atoms such as pentenyloxy group; carbon number such as methylthio group, ethylthio group, n-propylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group 1-18 linear or branched alkylthio group; halogen atom such as fluorine atom, chlorine atom, bromine atom; nitro group; cyano group; hydroxyl group Formyl group; a sulfonic group; a carboxyl group; an acyloxy group represented by -OCOR ^31; carbamates represented by -NHCOOR ^35; acylamino group represented by -NHCOR ^34; -NR ³² amino group represented by R ³³ Group; -sulfonamide group represented by NHSOOR ³⁶ ; -carboxylic acid ester group represented by -COOR ³⁷ ; -carbamoyl group represented by -CONR ³⁸ R ³⁹ ; -sulfamoyl group represented by -SOONR ⁴⁰ R ⁴¹ ;- Examples thereof include a sulfonic acid ester group represented by SO ₂ OR ⁴² ; a sulfonyl group represented by SO ₂ R ⁴³ and the like.

R ^{1 to} R ¹⁶ contained in one compound may be the same group or different groups.

R ^{31 to} R ⁴³ represent a hydrogen atom or an arbitrary substituent. Among these, as an arbitrary substituent, specifically, an alkyl group exemplified as a specific example of R ^{1 to} R ¹⁶ ; Alkenyl group; cycloalkenyl group; heterocyclic group; aryl group; aralkyl group; acyl group; alkoxy group; alkenyloxy group; alkylthio group; cyano group, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl Groups, carboxylic acid ester groups having 2 to 18 carbon atoms, such as a tert-butoxycarbonyl group, a phenoxycarbonyl group, and a benzyloxycarbonyl group.

In the general formulas [I] and [III] to [VII], R ¹ and R ¹⁶ which are substituents on the nitrogen atom are preferably each independently a hydrogen atom; A branched alkyl group; a cycloalkyl group having 3 to 18 carbon atoms; a linear or branched alkenyl group having 2 to 18 carbon atoms; a cycloalkenyl group having 3 to 18 carbon atoms; a saturated or unsaturated heterocyclic group; A 6-18 aryl group; an aralkyl group having 7-20 carbon atoms; a linear or branched acyl group having 2-18 carbon atoms; a hydroxyl group; a sulfonyl group, more preferably a hydrogen atom, an alkenyl group, a cyclo An alkenyl group and an aryl group are mentioned.

In the general formulas [I] and [III] to [VII], R ^{2 to} R ⁵ which are substituents on the nitrogen-containing 5-membered ring are preferably each independently a hydrogen atom; 18 linear or branched alkyl group; C3-C18 cycloalkyl group; C2-C18 linear or branched alkenyl group; C3-C18 cycloalkenyl group. Among these, in particular, R ² and / or R ³ is preferably not an hydrogen atom but an arbitrary substituent, for example, an alkyl group or a cycloalkyl group.

In the general formulas [I] and [III] to [VII], R ⁶ and R ⁹ which are substituents on the benzene ring are preferably each independently a hydrogen atom; A linear or branched alkyl group having 3 to 18 carbon atoms; a linear or branched alkenyl group having 2 to 18 carbon atoms; a cycloalkenyl group having 3 to 18 carbon atoms; a saturated or unsaturated heterocyclic ring A group having 6 to 18 carbon atoms; an aralkyl group having 7 to 20 carbon atoms; a linear or branched acyl group having 2 to 18 carbon atoms; a linear or branched alkoxy group having 1 to 18 carbon atoms; A linear or branched alkenyloxy group having 3 to 18 carbon atoms; a linear or branched alkylthio group having 1 to 18 carbon atoms; a halogen atom; a nitro group; a hydroxyl group; a sulfonic acid group; a carboxyl group; an acyloxy group; A carbamate group; a sulfonamide group; a carboxylic acid ester group; a carbamoyl group; a sulfamoyl group; a sulfonic acid ester group; a sulfonyl group, and more preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkylthio group, a nitro group. Group, hydroxyl group and amino group.

R ⁷ which is a substituent on the benzene ring in the general formula [I] and R ⁸ which is a substituent on the benzene ring in the general formulas [I] and [III] to [V] are preferably respectively Independently, a hydrogen atom; a linear or branched alkyl group having 1 to 18 carbon atoms; a cycloalkyl group having 3 to 18 carbon atoms; a linear or branched alkenyl group having 2 to 18 carbon atoms; A saturated or unsaturated heterocyclic group; an aryl group having 6 to 18 carbon atoms; an aralkyl group having 7 to 20 carbon atoms; a linear or branched acyl group having 2 to 18 carbon atoms; 18 straight-chain or branched alkoxy groups; straight-chain or branched alkenyloxy groups having 3 to 18 carbon atoms; straight-chain or branched alkylthio groups having 1 to 18 carbon atoms; halogen atoms; nitro groups; hydroxyl groups; amino groups ; Acylamino group Include groups represented by the general formula [II], in particular, hydrogen atoms as R ^8, an alkyl group, a cycloalkyl group, an alkoxy group, an alkylthio group, an amino group, an acylamino group are preferred, also, R ⁷ is The substituent represented by the general formula [II] is preferable. X in the general formula [II] is an oxygen atom; a sulfur atom; a substituted or unsubstituted methylene group having 1 to 18 carbon atoms; a substituted or unsubstituted imino group; more preferably an oxygen atom, substituted or Examples thereof include an unsubstituted methylene group and a substituted or unsubstituted imino group.

