TW201007360A - Photosensitive resin composition, photosensitive element wherein same is used, method for forming a resist-pattern, and method for producing a printed wiring board - Google Patents

Abstract

Provided is a photosensitive resin composition containing (A) binder polymer, (B) photo-polymerizable compound having at least one ethylenic unsaturated bond and (C) photo-polymerization initiator, wherein the photo-polymerization initiator (C) includes a compound represented by general formula (I) and a compound represented by general formula (II).

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] Conventionally, in the field of manufacturing printed circuit boards, a photosensitive resin composition is widely used as a photoresist material for φ such as etching or plating, or a photosensitive resin is laminated on a support and coated with a protective film. Sexual components. When a printed circuit board is manufactured by using a photosensitive element, first, a photosensitive element is laminated on a circuit-forming substrate such as a copper substrate, and the pattern is exposed through a mask film or the like, and the photosensitive element is not exposed. The portion is removed by a developing solution to form a photoresist pattern. Next, the photoresist pattern is used as a mask, and a circuit pattern is formed by applying a uranium engraving or mineralization treatment to the substrate for forming a photoresist pattern, and finally the hardened portion of the photosensitive element is peeled off from the substrate. . In the manufacturing method of such a printed circuit board, in recent years, a direct laser direct drawing method in which active light is directly irradiated with an image using a data sheet without using a mask film has been put into practical use. The light source used in the direct drawing method uses a YAG laser and a semiconductor laser for safety or operability, and has recently proposed a technique using a long-life and high-output GaN-based blue laser. In addition, in recent years, with the high definition and high density in the printed circuit board, it is directly used as a DLP (Digital Light Processing) exposure method which can form a finer pattern (Fine pattern) 201007360. Depiction. In general, active light rays having a wavelength of 390 to 430 nm using a blue-violet semiconductor laser as a light source are used in the DLP exposure method. Moreover, in the main general-purpose printed circuit board, a multi-beam type multi-beam having a wavelength of 355 nm which can correspond to a small number of YAG lasers as a light source is used.

Polygon Multibeam) exposure method. Here, various sensitizers in the photosensitive resin composition are discussed in order to correspond to the respective wavelengths (for example, refer to Patent Documents 1 and 2). [Patent Document 1] [Patent Document 1] JP-A-2004-3 0 1 996 [Patent Document 2] JP-A-2005- 1 07 1 9 1 [Invention] [Invented Problem] However, the direct drawing method of exposing the laser to high-speed exposure is integrated with the light source that effectively emits ultraviolet light such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, and a xenon lamp. Compared with the conventional exposure method, the exposure energy at each point is small, and the production efficiency is low. Therefore, in the direct drawing method, a photosensitive resin composition requiring higher sensitivity is required. However, in order to increase the light sensitivity, if the light-initiating agent or the sensitizer contained in the photosensitive resin composition is increased, the local hardening reaction is performed on the upper portion of the photosensitive resin composition layer, and the hardenability of the bottom portion is lowered. The resolution obtained after photohardening -6 - 201007360 is lowered and the shape of the photoresist is deteriorated (inverted trapezoid). With the high resolution and high density of the photoresist pattern, the problem of the shape of the photoresist becomes profound, and since the shape of the photoresist is an inverted trapezoid, it is broken or short-circuited after uranium engraving or plating. The possibility of a bad situation. In such a conventional photosensitive resin composition, it is difficult to sufficiently achieve the desired light sensitivity, resolution, and photoresist shape. The present invention has been made in view of the above problems, and provides excellent photosensitivity and φ resolution, and can form a photosensitive resin composition having a good photoresist shape and a photosensitive resin composition even when a direct drawing method is used. The photosensitive element, the method of forming the photoresist pattern, and the manufacturing method of the printed circuit board are aimed at. [Means to solve the problem]

The present invention provides a photosensitive resin composition comprising (A) a binder polymer, (B) a photopolymerizable compound having at least one ethylenically unsaturated bond, and (C) a photopolymerization initiator, and the above ( C) The photopolymerization initiator contains a photosensitive resin composition of the compound represented by the following general formula (I) and a compound represented by the following general formula (Π).

201007360 [In general formula (I), 'R1 represents an alkylene group having 2 to 20 carbon atoms, an oxadialkylene having a carbon number of 2 to 2 0 or a thiodialkylene group having a carbon number of 2 to 20. (thiodialkylene)]. [Chemical 2]

[In the general formula (II), R2 represents an aromatic group which may have a substituent].

The photosensitive resin composition of the present invention has the above-described configuration and is excellent in light sensitivity and resolution. Further, the photosensitive resin composition of the present invention can form a photoresist pattern having a good photoresist shape even when a direct drawing method is used. The photoresist shape is a good photoresist pattern, and there is no problem of disconnection or short circuit after etching or plating treatment, and a printed circuit board having a fine pattern with high definition and high density can be effectively formed. The above (C) photopolymerization initiator preferably contains a compound represented by the following formula (in). As a result, the photosensitive resin composition of the present invention is more excellent in light sensitivity and resolution, and can be suitably used in the formation of a photoresist pattern formed by a direct drawing method. [Chemical 3] CHbl

Further, in the present invention, a photosensitive element comprising a support and a photosensitive resin composition layer composed of the photosensitive resin composition formed on the support 201007360 is provided. According to the photosensitive element of the present invention, the photosensitive resin composition layer can be easily laminated on a substrate or the like. Further, the photosensitive element of the present invention is excellent in light sensitivity and resolution, and has a photoresist pattern formed using the photosensitive element, and has a good resist shape. Furthermore, the present invention provides an irradiation step of irradiating an active portion with a predetermined portion of a photosensitive resin composition layer formed of the photosensitive resin composition formed on a circuit-forming substrate, and curing the exposed portion. A method of forming a photoresist pattern in which a portion other than a predetermined portion of the photosensitive resin composition layer is removed by the substrate. The photoresist pattern formed by the formation method of the present invention has a good photoresist shape by using the photosensitive resin composition of the present invention described above. Further, the present invention provides a predetermined portion of the photosensitive resin composition layer formed of the photosensitive resin composition formed on the circuit-forming substrate, and the active light is irradiated in an image by a direct drawing method. A method of forming a photoresist pattern in which the step of irradiating the photocuring of the light portion and the step of removing the portion other than the predetermined portion of the photosensitive resin composition layer are removed from the substrate. In the method for forming the present invention, the direct drawing method is employed as the irradiation method in the above irradiation step, and a high-definition/high-density photoresist pattern can be easily formed. Further, according to the 'forming method of the present invention, since the photosensitive resin composition of the present invention is used, even when the active light is irradiated by the direct drawing method, a photoresist pattern having a good photoresist shape can be obtained. Further, the invention further provides a method of manufacturing a printed circuit board which is etched or plated by a circuit for forming a circuit pattern of a resist pattern by the above-described method for forming a photoresist pattern -9 - 201007360. By this manufacturing method, a high-definition, high-density printed circuit board with good production efficiency can be obtained. [Effects of the Invention] According to the present invention, it is possible to provide a photosensitive resin composition having a photoresist pattern having a good photoresist shape and a photosensitive property using the same, even when a direct drawing method is used. Sex element, method of forming photoresist pattern, and manufacturing method of printed circuit board. [Embodiment] [Formation for implementing the invention]

