TW201207554A - Photosensitive resin composition and photosensitive element using same, resist pattern formation method and printed circuit board manufacturing method - Google Patents

Abstract

The disclosed photosensitive resin composition is used in the formation of a resist pattern by a direct-write method, and contains a binder polymer (A), a photopolymerisable compound (B) and a photopolymerisation initiator (C). The photopolymerisable compound (B) includes a compound represented by general formula (I). (In the formula R1 and R2 each independently represent a hydrogen atom or a methyl group and n represents an integer from 0-50.)

Description

201207554 VI. Description of the Invention: 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] In the field of manufacturing printed circuit boards, a photosensitive resin composition is widely used as a photoresist material used for etching or plating. The photosensitive resin composition is often used in a photosensitive element, and is provided with a support film and a layer formed of a photosensitive resin composition formed on the support film (hereinafter referred to as "photosensitive resin layer"). In the case of manufacturing a printed circuit board using a photosensitive element, a printed circuit board is manufactured, for example, in the following manner. First, the photosensitive resin layer of the photosensitive element is laminated on the substrate (laminating step). Next, after the support film is peeled off as the case may be, the predetermined portion of the photosensitive resin layer is irradiated with the active light to expose the predetermined portion to be hardened (exposure step). Thereafter, the other portion (unexposed, unhardened portion) other than the predetermined portion is removed (developed) from the substrate, and a resist pattern formed by the cured product of the photosensitive resin composition is formed on the substrate ( Development step). Next, using the photoresist pattern as a mask, etching or plating the substrate on which the photoresist pattern is formed, forming a circuit pattern, and finally removing the photoresist pattern from the substrate (circuit pattern forming step) . In this way, a printed circuit board having a circuit pattern formed on a substrate can be manufactured. In the above exposure step, conventionally, a reticle exposure method was employed to irradiate active light rays through a mask film having a pattern of -5 to 201207554. As the light source of the active light, a light source that effectively emits ultraviolet rays such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, or a xenon lamp can be used. In recent years, a direct drawing method in which digital light is used without using a photomask film and direct irradiation of active light in an image form is being put to practical use instead of the above-described photomask exposure method. Considering safety or operability, the direct light source uses YAG lasers, semiconductor lasers, etc., and recently introduced a technology that uses long-life and high-output GaN blue. Laser and so on. Further, with the increase in the precision and density of the printed circuit board, a direct drawing method called DLP (Digitai Light Processing) exposure method is employed, and a more detailed pattern can be formed than in the related art. In general, in the DLP exposure method, active light having a wavelength of 390 to 430 nm using a blue-violet semiconductor laser as a light source is used. In addition, an exposure method using a multi-beam of a polygon having a wavelength of 3 55 nm for a YAG laser as a light source is used, which corresponds to a small number of types of production in terms of a main general-purpose printed circuit board. On the other hand, from the viewpoint of environmental and safety, the developing liquid used for removing the unexposed portion of the photosensitive resin layer from the substrate in the above developing step is an aqueous solution of sodium carbonate or carbonic acid. An alkali developing solution such as an aqueous solution of sodium hydrogen is the mainstream. The unexposed portion of the photosensitive resin layer is removed from the substrate by developing with the developing liquid or by spraying with water. Therefore, the photosensitive resin composition is required to have excellent cap hole reliability (cap porosity) which is not damaged by the spray pressure of development or washing after exposure. -6- 201207554 In the conventional reticle exposure method, a photosensitive resin composition containing a difunctional or trifunctional monomer has been proposed in the literature for a photosensitive resin composition having excellent cover hole reliability (see, for example, a patent) Documents 1 and 2). [PRIOR ART DOCUMENT] [Patent Document 1] Patent Document 1 Japanese Patent Application No. 3, 196, 196. The photosensitive resin composition of the trifunctional monomer has excellent cap hole reliability in the conventional mask exposure method, but the cap hole reliability is insufficient in the above direct drawing method. Accordingly, an object of the present invention is to provide a photosensitive resin composition which has excellent cap hole reliability in the case of exposure by a direct drawing method. Further, an object of the present invention is to provide a method for forming a photoresist pattern and a method for producing a printed circuit board, which are photosensitive elements using the above-mentioned photosensitive resin composition. [Means for Solving the Problems] As a result of reviewing the above problems, the present inventors have found that a photosensitive resin composition can be provided by using a compound having a specific chemical structure as a photopolymerizable compound. Direct drawing method 201207554 In the case of exposure, it has excellent cover hole reliability, and the present invention is completed. That is, the present invention is a photosensitive resin composition used for forming a photoresist pattern by a direct drawing method, which comprises (A) an adhesive polymer, (B) a photopolymerizable compound, and (C) photopolymerization. The starting agent, the (b) photopolymerizable compound contains a compound represented by the following formula (I). By using the compound represented by the following formula (I) as the (B) photopolymerizable compound, the photosensitive resin composition of the present invention has a high sensitivity, and is excellent in the case of exposure by a direct drawing method. Cover hole reliability [Chemical 1]

In the above formula (I), R1 and R2 each independently represent a hydrogen atom or a methyl group. η represents an integer of 〇 50. From the viewpoint of further improving the reliability of the cover hole, the η system is preferably an integer of 4 to 2 5 . The above (Β) photopolymerizable compound is more preferably a compound represented by the following formula (Π), from the viewpoint of further improving the releasability. -8- 201207554 [化2]

In the above formula (II), R3 represents a hydrogen atom or a methyl group, r4 represents a hydrocarbon group having 9 carbon atoms, and m represents an integer of 〇20. From the viewpoint of further improving the reliability of the cover hole, the m system is preferably an integer of 4 to 8. From the viewpoint of further enhancing the sensitivity, the above (C) photopolymerization & initiator is preferably a compound represented by the following formula (III) and/or a compound represented by the following formula (IV). . [Chemical 3]

R5 2 (III) In the above formula (ΙΠ), R5 represents an alkylene group having 2 to 20 carbon atoms, an oxaalkylene group or a thiodialkylene group. 201207554 [化4] R6

In the above formula (IV), R6 represents a J-containing aromatic group. Further, the present invention relates to a photosensitive resin film formed of a photosensitive stretch film and a use formed on the support film. Further, the present invention relates to a photoresist pattern comprising: a lamination step of laminating a photosensitive resin composition using the above-mentioned photosensitive resin composition, and a step of irradiating active light rays in an image form by direct drawing; The photosensitive resin layer is not removed, and a development step of a photoresist pattern of the photosensitive resin group is formed on the substrate. Further, the present invention relates to a printed circuit comprising a photoresist pattern formed by the above method. [Effects of the Invention] According to the present invention, it is possible to provide an element having a sensitivity which is excellent in photosensitivity, and which is a monovalent member having a substituent, which is provided with a photosensitive resin composition. a method for forming a method for forming a circuit board on a photosensitive resin layer formed of a photosensitive resin layer by a cured portion of the exposed portion, wherein the exposed portion is cured by a cured object on the substrate, and the substrate is etched or plated The resin composition, which has an excellent cover hole reliability with a line exposure of -10 - 201207554. Further, Liao provides a method for forming a photoresist pattern and a method for producing a printed circuit board, and a photosensitive member having a high-precision circuit pattern can be manufactured by using the photosensitive member of the above-mentioned photosensitive resin composition. [Embodiment] Hereinafter, the embodiments will be described in detail with reference to the drawings. However, the present invention is not limited by the following embodiments. In the drawings, the same elements are denoted by the same reference numerals, and the repeated description is omitted. In addition, the dimensional ratio of the drawings is not limited to the illustrated ratio. In the present specification, "(meth)acrylic acid" means "acrylic acid" and its corresponding "methacrylic acid" '"(meth)acrylate" means "acrylate" and its corresponding "methacrylate" "(Meth)acryloyl group" means "acryloyl fluorenyl group" and its corresponding "methacryl fluorenyl group" (photosensitive resin composition) The photosensitive resin composition of the present embodiment contains ( A) Adhesive polymer (hereinafter also referred to as "(A) component"), (B) photopolymerizable compound (hereinafter also referred to as "(B) component"), and (C) photopolymerization initiator (below) Also known as "(C) component"), a photosensitive resin composition used in forming a photoresist pattern by a direct drawing method. Here, the "direct drawing method" means that the desired pattern is directly applied to the photosensitive resin layer by irradiating active light such as laser light on the photosensitive resin layer without using a photomask film or the like. A method of exposing the photosensitive resin layer. -11 - 201207554 < (B) Component: Photopolymerizable Compound> The photosensitive resin composition of the present embodiment contains a compound represented by the following formula (I) as a photopolymerizable compound of the component (B). As a result, the photosensitive resin composition of the present embodiment has excellent cap hole reliability when exposed by a direct drawing method. Here, "cover hole reliability" means the property of not being damaged by the spray pressure of development or washing after exposure (caphole property), and the evaluation of the reliability of the cover hole is performed using the hole shown in FIG. The substrate for measuring the number of cracks was measured by measuring the crack rate (%) of the irregular lid hole.