Of the substituents described above as the substituents for R ^{1 to} R ¹⁶ , the preferred ring substituents for R ¹⁰ in the general formula [II] are as shown in the following table, and more preferably the ring substituents for R ^10. Are different from each other in the general formulas [III] to [VII] and are as shown in the following table (in the following table, preferred substituents are marked with ○, and particularly preferred substituents are marked with ◎). )

Moreover, among the substituents described above as the substituents for R ^{1 to} R ¹⁶ , preferred substituents for R ^{11 to} R ^{14 in} the general formulas [IV] to [VI] are independently as shown in the following table. (In the table below, preferred substituents are marked with ○, and particularly preferred substituents are marked with ◎).

  In the general formula [VI], Y is preferably an oxygen atom; an amino group; a linear or branched alkylamino group having 1 to 18 carbon atoms; a linear or branched acylamino group having 1 to 18 carbon atoms, and more preferably. Includes an amino group and an alkylamino group.

In the general formula [VII], R ¹⁵ is preferably a substituent represented by Table 1 as a preferred substituent for R ^{10 in the} general formula [VII].

In the general formula [I], ^{one or more} of R ^{1 to} R ⁹ which are adjacent to each other (substituents substituted with atoms adjacent to each other), R ¹ and R ⁹ , and R ⁵ and R ⁶ . May be combined with each other to form a ring which may have a substituent. The case where such a ring is formed is illustrated below. However, in the following, substituents on the formed ring are omitted.

In addition, the alkyl group, alkenyl group, aryl group, and heterocyclic group exemplified as groups represented by R ^{1 to} R ¹⁶ and R ^{31 to} R ⁴³ may be further substituted. Further, two adjacent of R ¹ to R ⁹ as described above, R ¹ and R ^9, R ⁵ and R ^6, R ⁶ and R ^10, R ⁸ and R ^10, R ¹⁰ and R ^11, R ⁸ The ring formed by combining R ¹² , R ¹¹ and R ¹² , R ¹⁰ and R ¹³ , R ⁸ and R ¹³ , R ¹⁰ and R ¹⁴ , and R ¹⁰ and R ¹⁵ may also have a substituent. In this case, examples of the substituent include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group and the like, an alkoxy group having 1 to 10 carbon atoms; Group, ethoxymethoxy group, propoxymethoxy group, ethoxyethoxy group, propoxyethoxy group, methoxybutoxy group, etc., alkoxyalkoxy groups 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) Phenoxy group, tolyloxy An aryloxy group having 6 to 12 carbon atoms such as a silyl group, a xylyloxy group, and a naphthyloxy group; an alkenyloxy group having 2 to 12 carbon atoms such as an allyloxy group and a vinyloxy group; an acyl group such as an acetyl group and a propionyl group; A nitro group; a hydroxyl group; a tetrahydrofuryl group; an amino group; an alkylamino group having 1 to 10 carbon atoms such as an N, N-dimethylamino group and an N, N-diethylamino group; a methylsulfonylamino group, an ethylsulfonylamino group; C1-C6 alkylsulfonylamino groups such as n-propylsulfonylamino group; halogen atoms such as fluorine atom, chlorine atom and bromine atom; methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group , N-butoxycarbonyl, etc. Nyl group; C2-C7 alkylcarbonyloxy group such as methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group; methoxycarbonyloxy group, ethoxy Examples thereof include an alkoxycarbonyloxy group having 2 to 7 carbon atoms such as a carbonyloxy group, an n-propoxycarbonyloxy group, an isopropoxycarbonyloxy group, and an n-butoxycarbonyloxy 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 compounds represented by the general formulas [III] to [VII], which are preferable compounds among the compounds represented by the general formula [I], include the following. It is not limited to.

  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 reliably 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 A cycloalkenyl group having 3 to 18 carbon atoms such as a cyclohexenyl group; a saturated group such as 2-thienyl group, 2-pyridyl group, furyl group, thiazolyl group, benzothiazolyl group, morpholino group, pyrrolidinyl group, tetrahydrothiophene dioxide group Or unsaturated heterocyclic group; carbon 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. A linear or branched alkenyloxy group having 3 to 18 carbon atoms such as propenyloxy group, butenyloxy group, pentenyloxy group; methylthio group, ethylthio group, n-propylthio group, n-butylthio group, sec-butylthio group, tert; -C1-C18 linear or branched alkylthio group such as butylthio group; fluorine atom, chlorine atom, odor Nitro group; cyano group; hydroxyl group; formyl group; sulfonic acid group; carboxyl group; acyloxy group represented by —OCOR ′; amino group represented by —NR′R ″; An acylamino group represented by '; a carbamate group represented by -NHCOOR'; a sulfonamide group represented by -NHSOOR '; a carboxylic acid ester group represented by -COOR'; and a -CONR'R '' Carbamoyl group; a sulfamoyl group represented by —SOONR′R ″; a sulfonic acid ester group represented by —SO ₂ OR ′, and the like (R ′ and R ″ are alkyl groups).

  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 optionally substituted aryl group, an optionally substituted aralkyl group, or an optionally substituted camphor group 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 and 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, when the light source is a blue-violet laser, when 5 ml of a 2.0 mmol / dm ³ acetonitrile solution of the acid generator is irradiated with 250 mJ of laser having a wavelength of 405 nm. Say something that does not generate acid. 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. Then, an equivalent amount of CVL 2.0 mmol / dm ³ acetonitrile solution is added after laser irradiation, and no acid is generated if the absorption at a wavelength of 610 nm is 0.01 or less.