Hereinafter, embodiments of the present invention will be described in detail.本 In the present invention, (meth)acrylic means acryl or methacrylic acid, (meth) acrylate means acrylate or methacrylate corresponding thereto, and (meth) acryloyl group means propylene fluorenyl Or corresponding to its methacrylinyl group. G (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 (hereinafter referred to as "(A) component" as the case may be), and (B) a photopolymerizable compound having at least one ethylenically unsaturated bond. (hereinafter, referred to as "(B) component") and (C) photopolymerization initiator (hereinafter, referred to as "(C) component"). -10-201007360 The (A) component may, for example, be an acrylic resin, a styrene resin, an epoxy resin, a guanamine resin, a guanamine epoxy resin, an acid alcohol tree or a phenol resin. These may be used alone or in combination of two or more. The component (a) is such that the alkali developability of the photosensitive resin composition is good, and the acrylic acid resin is preferred. The component (A) can be produced, for example, by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include styrene; vinyl-methyl benzene; a polymerizable styrene derivative having a substituent at the α-position or an aromatic ring such as α-methyl styrene; and diacetone propylene oxime; Acrylamide such as amine; acrylonitrile; vinyl alcohol ester such as ethylene-η-butyl ether; alkyl (meth)acrylate, cycloalkyl (meth)acrylate, (meth)acrylic acid Cyclopentyl ester, alkyl methacrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, decyl (meth) acrylate, dimethylamino (meth) acrylate Ethyl ester, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl(methyl) #acrylate, 2,2,3, 3-tetrafluoropropyl (meth) acrylate, (meth)acrylic acid, α-bromo (meth)acrylic acid, α-chloro(methyl)acrylic acid, β-furyl (meth)acrylic acid, β - Styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, maleic acid monoisopropyl vinegar, etc. Acid monoethyl acetate, fumaric acid, cinnamic acid, Paper # alpha # _ cyano Gui acid, itaconic acid, crotonic acid, propiolic acid and the like. These may be used alone or in combination of two or more. The (meth)acrylic acid alkyl ester may, for example, be a compound represented by the following general formula (IV). -11 - 201007360 H2C-C(R3)-COOR4 (IV) In the above general formula (IV), 'R3 represents a hydrogen atom or a methyl group, and R4 represents an alkyl group having 1 to 12 carbon atoms which may have a substituent. . Here, examples of the substituent include a hydroxyl group, an epoxy group, and a halogen group. Further, the alkyl group having 1 to 12 carbon atoms represented by R4 may be a linear chain or a branched form, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Heptyl, octyl, decyl, decyl, undecyl, dodecyl and structural isomers thereof. _ The polymerizable monomer represented by the above general formula (IV) includes methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and isopropyl (meth)acrylate. Ester, butyl (meth)acrylate, t-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate Ester, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, and the like. These may be used alone or in combination of two or more. @又的 (A) component, in order to improve the alkali-developing property of the photosensitive resin composition, it is preferable to use a binder polymer having a carboxyl group (hereinafter, referred to as "carboxyl-containing polymer" depending on the case). The carboxyl group-containing polymer can be produced, for example, by radically polymerizing a polymerizable monomer having a carboxyl group with another polymerizable monomer. As the above polymerizable monomer having a carboxyl group, (meth)acrylic acid is preferable, and methacrylic acid is more preferable. The carboxyl group-containing polymer is derived from the content of the repeating unit of the polymerizable monomer having a carboxyl group (hereinafter referred to as "carboxyl group content"), and is 12% under the total amount of the carboxyl group-containing poly-12-201007360 compound. 50% by mass is preferred, 12-40% by mass is preferred, 15 to 30% by mass is more preferred, and 15 to 25% by mass is particularly preferred. The photosensitive resin composition containing a carboxyl group-containing polymer as described above is more excellent in alkali developability, and is also excellent in alkali resistance after curing. When the carboxyl group content is less than 12% by mass, the alkali developability tends to be deteriorated, and if it exceeds 50% by mass, the alkali resistance tends to be deteriorated. Further, in order to improve the adhesion and peeling properties of the substrate or the like of the photosensitive resin composition layer composed of the photosensitive resin composition φ, the component (A) is characterized in that styrene or a styrene derivative is used as a polymerizable property. The binder polymer contained in the monomer unit is preferred. The content of the repeating unit derived from the styrene or the styrene derivative is preferably 0 to 30% by mass, preferably 1 to 28% by mass, and 1.5 to 27% by mass based on the total amount of the binder polymer. For better. When the content is less than 0.1% by mass, the adhesion tends to be deteriorated. When the content exceeds 30% by mass, the peeling sheet tends to be large and the peeling time tends to be long. The weight average molecular weight of the φ (A) component is preferably 2 〇 〇 3 3 , , , 300 300 300 300 300 300 300 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 When the weight average molecular weight of the component (A) is in the above range, the alkali developability of the photosensitive resin composition and the mechanical strength of the photocured material are further improved. When the weight average molecular weight of the component (A) is less than 20,000, the cured liquid resistance of the cured resin composition tends to be lowered, and if it exceeds 300,000, the time required for development tends to be long. The weight average molecular weight in the present invention is a enthalpy converted from a standard curve -13-201007360, which is determined by a gel permeation chromatography method using a standard polystyrene. As the component (A), the above-mentioned binder polymers may be used singly or in combination of two or more kinds. A combination of two or more types of binder polymers composed of two different types of copolymerized components, and a combination of two or more kinds of binder polymers having different weight average molecular weights, A combination of two types of adhesive polymers, such as a binder polymer. The component (B) is a photopolymerizable compound having at least one ethylenically unsaturated bond. The component (B) may, for example, be a compound obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid, a bisphenol fluorene (meth) acrylate compound, or a compound containing an epoxy propyl group. a compound obtained by the reaction of an α,β-unsaturated carboxylic acid, an ethyl urethane monomer (for example, a (meth) acrylate compound having a urethane-bonded), a nonyl phenoxy polyalkylene Alkoxy (meth) acrylate, γ-chloro-β-hydroxypropyl-β'-(meth) propylene oxiranyl ethyl hydrazine-decanoate, β-hydroxyethyl-β'- ( Methyl)propenyloxyethyl-indole-decanoate, β-hydroxypropyl-β'_(methyl)propene G methoxyethyl-quinone-caprate, alkyl (meth)acrylate Wait. These may be used alone or in combination of two or more types. Examples of the compound obtained by the reaction of a polyhydric alcohol with an α,β-unsaturated carboxylic acid include polyethylene glycol di(meth)acrylate having a number of ethyl groups of 2 to 14 and a propyl group. Polypropylene glycol di(meth) acrylate with a number of 2 to 14 and a polyethylene propylene glycol di(meth) acrylate having a number of 2 to 14 and a propyl group of 2 to 14 Polypropylene glycol di(meth)acrylate having a base number of 2 to 14, trimethylolpropane di(methyl-14-201007360) acrylate, trimethylolpropane tri(methyl)acrylic propane ethoxylate Tris(meth)acrylate, trimethyloltri(meth)acrylate, trimethylolpropane tripolyethyl)acrylate, trimethylolpropane polypropoxytri(methyl), trihydroxyl Methyl propane polyethoxypolypropoxy tris(methyl, pentaerythritol tri(meth)acrylate, pentaerythritol tetraenoate, pentaerythritol polyethoxy tetrakis(meth)acrylate decyl alcohol penta(meth)acrylic acid Ester, dipentaerythritol hexa(methyl ester, etc.) These may be used alone or in combination of two or more kinds. (B) In order to make the photosensitive resin composition more excellent in luminosity, it is preferable to contain bisphenol A-based (meth)acrylic acid. As the above bisphenol A-based (meth)acrylate, 2,2-bis(4-( (Meth) propylene decyloxypolyethoxy), 2,2-bis(4-((methyl) propylene oxypolypropoxy), 2,2 bis (4_((meth) propylene)醯oxypolyethoxy)phenyl)propane, etc. As the above 2,2·bis(4-((meth)propenyloxy)phenyl)propane, 2,2-bis(4-(( Methyl)diethoxy)phenyl)propyl, 2,2-bis(4-((methyl)triethoxy)phenyl)propane, 2,2-bis(4-((methoxy) Tetraethoxy)phenyl)propane, 2,2-bis(4-((decyloxypentaethoxy)phenyl)propane, 2,2-bis(4-(ethenyloxyhexaethoxy) Phenyl)propane, 2,2-bis(4-ester, trimethylolpropanediethoxyoxytri(meth)acrylic acid) acrylate (meth) propyl ester, dipentaerythritol) acrylic acid sensitivity and resolution The ester compound is a compound, and a phenyl) propane) phenyl) propyl polypropoxy ethoxy propylene oxy) propylene oxy group) Iridinium methyl) propylene (methyl) propyl ((methyl) -15- 201007360 propylene decyloxy heptaethoxy) phenyl) propane, 2,2-bis(4-((methyl) propylene oxy) Ethyl ethoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxy)ethoxy)phenyl)propane, 2,2-bis(4-((methyl) ) propylene decyloxy decethoxy) phenyl) propane, 2,2-bis(4-((methyl) propylene oxy) eleven ethoxy) phenyl) propane, 2, 2- bis ( 4 -((Meth)acryloxy-dodecyloxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxytridecyloxy)phenyl)propane, 2 ,2-bis(4-((meth)propenyloxytetradecyloxy)phenyl)propane, 2,2-bis(4-((methyl)propenyloxypentadecane) Phenyl)propane, 2,2-bis(4-((meth)propenyloxyhexadecyloxy)phenyl)propane, and the like. Bismuth, 2,2-bis(4-(methacryloxypentapentaethoxy)phenyl)propane' can be obtained commercially as BPE-500 (product name of Shin-Nakamura Chemical Industry Co., Ltd.) or FA- 321M (product name of Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecane)ethoxypropane), commercially available as BPE-13〇〇 ( New Nakamura Chemical Industry Co., Ltd., product name). The tiles may be used alone or in combination of two or more types. As the above 2,2-bis(4-((meth)propenyloxypolypropoxy)phenyl)propane, 2,2-bis(4.((meth)acryloxy)-propyl Oxy)phenyl)i, propylene, 2,2_bis(4.((methyl)propionateoxytripropoxy)phenyl)propane, 2,2-bis(4-((methyl)) Propylene-oxylated tetrapropoxy)phenyl)propane, 2,2.bis(4-((methyl)propanoateoxypentapropoxy)phenyl)propyl, 2,2-di (4 -((Meth)propenyloxyhexapropoxy)phenyl)propane, 2,2-bis(4-((methyl)-16-201007360 propylene decyloxypentapropoxy)phenyl)propane , 2,2-bis(4-((meth)propenyloxy octapropoxy)phenyl)propane, 2,2-bis(4-((methyl) propylene oxy) pentyloxy) Phenyl)propanoid, 2,2-bis(4-((methyl)propenyloxydapoxy)phenyl)propane, 2,2-bis(4-((methyl)propenyloxy) Eleven propoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxydipyloxy)phenyl)propane, 2,2-bis(4-((A) Base) propylene decyloxytridecyloxy)phenyl)propane, φ 2,2-bis(4-(( Acryloxytetradecyloxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxypentadecapropoxy)phenyl)propane, 2,2-double (4-((meth)acryloxycarbonylhexadecyloxy)phenyl)propane or the like. These may be used alone or in combination of two or more types. As the above 2,2-bis(4-((meth)propenyloxypolyethoxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)acrylofluorene) is exemplified. Oxydiethoxyoctyloxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxytetraethoxytetrapropoxy)phenyl)propane, φ 2, 2-bis(4-((meth)acryloxy)hexaethoxyhexapropyloxy)phenyl)propane or the like. These may be used alone or in combination of two or more types. (B) component contains 2,2-bis(4-((meth) propylene oxy ethoxy) phenyl) propane in order to improve the light sensitivity and resolution of the photosensitive resin composition. Preferably, it is more preferable to contain 2,2_bis(4-(methylpropionyloxypentaethoxy)phenyl)propane (for example, "product name "FA-321M" manufactured by Hitachi Chemical Co., Ltd.). . (B) In the case where the component contains a bisphenol a-based (meth) acrylate compound, the content thereof is from 10 to 50 with respect to the total amount of the component (A) and the component (B) -17 to 201007360 100 parts by mass. The mass fraction is preferably 15 to 40 parts by mass. When the content of the bisphenol A-based (meth) acrylate compound is within the above range, the photosensitivity and resolution of the photosensitive resin composition are balanced. The component (B) preferably contains an ethyl urethane monomer in order to improve the flexibility and capping property of the cured film of the photosensitive resin composition. Here, the urethane monosystem means a photopolymerizable compound having at least one ethylenic unsaturated bond bonded to urethane. Examples of the ethyl urethane monomer include (@methyl) propylene monomer having a hydroxyl group at the β position, isophorone diisocyanate, 2,6-toluene diisocyanate, and 2,4-toluene diisocyanate. An addition reaction product of a diisocyanate compound such as 1,6-hexamethylene diisocyanate; a compound represented by the following general formula (V); a guanidine-modified urethane di(meth) acrylate; , decyl urethane di(meth) acrylate, and the like. In fact, the lanthanide represents ethylene oxide, and the yttrium-denatured compound has a block structure of an epoxy vinyl group. Further, the fluorene represents epoxy propylene, and the cerium-denatured compound has a block structure of an oxypropylene group. For example, the product name UA-11, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., is exemplified as the oxime-modified amino group G ethyl acrylate di(meth) acrylate. Further, as the hydrazine or hydrazine-modified urethane di(meth) acrylate, for example, a product name UA-13 manufactured by Shin-Nakamura Chemical Industry Co., Ltd. is mentioned. The (Β) component is preferably a compound represented by the following general formula (V) as the ethyl urethane monomer. -18- 201007360 [化5]