In the compound represented by the above formula (I), R1 and R2 each independently represent a hydrogen atom or a methyl group. From the viewpoint of enhancing the resistance of the developing solution, it is preferred that R1 and R2 are methyl groups. Further, in the compound represented by the above formula (I), η represents an integer of 0 to 50. From the viewpoint of further improving the reliability of the cap hole, the above η is preferably an integer of 4 to 25, an integer of 9 to 24 is preferable, and an integer of 9 to 14 is more preferable. The compound represented by the above formula (I) includes di(meth)acrylic anhydride (? = 0) and (poly) ethylene glycol di(meth) acrylate (? = 1 to 50). (Poly)ethylene glycol di(meth)acrylate is obtained by reacting (poly)ethylene glycol with (meth)acrylic acid. -12-201207554 Commercially available compounds represented by the above formula (I) include 9 G, 1 4 G, and 2 3 G (all of which are manufactured by Nakamura Chemical Co., Ltd., and are commercially available. Name) and other polyethylene glycol dimethacrylate vinegar. The content of the compound represented by the above formula (I) is preferably from 5 to 90% by mass based on the total mass of the component (B), from the viewpoint of excellent balance between sensitivity and resolution. From the viewpoint of excellent reliability of the lid hole, the content is preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 15% by mass or more, and particularly preferably 20% by mass or more. In addition, from the viewpoint of excellent coating property, the content is preferably 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less. The photosensitive resin composition of the present embodiment may further contain the component (B) other than the compound represented by the above formula (I). The component (b) is not particularly limited as long as it has an ethylenically unsaturated bond and can be photocrosslinked, and examples thereof include the following compounds (B!) to (B5). These compounds may be used alone or in combination of two or more (B1) bisphenol A-based di(meth)acrylate compound (B2) having an ethylenically unsaturated bond (B3) to make a polyvalent alcohol with α, /3 - a compound obtained by reacting an unsaturated carboxylic acid (Β4), a compound (B5) obtained by reacting a glycidyl group-containing compound with α-unsaturated decanoic acid, having an urethane-bonded (meth)acrylic acid Ethyl carbamate monomer such as an ester compound-13-201207554 From the viewpoint of excellent sensitivity and resolution, the component (B) is preferably a bisphenol A-based di(meth)acrylate compound (B1). The (B1) may, for example, be 2,2-bis(4-((meth)propenyloxypolyethoxy)phenyl)propane, 2,2-bis(4-((methyl))). Propylene decyloxypolypropoxy)phenyl)propane and 2,2-bis(4-((methyl) propyleneoxypolyethoxypolypropoxy)phenyl)propane. With respect to the above 2,2-bis(4-((meth)propenyloxypolyethoxy)phenyl)propane, for example, 2,2-bis(4-((meth)acryloxy)oxy group is exemplified. Diethoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxy)triethoxy)phenyl)propane, 2,2.bis(4-((methyl)) Propylene decyloxytetraethoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxypentaethoxy)phenyl)propane, 2,2-bis(4-( (methyl)propenyloxyhexaethoxy)phenyl)propane, 2,2-bis(4-((methyl)propenyloxyheptaethoxy)phenyl)propane, 2,2-double (4-((Methyl) propylene methoxy octaethoxy) phenyl) propane, 2,2-bis(4-((methyl) propylene oxy) pentoxide) phenyl) propane, 2 , 2-bis(4-((meth)propenyloxy-l-ethoxy)phenyl)propane, 2,2-bis(4-((methyl)propenyloxy eleven ethoxy)benzene Base) propane, 2,2-bis(4-((meth)propenyloxydodecyloxy)phenyl)propane, 2,2-bis(4.((methyl)acryloxy) Triethoxy)phenyl)propane, 2,2-bis(4-((methyl) Acryloxytetradecyloxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxypentadecane)ethoxy)phenyl)propane, 2,2-bis ( 4-((Meth)acryloxycarbonylhexadecyloxy)phenyl)propane. 2,2-bis(4-(methacryloxy pentoxide-5-201207554 oxy)phenyl)propane, commercially available as ΒΡΕ-5 00 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name In the form of 2,2-bis(4-(methacryloxypentadecane)-p-ethoxy)phenyl)propane, commercially available as ΒΡΕ- 1 3 00 (manufactured by Shin-Nakamura Chemical Co., Ltd.) , the product name) is obtained in the form. These may be used alone or in combination of two or more. With respect to the above 2,2-bis(4-((meth)propenyloxypolypropoxy)phenyl)propane, for example, 2,2-bis(4-((meth)acrylofluorene) can be mentioned. Dipropoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxytripropoxy)phenyl)propane, 2,2-bis(4-((methyl) Propylene decyloxytetrapropoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxypentapropyloxy)phenyl)propane, 2,2-bis(4- ((Meth)propenyloxyhexapropoxy)phenyl)propane, 2,2-bis(4-((methyl)propenyloxy-7-propoxy)phenyl)propane, 2,2- Bis(4-((meth)propenyloxy octapropoxy)phenyl)propane, 2,2-bis(4-((methyl) propylene oxy) pentyloxy)phenyl)propane, 2,2-bis(4-((meth)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-((meth)propenyloxy) Thirteen propoxy)phenyl)propane, 2,2-bis(4-((meth)propene)醯oxytetradecyloxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxypentadecapropoxy)phenyl)propane, 2,2-bis(4- ((Meth)acryloxycarbonylhexadecyloxy)phenyl)propane. These may be used alone or in combination of two or more. With respect to the above 2,2-bis(4-((meth)acrylomethoxypolyethoxylated poly-15-201207554 propoxy)phenyl)propane, for example, 2,2-bis(4- ((Meth)propenyloxydiethoxyoctyloxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxytetraethoxytetrapropoxy)benzene Base) propane, 2,2-bis(4-((meth)propenyloxyhexaethoxyhexapropyloxy)phenyl)propane. These may be used alone or in combination of two or more. In the case where the component (B) contains the bisphenol A-based di(meth)acrylate compound (B 1 ), the content is preferably 20 to 80% by mass based on the total mass of the component (B), and 30 to 70%. The mass % is preferred. Further, from the viewpoint of excellent reliability of the lid hole, the component (B) preferably contains the compound (B2) having one ethylenically unsaturated bond in the molecule. (B2), a mercaptophenoxy (meth) acrylate compound represented by the following general formula (II), r-chlorohydroxypropyl-/3 (meth) propylene fluorenyl oxygen Ethyl phthalate, hydroxyethyl-/3 (meth) propylene decyl oxyethyl phthalate, stone-hydroxypropyl-/3'-(methyl) propylene fluorenyl oxygen Ethyl phthalate and the like. Among them, a mercaptophenoxy (meth) acrylate compound represented by the following formula (Π) is preferred. [Chemical 6]