[Alkali-soluble resin and crosslinking agent in chemically amplified negative photosensitive resin composition]
The alkali-soluble resin in the chemically amplified negative photosensitive resin composition is not particularly limited as long as the unexposed portion becomes alkali-soluble during development and can be eluted in an alkali developer. Polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, polymers containing acrylic acid, vinyl alcohol or vinyl phenol as monomer units, 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 condensed with at least one aldehyde or ketone 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. , 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, Examples of 1141, 272, 254, 202, 1156, 1158, Sanka Chemical's Nicarac (registered trademark) E-2151, MW-100LM, MX-750LM, a compound obtained by allowing formalin to act on melamine, or 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, glycidyl ether adipate, glycidyl phthalate, 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 an alkoxy group having 1 to 15 carbon atoms such as a methoxy group, an ethoxy group, an i-propoxy group, and a t-butoxy group, a methoxymethoxy group, a dimethoxymethoxy group, and an ethoxymethoxy group. 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 terminal, such as an alkoxycarbonyloxyalkoxy group having 2 to 15 carbon atoms 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 of at least a part of phenolic hydroxyl groups of phenolic hydroxyl group-containing resins such as phenolic resins such as novolac resins and resol resins, and polyvinylphenol resins. A resin in which the acid-decomposable group is introduced by esterification is preferred. Among them, in the present invention, a resin in which the acid-decomposable group is introduced into a polyvinylphenol resin or a novolak resin is preferable, and a resin in which the acid-decomposable group is introduced into a polyvinylphenol resin is particularly preferable.

  Here, as described above, the novolak resin is, for example, phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, o-ethylphenol, m-ethylphenol, p -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 allowed to react with an aldehyde such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, furfural, etc. under an acid catalyst. 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 ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. The resol resin is a resin obtained by polycondensation 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 atoms of 1 to 4 Or an alkyl group may be substituted 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 the polymer containing the acid-decomposable group, for example, a resin in which at least a part of the carboxyl group of the carboxyl group-containing vinyl resin is esterified to introduce the acid-decomposable group can be mentioned as a preferable one. . 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 as measured by GPC (in this specification, “( “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 of 0.01 to 30 parts by weight, preferably 0.1 to 20 parts by weight are used. 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 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, an organic borate And organic peroxides. Of these, hexaarylbiimidazole compounds, organoborates and titanocene compounds are preferred from the standpoints of sensitivity as a photosensitive resin composition, adhesion to a substrate, and storage stability, and hexaarylbiimidazole compounds are preferred. Particularly preferred.

  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) Bi Midazole, 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'-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.

  In addition, the hexaarylbiimidazole compound conventionally known as a photopolymerization initiator in the photosensitive resin composition has a melting point of 190 ° C. or higher, for example, about 196 to 202 ° C., and an X-ray having a wavelength of 1.54 mm. Although it has a maximum diffraction peak at a Bragg angle (2θ ± 0.2 °) of 9.925 ° in the diffraction spectrum, the hexaarylbiimidazole compound in the present invention has a solubility in a coating solvent and a photosensitive resin composition. From the standpoint of dispersion stability in the material, etc., the melting point is 180 ° C. or lower, further 175 ° C. or lower, and the Bragg angle (2θ ± 0.2 °) in the X-ray diffraction spectrum at a wavelength of 1.54 ° 21. It is optimal to have a maximum diffraction peak at 16 °, and examples of the optimal hexaarylbiimidazole compound include 2.2′- Bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5 5'-tetra (p-methoxyphenyl) biimidazole and the like are mentioned. Among them, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2' -Bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetra (p-methoxyphenyl) biimidazole is particularly preferred.

  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.

  Examples of the organic borates include organic boron ammonium complexes, organic boron phosphonium complexes, organic boron sulfonium complexes or organic boron oxosulfonium complexes, organic boron iodonium complexes, and organic boron transition metal coordination complexes. Examples of the organic boron anion include n-butyl-triphenyl boron anion, n-butyl-tris (2,4,6-trimethylphenyl) boron anion, n-butyl-tris (p-methoxyphenyl) boron anion, n-butyl-tris (p-fluorophenyl) boron anion, n-butyl-tris (m-fluorophenyl) boron anion, n-butyl-tris (3-fluoro-4-methylphenyl) boron anion, n-butyl- Tris (2,6-difluorophenyl) boron anion, n-butyl -Tris (2,4,6-trifluorophenyl) boron anion, n-butyl-tris (2,3,4,5,6-pentafluorophenyl) boron anion, n-butyl-tris (p-chlorophenyl) boron Anions and alkyl-triphenyl boron anions such as n-butyl-tris (2,6-difluoro-3-pyrrolylphenyl) -boron anion are preferred, and examples of counter cations include ammonium cation, phosphonium cation, sulfonium cation, Onium compounds such as iodonium cations are preferred, and organic ammonium cations such as tetraalkylammonium are particularly preferred.

[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. .