(V) In the above general formula (V), R5 represents a divalent organic group, R6 represents a group represented by the following general formula (VI), and a plurality of R5 groups may be mutually identical or different, and the plural exists. R6 can be identical or different from each other. R7 ~c=ch2 (VI) ο In the above general formula (VI), R7 represents a hydrogen atom or a methyl group, X represents an exoethyl group or a propyl group, m represents an integer of 1 to 14, and m is present. The Xs may be identical or different from each other.尙, the propyl group contains 1-methyl-extended ethyl group and • 2·methyl-extended ethyl group. As a compound represented by the above general formula (V), a commercially available product 'is UA-21 (in the general formula (V), R7 is a methyl group, X is an exoethyl group, and m is 4 (an average 値). , R5 is a hexamethylene compound, the brand name of Xinzhongcun Chemical Industry Co., Ltd., UA-41 (in the general formula (V), R7 is a methyl group, X is a stretching propyl group, and m is 5 (average 値) , R5 is a hexamethylene compound, brand name of New Nakamura Chemical Industry Co., Ltd., UA_42 (in the general formula (V), R7 is a methyl group, X is a stretching propyl group, m is 9 (average 値), R5 Hexamethylene compound, Xinzhongcun Chemical Industry Co., Ltd. -19-201007360, trade name), UA-44 (Generally, 'R7 is a hydrogen atom, X is a propyl group, and m is 6 ( The average 値), R5 is a hexamethylene compound, and the brand name of Shin-Nakamura Chemical Industry Co., Ltd.). These may be used alone or in combination of two or more types. In the above general formula (V), R5 is preferably a stretching base having a carbon number of 1 to 12. Further, in the above general formula (VI), X is preferably an ethyl group. The cured product of the photosensitive resin composition containing the component (B) is more excellent in flexibility and capping property. In the case where the component (B) contains the compound represented by the above formula (V), the content thereof is preferably 5 to 25 parts by mass based on 100 parts by mass of the total of the components (A) and (B). 7 to 15 parts by mass is more preferred. When the content of the compound represented by the above formula (V) is within the above range, the flexibility and the capping property of the cured product of the photosensitive resin composition are further improved. (B) component containing a mercaptophenoxy polyalkylene group (methyl)

