TW201115268A - Photosensitive resin composition, photosensitive element utilizing the composition, method for formation of resist pattern, and process for production of printed circuit board - Google Patents

Abstract

Disclosed is a photosensitive resin composition comprising a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and at least one pyrazine compound selected from the group consisting of compounds each having a structure represented by formula (1), compounds each having a structure represented by formula (2) and compounds each having a structure represented by formula (3). [In formulae (1) to (3), R1 to R12 independently represent a univalent organic group containing an alkyl group, a cycloalkyl group, a phenyl group, a naphthyl group or a heterocyclic group, wherein R1 and R2, R3 and R4, R5 and R6, R7 and R8, R9 and R10, or R11 and R12 may be bound to each other and, together with two carbon atoms contained in a pyrazine skeleton, form a ring. In formula (2), X and Y independently represent an atom group that constitutes an aromatic ring formed together with two carbon atoms contained in a pyrazine skeleton and having a monocyclic or condensed polycyclic structure. In formula (3), Z represents an atom group that constitutes an aromatic ring having a monocyclic or condensed polycyclic structure and formed together with four carbon atoms contained in a pyrazine skeleton or a hetero ring.

Description

[Technical Field] The present invention relates to a photosensitive resin composition, a photosensitive element using the same, a method for forming a photoresist pattern, and a method for producing a printed circuit board. [Prior Art] Photosensitive resin composition or photosensitive element is widely used in the manufacture of fine electronic circuits such as printed circuit boards, wiring boards for plasma displays, wiring boards for liquid crystal displays, large-scale integrated circuits, thin transistors, and semiconductor packages. (Laminate) As a photoresist material for etching or plating, etc. The microelectronic circuit is manufactured as follows. First, a photosensitive resin composition layer of a photosensitive element is laminated on a circuit-forming substrate. Next, after the support film is peeled off and removed, the predetermined portion of the photosensitive resin composition is irradiated with active light rays to cure the exposed portion. Then, the unexposed portion is removed (developed) from the substrate, and a resist pattern composed of a cured product of the photosensitive resin composition is formed on the substrate. The obtained photoresist pattern is subjected to an etching treatment or a plating treatment to form a circuit on the substrate, and finally, the photoresist is removed and finally removed to fabricate a fine electronic circuit. In the above exposure method, a method in which a mercury lamp having a wavelength of 365 nm is used as a light source and is exposed to a photomask is conventionally used. In addition, in recent years, a long-lived wavelength of 405 nm is proposed, and a high-output GaN-based semiconductor blue laser or a solid laser with a wavelength of 355 nm is used as a light source, and the digital data of the pattern -5 - 201115268 is directly imaged on the photosensitive light. A direct light method of a resin composition layer (see, for example, Non-Patent Document 1). The DLP (Light Processing) or LDI (Laser Direct Imaging) direct-drawing exposure method is better than the exposure method of the reticle, and the position is better, and a high-definition pattern can be obtained, and is introduced into the high-density board. Production. Photosensitive materials suitable for laser exposure are also reviewed. For example, a photosensitive material used as a light source with a semi-violet laser is disclosed in the patent literature as a photosensitive resin composition using a specific initiator. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2002-296764 [Patent Document 2] JP-A-2004-45596 [Non-Patent Document] [Non-Patent Document 1] Electronic Assembly Technology 2002 6 ρ·74~79) [Summary of the Invention] [Inventive Summary] [Problems to be Solved by the Invention] In order to improve production efficiency in the exposure step, it is necessary to reduce the time as much as possible. However, in the above direct drawing exposure method, in addition to the use of light-emitting light by the light source, the substrate is scanned while irradiating the light. Therefore, compared with the previous description of the digital display of the quasi-precision package base conductor Blue 12 (short exposure shot, etc.) -6- 201115268 The exposure method of the mask has a tendency to require a long exposure time. Therefore, it is necessary to increase the sensitivity of the photosensitive resin composition more than ever. In addition, with the recent increase in the density of printed circuit boards, The photosensitive resin composition is required to have high resolution and high adhesion. As the wiring is miniaturized, the problem of voltage drop due to the resistance of the power supply line is also apparent, and formation of a plating layer (conductor layer) having a thickness of 10 μm or more is also a problem. When the thickness is l〇 or more than zm, the photoresist must have a film thickness of 15 μm or more. However, when the film thickness of the photosensitive layer is generally increased, the resolution tends to be lowered. Therefore, it is necessary to satisfy the film thickness and the solution. A photosensitive resin composition having two properties. The photosensitive resin composition is also important for low contamination of plating. Photosensitive resin composition contamination plating In the case of bathing, the appearance of the substrate subjected to the plating treatment is discolored, or the plating formability is lowered, causing problems such as the cause of disconnection. The photosensitive resin composition is required to have excellent peeling characteristics of the resist after the mineral. In the photoresist peeling step after the plating treatment, it is difficult to peel off the photoresist between the fine wirings, and the peeling time is improved, and the production efficiency is lowered. Further, there is a problem that the wiring remains between the wirings, and the yield is lowered. The purpose is to provide a photosensitive resin composition having low sensitivity, resolution, adhesion, peeling property, and smear formation property to light having a wavelength of from 3 to 400 nm, which is low in contamination with plating, and uses this composition. Photosensitive element, method for forming photoresist pattern, and method for manufacturing printed circuit board [means for solving problems]

S 201115268 The present invention provides a photosensitive resin composition which comprises a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and is selected from the group consisting of the following formula (1), (2) or (3) In the compound of the structure, at least one pyrazine compound is formed, and in the formula (1), R1, R2, R3, and R4 each independently represent an alkyl group or a cycloalkyl group. A phenyl group, a naphthyl group or a monovalent organic group containing a heterocyclic group, and R1 and R2, or R3 and R4 may be bonded to each other to form a ring together with two carbon atoms of the pyrazine skeleton. [Chemical 2]

.N ', J R7

X , , N^"R8 (2) In the formula (2), R5, R6, R7, and R8 each independently represent an alkyl group, a cycloalkyl group, a phenyl group, a naphthyl group or a monovalent organic group having a heterocyclic group. The group, R5 and R6, or R7 and R8 may be bonded to each other to form a ring together with two carbon atoms of the pyrazine skeleton. Each of X and Y independently represents an atomic group of an aromatic ring constituting a monocyclic structure or a condensed polycyclic structure which is formed together with two carbons of a pyrazine skeleton. 201115268 [Chemical 3]

N N R11

Z (3), R12 R10 , and (3), R9, R10, rH, and r12 each independently represent an alkyl group, a ring-based group, a phenyl 'naphthyl group or a monovalent organic group containing a heterocyclic group, R9 and R1Q. Or R11 and RU can be combined with each other to form a ring together with two carbon atoms of the pyrazine skeleton. The Z system represents an atomic group of an aromatic ring or a heterocyclic ring which is formed together with four carbons of a pyrazine skeleton and which constitutes a monocyclic structure or a condensed polycyclic structure. Since the above pyrazine compound has a strong absorption of light having a wavelength of from 550 to 4 1 Onm, the photosensitive resin composition of the present invention can give a good sensitivity to light having a wavelength of from 550 to 41 Onm. In addition, the photosensitive resin composition of the present invention containing the pyrazine compound is excellent in resolvability (peeling property) and plating formability of the photosensitive resin composition after resolution, adhesion, and curing, and is suitable for plating. The pollution is also low. The pyrazine compound is preferably a compound having the structure represented by the above formula (1). In the photosensitive resin composition of the present invention, the maximum absorption wavelength of the pyrazine compound is preferably in the range of from 3 to 50 nm. Thereby, good sensitivity can be obtained for light having a wavelength of 3 50 to 4 10 nm, and absorption at a long wavelength side of a wavelength of 500 nm or more can be reduced, and the stability under yellow light is good. In the photosensitive resin composition of the present invention, the binder polymer preferably contains (meth)acrylic acid and styrene or a styrene derivative as a copolymerization -9 - 201115268 component. Thereby, the alkali developability, the resolution, and the adhesion of the photosensitive resin composition can be further improved. The photosensitive resin composition of the present invention preferably contains a compound represented by the following formula (4). Therefore, the resolution and adhesion of the photosensitive resin composition can be maintained, and the sensitivity and developability (color developability of photoresist) tend to be improved. [Chemical 4]

(R16)丨

R14 (4) In the formula (4), X represents a carbon atom or a nitrogen atom, and R13, R14 and R15 each independently represent a halogen atom or an alkyl group having 1 to 5 carbon atoms, and at least one of R13, R14 and R15. Indicates a halogen atom. R10 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and 1 is an integer of 〇~4. When 1 is 2 to 4, the plural R16s may be the same or different. The photosensitive resin composition of the present invention preferably further contains a hydrogen-donating compound. Thereby, the sensitivity of the photosensitive resin composition can be improved. In the photosensitive resin composition of the present invention, the hydrogen-donating compound preferably contains a compound represented by the following formula (5). Thereby, there is a tendency that the sensitivity of the photosensitive resin composition can be further improved. [Chemical 5]

