TW200921275A - Photosensitive composition and laminated body thereof - Google Patents

Abstract

Disclosed is a photosensitive resin composition containing 20-90% by mass of an alkali-soluble polymer (a) containing a carboxylic acid and having an acid equivalent weight of 100-600 and a weight average molecular weight of 5,000-500,000, 5-70% by mass of a specific ethylenically unsaturated addition polymerizable monomer (b), and 0.01-30% by mass of a photopolymerization initiator (c).

Description

200921275 IX. Description of the Invention: [Technical Field of the Invention] The invention relates to a photosensitive resin which can be developed by an aqueous solution of an aqueous solution, which is formed by laminating the photosensitive resin composition on a support. A method for forming a photoresist pattern on a substrate and a use of the photoresist, the tea. More specifically, the present invention relates to a photosensitive resin composition, a photosensitive resin composition, and a printed circuit board, which are manufactured as a flexible printed circuit board. Wafer mounting lead frame (hereinafter referred to as guide (four)), with metal mask

(_丨mask) is manufactured by metal flute precision processing, and is manufactured by semiconductor package represented by BGA (Ba11 Gnd Array) or CSP (Chip Scale Package), with TAB (Tape)

Automated Bonding, media white tank r person 8 rolls with automatic joint) or COF (Chip on

Film's film-on-chip package: The manufacture of a tape-and-reel substrate represented by a semiconductor device (which is mounted on a thin film-like circuit board), and the manufacture of semiconductor bumps in the field of flat panel displays (Ιη( ΗιπηΤίη〇χ*, indium tin oxide) electrode, address electrode or electromagnetic wave mask as a representative of the manufacturing of components to provide better photoresist pattern, and can be used as a processing method using sandblasting The protective mask member of #时 provides a better photoresist pattern. [Prior Art] Previously, the method of manufacturing a printed circuit board by photolithography refers to the following method: a photosensitive resin composition Applying on the substrate, the feed circumference is also exposed by the β-stitch pattern, and the exposed portion of the photosensitive resin composition is polymerized and cured, and the unexposed portion is removed by the developer to form a photoresist pattern on the substrate. After the photoresist pattern is etched or plated to form a conductor pattern, the photoresist pattern is peeled off from the substrate to form a substrate. In the above photolithography method, 'the following method is used: when the photosensitive resin composition is applied onto a substrate, a photoresist solution is applied onto the substrate to dry it; or A photosensitive resin laminate having a support, a layer containing a photosensitive resin composition (hereinafter also referred to as "photosensitive resin layer"), and an optional protective layer (hereinafter referred to as "dry film photoresist layer") The method of laminating on a substrate. In addition, the latter dry film photoresist layer is often used in the manufacture of a printed circuit board. Hereinafter, a method of manufacturing a printed circuit board using the above-described dry film photoresist layer will be briefly described. First, when the dry film photoresist layer has a protective layer, for example, a polyethylene film, it is peeled off from the photosensitive resin layer. Then, a laminator is used in accordance with the substrate, the photosensitive resin layer, and the support. The photosensitive resin layer and the support volume layer are on a substrate, for example, a copper box laminate. Then, via a photomask having a wiring pattern, the inclusion of the super-pressure mercury lamp is included ( 36 Ultraviolet light of 5 nm) exposes the photosensitive resin layer, whereby the exposed portion is polymerized and cured. Then, the support, for example, polyethylene terephthalate is peeled off. Then, using a developer, for example, has a weak test property The aqueous solution dissolves or disperses to remove the unexposed portion of the photosensitive resin layer, thereby forming a photoresist pattern on the substrate. As a method of forming a wire by using a photoresist pattern on a substrate formed in such a manner, gold 133895.doc 200921275 There are roughly two methods, namely, a method of removing a metal portion not covered by a photoresist film and a method of plating a metal by electroplating. In particular, the method of the former is often used in consideration of the simplicity of the step. In the method of removing a metal portion by etching, a through hole (through hole) of a substrate or a via hole for interlayer connection is covered with a hardened photoresist film, thereby preventing metal in the hole from being etched. . This method is called tenting. In the etching step, for example, a copper chloride, a ferric chloride, or a copper ammonia complex solution is used. Ο