Acrylate is preferred. Thereby, the peeling property of the photoresist formed of the cured product of the photosensitive resin composition is improved. G, as a nonylphenoxy polyalkylene (meth) acrylate, may be exemplified by nonylphenoxypolyoxy (meth) acrylate or nonyl phenoxypolyoxy (A) Acrylate, nonylphenoxy polybutenyloxy (meth) acrylate, and the like. These may be used singly or in combination of two or more types. Examples of the nonylphenoxypolyvinyloxy (methyl) propylene vinegar include nonylphenoxyvinyloxy (meth) acrylate and nonyl phenoxy divinyloxy (methyl). Acrylate, nonylphenoxytriethyleneoxy (methyl-20-201007360) acrylate, nonylphenoxytetraethyleneoxy (meth) acrylate, nonylphenoxypentavinyloxy (A) Acrylate, nonylphenoxyhexaethyleneoxy (meth) acrylate, nonylphenoxy heptaethyleneoxy (meth) acrylate, nonylphenoxy octaethyleneoxy (methyl) Acrylate, nonylphenoxy hexaethyleneoxy (meth) acrylate, nonylphenoxy decyleneoxy (meth) acrylate, and the like. These may be used alone or in combination of two or more types. φ As the nonylphenoxypolypropyleneoxy (meth) acrylate, a nonylphenoxy propyleneoxy (meth) acrylate, a nonyl phenoxy bis propylene oxy (meth) acrylate Ester, nonylphenoxytripropenyloxy (meth) acrylate 'mercaptophenoxy tetrapropenyloxy (meth) propyl acrylate, nonyl phenoxy pentacene oxy (meth) acrylate Ester, nonylphenoxyhexapropyleneoxy (meth) acrylate, nonylphenoxy heptapropenyloxy (meth) acrylate, nonylphenoxy octadecyloxy (methyl) propylene sulphuric acid Ester, nonylphenoxy nonahexyloxy (meth) acrylate, nonylphenoxy phthalyl decyl oxy (meth) acrylate, and the like. These may be used alone or in combination of two or more types. The component (B) preferably contains a nonylphenoxy polyvinyloxy (meth) acrylate, and contains a nonylphenoxytetraethyleneoxy (meth) acrylate (for example, manufactured by Toagosei Co., Ltd.) The product name "M-113" or decylphenoxy octaethyl oxy (meth) acrylate (for example, manufactured by Kyoeisha Chemical Co., Ltd., product name "NP-8EA") is more preferable. The (B) component is more excellent in the peeling property of the photoresist comprising the compound of the photosensitive resin composition. -21 - 201007360 (B) In the case where the component contains a nonylphenoxypolyalkyloxy(meth)acrylate, the content thereof is 100 parts by mass based on the total amount of the component (A) and the component (B). '3 to 40 parts by mass is preferred, 5 to 30 parts by mass is preferred, and 5 to 20 parts by mass is more preferred. When the content of the nonylphenoxy polyalkylene (meth) acrylate is within the above range, the peeling property of the photoresist composed of the cured product of the photosensitive resin composition is further improved. In the component (B), the release property of the photoresist of the photosensitive resin composition and the cured product of the photosensitive resin composition is more excellent, and it is preferable to contain a compound represented by the following general formula (VII). .化OR8 一Ο~CH2~~C H2_0~^-~2 (r<广nr In the above general formula (VII), R8 represents a hydrogen atom or a methyl group, and R9 represents a hydrogen atom, a methyl group or a halogenated group A. The group R1Q represents an alkyl group having 1 to 6 carbon atoms, a halogen atom or a hydroxyl group, and η represents an integer of 0 to 4. The presence of n of R1() may be the same or different from each other as the above general formula (VII). The compound represented by γ-chloro-β-hydroxypropyl-Ρ'-(meth)acrylomethoxyethyl hydrazine-decanoate, hydrazine-hydroxyethyl-β'-(methyl) Propylene oxirane ethyl-0-decanoate, β-hydroxypropyl-β'-(meth) propylene oxiranyl ethyl hydrazine- decanoate, etc., among which chloro-hydrazine-hydroxypropyl- Preferably, β'-(meth)acryloyloxyethyl-indole-phthalate is γ-chloro-β-hydroxypropyl-β'-methacryloxyethyl-indenyl-phthalate. Commercially available as FA-MECH (manufactured by Hitachi Chemical Co., Ltd., product name) -22- 201007360 These may be used alone or in combination of two or more types. (B) The composition contains the above general formula (VII). The content of the compound expressed as a total amount relative to the total of (A) component and (B) component 1 part by mass, preferably 3 to 20 parts by mass, more preferably 5 to 15 parts by mass. The content of the compound represented by the above general formula (VII) is within the above range, and the resolution of the photosensitive resin composition is 1 part by mass. Further, the peeling property of the photoresist formed of the cured product of the photosensitive resin composition is more excellent. The photopolymerization initiator of the component (C) contains the above formula (I). The compound and the compound represented by the above general formula (II). In the above general formula (I), R1 is preferably an alkylene group having 2 to 20 carbon atoms, and an alkylene group having 4 to 14 carbon atoms is preferred, carbon. The alkylene group of the number 7 is more preferable, and the photosensitive resin composition containing such a compound can balance the light sensitivity and the resolution in a balanced manner, and by this photosensitive resin composition, a better good light resistance can be formed. In the case of the photosensitive resin composition, the compound of the photosensitive resin composition is a product of the product name "N-1717" manufactured by Asahi Kasei Kogyo Co., Ltd., which is a compound having a carbon number of 7 and an alkyl group. The content of the compound represented by the above general formula (I) is relative to (A) The total amount of the component and the component (B) is 100 parts by mass, preferably 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, and the compound represented by the above general formula (I). When the content is less than 0.01 parts by mass, the photosensitivity of the photosensitive resin composition tends to be inferior, and if it exceeds 20 parts by mass, it becomes difficult to obtain a good photoresist shape, and the adhesion and resolution of the photoresist are lowered. -23- 201007360 In the above general formula (π), 'R2 is preferably a phenyl group which may have a substituent, and more preferably a phenyl group. Here, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, and an amine group. The photosensitive resin composition containing such a compound is more excellent in light sensitivity and resolution. In the case of the compound in which R2 is a phenyl group, for example, Nippon Steel Chemical Co., Ltd., product name "9-PA". The content of the compound represented by the above formula (II) in the photosensitive resin composition is 100 parts by mass based on the total amount of the components (A) and (B), and is 1 to 10 parts by mass per 100 parts by mass. Preferably, 0.05 to 5 parts by mass is more preferred, and 0.07 to 3 parts by mass is particularly preferred. When the content of the compound represented by the above formula (π) is less than 1 part by mass, the photosensitivity of the photosensitive resin composition tends to be inferior, and if it exceeds 10 parts by mass, it becomes difficult to obtain a good quality. The shape of the photoresist, the adhesion of the photoresist, and the resolution tend to decrease. The component (C) preferably contains a compound represented by the above formula (in). The compound represented by the formula (ΙΠ) can be obtained, for example, as N-phenyglycin (product name, manufactured by Mitsui Chemicals, Inc.). A photosensitive resin composition containing 0 such a compound is more excellent in light sensitivity and resolution. When the component (c) contains the compound represented by the above formula (III), the content thereof is 100 parts by mass based on the total amount of the component (A) and the component (B), and is 〇1〇1〇 by mass. Preferably, 0.05 to 5 parts by mass is preferred, and 0.07 to 3 parts by mass is more preferred. When the content of the compound represented by the above formula (III) is within the above range, the photosensitivity and resolution of the photosensitive resin composition are more excellent. -24- 201007360 (C) Ingredients, it may also contain other photopolymerization initiators. Examples of other photopolymerization initiators include benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Mitchler), and N,N'. -tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino- Aromatic groups such as 1-(4-morpholinylphenyl)·butanone·1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1 Ketone; 2-ethyl fluorene, phenanthrenequinone, 2-tert-butyl hydrazine, octamethyl hydrazine, 1,2_ Φ benzofluorene, 2,3-benzopyrene, 2-phenyl fluorene Bismuth, 2,3-diphenyl hydrazine, chlorpyrifos, 2-methyl hydrazine, 1,4-naphthoquinone, 9,10-morphine, 2, methyl 1,4-naphthoquinone, 2 , dimethyl hydrazine and the like; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether; benzoin compounds such as benzoin, methyl benzoin, ethyl benzoin, etc; benzyl dimethyl ketal And other benzyl derivatives: 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10.dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10 - substituted quinones such as dipentyloxy hydrazine; 2- (〇-chlorobenzene) -4,5-diphenylimidate dimer, 2-φ(〇-chlorophenyl)-4,5-bis(methoxyphenyl)imidazole dimer, 2-(〇-fluorine Phenyl)-4,5-diphenylimidazole dimer, 2-(〇-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl a 4,4,5-triaryl imidazole dimer such as a 4,5-diphenylimidazole dimer; a coumarin compound; an oxazole compound; a pyrazoline compound. As the 2,4,5-triaryl imidazole dimer, the substituent of the aryl group may also be two dimers of 2,4,5-triaryl imidate which are identical to each other, and the substituent of the aryl group is also It may be a dimer of two 2,4,5-triaryl imidazoles which are different from each other. The former is a compound that is symmetrical, and the latter is an asymmetric compound. Further, a combination of a thioxanthone-based compound and a tertiary amine compound may be used as a photopolymerization initiator, as in the case of a combination of a dimethyl ketone-25-201007360 ketone and dimethylamino benzoic acid. These may be used alone or in combination of two or more types. The content of the component (A) in the photosensitive resin composition is preferably 30 to 80 parts by mass, more preferably 40 to 75 parts by mass, per 100 parts by mass of the total of the components (A) and (B). 