〇 (5) 201115268 In the formula (5), R17 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group or an ester group, a hydroxyl group, or a halogen atom. When the integer η of the η system 0 to 5 is 2 to 5, the plural R17 may be the same or different. The present invention provides a photosensitive resin member which is provided with a support and a photosensitive resin composition layer composed of the above-mentioned photosensitive resin composition formed on the support. By using such a photosensitive element, it is possible to efficiently form sensitivity, resolution, adhesion, peeling property, and plating formability, and a photoresist pattern having low contamination with plating. The present invention provides a method for forming a photoresist pattern, comprising: a lamination step of laminating a photosensitive resin composition layer composed of the photosensitive resin composition on a substrate, and a photosensitive resin composition layer In the exposure step of irradiating the active light with a predetermined portion, a photoresist pattern formed of a cured product of the photosensitive resin composition is formed on the substrate by removing a portion other than the predetermined portion of the photosensitive resin composition layer from the substrate. Imaging steps. According to the above method, it is possible to form a photoresist pattern which is excellent in sensitivity, resolution, adhesion, peeling property, and plating formability, and which is less polluting to plating. In the above method for forming a photoresist pattern, the wavelength of the active light is preferably from 390 to 4 10 nm. Thereby, a photoresist pattern excellent in sensitivity, resolution, adhesion, peeling property, and plating formability can be formed. The present invention provides a method of manufacturing a printed circuit board comprising the step of etching or plating a substrate having a photoresist pattern formed by the above method. According to this manufacturing method, a printed circuit board having a high-density wiring such as a high-density package substrate can be manufactured with high efficiency. -11 - 201115268 [Effect of the Invention] According to the present invention, it is possible to provide sensitivity, resolution, adhesion, peeling property, and plating formation property to light having a wavelength of 35 〇 to 410 nm. A low photosensitive resin composition, a photosensitive element using the composition, a method for forming a photoresist pattern, and a method for producing a printed circuit board. BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the invention will be described in detail below. However, the present invention is not limited to the following embodiments. Further, in the present specification, (meth)acrylic means acryl or methacrylic acid, (meth) acrylate means acrylate or methacrylate, and (meth) acryl oxime means propylene fluorenyl or Acryl fluorenyl. Further, the (poly)oxyethylene chain means an oxyethylene group or a polyoxyethylene chain, and the (poly)oxypropylene chain means an oxypropylene group or a polyoxypropylene chain. The "EO modified" means a compound having a (poly)oxyethylene chain, and the "PO modified" means a compound having a (poly)oxypropylene chain, and the "EO · PO modified" means having (poly) A compound of both an oxyethylene chain and a (poly)oxypropylene chain. (Photosensitive Resin Composition) First, the photosensitive resin composition of the present embodiment will be described. The photosensitive resin composition of the present embodiment contains (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator. -12- 201115268 First, the (A) binder polymer is explained. (A) Adhesive of the component The ruthenium polymer is, for example, an acrylic resin, a styrene resin, an epoxy resin, a guanamine resin, a guanamine epoxy resin, an alkyd resin, or a phenol resin. From the viewpoint of alkali developability, an acrylic resin is preferred. These may be used alone or in combination of two or more. (A) The binder polymer can be produced, for example, by subjecting a polymerizable monomer to radical polymerization. The polymerizable monomer may, for example, be a polymerizable phenylethylidene derivative such as styrene, vinyl methyl, α-methylstyrene, p-methylstyrene or pethylstyrene, acrylamide or acetonitrile. Ethyl alcohol esters such as vinyl n-butyric acid, alkyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, decyl (meth)acrylate, (methyl) ) propylene tetrahydroanthracene vinegar, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate 2 2, 2, 2-Trifluoroethyl (meth) acrylate, 2,2,3,3_tetrafluoropropyl (meth) acrylate, (meth)acrylic acid, hydrazine:-bromo (meth)acrylic acid, α-chloro (Meth)acrylic acid, stone-furyl (meth)acrylic acid, non-styryl (meth)acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, cis-butane Maleic acid monoester, maleic acid monoisopropyl ester, maleic acid monoester, fumaric acid, cinnamic acid, α-cyano cinnamic acid, itaconic acid, croton Acid, propiolic acid, etc. The alkyl (meth)acrylate may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate or (meth)acrylic acid. Butyl ester, tert-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate-13- 201115268, heptyl (meth)acrylate, octyl (meth)acrylate, ( Methyl) 2-ethylhexyl acrylate and such structural isomers. These may be used alone or in combination of two or more. (A) The binder polymer is preferably a carboxyl group-containing polymer from the viewpoint of alkali developability. For example, it can be produced by radically polymerizing a polymerizable monomer having a carboxyl group with another polymerizable monomer. The above polymerizable monomer having a carboxyl group is preferably (meth)acrylic acid. (A) The binder polymer preferably contains a styrene or a styrene derivative as a copolymerization component from the viewpoint of improving the adhesion. When the styrene or the styrene derivative is contained as a copolymerization component, the content is improved from the well-balanced state, and the content is preferably 5 in terms of the total nonvolatile content of the component (A). ~70% by mass, more preferably 10 to 65% by mass, particularly preferably 15 to 60% by mass. When the content is less than 5% by mass, the adhesion tends to be deteriorated. When the content is more than 70% by mass, the peeling time becomes long, and the peeling after plating tends to occur. The (A) binder polymer preferably contains benzyl (meth) acrylate as a copolymerization component. When benzyl (meth) acrylate is contained as a copolymerization component, from the viewpoint of improving the resolution and the peeling property from a well-balanced state, the content is preferably 5 to 30% of the total nonvolatile content of the component (A). 70% by mass, more preferably 10 to 65% by mass, particularly preferably 15 to 60% by mass. When the content is less than 5% by mass, the resolution is deteriorated. When the content is more than 70% by mass, the peeling time becomes long, and the peeling after plating tends to occur. -14- 201115268 However, the weight average molecular weight and the number average molecular weight of the present invention are measured by a gel permeation chromatography (GPC) using standard polystyrene-converted hydrazine. The weight average molecular weight of the (A) binder polymer compound is preferably from 5,000 to 300,000, more preferably from 1,000,000 to 150,000, more preferably from 20,000 to 80,000, and particularly preferably from 30,000 to 70,000. When the weight average molecular weight is less than 5,000, the development liquid resistance tends to decrease, and when it exceeds 300,000, the development time tends to be elongated, or the peeling property tends to be lowered. The acidity of the binder polymer of the component (A) is preferably from 50 to 250 mgKOH/g, more preferably from 10 to 2,300 m g Κ Ο H / g, more preferably from 130 to 200 mg KOH/g. When the acid strontium is less than 50 mgKOH/g, the development time tends to be elongated, and when it exceeds 25 mg KOH/g, the liquid resistance (adhesion) of the photoresist after photocuring tends to be lowered. Further, when the developing step uses an organic solvent-based developing solution, it is preferred to prepare a polymerizable monomer having a carboxyl group in a small amount. The dispersion (Mw/Mn) of the (A) binder polymer is preferably from 1.0 to 3.0', more preferably from 1.0 to 2.0. When the degree of dispersion exceeds 3.0, the adhesion and the resolution tend to be lowered. (A) The binder polymer may be used alone or in combination of two or more types. When the binder polymer used in combination of two or more types is used, for example, two or more types of binder polymers composed of different copolymerization components, two or more types of binder polymers having different weight average molecular weights, and different dispersity ratios may be used. More than 2 types of binder polymers. Further, a "15-201115268 polymer having a plurality of mode molecular weight distributions described in JP-A-11-31 27 1 37 can also be used. (A) The binder polymer may have a photosensitive group if necessary. Next, a photopolymerizable compound having an ethylenically unsaturated bond of the component (B) will be described. (B) The photopolymerizable compound is not particularly limited as long as it has at least one ethylenically unsaturated bond in the molecule, and for example, a bisphenol A-based (meth) acrylate compound is obtained by reacting a polyhydric alcohol with an unsaturated carboxylic acid. a urethane monomer such as a (meth) acrylate compound having a urethane bond in the molecule, a nonyl phenoxy ethoxy acrylate, a glycerol-containing compound and an unsaturated carboxylic acid The resulting compound is reacted with an acid. These may be used alone or in combination of two or more kinds of phthalocyanine-based photopolymerizable compounds, and it is preferable to use a bisphenol fluorene-based (meth) acrylate compound from the viewpoint of improving the resolution and the release property. The total amount of the components (B) is preferably from 20 to 80% by mass, more preferably from 30 to 70% by mass. The bisphenol A-based (meth) acrylate compound is, for example, 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((A) Propyloxypolypropoxy)phenyl)propane, 2,2-bis(4-(methyl)acryloxypolybutoxy)phenyl)propane, 2,2-bis(4-((A) A acryloxypolyethoxypolypropoxy)phenyl)propane or the like, wherein 2,2-bis(4-(meth)acryloxy group is preferred from the viewpoint of further improving the resolution and the peeling property. Polyethoxy)phenyl)propane. 2,2·bis(4-((meth)acryloxypolyethoxy)phenyl)propyl, for example, 2,2-bis(4-((methyl)propenylethoxy)phenyl) ) -16- 201115268 Propane, 2,2-bis(4-((meth)acryloxydiethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxy) Ethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxytetraethoxy)phenyl)propane, 2,2-bis(4-((meth)propeneoxy) Pentaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxyhexaethoxy)phenyl)propane, 2,2-bis(4-((methyl)) Propyleneoxyheptaethoxy)phenyl)propane, 2,2.bis(4-((meth)acryloxyoctaethoxy)phenyl)propane, 2,2-bis(4-((A) Propyloxy hexaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxy)decaethoxy)phenyl)propane, 2,2-bis(4-( (Meth)acryloxy eleven ethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxydodeoxy)ethoxy)phenyl)propane, 2,2-double (4-((Methyl)acryloxytridecyloxy)phenyl) Propane, 2,2-bis(4-((meth)acryloxytetradecylethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxy)pentadecyloxy Phenyl)propane, 2,2-bis(4-((meth)acryloxyhexadecyloxy)phenyl)propane, and the like. 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane such as 2,2-bis(4-((meth)acryloxydipropoxy)phenyl)propane , 2,2-bis(4-((meth)acryloxytripropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxytetrapropoxy)phenyl) ) propane, 2,2-bis(4-((meth)acryloxypentapropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxyhexapropoxy)) Phenyl)propane, 2,2-bis(4-((meth)propenyloxy heptapropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxy) octapropoxy Phenyl-17- 201115268) Propane, 2,2-bis(4-((meth)acryloxypentapropyloxy)phenyl)propane, 2,2-bis(4-((meth)propene) Oxydecapropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxy-l-propoxy)phenyl)propane, 2,2-bis(4-((A) Phenyloxydippropoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxytridecyloxy)phenyl)propane, 2,2-di ( 4-((Methyl)propenyloxytetradecylpropoxy)phenyl)propane, 2,2-double ( 4-((meth)acryloxypentadecane)phenyl)propane, 2,2-bis(4-((meth)acryloxyhexadecyloxy)phenyl)propane, etc. These may be used alone or in combination of two or more. Among these, 2,2-bis(4-(methacryloylethoxy)phenyl)propane can be commercially obtained from ΒΡΕ-100 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). 2,2-bis[4-(methacryloxypentaethoxy)phenyl]propane can be ΒΡΕ-500 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name) or FA-321M (Hitachi Chemical Industry Co., Ltd. ) Manufacturing, product name) is obtained commercially. 2,2-bis(4-(methacryloxypentadecylethoxy)phenyl)propane can be obtained commercially from ΒΡΕ-13 00 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). From the viewpoint of flexibility, resolution and adhesion of the cured product, ethylene oxide in one molecule of 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane The base number is preferably from 4 to 20, more preferably from 8 to 15. Further, the number of ethyleneoxy groups in one molecule of 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane is improved from the viewpoint of improving peelability, resolution, and adhesion. It is preferably 1 to 3, and particularly preferably a compound having 4 to 20 ethylene groups and 1 to 3 compounds in one molecule. -18- 201115268 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)) phenyl]'s, for example, 2,2-bis(4-((meth)propene) Oxydiethoxyoctyloxy)phenyl)propane, 2,2-bis(4-((meth)acryloxytetraethoxytetrapropoxy)phenyl)propane, 2 bis (4_ ((Methyl)propoxy hexaethoxyhexapropyloxy)phenyl)propane or the like. a compound obtained by reacting a polyhydric alcohol with hydrazine: a 0-unsaturated carboxylic acid, for example, a polyethylene glycol di(meth)acrylate having an ethyl group number of 2 to 14 and a polypropylene glycol having a propyl group of 2 to 14 (Meth) acrylate, trimethylol propyl di(meth) acrylate, trimethylolpropane tri (methyl) propylene vinegar, EO modified trimethylolpropane tri (meth) acrylate Ester, p〇 modified trimethylolpropane tri(meth)acrylate, EO, PO modified trimethylolpropane tri(meth)acrylate, tetramethylol methane tri(meth)acrylate Tetramethylolmethane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate dipentaerythritol hexa(meth)acrylate, and the like. These may be used alone or in combination of two or more. In this case, 'tetramethylol methane triacrylate can be obtained commercially from A-TMM-3 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name), and EO-modified trimethylolpropane trimethacrylate can be used. TMPT21E or TMPT3 0E (Hitachi Chemical Industry Co., Ltd., trade name) is commercially available. (B) The photopolymerizable compound preferably contains a (poly)oxyethylene chain or a (poly)oxypropylene chain in the molecule from the viewpoint of improving alkali developability, resolution, adhesion, and peeling properties. The methylpropane tri(meth) acrylate compound 'more preferably contains a tris-19-201115268 hydroxymethylpropane tri(meth) acrylate compound having a (poly)oxyethylene chain in the molecule. The total amount of the components (B) as a whole is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass. Further, (B) the photopolymerizable compound preferably contains a (poly)oxyethylene chain and a (poly)oxypropylene chain from the viewpoint of improving the flexibility of the cured product (cured film) of the photosensitive resin composition. Both polyalkylene glycol di(meth)acrylates. The total amount of the component (B) as a whole is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass. The above polyalkylene glycol di(meth)acrylate, for example, a molecule The (poly)oxyalkylene chain is preferably a (poly)oxyethylene chain and a (poly)oxypropylene chain ((poly)oxy-η-propylene) chain or a (poly)oxyisopropenyl chain). Further, the polyalkylene glycol di(meth)acrylate may further have (poly)oxy-η-butene chain, (poly)oxy-η-pentene chain, (poly)oxy-η-hexene A chain or a (poly)oxyalkylene chain having a carbon number of 4 to 6 such as these structural isomers. In the molecule of the polyalkylene glycol di(meth)acrylate, each of the (poly)oxyethylene chain and the (poly)oxypropylene chain may be continuously present in a block manner or in a random manner. Further, in the (poly)oxypropylene chain, the propylene-based secondary carbon may be bonded to the oxygen atom, or the first-order carbon may be bonded to the oxygen atom. The polyalkylene glycol di(meth)acrylate is particularly preferably a compound represented by the following general formula (6), (7) or (8). These may be used alone or in combination of two or more. -20 - 201115268 [化6] Ο ο