Ο In the compound represented by the above formula (II), R3 represents a hydrogen atom or a methyl group. From the viewpoint of enhancing the liquidity of the developer, R3 is preferably a hydrogen atom. R4 represents a hydrocarbon group having a carbon number of 9. Further, in the compound represented by the above formula (II), -16-201207554, &quot;^ represents an integer of 0 to 20. From the viewpoint of further improving the reliability of the cap hole, the above m is preferably an integer of 4 to 15 and is preferably an integer of 4 to 10, more preferably an integer of 4 to 8. With respect to the compound represented by the above formula (11), a nonylphenoxy (meth) acrylate (m = 0) and a nonyl phenoxy (poly) ethylene glycol (meth) acrylate can be cited. (m=l~20). Nonylphenoxy (poly)ethylene glycol (meth) acrylate is obtained by reacting (poly)ethylene glycol, nonylphenol and (meth)acrylic acid. As the nonylphenoxy (poly)ethylene glycol (meth) acrylate, mercaptophenoxytetraethylene glycol (meth) acrylate, nonyl phenoxy octaethylene glycol (A) Base) Acrylate, etc. Examples of the compound represented by the above formula (Π) which are commercially available include mercaptophenoxyl such as FA-314A and FA-318A (all of which are manufactured by Hitachi Chemical Co., Ltd., trade name). Base (poly)ethylene glycol acrylate. The content of the compound represented by the above formula (II) is preferably from 5 to 90% by mass based on the total mass of the component (B), from the viewpoint of excellent balance between sensitivity and resolution. From the viewpoint of excellent reliability of the lid hole, the content is preferably 5% by mass or more, more preferably 1% by mass or more, more preferably 15% by mass or more, and particularly preferably 2% by mass or more. In addition, it is preferable that the content is 90% by mass or less, preferably 70% by mass or less, and more preferably 5% by mass or less, more preferably 40% by mass or less, from the viewpoint of excellent coating properties. In the case of the compound (Β3) obtained by reacting the above polyvalent alcohol with an α, Θ-unsaturated carboxylic acid, for example, a polypropylene glycol di(methyl group) having an oxygen propyl group number of 2 -17 to 201207554 can be cited. Acrylate, trimethylol propyl acrylate, trimethylolpropane tris(methyl) propyl succinic acid trimethylolpropane tri(meth) acrylate (oxygen extension number is 1~5) ), PO-denatured trimethylolpropane tri(methyl), hydrazine, hydrazine-denatured trimethylolpropane tris(meth)acrylate methane tri(meth)acrylate, tetramethylol methane tetra(enoic acid) Ester, dipentaerythritol penta (meth) acrylate, diquaternary (meth) acrylate. These may be used alone or in combination of two or more, "deuterated" means having a (poly) oxyethylene chain block ( Polyoxyethylated compound), "deuterated" (poly)oxypropylene chain block structure compound (polyoxypropylene) '"ΕΟ-ΡΟ denatured" means having (poly)oxyethylene chain oxypropylene chain a compound of segment structure (polyoxyethylated and polyorganic compound). The above-mentioned urethane monomer (Β5) may, for example, be a (meth)acrylic monomer having a hydroxyl group at position and isophorone di-, 2,6-toluene diisocyanate, 2 Addition reaction of diisocyanate compound such as 4-toluene diisocyanate and methyl diisocyanate (meth) propylene oxime tetraethylene glycol isocyanate) hexa benzoate, decyl amide bis(methyl) Ethyl acrylate urethane di(meth) acrylate or the like is exemplified. For the decyl urethane di(meth) acrylate, for example, manufactured by Shin-Nakamura Chemical Co., Ltd., and the like. In addition, in the case of hydrazine, decyl urethane bis(methyl bis(methyl hydrazine, hydrazine-modified heavy total acrylate, tetrahydroxymethyl) pentylenetetraol hexahydrate is used. Compounding and (poly) oxypropylene propylene, for example, in the case of cold isocyanate 1,6-hexa-substrate, ginseng (iso-cyanuric acid, hydrazine, hydrazine, UA-11) acrylic acid-18 - 201207554 ester, For example, it is manufactured by Shin-Nakamura Chemical Co., Ltd., trade name UA-13, etc. Further, in the case of ginseng ((meth) propylene oxime tetraethylene glycol isocyanate) hexamethylene isocyanurate, For example, the product name UA-2 1 manufactured by Shin-Nakamura Chemical Co., Ltd., etc., from the viewpoint of further improving the reliability of the cap hole, the UA-21 is preferably 5 to 25 wt%, and 7 to 15 wt%. The content of the component (the photopolymerizable compound) is preferably 100 parts by mass based on the total amount of the component (A) and the component (B). 20 to 60 parts by mass is preferred. From the perspective of improving sensitivity and resolution The content of the component (B) is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, more preferably 30 parts by mass or more, and is considered from the viewpoint of imparting film properties and excellent photoresist shape after curing. The content of the component (B) is preferably 60 parts by mass or less, more preferably 55 parts by mass or less, more preferably 50 parts by mass or less. <A) Component: Adhesive polymer> (A) The adhesive polymer of the component is not particularly limited as long as it is soluble in an aqueous alkali solution and can form a film, and examples thereof include an acrylic resin, a styrene resin, an epoxy resin, and a guanamine system. A resin, a guanamine epoxy resin, an alkyd resin, and a phenol resin are preferable. From the viewpoint of alkali developability, it is preferable to use an acrylic resin. These may be used alone or in combination of two or more. The component can be produced, for example, by polymerizing a polymerizable monomer (monomer) from -19 to 201207554. Examples of the polymerizable monomer include styrene; «-methylstyrene, vinyl Toluene or the like, or an aromatic ring is substituted and can be aggregated Styrene derivative; propylene amide such as diacetone acrylamide; acrylonitrile; ether of vinyl alcohol such as ethylene n-butyl ether; benzyl (meth) acrylate (benzyl) (meth) acrylate, (methyl) Tetrahydrofuran methyl acrylate dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2, 2, 2-trifluoroethyl (Meth) acrylate, (meth) acrylate such as 2,2,3,3-tetrafluoropropyl (meth) acrylate; (meth)acrylic acid, α-bromo (meth)acrylic acid, chlorine ( (meth)acrylic acid; (meth)acrylic acid derivatives such as S-furyl (meth)acrylic acid, styryl (meth)acrylic acid; maleic acid, maleic anhydride, monomethyl maleate, Malay A maleic acid derivative such as monoethyl ester or monoisopropyl maleate; an organic acid derivative such as fumaric acid, cinnamic acid, α-aryl cinnamic acid, itaconic acid, crotonic acid or propiolic acid. These may be used alone or in combination of two or more. The alkyl (meth)acrylate may, for example, be a compound represented by the following formula (V). [7] R7

I /〇, Η〆R8 〇 (v) In the above formula (V), R7 represents a hydrogen atom or a methyl group, and R8 represents an alkyl group having 1 to 12 carbon atoms. In the above formula (V), the alkyl group having a carbon number of 1 to 12 represented by R8 is 20-201207554, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. , octyl, decyl, decyl, undecyl, dodecyl and such structural isomers. Examples of the compound represented by the above formula (V) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. Amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, bismuth (meth)acrylate Ester, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate. These may be used singly or in combination of two or more. Further, the above-mentioned (meth)acrylic acid alkyl ester may be a compound in which the alkyl group is substituted with a hydroxyl group, an epoxy group, a halogen group or the like in the compound represented by the above formula (V). From the viewpoint of alkali developability, the component (A) is preferably a carboxyl group. The carboxyl group-containing component (A) can be produced, for example, 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, and methacrylic acid is preferred. The carboxyl group content (the ratio of the polymerizable monomer having a carboxyl group to the total polymerizable monomer used) of the component (A) is based on (A) from the viewpoint of alkali development and balance of the resistance of the developing solution. The total mass of the components is preferably from 1 2 to 50% by mass based on the basis. The viewpoint of excellent alkali developability is preferably 12% by mass or more, and preferably 15% by mass or more. In addition, from the viewpoint of excellent liquid resistance, it is preferably 5 〇 mass% or less, and 4 〇 mass% or less is preferably '30% by weight or less, and more preferably 25% by mass or less. . From the viewpoint of adhesion and peeling characteristics, the component (A) is preferably a styrene-containing or styrene derivative as a polymerizable monomer. In the case where the above styrene or styrene derivative is used as a copolymerization component, the content (styrene or styrene derivative relative to all polymerization used) is from the viewpoint of both good adhesion and peeling properties. The ratio of the singular monomer is preferably 〜 〜 〜 〜 〜 〜 〜 。 。 。 。 。 。 。 。 。 。 。 。 。 。 From the viewpoint of excellent adhesion, the amount is preferably 0.1% by mass or more, more preferably 1% by mass or more, and most preferably 1.5% by mass or more. In addition, from the viewpoint of excellent releasability, it is preferably 30% by mass or less, more preferably 28% by mass or less, and still more preferably 27% by mass or less. These (A) components (adhesive polymers) may be used alone or in combination of two or more. Examples of the adhesive polymer in the case of using two or more types of the adhesive polymer include two or more kinds of adhesive polymers formed of different copolymerized components, and two or more kinds of weight average molecular weights. Adhesive polymer, two or more adhesive polymers with different dispersion. The weight average molecular weight of the component (A) is preferably from 20, 〇〇〇 to 300,000 from the viewpoints of development liquid resistance and alkali development balance. From the viewpoint of excellent performance of the developing solution, it is preferably 20,000 or more, more preferably 40,000 or more, and more preferably 50,000 or more. From the viewpoint of excellent alkali developability, it is preferably 150,000 or less, more preferably 120,000 or less. Further, in the present specification, the weight average molecular weight is measured by a gel permeation chromatography-22-201207554 method, and a calibration curve prepared by standard polystyrene is used for conversion. The content of the component (A) is preferably 40 to 80 parts by mass based on 100 parts by mass of the total of the components (A) and (B). From the viewpoint of imparting film properties, it is preferably 40 parts by mass or more, more preferably 45 parts by mass or more, and more preferably 50 parts by mass or more. In addition, from the viewpoint of excellent sensitivity and resolution, it is preferably 80 parts by mass or less, more preferably 75 parts by mass or less, and still more preferably 70 parts by mass or less. &lt;Component (C): Photopolymerization initiator> The photopolymerization initiator of the component (C) contains a compound represented by the following formula (ΠΙ) and/or a compound of the following formula (IV) The compound indicated is preferred. [化8]