50 to 70 parts by mass is particularly good. When the content of the component (A) is within this range, the coating properties of the photosensitive resin composition and the strength of the photocured material are further improved. The content of the component (B) in the photosensitive resin composition is preferably 20 to 60 parts by mass, and 30 to 55 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). Good, 35~50 parts by mass is especially good. (B) When the content of the component is within this range, the photosensitivity and coating properties of the photosensitive resin composition are further improved. The content of the component (C) in the photosensitive resin composition is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the total of the components (A) and (B). Preferably, 0.2 to 5 parts by mass is a special good. When the content of the component (C) is within this range, the photosensitivity of the photosensitive resin composition and the photocuring property inside the photosensitive resin composition layer are more excellent. The photosensitive resin composition may further contain a dye of malachite green, Victoria pure blue, bright green, methyl violet or the like according to requirements; tribromophenyl maple, crystal violet, diphenylamine, benzylamine, triphenyl Light coloring agent such as amine, diethyl aniline or hydrazine chloroaniline; thermal coloring preventive agent; plasticizer such as P-toluene sulfonamide; pigment; sputum filling agent; defoaming agent; flame retardant; Formulation agent; leveling -26-201007360 agent; stripping accelerator; antioxidant; perfume; imaging agent; thermal crosslinking agent, etc., relative to the total amount of (A) component and (B) component, 1 part by mass, Each may be contained in an amount of about 0.01 to 20 parts by mass. These may be used alone or in combination of two or more types. Further, the 'photosensitive resin composition' can be dissolved in methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, as needed. A solvent such as propylene glycol monomethyl ether or a mixed solvent of such φ can be applied as a solution having a solid content of about 30 to 60% by mass. These may be used alone or in combination of two or more types. The photosensitive resin composition is not particularly limited, and it is preferably used as a liquid resist after being applied to a metal surface and dried as a liquid photoresist, or used as a photosensitive member to be described later. For the metal surface, for example, a metal surface made of an iron-based alloy such as copper, a copper-based alloy, nickel, chromium, iron or stainless steel is preferably a metal surface made of copper, a copper-based alloy or an iron-based alloy. (Photosensitive Element) Next, the photosensitive element of this embodiment will be described. The photosensitive element of the present embodiment is a photosensitive resin composition layer comprising a support and a photosensitive resin composition formed on the support, and FIG. 1 shows the photosensitive material of the present invention. A schematic cross-sectional view of one embodiment of a suitable element. The photosensitive member 1 shown in Fig. 1 is composed of a support 10 and a photosensitive resin composition layer -27 - 201007360 14 which is provided on the support 10. The photosensitive resin composition layer 14 is a layer composed of the photosensitive resin composition of the above-described embodiment. Further, in the photosensitive element 1 of the present embodiment, the surface F1 opposite to the support 10 on the photosensitive resin composition layer 14 may be covered with a protective film. The support 10 is, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, or polyester. The photosensitive member 1 is obtained by coating a photosensitive resin composition on such polymer films and drying. As the support 10, it is preferable to use a polyethylene terephthalate film from the viewpoint of excellent transparency. These polymer films must be removed from the photosensitive resin composition layer 14 after being attached. A surface-treated film which can be easily removed from the photosensitive resin composition layer 14 or a film which can be easily removed can be suitably used as the support. The thickness of the above polymer film is preferably 1 to 1 ΟΟμηη, more preferably 1 to 50 μm, and particularly preferably 1 to 30 μη. When the thickness of the polymer film is less than 1 μm, the mechanical strength is lowered, and there is a tendency that the polymer film is easily broken during coating, and if it exceeds @ΙΟΟμιη, the photosensitive resin composition is transmitted through the polymer film. When the layer 14 is irradiated with active light, the resolution tends to decrease. Further, a support having a thickness exceeding ΙΟΟμιη tends to be inferior in cheapness. The polymer film may be used as a protective film, or the polymer film may be coated on the surface opposite to the support 10 of the photosensitive resin composition layer 14. The adhesion between the protective film and the photosensitive resin composition layer 14 is preferably 280 - 201007360 smaller than the adhesion of the photosensitive resin composition layer 14 to the support 10. Further, the protective film is preferably a film having a low fish eye.尙' "Fisheye" means a material in which foreign matter, undissolved matter, oxidative degradation, etc. of a material are drawn into a film by heat-melting, kneading, extruding, 2-axis stretching, casting, etc. . Examples of the method of applying the solution of the photosensitive resin composition to the support 1 roll include roll coating, twin roll coating, gravure coating, air knife coating, steel die coating, and bar coating. , spraying cloth, etc. Further, as a condition for drying the solution of the photosensitive resin composition coated on the support 10, for example, a drying temperature of 70 to 150 ° C and a drying time of about 5 to 30 minutes are exemplified. The amount of the residual organic solvent in the photosensitive resin composition layer 14 is preferably 2% by mass or less based on the total amount of the photosensitive resin composition layer 14 in order to prevent the diffusion of the organic solvent in the subsequent step. The thickness of the photosensitive resin composition layer 14 varies depending on the application, and the thickness after drying is preferably 1 to 200 μm, more preferably 5 to ΙΟΟμηη, and particularly preferably 10 to 50 μm. If the thickness is less than ιμηη, the industrial coating process φ tends to be difficult. When the effect exceeds 200 μm, the effect of the invention is small, and the photocurability of the photoresist bottom portion tends to be deteriorated. The photosensitive element 1 may further include an intermediate layer such as a buffer layer, an adhesive layer, a light absorbing layer, and a gas barrier layer. Further, the obtained photosensitive element 1 can be directly stored in a sheet shape or wound up in a roll shape on a winding core. It is preferable that the end face of the above-mentioned roll-shaped photosensitive element roller is provided with an end face spacer in order to protect the end face. Further, it is preferable that the end surface of the photosensitive element roll is provided with a moisture-proof end face separator in order to resist the dissolution. Examples of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride-29-201007360 resin, and ABS (acrylonitrile-butadiene-styrene copolymer). The core of the composition. (Method of Forming Photoresist Pattern) Next, a method of forming the photoresist pattern of the present embodiment will be described. In the method of forming the photoresist pattern of the present embodiment, the predetermined portion of the photosensitive resin composition layer formed of the photosensitive resin composition formed on the circuit-forming substrate is irradiated with active light rays to expose the exposed portion. The hardening step of irradiating is performed by removing the portion other than the predetermined portion of the photosensitive resin composition layer from the substrate. In other words, the substrate for forming a circuit refers to a substrate having an insulating layer and a conductive layer formed on the insulating layer. For laminating the photosensitive resin composition layer on the circuit-forming substrate, for example, the photosensitive resin composition can be applied by a screen printing method, a spray coating method, a roll coating method, a curtain coating method, an electrostatic coating method, or the like. The film was coated on a circuit-forming substrate, and the coating film was dried at 60 to 110 ° C. Further, the above-mentioned photosensitive element may be used for lamination of the photosensitive resin composition layer on the substrate. In the case where the photosensitive element is provided with a protective film, the protective film is removed, and the photosensitive resin composition layer is heated to about 70 ° C to about 130 ° C to the substrate at 0.1 MPa. A method of pressing at a pressure of ~1 MPa (about lkgf/cm 2 to 10 kgf/cm 2 ). This method is preferably carried out under reduced pressure from the viewpoint of adhesion and followability. Further, in order to further improve the lamination property, the remaining heat treatment of the substrate for circuit formation can be performed before pressing. The surface of the substrate on which the photosensitive resin composition layer is laminated is usually a metal surface, and is not particularly limited. -30-201007360 In the method of forming a photosensitive element, the photosensitive resin composition layer and the support are sequentially laminated on the circuit-forming substrate. When the support has