  Typically, compounds having two or more ethylenically unsaturated bonds include esters of unsaturated carboxylic acids and polyhydroxy compounds, (meth) acryloyloxy group-containing phosphates, and 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, polyethylene glycol (addition number 2-14), propylene glycol, polypropylene glycol (addition number 2-14), neopentyl glycol, Hexamethylene glycol, nonamethylene glycol, trimethylolethane, tetramethylolethane, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, sorbitol, and their ethylene oxide adducts, propylene oxide adducts, diethanolamine, triethanolamine, etc. Reaction products with aliphatic polyhydroxy compounds, such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethyl 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, trimethylolpropane di (meth) acrylate, trimethylolpropane Tri (meth) acrylate, trimethylolpropane ethylene oxide addition tri (meth) acrylate, glycerol di (meth) acrylate, glyce 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, di Pentaerythritol 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 hexa (meth) acrylate, etc., and similar crotonates, isochromes Examples include tonate, maleate, itaconate, and citraconic acid.

  Further, as the esters thereof, an unsaturated carboxylic acid as described above and an aromatic polyhydroxy compound such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A or the like, or an ethylene oxide adduct or a glycidyl group-containing compound adduct thereof. Reactants, specifically hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A Bis [trioxyethylene (meth) acrylate], bisphenol A bis [pentaoxyethylene (meth) acrylate], bisphenol A bis [hexaoxyethylene (meth) acrylate], bisphenol A reaction product of an unsaturated carboxylic acid as described above and a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, specifically, bis [glycidyl ether (meth) acrylate] 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) acrylic Condensate of acid, phthalic acid and ethylene glycol, condensate of (meth) acrylic acid, maleic acid and diethylene glycol, condensate of (meth) acrylic acid, terephthalic acid and pentaerythritol, (meth) acrylic acid and adipine Examples include condensates of acid, butanediol, and glycerin.

  Further, the (meth) acryloyloxy group-containing phosphates are not particularly limited as long as they are phosphate compounds containing a (meth) acryloyloxy group. Those are preferred.

（一般式(Ia)及び(Ib)中、Ｒ²¹は水素原子又はメチル基を示し、ｎは１〜２５の整数、ｍは１、２、又は３である。）

(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, and 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 polyisocyanates 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, a compound having 4 or more urethane bonds [—NH—CO—O—] and 4 or more (meth) acryloyloxy groups in one molecule is preferable. For example, obtained by reacting a compound having 4 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 and 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.

（一般式(II)中、Ｒ²²はアルキレンオキシ基又はアリーレンオキシ基の繰り返し構造を有し、且つＲ²³と結合し得るオキシ基を４〜２０個有する基を示し、Ｒ²³及びＲ²⁴は各々独立して炭素数が１〜１０のアルキレン基を示し、Ｒ²⁵は（メタ）アクリロイルオキシ基を１〜１０個有する有機残基を示し、Ｒ²²、Ｒ²³、Ｒ²⁴、及びＲ²⁵は置換基を有していてもよく、ｘは４〜２０の整数、ｙは０〜１５の整数、ｚは１〜１５の整数である。）

(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.

  Moreover, as the epoxy (meth) acrylates, specifically, (meth) acrylic acid or a 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. Furthermore, those containing a polymer binder component are preferred. The polymer binder is preferably a carboxyl group-containing resin from the viewpoint of alkali developability and the like. In the present invention, a styrene monomer, a (meth) acrylic acid ester monomer, and a (meth) acrylic are used. A copolymer having a constitutional repeating unit derived from each monomer of an acid is particularly preferable. In addition, as the copolymer, structural repeating units derived from styrene monomer, (meth) acrylic acid ester monomer, and (meth) acrylic acid monomer are each 3 to 30 mol. %, 10 to 70 mol%, and 10 to 60 mol% are preferable, and ratios of 5 to 25 mol%, 20 to 60 mol%, and 15 to 55 mol% are particularly preferable, respectively.

  Here, specific examples of the styrene monomer in the copolymer include α-substituted alkylstyrenes such as styrene, α-methylstyrene, α-ethylstyrene, o-methylstyrene, and m-methyl. Nuclear substituted alkyl styrene such as styrene, p-methyl styrene, 2,5-dimethyl styrene, o-hydroxy styrene, m-hydroxy styrene, p-hydroxy styrene, dihydroxy styrene, etc., nuclear substituted hydroxy styrene, p-chlorostyrene, p -Nuclear substituted halogenated styrene such as bromostyrene and dibromostyrene, etc., and examples of the acrylate ester monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate , (Meth) acrylic acid propyl, (meth) acrylic acid n-butyl, (meth) acrylic acid Preferably (C1-C12) of (meth) acrylic acid, such as i-butyl oxalate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and octyl (meth) acrylate, More preferably, carbon number 1-8 alkyl esters and substituted alkyl esters such as glycidyl (meth) acrylate, benzyl (meth) acrylate, aminoethyl (meth) acrylate, (meth) acrylic acid-N, N-dimethylaminoethyl, etc. Is mentioned.

  In addition, as the copolymer in the present invention, in addition to the structural repeating unit derived from each monomer of the styrene monomer, (meth) acrylic acid ester monomer, and (meth) acrylic acid. Furthermore, for example, unsaturated carboxylic acids such as crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N , N-dimethyl (meth) acrylamide, (meth) acrylic acid derivatives such as N, N-dimethylaminoethyl (meth) acrylamide, and other copolymerizable monomers such as vinyl compounds such as vinyl acetate and vinyl chloride The content of the constitutional repeating unit derived from these other monomers may be contained in the entire copolymer. Preferably 10 mol% or less of the.