In the compound represented by the above formula (III), R5 represents an alkylene group having 2 to 20 carbon atoms, an oxadialkylene group or a thiodialkylene group. From the viewpoint of further improving the sensitivity and the resolution, the component (C) is a compound containing an alkyl group having a carbon number of 7 and a cyclic -23-201207554 alkyl group (for example, a compound represented by the above formula (III). ADEKA Co., Ltd., the trade name "Ν-1717" is preferred. When the compound represented by the above formula (IV) is contained in the component (C), the content is 100% based on the total amount of the (Α) component and the (Β) component from the viewpoint of the balance of sensitivity and resolution. 0.01 to 20 parts by weight of the mass part is preferred, 〇"~! The 〇 part by weight is preferably 0.2 to 5 parts by weight. When the content is less than 0.01 part by weight, sufficient sensitivity may not be obtained. If it exceeds 20 parts by weight, the resist shape may become an inverted trapezoid and the sufficient adhesion and resolution may not be obtained. [Chemical 9] R6

In the compound represented by the above formula (IV), R6 represents a monovalent aromatic group which may have a substituent. From the viewpoint of further improving the adhesion and the resolution, the component (C) is a compound containing a compound represented by the above formula (IV) and R6 is a phenyl group (for example, manufactured by Nippon Steel Chemical Co., Ltd.). The product name "9-ΡΑ" is preferred. Further, from the viewpoint of further improving the sensitivity, the component (C) is preferably a compound containing a compound represented by the above formula (IV), and R6 is a phenyl group substituted with an alkyl group or a halogen atom. In the case of such a compound, R6 is a p-tolyl group, a m-tolyl group, an o-tolyl group, or a p-chlorophenyl group -24-201207554 (for example, manufactured by Changzhou Strong Electronic New Material Co., Ltd., trade name "TR" -P AD 1 04", "TR-PAD102", "TR-PAD103 TR-PAD105"). When the component (C) contains the compound represented by the above formula (IV), the content is based on the total amount of the component (A) and the component (B) from the viewpoint of the balance between the sensitivity and the resolution. 0.01 to 10 parts by weight of 100 parts by mass is preferably '005 to 5 parts by weight, more preferably 0.1 to 3 parts by weight. When the content is less than 0.01 part by weight, sufficient sensitivity may not be obtained. If it exceeds 1 part by weight, the resist shape may become an inverted trapezoid and the sufficient adhesion and resolution may not be obtained. The compound represented by the above formula (III) and the compound represented by the above formula (IV) may be used singly or in combination 'may also be represented by the compound represented by the above formula (III) or the above formula (IV) Two or more compounds are used in combination. Examples of the compound represented by the above formula (III) and the component (c) other than the compound represented by the above formula (IV) (photopolymerization initiator) include benzophenone and N, N' - Tetramethyl-4,4'-diaminobenzophenone (Mitchlerone), N,N,-tetraethyl-4,4, monoaminobenzophenone, 4·methoxy-4 -Dimethylaminobenzophenone, 2-benzyldimethylaminomorpholinophenyl)-1-butanone and 2-methyl-1-[4-(methylthio)phenyl]-2 - Aromatic ketones such as phenyl group _;!_acetone; 2-ethyl hydrazine, phenanthrenequinone, 2-tert-butyl fluorene, octamethyl hydrazine, 1,2-benzo oxime, 2,3· Benzene awake, 2, phenyl onion, 2,3-diphenyl citrate, gas awake, 2_methyl oxime, 1,4_ -25- 201207554 naphthoquinone, 9,10-phenanthrenequinone, 2-Methyl 1,4-naphthoquinone and 2,3-dimethylindole; benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin, methyl benzoin and ethyl benzoin and other benzoin: benzyl Benzyl derivative such as dimethyl ketal; 9,10-dimethoxy; 9,10-diethoxy fluorene, 9,10-dipropoxy fluorene, 9,10-dibutoxy 9,10- Dipentane Equivalent substituted hydrazine; 2-( 〇-chlorophenyl) phenylimidazole dimer, 2-(〇-chlorophenyl)-4,5-di(methoxy imidazole dimer, 2 -(〇-Fluorophenyl)-4,5-diphenylimidazodimeric (〇-methoxyphenyl)·4,5-diphenylimidazole dimer and 2-(p-phenyl)- 2,4,5-triaryl methoxide such as 4,5-diphenylimidazole dimer; coumarin compound, oxazole compound, pyrazoline system, and 2,4,5- The substituent of the aromatic group of the triaryl imidazole may also produce a symmetrical compound, or may be dissimilar to produce an asymmetry. In addition, as diethyl thioxanthone and dimethylamino benzoic acid, it may also be The thioxanthone-based compound and the tertiary amine compound may be used singly or in combination of two or more. The content of the component (C) is 0.01 with respect to the (Α) component and (the total amount of 100 parts by weight) It is preferably 10 parts by weight or more, preferably 0.2 parts by weight to 5 parts by weight. If the content of (C) is in this range, the sensitivity and internal hardenability of the photosensitive resin composition become better. &lt;Other components&gt; Further, the present embodiment The photosensitive resin composition is a ruthenium etherified compound based on a ruthenium, a ruthenium and a-4,5-diphenyl) or a 2-methoxyoxazole dipolymer. It may be a combination of phases. :Β) into, 0.1 ~ The light of the part of the component, can be due to -26- 201207554 should contain malachite green, Victoria pure blue, bright green, material; leuco crystal violet, diphenylamine, benzylamine, triphenylamine, a photochromic agent such as o-chloroaniline or tribromomethylbenzene; a plasticizer such as thermochromic toluenesulfonamide; a pigment; a sputum-filling agent; a defoaming agent adhesion imparting agent; a homogenizing agent; a peeling accelerator; The oxidizing developer, the thermal crosslinking agent, and the like are used alone or in combination of two or more kinds in an amount of from 0.01 to 20 parts by weight per 100 parts by weight of the total amount of the component (A). (Solution of the photosensitive resin composition) The photosensitive resin composition of the present embodiment can be dissolved in a solution having a solid content of about 30 to 60% by mass (for coating, examples of the organic solvent include methanol and ethanol. a propyl ketone, a methyl cellosolve, an ethyl cellosolve, toluene, N, N-amine, propylene glycol monomethyl ether or a mixed solvent thereof. By applying the above coating liquid onto a surface of a metal plate or the like, The photosensitive resin composition of the present embodiment can be used as the photosensitive resin composition. The metal plate is preferably an iron-based alloy such as copper, copper-based, iron or stainless steel, and is preferably copper or a copper-based alloy. The thickness of the photosensitive resin layer may be about 1 to 100/zm, depending on the application. The protective film may be coated on the opposite side of the metal plate of the grease layer. Polymer film such as polypropylene, etc., methyl violet, etc., dyeing diethylamine, preventive agent; pair: flame retardant; agent; perfume; B). These can be used in a single organic solvent, liquid form to form a ketone, methyl dimethyl dimethyl hydrazine and dry it to form a sensible alloy, nickel, gold, iron, and in the case of dry and photosensitive tree coatings. -27-201207554 (Photosensitive element) Fig. 1 shows that one embodiment of the photosensitive element of the present invention is formed by applying a solution of the above-mentioned photosensitive resin composition to a support film and drying it, and forming the same on the support film 2 The photosensitive resin layer 3 formed by the photosensitive product. Then, the protective film 4 is coated on the surface opposite to the support film 2 of the resin layer 3 to the photosensitive element 1 of the present embodiment, and the photosensitive resin layer 3 having the support film bonded to the support film 2 is provided. The protective film 4 laminated on the resin layer 3. It is not necessary to have the protective film g. In the case of the support film 2, a heat-resistant and solvent-resistant polymer film such as polyethylene terephthalate, polypropylene or polyethylene can be used. The thickness of the support film 2 (polymer film) is preferably from 1 to 100, preferably from 1 to 50/zm, more preferably from 1 to 30 #m. If the thickness is less than 1/ζπι, the film 2 tends to be easily broken when the support film 2 is peeled off, and if it exceeds 10 μm, a sufficient degree of resolution tends to be obtained. In the protective film 4, the adhesion to the photosensitive resin layer 3 is preferably smaller than that of the support film 2 to the photosensitive resin layer 3, which is preferably a low fisheye film. Here, "fisheye" means that a foreign matter, an undissolved substance, an oxidatively deteriorated substance, or the like is absorbed into a film when a film is formed by a material, kneading, extrusion, biaxial stretching, casting, or the like. In other words, "low fisheye" means a protective film 4 containing the above foreign matter in the film. Specifically, polyethylene terephthalate can be used. By taking the photosensitive property of the resin group, it is possible to obtain a thin layer of β m of a photosensitive I 4 〇 ester, and the support may be difficult to support and the amount of the phenomenon in the hot melt material is small. Diester, etc. • 28- 201207554 Polymer film with heat resistance and solvent resistance such as polyester, polypropylene, and polyethylene. For the commercially available products, Alphan MA-410, E-200C, manufactured by Oji Paper Co., Ltd.; polypropylene film manufactured by Shin-Etsu Film Co., Ltd.; and polystyrene-phthalate such as PS series such as PS-25 manufactured by Teijin Co., Ltd. Diester film and the like. Further, the protective film 4 can be the same as the support film 2. The thickness of the protective film 4 is preferably from 1 to i 〇 0jUm, more preferably from 1 to 30/zm. When the thickness is less than 1 Mm, the protective film 4 tends to be easily broken when the photosensitive resin layer 3 and the protective film 4 are laminated on the substrate. If it exceeds l〇〇#m, there will be Lack of cheapness. The photosensitive resin composition solution can be known by a roll coater, a comma-shaped blade coater, a gravure coater, an air knife coater, a die coater, a bar coater, and the like. It is applied onto the support film 2. The drying of the above solution is preferably carried out at 70 to 150 ° C for about 5 to 30 minutes. After the drying, the amount of the organic solvent remaining in the photosensitive resin layer is preferably from 2% by mass or less from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step. In the photosensitive element 1, the thickness of the photosensitive resin layer 3 varies depending on the application, and the thickness after drying is preferably from 1 to 200 // m, preferably from 5 to 100/zm, preferably from 10 to 50 μm. For better. If the thickness is