transparency, in the irradiation step, the photosensitive resin composition may be exposed by irradiating the active light to the support. Further, when the transparency of the support is low, the support can be removed from the possible resin composition layer, and the photosensitive resin composition can be directly irradiated with the active light. The irradiation step, for example, irradiates the active light into an image by a negative type φ or a positive mask pattern called an artwork. As the light source of the active light, for example, a carbon arc lamp, a mercury vapor arc lamp, an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, or the like having an effective ultraviolet ray can be used, or a luminaire bulb or a solar ray can be effectively radiated. Lights such as lights. As a method of irradiating the active light, a method of irradiating the active light into an image by a laser direct drawing method such as DLP (Digital Light Processing) exposure method can be employed. In such a method, as the light source of the active light, a light source such as a YAG laser, a semiconductor laser, or a gallium nitride-based blue-violet laser can be used. In the removing step, a portion other than the portion of the active light ray that has been irradiated onto the photosensitive resin composition layer is removed from the substrate. In the removal step, when the support is removed on the photosensitive resin composition layer, the support is removed, and the unexposed portion is removed by wet development or dry development to produce a resist pattern. As the wet development, a developing solution such as an alkaline aqueous solution, a water-based developing solution, or an organic solvent can be used for development by a method such as spraying, immersion immersion, brushing, or scraping. As a liquid image, it is possible to use an alkaline aqueous solution such as an aqueous solution, which has high safety and stability, and is excellent in workability. The alkaline aqueous solution is an aqueous solution containing a base, and as the base, an alkali hydroxide such as a hydroxide of lithium, sodium or potassium; a carbonate of lithium, sodium, potassium or ammonium or a carbonate of a bicarbonate or the like can be used. An alkali metal phosphate such as potassium phosphate or sodium phosphate; an alkali metal pyrophosphate such as sodium pyrophosphate or potassium pyrophosphate. Further, as an alkaline aqueous solution used for development, a thin solution of 碳.1 to 5% by mass of sodium carbonate is used as a thin solution of 1 to 5 mass% of potassium carbonate, and a thin solution of 0.1 to 5 mass% of sodium hydroxide. A solution, a 0.1 to 5% by mass thin solution of sodium tetraborate or the like is preferred. Further, the pH of the alkaline aqueous solution used for development is preferably from 9 to 11, and the temperature is adjusted in accordance with the developability of the photosensitive resin composition layer. Further, a surfactant or a small amount of an organic solvent such as a defoaming agent may be mixed in the alkaline aqueous solution. As the aqueous developing solution, water or an aqueous alkaline solution and one or more organic solvents are used. Here, as the @ base contained in the alkaline aqueous solution, the above-mentioned base group, borax, sodium decanoate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, and 2-amine may be mentioned. Alkyl-2-hydroxymethyl-1,3-propanediol, 1,3-diaminopropanol-2, morpholine, and the like. The pH of the water-based imaging liquid and the development of the photoresist can be fully exhibited as the smaller the better, the pH is preferably 8 to 12, and the pH is preferably 9 to 10. Examples of the organic solvent include 3-acetone alcohol, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, and the like. Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, -32-201007360 diethylene glycol monobutyl ether, and the like. These may be used alone or in combination of two or more types. The concentration of the organic solvent 'is usually 2 to 90 weight %, and the temperature ' can be adjusted in accordance with the developing property. Further, a surfactant or an antifoaming agent may be mixed in a small amount in the aqueous developing solution. Examples of the organic solvent-based developing solution used alone include 1,1,1-trichloroethane, Ν-methylpyrrolidone, hydrazine, hydrazine-dimethylformamide, cyclohexanone, and methyl isobutylene. Ketone, γ-butyrolactone and the like. These organic solvents are preferably added in an amount of from 1 to 20% by weight in order to prevent ignition. Further, two or more of the above-described development methods can be used as needed. Regarding the way of development, there are dipping methods, smelting methods, spraying methods, brushing, scraping, etc., and the high-pressure spraying method is most suitable for improving the resolution. After the development, the photoresist pattern can be more hardened by heating at about 60 to 250 ° C or about 2 to 10 μm/cm 2 as needed. φ (Manufacturing Method of Printed Circuit Board) Next, a method of manufacturing the printed wiring board of the present embodiment will be described. The method of manufacturing a printed wiring board according to the present embodiment is characterized in that the circuit pattern forming substrate of the resist pattern is etched or plated by the above-described patterning method of the resist pattern. In the above manufacturing method, the surface of the circuit-forming substrate is etched or plated by using the developed photoresist pattern as a mask. Thereby, a conductor pattern according to a photoresist pattern is formed on the substrate for circuit formation. For the above etching, a cuprous chloride solution, a ferrous chloride solution, an alkali etching-33-201007360 etching solution, a hydrogen peroxide-based uranium engraving solution, or the like can be used. Among these, it is preferred to use a second iron chloride solution from the viewpoint that the etching factor is good. Examples of the plating method include copper plating such as copper sulfate ore plating and copper pyrophosphate plating; welding ore plating such as High throw welding; Watt bath (nickel sulfate-nickel chloride) plating and amine Nickel plating such as nickel sulfonate plating; gold plating such as hard gold plating and soft gold plating. A well-known method can be suitably used for such. After the etching or plating is completed, the photoresist pattern can be peeled off, for example, by an aqueous solution which is more alkaline than the aqueous alkaline solution used for development. As the aqueous solution having a strong basicity, a 1 to 10% by mass aqueous sodium hydroxide solution, a 1 to 10% by mass aqueous potassium hydroxide solution, or the like can be used. Examples of the peeling method include an immersion method and a spray method, and these may be used alone or in combination. In other words, the manufacturing method of the printed circuit board described above can be applied not only to a single-layer printed circuit board but also to the manufacture of a multilayer printed circuit board, and can also be applied to a printed circuit board having a small-diameter through hole. Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments. [Examples] Hereinafter, the present invention will be described in further detail by way of examples. First, the adhesive polymer shown in Table 1 was synthesized in accordance with Synthesis Example 1 - 34-201007360 (Synthesis Example 1). A flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen introduction tube was added in a mass ratio of 6 40 g of a mixture of methyl cellosolve and toluene of /4 (methyl cellosolve/toluene) was stirred while blowing nitrogen gas, and heated to 80 °C. On the other hand, as a copolymerization monomer, a solution prepared by mixing 100 g of methacrylic acid, 250 g of methyl methacrylate, 100 g of ethyl acrylate, and 50 g of styrene and argon diisobutyronitrile 〇 8 g was prepared. φ is referred to as "solution a"), and the solution a is added to the above-mentioned complex of methyl cellosolve and toluene at a mass ratio of 6/4 heated to 80 ° C for 4 hours, and then at 80 ° C. Stir for 2 hours. Further, a solution of 1-2 g of azobisisobutyronitrile dissolved in a mixture of methyl cellosolve and toluene in a mass ratio of 6/4 was added dropwise to the flask over 10 minutes. The solution after the dropwise addition was kept at 80 ° C for 3 hours while stirring, and then heated to 90 ° C over 30 minutes. After holding at 90 ° C for 2 hours, it was cooled to obtain a binder polymer solution of the component (A). To the binder polymer solution, acetone was added to adjust the non-φ volatile component (solid content) to 50% by mass. The binder polymer has a weight average molecular weight of 80,000. Further, the weight average molecular weight is measured by a gel permeation chromatography (GPC) method and is derived by conversion using a standard curve of standard polystyrene. The conditions of GPC are as follows. (GPC condition) Pump: Hitachi L-6000 type [manufactured by Hitachi, Ltd.] Pipe column: Gelpack GL-R420 + Gelpack GL-R4 3 0 + Gelpack GL-R440 (3 books) [above, Hitachi Chemical Co., Ltd. System, system-35-201007360 Product name] Solvent: Tetrahydrofuran Measurement temperature: 2 5 °C Flow rate: 2.05mL / min Detector: Hitachi L-3 3 00 type RI [Hybrid company Hitachi, Ltd., product name] (Example 1 to 5, Comparative Examples 1 to 3) The materials were blended in the amount (g) shown in Table 1, to obtain a solution of a photosensitive resin composition. [Table 1] Material Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 (A-partition binder polymer *1 Solid content: 55 (9) Component FA-321M *2 20 30 25 25 25 20 20 20 UA-21 *3 10 10 10 10 10 10 10 FA-MECH *4 5 5 5 5 5 5 5 M-113 *5 5 5 5 - 5 5 5 5 NP-8EA *6 5 5 5 5 _ 5 5 5 (Q component N-1717 *7 0.5 0.5 0.5 0.5 0.5 _ 0.5 _ 9-PA *8 0.1 0.1 0.1 0.1 0.1 0.1 _ 0.5 N-phenylglycine*9 0.1 Additive malachite green 0.05 Crystal Violet 0.5 Solvent Toluene 10 Methanol 10 Acetone 10