HzC=c c_〇^E〇^p〇yE0^_| 2 (6) R R19 [化7]

O Q H2C=?:u ten la E weeping seven i_〒=CH2(7) R R21 [化8]

〇O H2C卞C—〇士妙七|1卞% R22 r23 In the above formulas (6), (7) and (8), r18~r23 each independently represents a hydrogen atom or a methyl group, and EO represents an oxyethylene group. The base, p〇 represents an oxypropylene group. M1, m2, m3 and m4 represent repeating units of structural units composed of oxyethylene groups, and η1, η2, η3 and η4 represent repeating units of structural units composed of oxypropylene groups, and repeating of oxyethylene groups The total number of units mi+m2, m3, and m4 (average 値) are each an integer representing ^30, and the total number of repeating units of oxypropylene groups n1, n2 + n3, and n4 (average 値) are independent integers of 1 to 30, respectively. In the compound represented by the above general formula (6), (7) or (8), the total number of repeating units of the oxyethylene group m1, m2, m3 and m4 is an integer of 1 to 30, and preferably an integer of 1 to 10, More preferably, it is an integer of 4 to 9, and particularly preferably an integer of 5 to 8. When the total number of repeating units exceeds 30, the resolution and the adhesion are deteriorated, and it is difficult to obtain a good resist shape. Further, the total number of repeating units of the oxypropylene group η1, n2 + n3, and η4 is an integer of from 21 to 201115268 1 to 30, and preferably an integer of 5 to 2 ,, more preferably an integer of 8 to 16 'extra good An integer from 10 to 14. When the total number of the repeating units exceeds 30, it is difficult to obtain sufficient resolution and tend to cause sludge. The compound represented by the general formula (6), for example, a vinyl compound having R18 and r!9=methyl, 11^+1^=6 (average 値), and 2 (average 値) (manufactured by Hitachi Chemical Co., Ltd.) Product name: FA-023M) and so on. The compound represented by the above formula (7) is, for example, a vinyl compound having a size of 2〇 and R2i = methyl, m3 = 6 (average 値), and n2 + n3 = 12 (average 値) (product manufactured by Hitachi Chemical Co., Ltd.) Name FA-024M) and so on. The compound represented by the above formula (8) is, for example, a vinyl compound having R22 and R23 = a hydrogen atom, m4 = 1 (average 値), and n4 = 9 (average 値) (manufactured by Shin-Nakamura Chemical Co., Ltd., sample name: NK Ester ΗΕΜΑ-9Ρ )) and so on. These may be used alone or in combination of two or more. The (meth) acrylate compound having a urethane bond in the above molecule, for example, a (meth)acrylic monomer having a OH group at the β position and a diisocyanate compound (isophorone diisocyanate, 2, 6 An addition reaction product of -toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate or the like, tris((meth)acryloxytetraethyleneethylene glycol isocyanate) hexamethylene trimeric isocyanate, ΕΟ modified ethyl urethane di(meth) acrylate, hydrazine, hydrazine modified ethyl urethane di(meth) acrylate, and the like. The hydrazine-modified urethane di(meth) acrylate is, for example, UA-1 1 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name). Further, ytterbium, yttrium modified urethane di(meth) acrylate is, for example, UA-13 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name). These can be used -22-201115268 alone or in combination of two or more. The above nonylphenoxy polyethylene oxyacrylates are, for example, nonylphenoxytetraethylene oxyacrylate, nonylphenoxypentaethylene oxyacrylate, nonylphenoxy hexaoxy acrylate, decyl phenoxy VII Ethylene oxy acrylate, nonyl phenoxy octaethylene oxy acrylate, nonyl phenoxy non-vinyl oxy acrylate, decyl phenoxy decylene oxy acrylate, nonyl phenoxy decylene oxy acrylate, and the like. These may be used singly or in combination of two or more. The above phthalic acid-based compound is, for example, r-chloro-hydroxypropyl-non-(meth)acryloyloxyethyl-phthalate, /3-hydroxyalkyl-stone (meth)acryloyl group. Oxyethyl-phthalate and the like. These may be used alone or in combination of two or more. The (photo) polymerizable compound preferably contains a photopolymerizable compound having one ethylenically unsaturated bond in the molecule, from the viewpoint of improving the peeling property of the compound (cured film) of the photosensitive resin composition. The total amount of the (Β) component is preferably from 3 to 30% by mass, preferably from 5 to 20% by mass. The content of the (Β) component is 100% of the (Α) component and the (Β) component. The mass portion is preferably 30 to 70 parts by mass, more preferably 35 to parts by mass, particularly preferably 40 to 60 parts by mass. The content is less than 30 parts by mass, and it is difficult to obtain sufficient sensitivity and resolution. When the amount is more than 70 parts, the film tends to be difficult to form, and it tends to be difficult to obtain a good shape. Next, the photopolymerization initiator of the component (C) will be described. Further, the photopolymerization initiator of the component (C) contains a pyrazine compound selected from the group (1) having the structure represented by the following formula (1) (hereinafter sometimes referred to as "(C1). ) component "), (C2) pyrazine compound having a structure represented by the following formula (2) (hereinafter, referred to as "(C2) component") and (C3) at least 1 of a pyrazine compound having a structure represented by the following formula (3) (hereinafter sometimes referred to as "(C3) component") a pyrazine compound. [Chemistry 9]