less than 1 m, it tends to be difficult to carry out industrial scale coating. If it exceeds 200 #m, it is difficult to obtain sufficient sensitivity and photocurability at the bottom of the photoresist. The photosensitive element 1 may further have a buffer layer, an adhesive layer, a light absorbing layer -29-201207554, an intermediate layer such as a gas barrier layer, and the like. The obtained photosensitive element 1 can be stored in a roll shape in a sheet shape or a winding axis. In the case of winding into a roll shape, it is preferable to wind the support film 2 on the outer side. Examples of the axial center include plastics such as a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyvinyl chloride resin, and an ABS resin (acrylonitrile-butadiene-styrene copolymer). The roll-shaped photosensitive member obtained in this manner is preferably provided with an end face spacer on the end face of the roll from the viewpoint of end face protection, and is provided with a moisture-proof end face separator from the viewpoint of edge fusion resistance. It is better. In the case of the packing method, it is preferable to carry out packaging by coating a black sheet having low moisture permeability. (Method of Forming Photoresist Pattern) A photoresist pattern can be formed by using the above photosensitive resin composition. The method for forming a photoresist pattern according to the present embodiment includes (i) a lamination step of laminating a photosensitive resin layer formed using the photosensitive resin composition on a substrate, and (ii) The photosensitive resin layer is formed by exposing the active light to the image by a direct drawing method to expose the exposed portion, and (iii) removing the unexposed portion of the photosensitive resin layer from the substrate to form on the substrate. A step of developing a photoresist pattern formed by a cured product of a photosensitive resin composition. (ΟLamination step First, a photosensitive resin composition is used, and the formed photosensitive resin layer is laminated on a substrate. As for the substrate, an insulating layer and an insulating layer can be formed on the insulating layer. The substrate (circuit formation substrate) of the conductor layer. The photosensitive resin layer can be heated by the photosensitive resin layer 3 of the photosensitive element 1 and then crimped, for example, by removing the protective film 4 of the photosensitive element 1 described above. The substrate is laminated on the substrate, whereby a laminate composed of the substrate, the photosensitive resin layer 3, and the support film 2, which are sequentially laminated, can be obtained. From the viewpoint of adhesion and followability Therefore, it is preferred that the layer is carried out under reduced pressure. When crimping, the heating of the photosensitive resin layer and/or the substrate is preferably carried out at a temperature of 70 to 130 ° C, and is preferably 〇. It is preferable that the pressure is about 1 to 1.0 MPa (about 1 to 1 〇 kgf/cm 2 ), and the conditions are not particularly limited. Further, if the photosensitive resin layer is heated to 70 to 130 ° C, It is not necessary to pre-heat the substrate in advance, but The laminate may be preheated in one step. (ii) Exposure step Next, exposure is performed by direct drawing, that is, without using a photomask film, based on digital data, the photosensitive resin layer is used. 3, the active light rays such as laser light are irradiated with an image, and the desired pattern is directly drawn on the photosensitive resin layer. At this time, the support film 2 existing on the photosensitive resin layer 3 is transparent to the active light. The support film 2 can be irradiated with active light, and when the support film 2 has light-shielding properties, the support film 2 is removed first, and then the photosensitive resin layer is irradiated with active light. Direct direct exposure method or DLP (Digital Light Processing) exposure method. For the source of active light -31 - 201207554, it is better to use YAG laser, semiconductor laser, gallium nitride blue-violet laser, etc. It is also possible to use a carbon arc lamp, a mercury vapor arc lamp, an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, and the like to effectively emit ultraviolet light, or a photographic floodlight or a sun lamp. A light source that emits visible light. (iii) The developing step further removes the unexposed portion of the photosensitive resin layer 3 from the substrate, and forms a photoresist pattern formed of a cured product of the photosensitive resin composition on the substrate. When the support film 2 is present on the photosensitive resin layer 3, the support film 2 is removed first, and then the unexposed portion is removed (developed). The development method includes wet development and dry development, and is widely used. In the case of performing wet development, development is carried out by a known development method using a developing liquid corresponding to the photosensitive resin composition. In terms of the development method, dipping is used. The method of liquid-coating, spray-on, spray-on, brushing, slap-off, scraping, shaking, etc., is most suitable from the viewpoint of resolution improvement. Two or more of these methods may be combined to perform development. Examples of the developing solution include an alkaline aqueous solution, a water-based developing liquid, and an organic solvent-based developing liquid. In the case where an alkaline aqueous solution is used as the developing solution, it is safe and stable, and its handleability is good. As the base of the alkaline aqueous solution, an alkali hydroxide such as a lithium, sodium or potassium hydroxide; a lithium 'sodium' potassium or ammonium carbonate or a bicarbonate such as a carbonate; a base such as potassium phosphate or sodium phosphate; Metal phosphate; -32- 201207554 Alkali metal pyrophosphate such as sodium pyrophosphate or potassium pyrophosphate. In the case of an alkaline aqueous solution, a thin solution of 〇·1 to 5 mass% of sodium carbonate, a thin solution of 0.1 to 5 mass% of potassium carbonate, a thin solution of 0.1 to 5 mass% of sodium hydroxide, and 0.1 to 5 mass% of tetraboric acid A thin solution of sodium or the like is preferred. The pH of the alkaline aqueous solution is preferably in the range of 9 to 1 1 and the temperature thereof is adjusted in accordance with the alkali developability of the photosensitive resin layer. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be incorporated. The aqueous developing solution is, for example, a developing liquid formed of water or an aqueous alkaline solution and one or more organic solvents. Here, as the base of the alkaline aqueous solution, in addition to the substances previously described, for example, borax or sodium metasilicate, 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 aqueous imaging solution is preferably as small as possible within a range in which development is sufficiently performed, preferably at a pH of 8 to 12, and preferably at a pH of from 9 to 10, which is used in an aqueous imaging solution. Examples of the solvent include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropanol, butanol, diethylene glycol monomethyl ether, and diethylene glycol alone. Ether, diethylene glycol monobutyl ether, and the like. These may be used alone or in combination of two or more. In the aqueous developing solution, the concentration of the organic solvent is usually from 2 to 90% by mass, and the temperature can be adjusted in accordance with the alkali developability. A small amount of a surfactant, an antifoaming agent, or the like may be mixed in the aqueous developing solution. Examples of the organic solvent-based developing solution include 1,1,1-trichloroethane, -33-201207554 methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, and methyl ketone. , organic solvents such as r-butyrolactone. In order to prevent ignition, it is preferred to add water to the organic solvents in a range of -20% by mass. After the unexposed portion is removed, it is also necessary to perform heating at about 60 ° C or about 0.2 to 10 J/cm 2 for further hardening of the photoresist. (Manufacturing Method of Printed Circuit Board) A printed circuit board can be manufactured by etching the substrate on which the photoresist pattern is formed by the above method. The substrate is etched or plated on the conductor layer of the substrate or the like using the formed photoresist pattern. In the case of etching, examples of the etching liquid include a chlorinated II) solution, an iron (III) chloride solution, an alkali etching solution, and a peroxidation etching solution. Among these, from the viewpoint of good etching factor Preferably, an iron (III) chloride solution is preferred. In the case of plating, examples of the ore-plating method include copper plating such as sulfur plating or copper pyrophosphate plating; high-uniformity solder plating; and bath (nickel sulfate/nickel chloride) plating. Nickel plating such as nickel sulfamate; gold plating such as hard and soft gold plating. After the etching or plating is completed, the photoresist pattern can be peeled off by, for example, an aqueous solution which is more alkaline than the alkaline aqueous solution for development. For the strong alkaline liquid, for example, a 1 to 10% by mass aqueous sodium hydroxide solution, a 10% by mass aqueous potassium hydroxide solution or the like can be used. Among them, it is preferred to use 1~10% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution, use 1~ isobutyl in 1-250 pattern or reticle copper (hydrogen etching to make acid copper watt plating to make water soluble 1~ The mass is preferably -34 to 201207554, and the amount of the sodium hydroxide aqueous solution or the potassium hydroxide aqueous solution is preferably a immersion type, a spray type, etc., which may be used alone or in combination. In addition, the printed circuit board on which the photoresist pattern is formed may be a multilayer printed circuit board or a through-hole having a small aperture. EXAMPLES Hereinafter, the present invention will be specifically described with reference to the embodiments. However, the present invention is not limited to the following embodiments. [Example (A) component: adhesive polymer] (Preparation of solution a) In the mixed solution of the polymerizable monomer (copolymerizable monomer, monomer) disclosed in Table 1, The azobisisobutyronitrile as a radical reaction initiator was dissolved in 0. 8 g to prepare a "solution a". [Table 1] Polymerizable monomer mass (g) Mass ratio (%) Methacrylic acid 125 25 A Acrylic acid ester 200 40 ethyl acrylate 75 15 Ethylene 100 20 (Preparation of Solution b) In a mixture of 60 g of methyl cellosolve and 40 g of toluene (mass ratio: 3:2) as an organic solvent, azobisisodin is used as a radical reaction initiator. 1.2 g of nitrile was dissolved to prepare "solution b." -35- 201207554 (radical polymerization)