-36- 201007360 In the table, the compounding amount of each component (B) is a solid component (g). *1: methacrylic acid/methyl methacrylate/ethyl acrylate/styrene = 20/50/20/10 (mass ratio), weight average molecular weight = 80000 '50% by mass methyl cellosolve/toluene=6 / 4 (mass ratio) solution *2: 2,2-bis(4-((methyl) propylene oxypolyethoxy)phenyl)propane [manufactured by Hitachi Chemical Co., Ltd., product name] φ *3 : ginseng (methacryloxytetramethylene glycol isocyanate hexamethylene) isocyanurate [manufactured by Shin-Nakamura Chemical Co., Ltd., product name] *4: γ-chloro-β-hydroxypropyl-β' -Methyl propylene oxiranyl ethyl oxime phthalate [product name, manufactured by Hitachi Chemical Co., Ltd.] *5: nonylphenoxytetraethyleneoxy acrylate [manufactured by Toagos Corporation, product name] *6: Nonylphenoxy octaethyleneoxy acrylate [manufactured by Kyoeisha Chemical Co., Ltd.] ❶ * 7 : I,7-bis(9,9-acridinyl)heptane [Asahi Chemical Industry Co., Ltd., product name] * 8 : 9-benzopyridinium [manufactured by Nippon Steel Chemical Co., Ltd.] * 9 : Ν-phenylglycine [manufactured by Mitsui Chemicals Co., Ltd.] Photosensitive resin composition The solution was uniformly applied to a film of polyethylene terephthalate (manufactured by Teijin Co., Ltd., product name "G2-16") of a thickness of 16 μm, and a hot air convection dryer of 1 ° C for 1 minute. After drying, it was protected with a polyethylene protective film (manufactured by TAM APOLY Co., Ltd., product name "NF-1 3") to obtain a photosensitive resin composition layer -37-201007360 (photosensitive element). The film thickness after drying of the photosensitive resin composition layer was 3 Ομιη. Next, the copper surface of a copper-clad laminate (made by Hitachi Chemical Co., Ltd., product name "MCL-E-67") of a glass epoxy material having a copper foil (thickness: 35 μm) laminated on both sides is used. The 600-brush honing machine (made by Sanqi Co., Ltd.) was honed, washed with water, and dried by air circulation. The obtained copper-clad laminate was heated to 80 ° C, and the protective film of the photosensitive resin composition laminate was peeled off on the copper surface, and the photosensitive resin composition layer was heated at 110 ° C while using the photosensitive resin composition layer. The rolls were laminated at a speed of 1.5 m/min to obtain a test substrate. <Evaluation of Light Sensitivity> A Hitachi 41-stage staged exposure meter was placed on the test substrate, and an LDI exposure machine having a wavelength of 35 5 nm using a semiconductor laser as a light source (manufactured by Orbotech Co., Ltd., Japan) was used. Paragon-9000m"), exposed at 17mJ/cm2. Next, the polyethylene terephthalate film was peeled off, and a 1.0 mass% sodium carbonate aqueous solution was sprayed at 60 ° C for 60 seconds to remove the unexposed portion, and then formed on the copper-clad laminate by measurement. The number of stages of the stage exposure meter of the photocured film was evaluated for the light sensitivity of the photosensitive resin composition. The light sensitivity is expressed by the number of segments of the stage exposure meter. The higher the number of segments of the stage exposure meter, the higher the light sensitivity. <Evaluation of Resolution> The drawing data of the wiring pattern having a line width/line pitch of -38 to 201007360 5/5 to 47 / 47 (unit: μπι) was used as the resolution on the test substrate after lamination. For the evaluation pattern, the number of residual stages after the development of the Hitachi 41-stage stage exposure meter becomes an energy down-draw of 20.0. After performing the development treatment under the same conditions as the above evaluation of the light sensitivity, the pattern of the photoresist is observed by an optical microscope, and the unexposed portion can be removed, and the line having no line is serpentine, and the line width between the line widths of the defects is minimized.値 is evaluated as the resolution. The smaller the number, the better the resolution. <Evaluation of Caphole Property> For the evaluation of the cap hole property, a copper-clad laminate having a diameter of 6 mm and a diameter of 6 mm was used. In the above-mentioned copper-clad laminate, copper-clad laminate (manufactured by Toray Chemical Industry Co., Ltd., product name "MCL-Ε-67"), which is laminated with a copper foil (thickness of 35 μm) on both sides of the glass epoxy material, is cast. In the machine, 24 holes having a diameter of 6 mm were produced, and the burrs generated when the holes were formed were removed by a honing machine (manufactured by Sanke Co., Ltd.) having a brush equivalent to #600, which was used as a substrate for evaluation of the cover porosity. . The photosensitive element was laminated on both surfaces of the above-mentioned cover hole evaluation substrate, and the entire exposure was performed at 17 mJ/cm 2 using the above LDI exposure machine. Next, a polyethylene terephthalate film was spray-developed twice with a 1.0 mass% sodium carbonate aqueous solution for 60 seconds at 30 °C. After the development, the number of pore ruptures was visually measured, and the lid hole breaking rate was evaluated as the capping property. The lower the hole breaking rate, the lower the capping property, and the zero is ideal. <Evaluation of the peeling property> -39-201007360 On the test substrate after the lamination, the drawing data having a pattern of 60 mm X 4 5 mm was used as the pattern for evaluation of the peelability, and the Hitachi 4 1 was used. The number of residual stages after development of the staged exposure meter was exposed to an energy of 20.0. The development time was carried out under the same conditions as the evaluation of the photosensitivity and the resolution, and the time (unit: second) after immersing in a 3.0% by mass aqueous sodium hydroxide solution at 50° C. and completely removing the photoresist from the surface of the substrate was carried out. Time was evaluated and this was taken as peelability. The shorter the peeling time, the better the peelability. <Evaluation of photoresist shape> On the test substrate after lamination, a wiring pattern having a line width/space (Space) of 5/5 to 47/47 (unit: μιη) was used. The drawing data was used as a pattern for evaluating the shape of the resist, and exposure was performed under the energy of 20.0 after the development of the Hitachi 41-stage staged exposure meter. After the development process was carried out under the same conditions as the evaluation of the above-mentioned photosensitivity, the shape of the resist was observed using a scanning electron microscope of S-2100A type manufactured by Hitachi, Ltd., a company. In the resistive shape, if the cross section of the pattern is trapezoidal or inverted trapezoidal, the pattern cross section is preferably rectangular due to the inability to obtain a wiring pattern of a design width after the etching or plating treatment. The results of the above evaluations of the photosensitive elements or test substrates of Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Table 2. -40- 201007360 [Table 2] Evaluation project implementation implementation Implementation comparison Comparative example 1 Example 2 Example 3 Example 4 Example 5 Example 1 Example 2 Example 3 Photosensitivity (segment/41 segment) 20.0 20.0 20.0 20.0 20.0 18.0 18.0 19.0 Resolution (μιη) 30 30 32 30 32 37 37 40 Cover hole breaking rate (%) 0 10 0 0 0 20 20 10 Peeling time (seconds) 40 35 45 47 47 30 32 40 Resistor shape rectangular rectangular rectangular rectangular rectangular rectangle As shown in Table 2, the inverted trapezoid was confirmed to have excellent light sensitivity, resolution, and photoresist shape in Example 5, and had sufficient peeling property. Further, in Examples 1, 3 to 5, excellent cap porosity was further exhibited. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a preferred embodiment of a photosensitive element of the present invention. [Explanation of main component symbols] 1 : Photosensitive element 10 : Support 14 : Photosensitive resin composition layer -41 -