Rk/N^R3 | (1) r2^^n^^r4 In the formula (1), R1, R2, R3 and R4 each independently represent an alkyl group, a cycloalkyl group, a phenyl group, a naphthyl group or a heterocyclic ring. The monovalent organic group, R1 and R2, or R3 and R4 may be bonded to each other to form a ring together with two carbon atoms of the pyrazine skeleton. [化10]

In the formula (2), 'R5, R6, R7 and R8 each independently represent an alkyl group, a cycloalkyl group, a phenyl group, a naphthyl group or a monovalent organic group containing a heterocyclic group, and R5 and R6, or R7 and R8 are each independently They can be combined with each other to form a ring together with two carbon atoms of the pyrazine skeleton. The X and Y series each independently represent an atomic group of an aromatic ring constituting a monocyclic structure or a condensed polycyclic structure formed together with two carbons of a pyrazine skeleton, and the two aromatic ring systems are defined by a single atom Key-24- (3) 201115268 combined. [11]

-N R11

Z

N R12 In the formula (3), R9, R10, Rii, and Ri2 each independently represent an alkyl group, a cycloalkyl 'phenyl group, a naphthyl group or a monovalent organic group containing a heterocyclic group, and R9 and R1Q, or R11 and The R12 system may be bonded to each other to form a ring together with two carbon atoms of the pyrazine skeleton. The Z system represents an atomic group of an aromatic ring or a heterocyclic ring which is formed together with four carbons of a pyrazine skeleton and which constitutes a monocyclic structure or a condensed polycyclic structure. In the pyrazine compound, for example, the (C 1 ) component, the (c 2 ) component, and the (c 3 ) component, the component (C1) can be used from the viewpoint of improving the sensitivity of the photosensitive resin composition. In the above formulae (1) to (3), the alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a fluorenyl group, and the structural isomers thereof. . The cycloalkyl group is preferably a cycloalkyl group having 4 to 10 carbon atoms, a cyclobutyl 'cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group or a cyclodecyl group. Further, for example, a hydrogen atom of a cycloalkyl group is substituted with an arbitrary substituent. The heterocyclic group may, for example, be a furyl group, a thienyl group, an imidazolyl group, an oxazolyl group, a pyridyl group or the like. The hydrogen atom of the phenyl group, the naphthyl group and the heterocyclic group may be substituted with an arbitrary substituent. Any of the above substituents may, for example, be a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 1 carbon atom, an ester group having 1 to 10 carbon atoms, or carbon. Alkylamine groups of 1 to 10, and the like. -25- 201115268

When Ri to R4, R5 to R8 or r9 to r12 are a phenyl group, a naphthyl group or a monovalent organic group containing a heterocyclic group, the solubility of the compound is adjusted to a visible portion (near 405 nm) from the viewpoint of improving solubility. In view of the fact, at least one of R1 to R4, at least one of R5 to R8, or at least one of R9 to R12 preferably contains a linear or branched alkoxy group having 1 to 10 carbon atoms. The aromatic ring having a monocyclic structure or a condensed polycyclic structure may, for example, be a benzene, a naphthalene, an anthracene, a pentane, a phenanthrene, a triphenylene, a fluorene or a hydrogen atom of such an aromatic ring, which may be substituted by an arbitrary substituent, etc. From the viewpoint of the price or the solubility at the time of synthesis, benzene or naphthalene is preferred. The heterocyclic ring may, for example, be a pyridine, a pyrimidine, a pyrazine, a pyrrole, a furan, a thiophene or the like, and a hydrogen atom of the heterocyclic ring may be substituted with an arbitrary substituent. From the viewpoint of synthesis and inexpensiveness, pyridine is preferred.

R1 and R2, R3 and R4, uldent 5 and R6, 艮7 and r8, uldent 9 and R10 or R11 and R12 are bonded to each other, and when formed together with two carbon atoms of the pyrazine skeleton, the ring formed may be fat. The aromatic ring or the aromatic ring is preferably an aromatic ring from the viewpoint of improving solubility and adjusting the light absorption wavelength of the compound to a visible portion (near 405 nm). The aromatic ring is more preferably a benzene ring or a naphthalene ring. When the pyrazine compound R3 and R4 represented by the above formula (1) are bonded to each other and form a ring together with two carbon atoms of the pyrazine skeleton, the ring formed is preferably an aromatic ring, and more preferably a naphthalene ring. R1 and R2 are preferably a phenyl group, and more preferably a hydrogen atom of a phenyl group is substituted by a linear or branched alkoxy group having 1 to 1 carbon number. The position of the substituent is arbitrary. The pyrazine compound represented by the above formula (1) is, for example, a compound represented by the following formulas (9), (10), (11), and (12). -26- 201115268 [Chem. 12]

[Chem. 13]

[化14] och3

〇ch3 -27- 201115268 [Chem. 15]

The pyrazine compound represented by the above formula (2) is, for example, a compound represented by the following formulas (1 3 ) and (1 4 ). [Chemistry 16]

[Chem. 17]

-28-201115268 The pyrazine compound represented by the above formula (3) is, for example, a compound represented by the following formulas (15) and (16). [Chem. 18]

In the photosensitive resin composition, the maximum absorption wavelength of the (Cl), (C2) and (C3) components is preferably in the range of 3 5 0 - 4 1 Onm. Thereby, a good sensitivity can be obtained for light having a wavelength of 3 5 0 to 41 Onm, and absorption at a long wavelength side of a wavelength of 500 nm or more is reduced, and stability under yellow light is good. Particularly, when a direct drawing exposure apparatus having a wavelength of 405 nm having a plurality of exposure heads is used, the maximum absorption wavelength of the (Cl ) , ( C2 ) and (C3 ) components is preferably in the range of 380 to 41 Onm. When the maximum absorption wavelength is in the range of -29 - 201115268 3 80 to 410 nm, even when the emission wavelength is dispersed slightly under the light source of each exposure head, the absorption amount of light near the wavelength of 405 nm is substantially constant. As a result, the sensitivity deviation that may occur per exposure head can be reduced. Since the high sensitivity can be obtained by stabilization, the amount of the photopolymerization initiator added can be reduced. The content of the above (Cl), (C2) and (C3) components is preferably from 50 to 100% by mass, more preferably from 70 to 100% by mass, particularly preferably from 80 to 100% by mass based on the total amount of the component (C). 100% by mass. When the content is less than 5% by mass, the sensitivity and the resolution tend to be lowered. Here, the "content" means the content of the total of (C), (C2), and (C3) components, and when they are contained in two or more types. (C) The photopolymerization initiator may contain other photopolymerization initiators to the extent that the effects of the (Cl), (C2) and (C3) components are not affected. Other photopolymerization initiators are, for example, benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methyl-1. An aromatic ketone such as [4-(methylthio)phenyl]-2-morpholinyl-acetone-1; an anthracene such as an alkyl hydrazine; a benzoin ether compound such as a benzoin alkyl ether; a benzoin compound such as a benzoin or an alkyl benzoin; a benzyl derivative such as a benzyl dimethyl ketal; and a 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer. 2,4,5-triarylimidazole dimer of 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer; phenyl acridine, I,7-bis (9,9 An acridine derivative of '-acridinyl) heptane or the like. These may be used alone or in combination of two or more. Further, the substituents of the aryl groups of the above two 2,4,5-triarylimidazoles may be the same or different. These may be used alone or in combination of two or more. Other photopolymerization initiators are, for example, those represented by the following formula (4) -30- 201115268

In the formula (4), X represents a carbon atom or a nitrogen atom, and R13, R14 and R15 each independently represent a halogen atom or an alkyl group having 1 to 5 carbon atoms, and at least one of R15 represents a halogen atom. R16 represents a hydrogen atom, an alkyl group of carbon number 5, or an alkoxy group having 1 to 5 carbon atoms, and 1 represents an integer of 〇~4. When 1 is 2 to 4, the plural R16s may be the same or different. When the photosensitive resin composition of the present invention is used in combination with the compound represented by the above formula ((C1) component or (C2) component as (C) photopolymerization initiator, it is possible to maintain resolution and adhesion. The tendency to improve the sensitivity and the development (the color developability of the photoresist). The content of the photopolymerization initiator of the component (C) is 1% by mass relative to the total amount of the components (A) and (B). The parts are preferably 〇.〇1~1〇 parts by mass, more preferably 0. 〇5~6 parts by mass, particularly preferably 0·1~4 parts by mass. When the content is less than 0 · 0 1 parts by mass, There is a tendency that a good sensitivity or resolution is not obtained, and when it is more than 1 part by mass, there is a tendency that a good shape cannot be obtained. The photosensitive resin composition of the present invention preferably further contains (D) a hydrogen-donating compound. Hydrogen-donating compounds are, for example, bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane, colorless crystal-31 - 201115268 leuco crystal violet 2-Hydroxythiobenzoxazole, a compound represented by the following formula (5), etc., can further improve the sensitivity. From the viewpoint of further improving the sensitivity, it is preferred. .-Containing compound represented by the compound represented by the following formula (5) of formula (5) for example, N - phenyl glycine, etc. [of 21].