  In addition, these copolymers preferably have an acid value of 30 to 250 mg-KOH / g and a polystyrene equivalent weight average molecular weight of 1,000 to 300,000.

  Further, as the carboxyl group-containing resin, those having an ethylenically unsaturated bond in the side chain are also suitable. Specifically, for example, 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.

  Further, as the carboxyl group-containing resin, an unsaturated group and carboxyl group-containing epoxy resin in which a polyvalent carboxylic acid or an anhydride thereof is added to an α, β-unsaturated monocarboxylic acid adduct of an epoxy resin can also be mentioned. .

  In the present invention, the unsaturated group- and carboxyl group-containing epoxy resin is specifically an ester bond formed by ring-opening addition of a carboxyl group of an α, β-unsaturated monocarboxylic acid to an epoxy group of an epoxy resin. An ethylenically unsaturated bond is added via (-COO-), and the residual hydroxyl group is formed via the ester bond formed by the reaction of the carboxyl group of the polyvalent carboxylic acid or its anhydride with the resulting hydroxyl group. To which a carboxyl group is added.

  Specific examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, and trisphenol epoxy resin. Of these, phenol novolac epoxy resins or cresol novolac epoxy resins are particularly preferable. Specific examples of the α, β-unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and the like. (Meth) acrylic acid is particularly preferred. Specific examples of the polyvalent carboxylic acid or anhydride thereof include oxalic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendo Examples include methylenetetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, and anhydrides thereof, among which maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferable, Tetrahydrophthalic anhydride is particularly preferred.

  Among the unsaturated group- and carboxyl group-containing epoxy resins described above, in the present invention, the epoxy resin is a phenol novolac epoxy resin from the aspects of sensitivity as a photopolymerizable composition, resolution, adhesion to a substrate, and the like. Alternatively, a cresol novolac epoxy resin, in which the α, β-unsaturated monocarboxylic acid is (meth) acrylic acid, and the polyvalent carboxylic acid or anhydride thereof is tetrahydrophthalic anhydride is particularly preferable. Moreover, what has an acid value of 20-200 mg-KOH / g is preferable, and it is still more preferable that it is 30-180 mg-KOH / g. Moreover, the thing whose weight average molecular weights by a gel permeation chromatography are 2,000-200,000 is preferable, and it is still more preferable that it is 3,000-150,000.

  Specific examples of the structural repeating unit of the unsaturated group- and carboxyl group-containing epoxy resin in the present invention are shown below.

  Further, the negative photosensitive resin composition in the present invention preferably further contains a hydrogen donating compound for the purpose of improving the photopolymerization initiation ability and the like. -Mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, ethylene glycol dithiopropio 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 a bipolar ion compound thereof, phenylalanine or a salt thereof such as ammonium or sodium salt thereof, An amino acid having an aromatic ring such as a derivative such as a bipolar ion compound or a derivative thereof may be mentioned. Among them, in the present invention, mercapto group-containing compounds, N-phenylglycine, or salts thereof such as ammonium and sodium salts, and derivatives such as bipolar ion compounds thereof are preferable.

  The content ratio of such a hydrogen-donating compound in the negative photosensitive resin composition is preferably 0.05 to 20 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated compound, and 0.1 to 10 More preferably, it is part by weight.

  Further, the negative photosensitive resin composition in the present invention preferably contains an amine compound for the purpose of improving the storage stability and the like as the photosensitive resin composition, and the amine compound is aliphatic, Either alicyclic or aromatic amines may be used, and the amines are not limited to monoamines, and may be polyamines such as diamines and triamines, and may be any of primary amines, secondary amines and tertiary amines. 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 such as dibenzylamine and tribenzylamine, which may be substituted with a hydroxyl group or a phenyl group. Among them, tribenzylamine is preferable in the present invention.

  The content ratio of such an amine compound in the negative photosensitive resin composition is preferably 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated compound. More preferably.

  In addition, the negative photosensitive resin composition in the present invention is nonionic, anionic for the purpose of improving the coating property when forming a photosensitive resist material layer on a substrate and the developability of the photosensitive resist material layer. , Cationic, amphoteric, and fluorine-containing surfactants are preferable, and as such surfactants, specifically, nonionic surfactants include 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, and amine salts. Examples of the amphoteric surfactants include betaine-type compounds, imidazolium salts, and 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 for improving 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-aminopropyltriethoxysila 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) propyltrimethoxysilane, 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-mercaptopropyl Limethoxysilane, 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] amine, N-glycidyl-N, Examples include silane compounds such as N-bis [3- (methyldiethoxysilyl) 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.

  Furthermore, the photosensitive resin composition of the present invention may contain an epoxy group-containing compound for the purpose of imparting heat resistance, chemical resistance, etc. to the film after exposure, which will be described later. Examples of the compound include a repeating unit of a so-called epoxy resin, a polyglycidyl ether compound obtained by reacting a polyhydroxy compound and epichlorohydrin, a polyglycidyl ester compound obtained by reacting a polycarboxylic acid compound and epichlorohydrin, and a polyamine Examples include compounds ranging from low molecular weight substances to high molecular weight substances such as polyglycidylamine compounds obtained by reacting compounds with epichlorohydrin.