In a flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel gas introduction tube, 400 g of a mixture of methyl cellosolve and 160 g of toluene (mass ratio: 3:2) as an organic solvent was added. The flask was stirred with nitrogen, and the mixture was stirred and heated to 8 (TC) in the above mixture in the flask. After the dropwise addition of the above for 4 hours, the solution in the flask was stirred while maintaining the temperature at 80 ° C for 2 hours. Into the solution in the flask, it took 10 minutes to drip the above solution b, and the solution in the flask was stirred while maintaining the temperature at 80 ° C for 3 hours. It took 30 minutes to raise the temperature of the solution in the flask to 90 ° C at 90 °. After cooling for an hour, it was cooled to obtain an adhesive polymerization liquid as the component (A). Acetone was added to the adhesive polymer solution to prepare a nonvolatile (solid content) of 50% by mass. The weight of the weight is 80, 〇〇〇. In addition, the 'weight average molecular weight is determined by gel permeation chromatography ( ) and is calculated using standard polystyrene calibration lines. The conditions of GPC are as follows: Revealed. GPC condition: Lili L-6000 type (Hitachi Manufacturing Co., Ltd. pipe column: the following total 3

After the gelpack GL-R420 and nitrogen 240g immersion solution are connected, the temperature is 2, the composition of the solution is equal to the GPC calculation -36- 201207554

GelpackGL-R43 0

Gelpack GL-R440 (above, manufactured by Hitachi Chemical Co., Ltd., trade name) Solvent: Tetrahydrofuran Measurement temperature: 25 ° C Flow rate: 2.05 mL / min. Detector: Hitachi L-3 00 type RI (Hitachi Manufacturing Co., Ltd. limited Co., Ltd.) [Solution of photosensitive resin composition] In the solution of the obtained adhesive polymer (component (A)), the components disclosed in Table 2 are blended in the same table (g) Incorporation, and in the obtained mixed liquid, the components (B) and (C) disclosed in Table 3 were blended in the same amount (g) as disclosed in the same table to prepare Examples 1 to 1 And a solution of the photosensitive resin composition of Comparative Examples 1 to 4. Further, the blending amount of the component (A) disclosed in Table 2 is the mass (solid content) of the nonvolatile component. [Table 2] Ingredient amount (g) (A) Adhesive U polymer (solid content) 60 Photochromic agent BMPS 1 LCV 0.5 Dye MKG 0.05 Solvent Acetone 7 Toluene 7 Methanol 7 -37- 201207554 [Table 3] Ingredient m 6 cases Comparative example 1 2 3 4 5 6 7 8 9 10 1 2 3 4 B-1 10 — — 10 10 10 10 10 10 10 One — One one B-2 — 10 B-3 B-4 25 25 25 25 25 25 25 20 20 25 25 25 25 25 B B-5 5 5 5 5 5 5 — 5 10 5 5 5 One — B-6 5 5 B-7 5 5 B-8 10 One B-9 10 — 10 C-1 0.3 0.3 0.3 One by one 0.3 0.3 0.3 0.2 0.3 0.3 0.3 0.3 C-2 One - 0.3 One - One 0.1 One One One - C C-3 C-4 C-5 About the table The details of each component disclosed in Table 2 and Table 3 are as follows. (Photochromic agent) • BMPS (manufactured by Sumitomo Seika Co., Ltd., trade name): Tribromomethylbenzene mill • LCV (manufactured by Yamada Chemical Co., Ltd., trade name): leuco crystal violet (dye) • MKG (Made in Osaka Organic Chemical Industry Co., Ltd., trade name): Malachite green ((B) component: photopolymerizable compound) (1) Compound represented by the formula (I). (B-1) 9G (Xinzhongcun) Chemical Industry Co., Ltd., trade name) -38- 201207554 Polyethylene glycol #4 00 Dimethacrylate In the general formula (I), R1 and R·2 are methyl groups, n=9 • ( B-2 )