In the formula (5), R17 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group or an ester group, a thiol group or a halogen atom. The integer of η is 0 to 5, and when η is 2 to 5, the plural R 17 may be the same or different. The photosensitive resin composition of the present invention has a tendency to increase the sensitivity to light having a wavelength of from 3 to 450 nm by using the compound represented by the above formula (5) in combination with the component (C1) or (C2). (D) The content of the hydrogen-donating compound is 1 part by mass based on the total amount of the component (A) and the component (B), preferably 〇1〇1 〇1 parts by mass, more preferably 0.05 〜5 parts by mass. The mass fraction is particularly preferably 〇.1 to 2 parts by mass. When the amount is less than 1 part by mass, there is a tendency that a good sensitivity is not obtained. When the amount is more than 10 parts by mass, the film may be precipitated in the form of foreign matter after formation. These may be used alone or in combination of two or more. In order to further improve the sensitivity, (E) a sensitizing dye may be further contained. The sensitizing dye may be selected from those having an absorption wavelength of the active light used in combination, but a compound having a large absorption wavelength of from 37 Å to 420 nm is preferred. The photosensitive resin composition can have sufficient high sensitivity by using such a sensitizing dye, particularly for direct exposure light having a wavelength of 4 〇 5 nm. When the maximum absorption wavelength of the sensitizing dye -32-201115268 is less than 370 nm, the sensitivity for directly drawing the exposure light tends to decrease, and when it is 42 Onm or more, the stability under yellow light tends to decrease. (E) sensitizing dyes are, for example, dialkylaminobenzophenones, pyrrolines, anthraquinones, coumarins, xanthones, oxazoles, benzoxazoles, thiazoles, benzene And thiazoles, triazoles, anthracenes, triazines, thiophenes, naphthyl imines, triarylamines and the like. These may be used alone or in combination of two or more. In particular, when exposure of the photosensitive resin composition layer is carried out using active light of 390 to 420 nm, (E) the sensitizing dye preferably contains a pyrimide selected from the group consisting of pyrazolines, anthraquinones, and fragrances from the viewpoint of sensitivity and adhesion. At least one of the group consisting of a soybean and a triarylamine, more preferably a pyrazoline, an anthracene or a triarylamine. (E) The content of the sensitizing dye is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). 2 parts by mass. When the amount is less than 质量1 parts by mass, there is a tendency that a good sensitivity or resolution is not obtained, and when it exceeds 10 parts by mass, a good shape tends not to be obtained. The photosensitive resin composition of the present embodiment may contain a photopolymerizable compound (such as a propylene oxide compound) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, and malachite green. (Malachite green) and other dyes, colorless crystal violet, etc., photochromic agent, thermal hair color preventive agent, p-toluenesulfonamide and other plasticizers, pigments, chelating agents, defoamers, flame retardants, stabilizers , adhesion imparting agent, flat agent, -33- 201115268 peeling accelerator, antioxidant, fragrance, imaging agent (Imaging Agent), thermal crosslinking agent, and the like. These may be used alone or in combination of two or more. The content is preferably 0.01 to 20 parts by mass per 10 parts by mass of the total of the components (A) (adhesive polymer) and (B) (photopolymerizable compound). The photosensitive resin composition of the present embodiment is dissolved in a solution (coating liquid) of a photosensitive resin composition having a solid content of about 30 to 60% by mass in an organic solvent, and then applied to the surface of a metal plate, for example. After drying, a photosensitive resin composition layer composed of the photosensitive resin composition of the present embodiment can be formed. The organic solvent is, for example, methanol, ethanol, acetone, methyl ethyl ketone, methyl sulphide (cell 〇s〇lve), ethyl siroli, toluene, hydrazine, hydrazine-dimethylformamide, propylene glycol Methyl ether or a mixed solvent of these. The metal plate is, for example, an iron-based alloy such as copper, a copper-based alloy, nickel, chromium, iron or stainless steel, and is preferably a copper, a copper-based alloy or an iron-based alloy. The thickness of the photosensitive resin composition layer varies depending on the application, and the thickness after drying is preferably about 1 to 100 Å. The surface on the opposite side to the metal plate of the photosensitive resin composition layer may be coated with a protective film. The protective film is, for example, a polymer film of polyethylene or polypropylene. <Photosensitive element> Next, the photosensitive resin composition layer and the photosensitive element of the present embodiment will be described. Fig. 1 is a schematic cross-sectional view showing an example of a photosensitive element. The photosensitive element 1 is a laminate in which the support film 2, the photosensitive resin composition layer 3, and the protective film 4 as necessary are laminated in this order. -34- 201115268 The support film 2 may be a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate or polypropylene, polyethylene or the like. The thickness of the support film (polymer film) is preferably from 1 to 100 / zm, more preferably from 5 to 50 #m, still more preferably from 5 to 30 μm. When the thickness is less than 1/zm, when the support film is peeled off, the support film tends to be easily broken, and when it exceeds 100 // m, the resolution tends not to be sufficiently obtained. The solution of the photosensitive resin composition of the present embodiment described above is applied onto the support film 2, and the photosensitive resin composition layer 3 composed of the photosensitive resin composition is formed on the support film 2 by drying. A solution of the photosensitive resin composition is applied onto the support film 2 by a roll coater, a comma coater, a gravure coater, an air knife coater (Air knife). Known methods such as coater, slit coater, coating bar, and the like are carried out. The drying of the photosensitive resin composition solution is preferably carried out at 70 to 150 ° C for 5 to 30 minutes. Further, the amount of the residual organic solvent in the photosensitive resin composition layer 3 after drying is preferably 2% by mass or less from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step. The thickness of the photosensitive resin composition layer 3 of the photosensitive element 1 varies depending on the application, but the thickness after drying is preferably from 1 to 10 Å, more preferably from 1 to 50 /zm, still more preferably from 5 to 50. //m, especially good for 10~40/zm. When the thickness is less than 1 //m, coating is difficult in the industry, and when it exceeds 100 μm, it is difficult to sufficiently obtain adhesion and resolution. The ultraviolet ray transmittance of the photosensitive resin composition layer 3 is preferably 5 to 75%, more preferably S--35-201115268 10 to 65%, and particularly preferably 15 at a wavelength of 4 〇 5 nm. ~55%. When the transmittance is less than 5%, there is a tendency that it is difficult to obtain sufficient adhesion, and when it exceeds 75 %, it is difficult to obtain sufficient resolution. The above transmittance can be measured by a UV spectrometer. The UV spectrometer is, for example, a Model 228A W beam spectrophotometer manufactured by Hitachi, Ltd. The photosensitive element 1 may have a protective film 4 covering the surface on the opposite side of the support film 2 of the photosensitive resin composition layer 3 as necessary. The adhesion of the protective film 4 to the photosensitive resin composition layer is preferably smaller than the adhesion of the support film 2 to the photosensitive resin composition layer, and a film of a Fish Eye is preferable. The term "fisheye" refers to a material in which a material is melted, kneaded, extruded, and a film is produced by a two-axis extension casting method, such as foreign matter, undissolved matter, or oxidative degradation of the material. In other words, "low fisheye" means less of the above-mentioned foreign matter in the film, and specifically, the protective film 4 may be made of polyester such as polyethylene terephthalate, polypropylene, polyethylene or the like. A polymer film that is heat resistant and solvent resistant. Commercially available products include, for example, a polypropylene film produced by Oji Paper Co., Ltd., a propylene resin film manufactured by Oji Paper Co., Ltd., and a PS series such as PS-25 manufactured by Teijin Co., Ltd., and the like. The ethylene glycol ester film «protective film 4 can be the same as the support film. The thickness of the protective film is preferably from 1 to 100/zm, more preferably from 5 to 50 #m, more preferably from 5 to 30 #m, and particularly preferably from 15 to 30 "m. When the thickness is less than 1/zm, 'when the photosensitive resin composition layer 2 and the protective film 4 are laminated on the substrate, the protective film 4 tends to be easily broken, -36-201115268 and exceeds 100/zm. 'And there is a tendency to be cheap. The photosensitive member may further have an intermediate layer of a buffer layer, an adhesive layer, a light absorbing layer, a gas barrier layer, or the like. The obtained photosensitive element 1 can be stored in a sheet shape or wound in a roll shape on a winding core. When winding into a roll shape, it is preferable to wind the support film 2 on the outer side. The core is made of, for example, a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyvinyl chloride resin, or an ABS resin (acrylonitrile-butadiene-styrene copolymer). The end surface of the roll-shaped photosensitive element roll obtained as described above is preferably provided with an end face spacer from the viewpoint of end face protection, and a moisture-proof end face spacer is preferably provided from the viewpoint of resistance to melting. The method of packing is preferably a method of packaging a black sheet bundle having a low moisture permeability. <Formation Method of Photoresist Pattern> The photoresist pattern can be formed using the above photosensitive resin composition. The method for forming a photoresist pattern of the present embodiment includes (i) a lamination step of laminating a photosensitive resin composition layer composed of the photosensitive resin composition on a substrate, and (ii) a photosensitive resin. An exposure step of irradiating the active light to a predetermined portion of the composition layer, (iii) removing a portion other than the predetermined portion of the photosensitive resin composition layer from the substrate, and forming a cured product of the photosensitive resin composition on the substrate The imaging step of the formed photoresist pattern. (i) Lamination process - 37 - 201115268 First, a photosensitive resin composition layer composed of a photosensitive resin composition is laminated on a substrate. As the substrate, a substrate (circuit forming substrate) having an insulating layer and a conductor layer formed on the insulating layer can be used. The photosensitive resin composition layer is laminated on the substrate, for example, after removing the protective film of the photosensitive element, and then the photosensitive resin composition layer of the photosensitive element is heated and pressure-bonded to the substrate. Thereby, the substrate and the photosensitive resin composition layer and the support film are formed, and the laminates which are sequentially laminated can be obtained. This layer cooperation is carried out under reduced pressure from the viewpoint of adhesion and compliance. good. The conditions