Claims (1)

201007360 VII. Patent application group: 1 · A photosensitive resin composition comprising (A) a binder polymer, (B) a photopolymerizable compound having at least one ethylenically unsaturated bond, and (C) The photosensitive resin composition of the photopolymerization initiator is characterized in that the (C) photopolymerization initiator contains a compound represented by the following general formula (I) and a compound represented by the following general formula (II), ❻ [Chemical 1] (I) [In general formula (I), R1 represents a carbon number of 2 to 2 Å, a carbon number of 2 to 20 oxadialkylene or a carbon number of 2 to 20 thio - _ Thiodialkylene], [H2] (II) [In the general formula (II), R2 represents an aromatic group which may have a substituent]. 2. The photosensitive resin composition according to the first aspect of the invention, wherein the (C) photopolymerization initiator further contains a compound represented by the following formula ( ΠΙ ). -42- 201007360 [Chemical 3] / y - NH - CHz - jj - OH (III) o 3 - a photosensitive element 'characterized by having a support, and a patent application scope formed on the support A photosensitive resin composition layer composed of the photosensitive resin composition according to the first or second aspect. A method for forming a photoresist pattern, comprising: φ comprising a photosensitive resin composed of a photosensitive resin composition described in the first or second aspect of the patent application form formed on a circuit-forming substrate; The irradiation step of irradiating the active light with a predetermined portion of the layer, the step of irradiating the exposed portion to photoharden, and the step of removing the portion other than the predetermined portion of the photosensitive resin composition layer from the substrate are removed. 5. A method for forming a photoresist pattern, comprising: a photosensitive resin comprising a photosensitive resin composition according to the first or second aspect of the patent application form formed on a circuit-forming substrate; a predetermined portion of the composition layer is irradiated with an active light in an image by a direct drawing method, and an irradiation step of curing the exposed portion is performed, and a portion other than a predetermined portion of the photosensitive resin composition layer is removed from the substrate. Step of removing the present invention. 6. A method of manufacturing a printed circuit board, which is characterized in that a pattern of a photoresist pattern is formed by a method for forming a photoresist pattern of the fourth or fifth aspect of the patent application. The substrate is etched or plated. -43-