  Specific examples of these polyglycidyl ether compounds include diglycidyl ether type epoxy of polyethylene glycol, diglycidyl ether type epoxy of bis (4-hydroxyphenyl), and bis (3,5-dimethyl-4-hydroxyphenyl). ) Diglycidyl ether type epoxy, bisphenol F diglycidyl ether type epoxy, bisphenol A diglycidyl ether type epoxy, tetramethylbisphenol A diglycidyl ether type epoxy, ethylene oxide-added bisphenol A diglycidyl ether type epoxy, phenol novolac Type epoxies, cresol novolac type epoxies, etc. These polyglycidyl ether compounds include acid anhydrides and divalent acid compounds on the remaining hydroxyl groups. It is also possible to introduce a carboxyl group to respond. Further, as the polyglycidyl ester compound, specifically, for example, diglycidyl ester type epoxy of hexahydrophthalic acid, diglycidyl ester type epoxy of phthalic acid, etc., and specifically, as the polyglycidyl amine compound, For example, diglycidylamine type epoxy of bis (4-aminophenyl) methane, triglycidylamine type epoxy of isocyanuric acid, and the like can be mentioned.

  For the same purpose, a tetracarboxylic acid such as pyromellitic dianhydride or a derivative thereof such as described in JP-A-2-182378, for example, and 3,3′-dimethyl-4 , 4′-diaminobiphenyl and other diamines are obtained by forming an amide bond, and include a polyimide precursor having an acid functional group or an ethylenically unsaturated bond, and a polyimide obtained by thermal polymerization thereof, and the like. Furthermore, various additives, for example, thermal polymerization inhibitors such as hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-p-cresol, and the like are 2% by weight or less based on the total amount of the photosensitive resin composition. 20% by weight or less of a colorant comprising an organic or inorganic dye / pigment, and a plasticizer such as dioctyl phthalate, didodecyl phthalate, tricresyl phosphate, etc. Also 40 wt% or less, also 10 wt% of the tertiary amine and sensitivity improving agent such as a thiol or less, the dye precursor also 30 wt% or less, may contain a proportion of.

  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 a good coating property. 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 Esters 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. When having a maximum peak of spectral sensitivity in a wavelength region less than the above range, the sensitivity to laser light having a wavelength of 320 to 450 nm tends to be inferior as a photosensitive resin composition, whereas, when having in a 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. Exposure light wavelength is linear in the horizontal axis direction when the spectral image of a photosensitive image-forming material sample with a photosensitive resin composition layer formed on the substrate surface is split from a light source such as a xenon lamp or tungsten lamp. In addition, the exposure intensity is set to change logarithmically 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. If the ratio [S ₄₁₀ ] / [S ₄₅₀ ] exceeds the above range, it tends to be difficult to achieve both blue-violet laser sensitivity and safe light performance 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.

The minimum exposure amount [S ₄₁₀ ] capable of forming an image at a wavelength of ₄₁₀ nm, the minimum exposure amount [S ₄₅₀ ] capable of forming an image at a wavelength of 450 nm, and the minimum exposure capable of forming an image at each wavelength exceeding 450 nm and not more than 650 nm. The amount [S _450-650 ] is obtained as exposure energy capable of image formation calculated from the obtained image height in the measurement of the maximum peak of spectral sensitivity using the above-described spectral sensitivity measuring apparatus. The minimum exposure amount that can form an image under optimum development conditions determined by changing development conditions such as the type of developer, development temperature, development time, etc., and the optimum development conditions are usually pH 11-14. The condition of immersing in an alkaline developer of 5 at a temperature of 25 ° C. for 0.5 to 3 minutes is 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 capable of displaying an image having a line width of 10 μm 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 sensitivity change 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, 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 thickness of the metal foil is sputtered, vapor deposited or plated. 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 is formed; a glass substrate A substrate on which an ITO film is formed is used. Of these, metal-clad laminates and wafers are preferably used.

  As a coating method of the photosensitive resin composition when forming a 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 Application, roll application, blade application, screen application, curtain application, 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.

  When the photosensitive resin composition of the present invention is a photopolymerization negative type, it is applied on a temporary support film and dried as a coating solution in which the above components are dissolved or dispersed in an appropriate solvent, and formed as necessary. By covering the surface of the photosensitive resin composition layer with a coating film, a photosensitive image forming material as a so-called dry film resist material or the like is obtained, and the photosensitive resin composition layer side of the image forming material is coated with the coating film. If it is covered with a coating film, the coating film is peeled off and laminated on the substrate to be processed, or as a coating solution in which each of the above components is dissolved or dispersed in an appropriate solvent, By directly applying and drying, a photosensitive image forming material in which a layer of the photosensitive resin composition of the present invention is formed on a substrate to be processed, and the photosensitive resin composition layer of the image forming material has a wavelength 390-43 nm of scanning exposure by a laser beam, is suitably used in the use form as an image forming method for revealing a negative image by development.

  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 solvent resistance, heat resistance, etc. 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 produced 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.

  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 is 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 by using a negative image that has been developed by scanning exposure and developing the photosensitive resin composition layer formed thereon with a laser beam 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 or 436 nm of a high-pressure mercury lamp can be used. From the viewpoints of output, stability, photosensitivity, cost, etc., blue such as argon ion laser, helium neon laser, YAG laser, and semiconductor laser can be used. 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, conditions of 90 to 140 ° C. and about 1 to 30 minutes are 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. The developer may be used after adding alcohol, surfactant or the like, if necessary.