of the heating temperature, pressure, and the like of the photosensitive resin composition layer and/or the substrate at the time of pressure bonding are not particularly limited, but are preferably carried out at a temperature of 70 to 130 ° C, to a degree of 0.1 to 1.0 MPa (l It is preferred to carry out pressure bonding under a pressure of ~10 kgf/cm2. When the photosensitive resin composition layer is heated to 70 to 130 °C, it is not necessary to preheat the substrate in advance, but in order to improve the laminate property, the substrate may be preheated. (ii) Exposure step Next, a predetermined portion of the photosensitive resin composition layer on the substrate is irradiated with the active light to expose and harden the predetermined portion. When the support film existing on the photosensitive resin composition layer is permeable to the active light ray, the active light can be irradiated through the support film, but when the support film is opaque to the active light, the photosensitive resin is removed after the support film is removed. The composition layer illuminates the active light. The exposure method is a method in which active light is irradiated onto an image (mask exposure method), for example, by a negative type called an artwork or a positive mask pattern of -38 - 201115268. It is also possible to use a direct drawing exposure method such as LDI (Laser Direct Imaging) exposure method or DLP (Digital Light Processing) exposure method to irradiate active light rays in an image form. As the light source of the active light, a known light source such as a carbon arc lamp, a mercury vapor arc lamp, a high pressure mercury lamp, a xenon lamp, a gas laser such as an argon laser, or a solid laser such as a YAG laser can be used. , such as semiconductor radiation, which emits ultraviolet light, visible light, etc. effectively. The wavelength of the active light (exposure wavelength) is preferably in the range of 305 to 41 Onm, more preferably in the range of 390 to 410 nm, from the viewpoint of obtaining the effect of the present invention. (The ΠΟ imaging step is performed by removing a portion other than the above-described predetermined portion of the photosensitive resin composition layer from the substrate, and forming a resist pattern composed of a cured product of the photosensitive resin composition on the substrate. Photosensitive resin When the support film is present on the composition layer, after the support film is removed, a portion other than the predetermined portion (exposed portion) (unexposed portion) (development) is removed. The development methods include wet development and dry development. However, wet development is widely used. By wet development, 'development using a photosensitive liquid corresponding to a photosensitive resin composition' is carried out by a known development method. The development method is, for example, a dipping method or a stirring method. The method of the method, the spray method, the rinsing, the brushing, the squeegee, and the immersion immersion is preferably a high-pressure spray method from the viewpoint of improving the resolution. It is also possible to combine two or more methods for development. - 201115268 The developing solution is, for example, an alkaline aqueous solution, a water-based developing solution, or an organic solvent-based developing solution. When the alkaline aqueous solution is used as a developing solution, it is safe and stable, and has good workability. As the base of the aqueous solution, an alkali metal hydroxide such as a hydroxide such as lithium, sodium or potassium may be used: a carbonate of lithium, sodium, potassium or ammonium or a bicarbonate: an alkali metal phosphate such as potassium phosphate or sodium phosphate. An alkali metal pyrophosphate such as sodium pyrophosphate or potassium pyrophosphate. The alkaline aqueous solution is preferably a dilute solution of sodium carbonate of 1-5.5% by mass, a dilute solution of potassium carbonate of 0.1 to 5% by mass, 0.1~ a dilute solution of 5 mass% of sodium hydroxide, a dilute solution of 0.1 to 5% by mass of sodium tetraborate, etc. The pH of the alkaline aqueous solution is preferably in the range of 9 to 1 1 , and the temperature is blended with the photosensitive resin composition layer. The alkali aqueous solution may be added with a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, etc. The aqueous developing solution may be, for example, water or an alkaline aqueous solution and one or more organic substances. A developing solution composed of a solvent. Here, the base of the alkaline aqueous solution includes, in addition to the above substances, borax or sodium metasilicate, tetramethylammonium hydroxide, ethanolamine 'ethylenediamine, diethylenetriamine, 2 -Amino-2-hydroxymethyl-1,3-propanediol, morpholine, etc. water The pH of the developing solution is preferably as small as possible in the range of sufficient image development, preferably from pH 8 to 12, more preferably from pH 9 to 10. The organic solvent used in the aqueous imaging solution, for example, acetone or ethyl acetate An ester, an alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropanol, butanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, etc. These may be used alone or in combination of two or more. The concentration of the organic solvent in the aqueous developing solution is usually preferably from 2 to 90% by mass, and the temperature -40 to 201115268 can be adjusted in accordance with the alkali developability. A small amount of a surfactant, an antifoaming agent, etc. may be added to the water-based developing solution. Examples of the organic solvent-based developing solution include 1,1,1-trichloroethane, N-methylpyrrolidone, and n,n-dimethyl An organic solvent such as carbamide, cyclohexanone, methyl isobutyl ketone or r-butyrolactone. Among these organic solvents, in order to prevent ignition, it is preferred to add water in the range of 1 to 20% by mass. After removing the unexposed portion, if necessary, the photoresist pattern can be further hardened by heating at a temperature of 60 to 25 ° C or an exposure of about 2 to 10 J/cm 2 . A substrate in which a photoresist pattern is formed by the above method can be manufactured by etching or plating. The formed photoresist pattern is used as a mask, and the substrate is etched or plated with respect to the conductor layer of the substrate. The etching liquid to be etched is, for example, a copper chloride solution, a ferric chloride solution, an alkaline etching solution, or a hydrogen peroxide etching solution. Among them, ferric chloride is preferably used from the viewpoint of good etching coefficient (etch factor). Solution. For the plating method at the time of plating, for example, copper plating such as copper sulfate plating or copper pyrophosphate plating, tin plating with high uniformity (High Throw) tin plating, and watt bath (nickel sulfate-nickel chloride) Gold plating such as plating, nickel sulfonate, etc., hard gold plating, soft gold plating, etc. After the etching or plating is completed, the photoresist pattern is peeled off, for example, in an aqueous solution which is more alkaline than the aqueous alkaline solution for development. The strongly alkaline aqueous solution can be, for example, 1 to 1% by mass of an aqueous sodium hydroxide solution, and 1 to 10% by mass of a -41 to 201115268 potassium hydroxide aqueous solution. Among them, an aqueous solution of sodium 1 or potassium hydroxide is preferably used, and more preferably an aqueous solution of sodium oxide or an aqueous solution of potassium hydroxide. The peeling pattern of the resist pattern can be used alone or in combination, for example, by dipping. Forming a photoresist pattern A multilayer printed circuit board or a small-diameter through hole. BEST MODE FOR CARRYING OUT THE INVENTION The above embodiment. [Embodiment] [Embodiment] Hereinafter, the following embodiments of the present invention will be more specifically described. [Preparation of photosensitive resin composition solution] The components shown in the following Tables 1 and 2 were combined to prepare solutions of Examples 1 to 13 and Comparative Example 1. The mass (solid content) of the component (A) shown in Tables 1 and 2. Table 1 and Table below are as follows. <(A) Adhesive Polymer> [Synthesis of the binder polymer (A-1)] The methyl group of the polymerizable monomer (monomer) is used in an amount of 1 to 5% by mass. A hydrogen type, a spray method, or the like may be used as the printed circuit board, but the present invention is not limited thereto. However, the present invention is not limited to the compounding amount of the photosensitive resin composition shown in the same table, and the amount of the olefinic acid is 150 g, and the methyl acrylate-42-201115268 acid sulfonate is 125 g. A solution obtained by mixing 25 g of methyl methacrylate and 200 g of styrene (mass ratio: 30/25/5/40) and 9.0 g of azobisisobutyronitrile was used as "solution a". A solution obtained by dissolving 1.2 g of azobisisobutyronitrile in a mixture of 60 g of cellosolve and 4 g of toluene (mass ratio: 3:2) was referred to as "solution b". A mixture of 270 g of methyl sarprosone and 18 〇g of toluene (mass ratio: 3:2) was placed in a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen gas introduction tube, and a nitrogen gas was blown into the flask. The mixture was stirred while heating, and the temperature was raised to 8 01. After the solution a was dropped into the mixture in the flask for 4 hours, the mixture was stirred while being kept at 80 ° C for 2 hours. Next, the above solution b was dropped into the solution in the flask for 10 minutes, and then the solution in the flask was stirred while being kept at 8 (TC for 3 hours. The solution in the flask was further heated to 90 ° in 30 minutes. C, after holding at 90 ° C for 2 hours, the solution containing the binder polymer (A-1 ) was obtained by cooling. The nonvolatile content (solid content) of the binder polymer (A-1) was 47.8 mass%. The weight average molecular weight is 30,000 mg of yttrium MGmgKOH/g. The weight average molecular weight is measured by gel permeation chromatography (GPC) and is derived using a calibration curve of standard polystyrene. The conditions of GPC are as follows (GPC) Condition) Pump: Hitachi L-6000 (manufactured by Hitachi, Ltd.) -43- 201115268 Pipe column: Gelpack GL-R420+ Gelpack GL-R43 0+ Gelpack GL-R440 (3 in total) (The above is Hitachi Chemical Industry ( Stock system 'product name' Solvent: tetrahydrofuran measurement temperature: 40 ° C Flow rate: 2.05 mL / min Detector: Hitachi L-3 3 00 type RI (manufactured by Hitachi, Ltd.) < (B) Photopolymerization Compound> TMPT21E: Trimethylolpropane polyoxyethylene ether trimethyl FA-321M: 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (manufactured by Hitachi Chemical Co., Ltd., trade name) FA-024M: a compound represented by the above formula (6), a compound of the formula 2〇 and R2i = methyl group, m3 = 6 (average 値), n2 + n3 = 12 (average 値) (曰立化成工业公司) System, trade name) M_114: 4-n-decylphenoxy octaethylene glycol acrylate (manufactured by Toagos Corporation, trade name) BPE-100: 2,2_bis(4-(methacryloxy) Polyethoxy)phenyl)propylidene) (average 2.6 moles of oxyethylene chain contained in one molecule) (manufactured by Shin-Nakamura Chemical Co., Ltd.) <Photopolymerization initiator (C) > [Synthesis of photopolymerization initiator (C-1)] • 44 - 201115268 Ethanol 2〇1111^, 3,3,,4,4'-biphenyltetramine 2111111〇1 and 3,3'- 4 mmol of methoxybiphenyl hydrazine was added to the flask, and after replacing the air in the flask with nitrogen, the mixture was refluxed at 80 ° C for 12 hours. After cooling to room temperature, 200 mL of water was added, and the product (C-1) was obtained by filtration under reduced pressure. The product (C-1) was confirmed to be a compound represented by the following formula (13) by the 1H-NMR spectrum shown in Fig. 2 and the i3C_NMR spectrum shown in Fig. 3 . [化22]