1 4G (product name of Shin-Nakamura Chemical Industry Co., Ltd.) Polyethylene glycol #600 dimethacrylate In the general formula (I), R1 and R2 are methyl groups, n=M • (B-3) 23 G (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name) Polyethylene glycol #1000 Dimethacrylate In the general formula (I), R1 and R2 are methyl group, n=23 (2) bisphenol A system Di(meth)acrylate compound ((B1)) • C B-4 ) FA- 3 2 1 Μ (manufactured by Hitachi Chemical Co., Ltd., trade name) 2,2-bis(4-(methacryl) a compound having an ethylenically unsaturated bond (the above (Β2)) • ( Β-5 ) FA-3 14A (manufactured by Hitachi Chemical Co., Ltd., a product of methoxy pentaethoxy)phenyl)propane (3) Name) Nonylphenoxytetraethylene glycol acrylate (the average enthalpy of the total number of oxygen-extended ethyl groups is 4) -39- 201207554 .(B-6) FA-3 18A (Manufactured by Hitachi Chemical Co., Ltd., trade name ) Nonylphenoxy octaethylene glycol acrylate (the average enthalpy of the total number of oxygen-extended ethyl groups is 8) • (B-7) FA-MECH (manufactured by 曰立化成工业股份有限公司, trade name r-chloro- Propyl-lu Propylene oxyethyl phthalate (4) ethyl urethane monomer (above (B5)) • ( B-8 ) UA-1 3 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name ΕΟ, ΡΟ ΡΟ 胺 胺 • • • ( ( ( 1 1 1 1 1 1 1 1 1 1 1 1 1 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Alcohol isocyanate) hexamethylene isocyanurate ((C) component: photopolymerization initiator) * (C-1) -40- 201207554 N-1717 (made by ADEKA CORPORATION, trade name) 1,7 a compound represented by bis(9-acridinyl)heptane (Π) (R3 is an alkylene group having a carbon number of 7) • (C-2) 9-PA (manufactured by Nippon Steel Chemical Co., Ltd., Name: 9-phenyl acridine compound represented by formula (III) (R4 is phenyl) • (C-3) TR-PAD103 (manufactured by Changzhou Power Electronic New Material Co., Ltd., trade name) 9- ( 3- Methylphenyl) acridine compound represented by formula (III) (R4 is m-methylphenyl) • (C-4) B-CIM (manufactured by Hampford Co., Ltd.) 2,2'-double (2- Chlorophenyl)-4,4',5,5'-tetraphenyl double Imidazole (C-5) 9,1 0-dibutoxy fluorene [photosensitive element] The solutions of the photosensitive resin group of the examples 1 to 1 and the comparative examples 1 to 4, respectively, were uniformly obtained. It was applied to a polyethylene terephthalate film (16-m thick) (manufactured by Teijin Co., Ltd., trade name "G2-16"), and dried in a hot air convection dryer at 100 ° C for 1 minute to form a dry film. A photosensitive resin layer having a film thickness of 38 μm. A protective film (manufactured by Tamapoly Co., Ltd., trade name "NF-1 3") was laminated on the photosensitive resin layer by a roll press method to obtain a polyethylene terephthalate film (supported). A photosensitive element of each of the photosensitive resin layers formed thereon and the protective films formed thereon, and the photosensitive elements of Examples 1 to 10 and Comparative Examples i to 4. [Laminated substrate] A 1.6 mm thick copper-clad laminate made of a glass epoxy material and a copper foil (thickness 35/zm) formed on both surfaces (manufactured by Hitachi Chemical Co., Ltd., trade name "MCL-E" The copper surface of -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. After heating the copper-clad laminate (hereinafter referred to as "substrate") to 80 ° C, the photosensitive elements of Examples 1 to 1 and Comparative Examples 1 to 4 were laminated to copper on both sides of the substrate. surface. The laminating system was a UOt hot roll, and the protective film was removed while the photosensitive resin layer of each photosensitive element was adhered to the respective copper surfaces of the substrate at a speed of 1.5 m/min. [Evaluation Test 1: Examples 1 to 10 and Comparative Examples 1 to 4] (Sensitivity) -42 - 201207554 The obtained laminated substrate was allowed to cool, and at a time point of 23 ° C, the staged exposure was performed. The working film of the watch is adhered to a polyethylene terephthalate film (support film) on the surface of the laminated substrate. The stage exposure meter uses a 41-stage stage exposure meter with a concentration range of 〇·〇〇~2.00, a concentration stage of 0.05, an exposure meter size of 20 mm x 87 mm, and a stage size of 3 mm x 12 mm. The photosensitive resin layer was exposed through a working film having such a staged exposure meter and a polyethylene terephthalate film. Exposure An exposure machine (trade name "Paragon-9000m", manufactured by Orbotech Co., Ltd., Japan) using a semiconductor-excited solid laser as a light source was used at an exposure amount of 20 mJ/cm2. After the exposure, the polyethylene terephthalate film was peeled off from the laminated substrate to expose the photosensitive resin layer. The exposed photosensitive resin layer was sprayed with a 1.0 mass% sodium carbonate aqueous solution at 30 ° C for 50 seconds (development treatment) to remove the unexposed portion. In this manner, a cured film formed of a cured product of the photosensitive resin composition is formed on the copper surface of the laminated substrate. The sensitivity (photosensitivity) of the photosensitive resin composition and the photosensitive element of Examples 1 to 1 and Comparative Examples 1 to 4 was evaluated by measuring the number of stages of the stepwise exposure table of the obtained cured film. The higher the number of segments of this staged exposure meter, the higher the sensitivity. The results are disclosed in Table 4. (Adhesion) The exposure pattern of the above-mentioned laser is used as a light source, and the wiring pattern of the line width/pitch of 5/400 to 200 M00 (unit: μπι) is drawn on the laminated substrate by the direct drawing method. Resin layer. In the Hitachi 41 stage -43-201207554 type exposure meter, the number of remaining stages after development is exposed to an energy intensity of 1 7.0. After the exposure, the same development process as the above-described sensitivity evaluation was performed. 线 In the case where a line portion (exposed portion) was formed without occurrence of defects or defects, the adhesion was evaluated by the minimum line width of the wiring pattern. The smaller the minimum, the better the adhesion. The results are disclosed in Table 4. (Resolution) Using an exposure machine using the above-described laser as a light source, a wiring pattern having a line width/pitch of 400/5 to 400/200 (unit: m) is drawn on the above laminated substrate by a direct drawing method. A photosensitive resin layer. The Hitachi 4 1 stage exposure meter was exposed to an energy intensity of 17.0 after the number of remaining stages after development. After the exposure, the same development processing as the above sensitivity evaluation is performed. 〇 In the case where the pitch portion (unexposed portion) is removed, the resolution is evaluated by the minimum width of the wiring pattern width. This minimum reduction means that the resolution is better. The results are disclosed in Table 4. (Peelability) A 60 mm x 45 mm pattern was drawn on the photosensitive resin layer of the laminated substrate by a direct drawing method using an exposure machine using the above laser as a light source. The Hitachi 41 staged exposure meter was exposed to an energy intensity of 17.0 after the number of remaining stages after development. After the exposure, the same development process as the above evaluation of the sensitivity was carried out to obtain a test piece in which a cured film of 60 m 4 4 4 m m -44 - 201207554 was formed on the substrate. After the test piece was allowed to stand at room temperature for one day and night, it was dipped in 5 (TC 3 mass% aqueous sodium hydroxide solution (release liquid), and stirred by a stirrer. The stirring was started until the hardened film was used by the substrate. The peeling time was evaluated by the time until the peeling was completely removed (peeling time (sec)). The shorter the peeling time, the better the peeling property. The results are shown in Table 4. (Cover hole reliability) The above-mentioned copper-clad laminate (Hitachi Chemical Co., Ltd.) Industrial Co., Ltd., trade name MCL-E-67), using a pattern puncher to make round holes with a diameter of 4 to 6 mm and 3 holes, using a honing machine with the equivalent of #600 bristles (Sanqi Co., Ltd.) The burr generated by the company was removed, and the substrate for measuring the number of cracks in the hole shown in Fig. 2 was obtained. The obtained substrate for measuring the number of cracks in the hole was heated to 80 ° C, and the surface of the copper was 120 ° C. The photosensitive element of Examples 1 to 1 and Comparative Examples 1 to 4 was laminated under the condition of 4 MPa. The protective film was removed and laminated, and the photosensitive resin layer of the photosensitive element was adhered to the number of holes to be broken. Copper surface of the substrate After that, the substrate for measuring the number of cracks in the hole was cooled, and when the temperature of the substrate for measuring the number of cracks in the hole was 23 ° C, the exposure machine using the laser as the light source was used, and the exposure was performed by a Hitachi 41-stage exposure meter. After the remaining number of stages, the energy intensity of 17.0 was applied to the surface of the polyethylene terephthalate film (support film) by exposure (direct drawing method). After exposure, it was allowed to stand at room temperature for 15 minutes, and then, polyparaphenylene was used. The ethylene dicarboxylate film was peeled off from the substrate for measuring the number of holes to be broken, and after development for 50 seconds, the number of cracks in the hole of the three-hole was measured - 45 - 201207554, and the crack rate of the special-shaped cap hole was calculated. Evaluation, which was defined as the cap hole reliability (%). The smaller the number, the higher the reliability of the cap hole. The results are disclosed in Table 4. [Table 4] Example Comparative Example 1 2 3 4 5 6 7 8 9 10 1 2 3 4 Sensitivity (section) 17.3 17 17 17.7 18.7 16.3 17.6 16.8 16.7 17.6 14.5 16.2 15 16.8 Adhesion (tf m) 30 32.5 32.5 30 32.5 30 27.5 32.5 32.5 30 30 35 32.5 35 Resolution (&quot ;m) 37.5 35 35 35 37.5 35 37.5 37.5 35 37.5 40 37 .5 37.5 40 Peelability (seconds) 55 50 50 52 52 50 64 52 50 55 40 48 47 61 Cover hole reliability (%) 3 6 6 4 3 2 6 2 2 4 15 12 23 19 It is apparent from Table 4. The sensitivity and the cover hole reliability of the photosensitive resin composition of Examples 1 to 10 were compared with the compound (B-1 to B-3) represented by the formula (I) as the component (B). The photosensitive resin composition of ～4 is more excellent. In particular, the contact hole reliability is 12 to 23% with respect to Comparative Examples 1 to 4, and Examples 1 to 1 are 2 to 6%, and the photosensitive resin composition of the present invention is clearly exhibited. Has a very good cover hole reliability. [Evaluation Test 2: Reference Examples 1 to 2] (Reference Example 1) Evaluation was carried out in the same order as in Example 1 except that the photosensitive resin composition of Example 1 was used and the exposure conditions were changed as follows. 46 - 201207554 Sensitivity, adhesion, resolution, peelability and cover hole reliability. The results are disclosed in Table 5. Exposure condition exposure machine: HMW-201GX (manufactured by ORC Co., Ltd.) Light source: Exposure for sensitivity evaluation of high-pressure mercury lamp: 40mJ/cm2 Exposure for evaluation other than sensitivity: Hitachi 41-stage stage exposure meter Energy intensity exposure method in which the number of remaining stages after development is 23.0: reticle exposure method (Reference Example 2) The exposure conditions were changed to the same exposure conditions as in Reference Example 1 except that the photosensitive resin composition of Comparative Example 1 was used. In the same procedure as in Comparative Example 1, the sensitivity, the adhesion, the resolution, the releasability, and the lid hole reliability were evaluated in the same manner as in Comparative Example 1. The results are disclosed in Table 5. [Table 5] Reference Example 1 Reference Example 2 Sensitivity (segment) _ 23 20.5 Adhesion (&quot;m) 25. 20 Resolution (&quot;m) 45 40 Peelability (seconds) 60 52 Cover hole reliability 20 3 - 47-201207554 As shown in Table 5, in the case of Reference Example 1 in which the photosensitive resin composition of Example 1 was exposed by a conventional mask exposure method, sufficient cap hole reliability was not obtained. On the other hand, as shown in Table 4, in the case of Example 1 in which the photosensitive resin composition having the same composition was used for exposure by a direct drawing method using a laser as a light source, excellent cap hole reliability was obtained. . Further, as shown in Table 5, in the case of Reference Example 2 in which the photosensitive resin composition of Comparative Example 1 was exposed by a conventional mask exposure method, sufficient sensitivity and lid hole reliability were obtained. On the other hand, in the case of Comparative Example 1 in which the photosensitive resin composition having the same composition was used and exposed by a direct drawing method using a laser as a light source, the sensitivity and the reliability of the cap hole were used. None of them got enough numbers. As a result of the above-mentioned results, it is understood that the photosensitive resin composition of the comparative example containing the compound represented by the formula (I) as the component (B) has sufficient sensitivity and a cover when exposed by a conventional mask exposure method. Hole reliability, however, in the case of exposure by direct delineation, neither the sensitivity nor the reliability of the cap hole has reached a sufficient number, and the present invention containing the compound represented by the formula (I) The photosensitive resin composition 'does not have sufficient cap hole reliability when exposed by a conventional mask exposure method. However, in the case of exposure by direct drawing method, 'there is superior to the comparative example. Sensitivity and cover hole reliability. [Industrial Applicability] The photosensitive resin composition and the photosensitive element of the present invention have excellent cap hole reliability when exposed by the direct-48-201207554 drawing method, and high precision can be realized. Formation of photoresist patterns and fabrication of printed circuit boards. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a plan view showing an embodiment of a photosensitive element of the present invention. Fig. 2 is a plan view showing a substrate for measuring the number of cracks in the hole used for evaluation of the reliability of the lid hole. [Explanation of main component symbols] 1 : Photosensitive element 2 : Support film 3 : Photosensitive resin layer 4 : Protective film -49-