  The development is usually performed by immersing an image forming material in which a photosensitive resist layer is formed in the developer, or 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. Depending on the development method, it is preferably performed 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 the polymerization-inhibiting action due to oxygen of the photopolymerizable photosensitive resin composition, or a light-transmitting adjusting layer for adjusting the wavelength region 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 by quaternary ammonium salt, etc., its anion-modified product by 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-based 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-based 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.

  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 blocking layer, which may contain surfactants, anionic properties such as sodium dodecylbenzenesulfonate, cationic properties such as alkyltrimethylammonium chloride, antifoaming agents, dyes, plasticizers, pH adjusters, etc. The total content of these 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 used sensitizer, 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 an image forming material into a size of 50 × 60 mm is 320 using a diffraction spectroscopic irradiation device (“RM-23” manufactured by Narumi) and a xenon lamp (“UI-501C” manufactured by USHIO INC.) As a light source. The light dispersed in the wavelength region of ˜650 nm was exposed by irradiating for 10 seconds with the exposure wavelength set linearly in the horizontal axis direction and the exposure intensity logarithmically changed in the vertical axis direction. By developing under the development conditions described in the examples, 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, and the horizontal axis indicates the wavelength and the vertical axis indicates the exposure. The maximum peak in the spectral sensitivity curve obtained by plotting the reciprocal of the energy 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>
The image forming material was allowed to stand for 1 minute, 2 minutes, 5 minutes, 10 minutes, 20 minutes, 30 minutes under yellow light illumination (conditions in which light having a wavelength of about 470 nm or less was blocked). 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: Leave time is 20 minutes or more B: Leave time is 10 minutes or more and less than 20 minutes C: Leave time is 1 minute or more and less than 10 minutes D: Leave time is less than 1 minute

<Storage stability of 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.

<Solubility of sensitizer in photosensitive solution solvent>
1 part by weight of a sensitizer and 100 parts by weight of poly-p-hydroxystyrene (weight average molecular weight Mw 5,000 by GPC measurement) were added to 290 parts by weight of propylene glycol monomethyl ether acetate and stirred with a magnetic stirrer at 25 ° C. for 30 minutes. Thereafter, the amount of undissolved sensitizer in the solution was visually determined.
A: The sensitizer is completely dissolved.
B: 10% or less of the sensitizer is undissolved and suspended.
C: More than half of the sensitizer is undissolved, and the sensitizer is precipitated at the bottom of the container.

  In addition, the compounds represented by the structural formulas (D-1) to (D-3) used as sensitizers in the following examples are included in the compounds represented by the general formula [VI]. is there.

(Example of chemically amplified negative resist)
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, a compound represented by the following structural formula (D-1) as a sensitizer (molar extinction coefficient / 405 nm = 4,300) 1 part by weight, 290 parts by weight of a compound represented by the following structural formula (S-1) as an acid generator is dissolved in 290 parts by weight of propylene glycol monomethyl ether acetate, and chemically amplified negative photosensitive resin A composition solution was obtained.

  By spin-coating this chemically amplified negative photosensitive resin composition solution on a glass substrate in an amount such that the dry film thickness is 10 μm or 20 μm, and drying at 90 ° C. for 10 minutes to form a photosensitive resist layer, A photosensitive image forming material was prepared.

The photosensitive resist layer of the obtained photosensitive image forming material was subjected to scanning exposure under the conditions described in the above-described exposure sensitivity evaluation method, followed by post-heating treatment in an oven at 100 ° C. for 10 minutes, and then as a developer. Development processing was performed by immersing in a 0.5 wt% aqueous solution of potassium hydroxide at 20 ° C. for 60 seconds.
Table 3 shows the evaluation results of the sensitizer used, the obtained photosensitive resin composition, and the photosensitive image forming material.

Comparative Example 1
An image forming material having a 10 μm-thick photosensitive resist layer was prepared in the same manner as in Example 1 except that no sensitizer was used, and developed by scanning exposure. It was dissolved in the developer and no image was formed.

Examples 2 and 3 and Comparative Example 2
Instead of the compound represented by the structural formula (D-1) as a sensitizer, compounds represented by the following structural formulas (D-2) to (D-4) were used as shown in Table 3. Except for the other, a negative photosensitive resin composition solution was obtained in the same manner as in Example 1, and a photosensitive image forming material was prepared in the same manner as in Example 1 using the obtained photosensitive resin composition solution. The evaluation results are shown in Table 3.

(Example of photopolymerization resist)
Example 4
The following blending components were added to 100 parts by weight of a mixed solvent of methyl ethyl ketone / isopropanol (weight ratio 8/2), and the coating liquid prepared by stirring at room temperature was prepared on a polyethylene terephthalate film (thickness 19 μm) as a temporary support film. Then, using an applicator, it is applied in an amount such that the dry film thickness is 10 μm, 20 μm, or 25 μm, and is dried in an oven at 90 ° C. for 5 minutes. On the formed photosensitive resin composition layer, a polyethylene film as a coating film A dry film resist material was prepared by laminating (thickness 25 μm) and allowing to stand for 1 day.