[Synthesis of Photopolymerization Initiator (C-2)] The substitution of hydrazine in the 3,3,-dimethoxy group (I4) indicates that the addition of 4,4'-dimethoxybiphenyl benzene is used. Further, a compound having a structure of || is obtained in the above (C-1). S- •45, 201115268 [Chem. 23]

[Synthesis of Photopolymerization Initiator (C-3)] In addition to using 2,3-diaminonaphthalene 2 mmol and 3,3'-dimethoxybiphenyl fluorene 2 mmol instead of 3,3',4,4'- A compound having the structure represented by the following formula (11) is obtained in the same manner as in the above (C-1) except that the biphenyltetraamine 2111111〇1 and the 3,3′-dimethoxybiphenyl fluorene are 4 mmol. [化 24] och3

OCH3 [Synthesis of photopolymerization initiator (C-4)] In addition to the use of 2,3-diaminonaphthalene 2 mmol and 4,4'-dimethoxy-linked-46 - 201115268, 3,-di-p-benzoquinone A compound having the structure represented by (j (12)) is obtained in the same manner as in the above (C-1) except that 2 mmol is substituted for 3,3',4,4'-biphenyltetraamine 2111111〇1 and methoxybiphenyl hydrazine 4 mmol. 》[化25]

[Other photopolymerization initiators] Light initiators other than (C-1), (C-2), (C-3) and (C-4) are as follows. BCIM: 2,2,-bis(2-chlorophenyl)-4,4,5,5,-tetraphenyl fluorene (manufactured by Hampford Co., Ltd., trade name) TPS: α,α,α-tribromo Phenylphenyl hydrazine (measurement of absorption spectrum) The external visible light absorption spectra of the products (Cl), (C-2), and (C-3) were measured as follows. The film containing the product (C-3) produced in Example 1 containing the product (C-1) produced in Example 1 was used, and the UV-visible light of each sample was measured using a UV-Vis spectrophotometer UV2550' manufactured by the company. Absorption spectrum. The results obtained are shown in Figure 4. -47- Polymeric Dimethicone and Shimadzu Film 201115268 Weigh the product (Cl) and (C-2) to a concentration of 1 X 1 (Γ5 m ο 1 / L in chloroform and place it in a quartz box ( In ce 11 ), the ultraviolet-visible absorption spectrum of each sample solution was measured using a UV-Vis spectrophotometer UV2550 manufactured by Shimadzu Corporation. The results obtained are shown in Fig. 5. The product was confirmed based on the spectra shown in Fig. 4 and Fig. 5 -1), (C-2), and (C-3) have a maximum absorption wavelength in the range of 350 to 410 nm. (D) Hydrogen supply compound > LCV: colorless crystal violet NPG: N-phenyl Glycine (R17 = hydrogen atom) (D-1) : 2-Hydroxythiobenzoxazole < (E) sensitizing dye >

Nikkafluor MC: 7-Diethylamino-4-methylcoumarin (product name, manufactured by Nippon Chemical Industry Co., Ltd.) DBA: 9,10-dibutoxy oxime (manufactured by Kawasaki Chemical Co., Ltd., trade name) (E-1) : 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)pyrazoline (manufactured by Nippon Chemical Industry Co., Ltd.) -48 - 201115268 [Table 1] Example 1 2 3 4 5 6 7 8 (A) (A-1) 50 50 50 50 50 50 50 50 (B) TMPT21 10 10 10 10 10 10 10 10 FA-321 M 15 15 15 15 15 15 15 15 FA-024M 5 5 5 5 5 5 5 5 M-114 5 5 5 5 5 5 5 5 BPE-100 15 15 15 15 15 15 15 15 (C) (C-1) 0.21 0.21 0.21 0.21 0.21 — — — (C-2) — — — — — 0.21 — — (C-3) 0.44 0.44 (C-4) BCIM TPS (D) LCV 0.1 — A 0.1 0.1 0.1 0.1 — NPG — 0.1 — 0.05 0.1 0.1 — 0.1 (D-1) — — 0.1 — — 一— — (E) Nikkafluor MC DBA (E-1) Dye Malachite Green 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 Solvent Acetone 9 9 9 9 9 9 9 9 Toluene 5 5 5 5 5 5 5 5 Methanol 5 5 5 5 5 5 5 5 -49 - 201115268 [Table 2] Example Comparative Example 9 10 11 12 13 14 15 1 (A) (A-1) 50 50 50 50 50 50 50 50 (B) TMPT21 10 10 10 10 10 10 10 10 FA-321M 15 15 15 15 15 15 15 15 FA-024M 5 5 5 5 5 5 5 5 M-114 5 5 5 5 5 5 5 5 BPE-100 15 15 15 15 15 15 15 15 (C) (C- 1) 0.21 0.21 0.21 0.21 一—一—(C-2) (C-3) -- — — — 0.44 0.44 一一(C-4) — — — — 一 — 0.45 一 BCIM — 0.5 0.5 0.5 一一一0.5 TPS 0.1 — — 1 — 0.1 0.1 — (D) LCV 0.1 0.1 0.1 0.1 — 0.1 0.1 0.1 NPG (D-1) — — 一 — 0.1 — 一 一 (E) Nikkafluor MC — 0.1 — 一 — — A 0.1 DBA — — 0.1 — 一—一一一(E-1) — 一— 0.1 — — 一 — Dye Malachite Green 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 Solvent Acetone 9 9 9 9 9 9 9 9 Toluene 5 5 5 5 5 5 5 5 Methanol 5 5 5 5 5 5 5 5 (Photosensitive element) The solutions of the photosensitive resin compositions of the above Examples 1 to 13 and Comparative Example 1 were uniformly applied to a polyphenylene terephthalate having a thickness of 16/zm. Ethylene formate film The Teijin Co., Ltd. product name "HTF-01" was dried by a hot air convection dryer of 70 C and 11 〇c to form a photosensitive resin composition layer having a film thickness of 40 m after drying. A protective film (manufactured by TAMAPOLY Co., Ltd., trade name "NF-15") was bonded to the photosensitive resin composition layer to obtain a sequentially laminated polyethylene terephthalate film (support film) and a photosensitive resin. The photosensitive elements of Examples 1 to 13 and Comparative Example 1 which constitute the material layer and the protective film. -50- 201115268 [Laminated substrate] A copper-clad laminate made of a glass epoxy material and a copper foil (thickness 35/zm) formed on both sides thereof (manufactured by Keli Chemical Industry Co., Ltd., trade name "MCL- The copper surface of E-67") was honed using a honing machine (manufactured by Sanqi Co., Ltd.) having a brush equivalent to #600, and after washing with water, it was dried by air flow. The copper-clad laminate (hereinafter referred to as "substrate") was heated to 8 °C after heating, and the photosensitive elements of Examples 1 to 13 and Comparative Example 1 were laminated on the copper surface of the substrate. The laminate was formed by laminating the protective film while the photosensitive resin composition layer of each photosensitive member was adhered to the copper surface of the substrate at a temperature of 20 ° C and a lamination pressure of 4 kgf/cm 2 . Thus, a laminated substrate in which a photosensitive resin composition layer and a polyethylene terephthalate film are laminated on the copper surface of the substrate is obtained. [Evaluation of Sensitivity] The obtained laminated substrate was left to cool, and at a temperature of 23 ° C, a phase having a concentration range of 0.00 to 2.00, a concentration stage of 0.05, a sheet size of 20 mm >< 187 mm, and a size of each section of 3 mm x 12 mm was used. A photo tool of a step tablet is adhered to the polyethylene terephthalate film of the laminated substrate. A direct-drawing exposure machine "DE-1 AH" (trade name) manufactured by Hitachi Via Mechanics Co., Ltd. using a blue-violet laser diode with a wavelength of 405 nm as a light source, with a predetermined energy (exposure amount), between the photographic tools and the poly The photosensitive resin composition layer was exposed to the ethylene terephthalate film. In addition, illuminance measurement was performed using an ultraviolet illuminometer (trade name "UIT-150" manufactured by Oxtail Motor Co., Ltd.) using a probe of 405 nm to -51 - 201115268. After the exposure, the polyethylene terephthalate film was peeled off from the laminated substrate to expose the photosensitive resin composition layer, and then a 1 mass% sodium carbonate aqueous solution was sprayed at 30 ° C for 24 seconds to remove the unexposed portion. Thus, a hardened film composed of a cured product of a photosensitive resin composition is formed on the copper surface of the substrate. The amount of the remaining portion of the step-type exposure meter (Step Tablet) obtained by the measurement of the cured film was measured as the exposure amount (mJ/cm 2 ) at the 20th stage, and the sensitivity of the photosensitive resin composition was evaluated. The smaller the number, the better the sensitivity. The results are shown in Tables 3 and 4. [Evaluation of resolution and adhesion] The drawing pattern of the line width (L) / pitch width (S) (hereinafter referred to as "L/S") is 5/5 to 30/30 (unit: μιη) The photosensitive resin composition layer of the laminated substrate was exposed (drawn) by the energy of 20 stages in the number of remaining stages of the 41-stage stage exposure meter. After the exposure, the same development processing as that of the above sensitivity was performed. After development, the pitch portion (unexposed portion) is completely removed, and the line portion (exposed portion) is free of meandering (bending) or missing, and the formed photoresist pattern is minimized by the minimum line width/space.値 Evaluation of resolution and adhesion. The smaller the number, the better the resolution and the adhesion. The results are shown in Tables 3 and 4. [Evaluation of Peeling Characteristics] -52- 201115268 The laminated substrate formed by the photoresist pattern obtained by the evaluation of the resolution and the adhesion is immersed in a plating solution of a copper sulfate/sulfuric acid aqueous solution, and is subjected to a full current 値2A. Electroplated copper for 15 minutes. The resulting copper plating is about 15/zm thick. A 3 % by mass aqueous sodium hydroxide solution at 5 ° C was sprayed onto the laminated substrate after plating, and the photoresist was peeled off from the substrate. The peeled laminated substrate was observed with an optical microscope, and the cured film between the electric shovel pattern (copper wiring) was examined for peeling residue. The results are shown in Tables 3 and 4. (Evaluation of Plating Formability) The peeled laminated substrate obtained by the evaluation of the peeling characteristics was observed with an optical microscope, and the electroplating pattern was not broken or short-circuited, and the plating thickness was evaluated by the minimum plating width formed. The smaller the number, the better the formation of the shovel. The results are shown in Tables 3 and 4. (Evaluation of contamination prevention of plating) Each photosensitive element was cut into a size of 4 〇 cm x 50 cm, and after removing the protective film, the exposure amount of the segment was changed to 20 stages, and the photosensitive resin composition layer was exposed. The polyethylene terephthalate film was peeled off to obtain a cured film. This cured film was immersed in 1 L of a plating solution of a copper sulfate/sulfuric acid aqueous solution for 3 days. The copper-clad laminate (substrate) was subjected to electrolytic copper plating for 15 minutes at a full current 値2A using a Hull Cell test bath (manufactured by Yamamoto Gold Plating Test Co., Ltd.). The plating using the plating solution of the unimpregnated film was used as a reference, and the appearance of the plating when the plating solution after the immersion cured film was used was visually observed. S. -53- 201115268 Compared with the reference, those who have no change in the appearance of plating are evaluated as non-polluting, and those who have changed in color change are evaluated as polluting. The results are shown in Table 3 and Table 4 [Table 3] Example 1 2 3 4 5 6 7 8 Sensitivity ^ (mJ/cm2) 38 8 34 29 22 40 32 8 Resolution and Adhesion (μ m) 12 12 12 12 12 12 12 12 Peeling residue y», Aut. 1ΙΙΓ J \ M te te J »w te Plating formation ("m) 12 12 12 12 12 12 12 12 Pollution of plating / 1 M /\\\ te and M /»>> * 1... Exposure amount of the number of residual segments of the stage exposure meter at 20 segments [Table 4] Example Comparative Example 9 10 11 12 13 14 15 1 Sensitivity ( mJ/cm2) 23 25 22 23 40 26 18 42 Resolution and Adhesion (“ m) 12 12 12 12 12 12 12 12 Stripped Residual Sister y»\\ Sister/», 4E Sister/»\\ Plating Formability (β m) 12 12 12 12 12 12 12 12 For the pollution of plating, Newy»\\ and /ί\Λ fte yn\ by <Μ,, sister/> ΝΛ te /», , * 1... Exposure amount of the stage exposure meter in the 20th stage - 54-201115268 The photosensitive resin composition of Examples 1 to 1 is compared with the comparative example 1, and the direct drawing exposure for the wavelength of 405 nm is High sensitivity, and good resolution, adhesion and plating formation. The peeling property and the prevention of contamination by plating are also maintained. In particular, the photopolymerization initiator uses the (c 1 ) component or the (C2 ) component, and the hydrogen donor compound uses only the N represented by the above formula (5). Examples 2 and 8 of the phenylglycine can improve the sensitivity. Further, the tribromomethylphenyl maple represented by the above formula (4) is used in combination with the (C1) component or the (C2) component. When the (C1) component or the (C2) component is used alone, the sensitivity is further improved. When α,α,α-tribromomethylphenylhydrazine represented by the above formula (4) is used, it is represented by the formula (C-4). Example 15 of the component (C1) is improved as compared with Example 14 using the component (C1) represented by the formula (C-3) and Example 9 using the component (C2) represented by the formula (C-1). Sensitivity As described above, the present invention can provide a photosensitive resin composition and a photosensitive element which are excellent in sensitivity, resolution, adhesion, peeling property, and plating formability, and have low contamination property to plating. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an example of a photosensitive element. [Fig. 2] 1H-NMR spectrum of (c-Ι) of the present example. Fig. 3 is a 13C-NMR spectrum of (C-1) of the present Example. Fig. 4 is an ultraviolet visible light absorption spectrum of (C -1 ) and (C - 3 ) of the present embodiment. [Fig. 5] The ultraviolet visible light absorption S·-55-201115268 spectrum of (C-1) and (C-2) of the present embodiment. [Explanation of main component symbols] 1 : Photosensitive element 2 : Support film 3 : Photosensitive resin composition 4 : Protective film -56-