Claims (1)

201207554 VII. Patent application scope: 1. A photosensitive resin composition which is a photosensitive resin composition used for forming a photoresist pattern by a direct drawing method, which comprises (A) an adhesive polymer, ( B) Photopolymerizable Compound and (C) Photopolymerization Initiator ' wherein the (B) photopolymerizable compound is a compound represented by the following formula (I), [Chemical Formula 1] The photosensitive resin composition of the above-mentioned (B) photopolymerizable compound further contains the following formula (11), and the photosensitive resin composition of the above-mentioned (B). Compound, [Chemical 2] (wherein R3 represents a hydrogen atom or a methyl group, R4 represents a hydrocarbon group having a carbon number of 9, and m represents an integer of 0 to 20). 3. The photosensitive resin composition according to the invention of claim 2 or 2, wherein n is an integer of 4 to 25 in the compound represented by the above formula (I). -50- 201207554 4. In the photosensitivity of the second item of the patent application; (), the number of m in the compound represented by the above formula (Π). 5. A composition according to any one of claims 1-4 to 4, wherein the aforementioned (C) photopolymerization initiator is a compound represented by (ΠΙ) and/or a compound of the following formula (compound 3) a fat composition comprising 4 to 8 of a photosensitive resin containing the following formula IV) (2), wherein R5 represents an alkylene group having a carbon number of 2 to 20, a thiodialkylene group [Chemical 4] (wherein, r6 represents a monovalent aromatic hexa- 1 type photosensitive element which can have a substituent, which is formed by the photosensitive resin composition of the first to fifth inventions which are used to support the support film; Photosensitive resin layer -51 - group base). And a method of forming a photoresist pattern of any one of the above-mentioned items, wherein the film is formed by using the photosensitive resin composition according to any one of claims 1 to 5. a laminating step of laminating a photosensitive resin layer on a substrate, and an exposure step of irradiating the active light with an image by a direct drawing method to cure the exposed portion, and the photosensitive resin The unexposed portion of the layer is removed from the substrate, and a development step of forming a photoresist pattern formed by the cured product of the photosensitive resin composition is formed on the substrate. 8. A method of manufacturing a printed circuit board, comprising etching or plating a substrate on which a photoresist pattern is formed according to the method of claim 7 of the patent application.