<Blending ingredients>
Ethylenically unsaturated compound Kyoei Chemical Co., Ltd. light ester 9EG (compound of the following structural formula (A-1)): 15 parts by weight Kyoei Chemical Co., Ltd. light ester BP-6EM (compound of the following structural formula (A-2))
: 30 parts by weight Sensitizer Compound of structural formula (D-1): 0.3 part by weight Photopolymerization initiator 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra Phenylbiimidazole (having a maximum diffraction peak at a Bragg angle (2θ ± 0.2 °) of 21.16 ° in an X-ray diffraction spectrum having a melting point of 172 ° C. and a wavelength of 1.54 °): 12 parts by weight Alkali-soluble resin Styrene / methyl Methacrylate / 2-hydroxyethyl methacrylate / methacrylic acid copolymer (molar ratio 10/50/20/20, acid value 129 KOH · mg / g, weight average molecular weight 68,000): 55 parts by weight Additive N-phenylglycine Bipolar ion compound: 0.2 part by weight Leucocrystal violet: 0.4 part by weight 9-phenylacridine: 0.2 part by weight

Separately, a 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 Limited. After washing with water, drying with an air flow and leveling, and then preheating this to 60 ° C. in an oven, on the copper foil of the copper-clad laminate, the dry film resist material obtained above is While peeling the polyethylene film, using a hand-type roll laminator on the peeling surface, laminating at a roll temperature of 100 ° C., a roll pressure of 0.3 MPa, and a laminating speed of 1.5 m / min on the copper-clad laminate. A photosensitive image forming material on which a photosensitive resist layer was formed was produced.
The photosensitive resist layer of the obtained photosensitive image forming material was subjected to scanning exposure under the conditions described in the method for evaluating exposure sensitivity, the polyethylene terephthalate film was peeled off, and then a 1% by weight aqueous solution of sodium carbonate at 30 ° C. The substrate to be processed having a resist image formed on the surface thereof was obtained by spraying the developer as 0.15 MPa to perform spray development.
Table 3 shows the evaluation results of the sensitizer used, the obtained photosensitive resin composition, and the photosensitive image forming material.

Comparative Example 3
Except that no sensitizer was used, an image forming material having a photosensitive resist layer having a thickness of 10 μm was prepared in the same manner as in Example 4, and developed by scanning exposure. It was dissolved in the developer and no image was formed.

Comparative Example 4
The image forming material was the same as in Example 4 except that the compound represented by the structural formula (D-4) was used as the sensitizer instead of the compound represented by the structural formula (D-1). Table 3 shows the evaluation results.

  From Table 3, the photosensitive resin composition of the present invention has a good solubility in a solvent, an excellent safe light property under a yellow light, a high sensitivity and high resolution in the blue-violet region. It can be seen that it is.

  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 board and plasma display wiring by direct drawing using blue-violet laser light. It is industrially very useful for forming fine electronic circuits such as boards, wiring boards for liquid crystal displays, large-scale integrated circuits, thin transistors, and semiconductor packages.

Claims (9)

A sensitizer,
In a negative photosensitive resin composition containing an active compound that generates at least one of a radical, an acid and a base by interaction with the sensitizer when exposed to light,
The negative photosensitive resin composition, wherein the sensitizer contains a compound represented by the following general formula [I].

(In the general formula [I], R ⁷ represents the following general formula [II].

(In the general formula [II], R ¹⁰ represents a hydrogen atom or an arbitrary substituent, and X represents an arbitrary divalent atom or substituent. However, R ⁶ and R ¹⁰ , or R ⁸ and R ^{10. May} be bonded to each other to form a ring which may have a substituent.), And R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ and R ⁹ each independently represents a hydrogen atom or an arbitrary substituent. However, adjacent substituents among R ¹ to R ⁶ , R ⁸ and R ⁹ , R ¹ and R ⁹ , and one or a combination of two or more of R ⁵ and R ⁶ are bonded to each other, A ring which may have a substituent may be formed. ) The negative photosensitive resin composition according to claim 1, wherein the sensitizer has a molar extinction coefficient (ε) at a wavelength of 405 nm of 100 or more and 100,000 or less. 3. The negative photosensitive resin composition according to claim 1, wherein the compound represented by the general formula [I] is any one of the compounds represented by the following general formulas [III] to [VII]. object.

(In the general formulas [III] to [VII], R ¹ to R ⁶ , R ⁸ and R ⁹ are as defined in the general formula [I]. Y represents an oxygen atom or an N—R ¹⁶ group; ^{10 to} R ¹⁶ each independently represents a hydrogen atom or an arbitrary substituent, provided that R ⁶ and R ¹⁰ , R ⁸ and R ¹⁰ , R ¹⁰ and R ¹¹ , R ⁸ and R ¹² , R ¹¹ and R ¹² , R ¹⁰ and R ¹³ , R ⁸ and R ¹³ , R ¹⁰ and R ¹⁴ , R ¹⁰ and R ¹⁵ , are bonded to each other to form an optionally substituted ring. Is also good.) The negative photosensitive resin composition according to any one of claims 1 to 3 , wherein R ² and / or R ³ in the general formula [I] is an arbitrary substituent. In any one of claims 1 to 4, the negative photosensitive resin composition characterized and Turkey to contain an alkali-soluble resin and a crosslinking agent. In any one of claims 1 to 4, the negative photosensitive resin composition characterized and Turkey to an ethylenically unsaturated compound. A negative photosensitive image forming material, wherein a layer of the negative photosensitive resin composition according to any one of claims 1 to 6 is formed on a temporary support film. On a substrate to be processed, negative photosensitive, wherein the negative photosensitive image forming material according to claim 7 is laminated to the negative photosensitive resin composition layer side is the substrate side Image forming material. 9. The negative photosensitive image forming material according to claim 8 , wherein the thickness of the negative photosensitive resin composition layer laminated on the substrate to be processed is 10 μm or more.