Claims (1)

201115268 VII. Patent application scope: 1. A photosensitive resin composition characterized by comprising a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and a group selected from the following formulas (1) and (2); Or (3) at least one pyrazine compound of the compound composition of the structure, [1] rV"nyr3 | (1) [In the formula (1), R1, R2, R3, and R4 are each independently And an alkyl group, a cycloalkyl group, a phenyl group, a naphthyl group or a monovalent organic group containing a heterocyclic group, and R1 and R2, or R3 and R4 may be bonded to each other to form a ring together with two carbon atoms of the pyrazine skeleton] [Chemical 2] , nvr7 Y (2) [In the formula (2), R5, R6, R7, and R8 each independently represent an alkyl group, a cycloalkyl group, a phenyl group, a naphthyl group or a monovalent organic group having a heterocyclic group, and R5 and R6, Or R7 and R8 may be bonded to each other to form a ring together with two carbon atoms of the pyrazine skeleton, and the oxime and the oxime each independently represent a single ring structure or a condensed polycyclic structure formed together with two carbons of the pyrazine skeleton. Atomic group of aromatic rings] 201115268 [Chemical 3] [In the formula (3), R9, R10, rU, and Rl2 each independently represent a group, a ring-based group, a phenyl group, a naphthyl group or a monovalent organic group having a heterocyclic group, r9 and r1q, or R11 and r12. The system may be combined with each other to form a ring together with two carbon atoms of the ocular skeleton, and the Z system represents an aromatic ring or a heterocyclic ring which is formed together with four carbons of the pyrazine skeleton to form a monocyclic structure or a condensed polycyclic structure. Atomic group]. 2. The photosensitive resin composition according to claim 1, wherein the pyrazine compound is a compound having a structure represented by the above formula (1). 3. The photosensitive resin composition of claim 1 or 2 wherein the pyrazine compound has a maximum absorption wavelength of from 3 to 50 nm. 4. The photosensitive resin composition of any one of claims 1 to 3, wherein the binder polymer contains (meth)acrylic acid and styrene or (meth)acrylic acid and a styrene derivative as The photosensitive resin composition of any one of the above claims, wherein the compound contains the compound represented by the following formula (4), -58- 201115268 [Chemical 4] R14 (4) [In the formula (4), X represents a carbon atom or a nitrogen atom, and R13, R14 and r15 each independently represent a halogen atom or an alkyl group having 1 to 5 carbon atoms, and at least 1 of r>3, Ri4 and R15. One represents a halogen atom, and R16 represents a hydrogen atom, a courtyard group having a carbon number of 1 to 5 or a hospitaloxy group having a carbon number of 1 to 5, 1 is an integer of 〇~4, and 1 is 2 to 4, and a plurality of R16 Can be the same or different]. 6. The photosensitive resin composition according to any one of claims 1 to 5, further comprising a hydrogen-donating compound. 7. The photosensitive resin composition of claim 6, wherein the hydrogen-donating compound contains a compound represented by the following formula (5): I: 5] (R17) NH-CHo-C-OHII 〇(9) [In the formula (5), R17 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group or an ester group, a hydroxyl group or a halogen atom, and an integer of η 〇 〜5, η When it is 2~5, the plural R 17 may be the same or different]. 8. A photosensitive element comprising a support, and a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 7 formed on the support. . A method for forming a photoresist pattern, characterized in that: S--59-201115268 The photosensitive composition of the photosensitive resin composition according to any one of claims 1 to 7 is laminated on a substrate. a step of laminating the resin composition layer, a step of exposing the active light to a predetermined portion of the photosensitive resin composition layer, and removing a portion other than the predetermined portion of the photosensitive resin composition layer from the substrate. A developing step of forming a photoresist pattern composed of a cured product of the photosensitive resin composition is formed on the substrate. 10. The method for forming a photoresist pattern according to claim 9 wherein the wavelength of the active light is 390 to 410 nm. A method of manufacturing a printed circuit board, comprising the step of etching or plating a substrate having a photoresist pattern formed by a method for forming a photoresist pattern according to claim 9 or 10; . -60-