Recently, with the miniaturization of wiring intervals in printed circuit boards, the demand for high resolution of dry film photoresist layers has increased. Generally, the thinner the thickness of the dry film photoresist layer, the higher the resolution, which can correspond to the requirement of high resolution. However, there is a problem in that as the thickness of the dry film becomes thinner, the cap hole property is deteriorated, and the hardened photoresist film covering the through hole of the substrate becomes (4) cracked, resulting in a decrease in the yield of the large towel field. For this reason, the industry is seeking a photosensitive resin composition which does not increase the thickness of the dry film resist layer and has a good capping property. In addition, in the manufacturing technology of printed circuit boards, the exposure of the direct-painting, that is, the exposure of the mask without the mask, has been rapidly advanced in recent years. As a light source for exposure without a mask, the wavelength is 350 to 410. _ 4 疋 疋 1 line (365 nm) or h line (4 〇 5 nm). However, compared with the contact exposure, the exposure time of the maskless exposure is more than one, and the yield of the exposure step is lower than that of the contact exposure. Therefore, in order to shorten the exposure, the sensitivity of the photosensitive resin composition is required. 133895.doc 200921275 Patent Document 1 discloses a photosensitive resin composition which can be exposed without a mask, but the sensitivity is not sufficient, a satisfactory yield cannot be obtained in the exposure step, and the cap hole property is also There is no disclosure, so the yield is unknown. Patent Document 2 discloses a photosensitive resin composition which is excellent in capping property and can be exposed to a mask, but the sensitivity of the photosensitive resin composition is also insufficient, and a satisfactory yield cannot be obtained. For this reason, a photosensitive resin composition for a dry film photoresist layer is required to exhibit good compatibility, especially for a light source of 4〇5±1〇^^, and excellent in capping property. The photosensitive resin composition' is a photosensitive resin composition which can contribute greatly to the improvement of yield I and the improvement of yield. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 2 〇〇 5 丨 丨 丨 丨 [ 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 In view of the above problems, it is an object of the present invention to provide a photosensitive resin composition which can greatly contribute to improvement in yield and improvement in yield, and a photosensitive resin laminate using the photosensitive resin composition. [Technical means for solving the problem] The above problems can be attained by the following constitution of the present invention. (1) A photosensitive resin composition containing 20 to 90% by mass of (4) an alkali-soluble polymer, wherein the alkali-soluble polymer contains a carboxylic acid having an acid equivalent of 100 to 600 and a weight average molecular weight of 5 〇〇〇 5〇〇,〇〇〇,5~7〇% by mass of (b) ethylenically unsaturated addition polymerizable monomer and 〇〇1 to 3〇% by mass of 133895.doc 200921275 Photopolymerization starter' The photosensitive resin composition contains at least one compound selected from the group consisting of compounds represented by the following general formula (1), at least one compound selected from the group consisting of the following general formula (π), and at least one selected from the group consisting of At least one of the compound groups represented by the above formula (10) is used as the (b) ethylenically unsaturated addition polymerizable monomer, and is contained in the following formula (IV). The compound is represented by the (4) photopolymerization initiator. 0 Rt 〇-(A-〇)mi-(B-0)m3*CC=CH2 Φ h3c-c-ch3 (1) ό 9 (R4R2 is independently hydrogen or methyl. 八和^ The alkylene group having a carbon number of 2 to 6 may be the same or different. In the case of the difference, the structure of the repeating unit containing _(A_0)_ may be formed irregularly or may be block-formed. Ml, m2, m3, and m4 are integers above 〇, ml+m2Am3 + m4 are each independently an integer of 〇~8, and ml+m2 + m3 + m4 is an integer of 2 to 8.) I33895.doc 200921275 [Chemical 2 ] o r3 〇—(C-0)nr,s-(0-0)m7-CC=CH2 φ H3C-C-CH3 (II) φ 〇-(C-〇)n,6-(D^D) rne-cC=CH2 (R_3 and R_4 are each independently a hydrogen atom or a sulfhydryl group. C and D represent a stretching group having a carbon number of 2 to & and the same or different, in the case of the difference, The structure of the repeating unit containing -(C-0)- and -(D-Ο)- may be randomly formed or block-formed. m5, m6, m7 and m8 are integers of 0 or more, m5+m6 and M7 + m8 are each independently an integer of 〇~28, m5 + m6+m7 + m8 is an integer of 10~28.) [Chemical 3] 0 r5 〇-(E-〇)m9-(F-0)ni11-CC =CH2

Φ (III) H3C—C—CHj φ Τ Ο Re °~(E*〇)mi〇*(F-0)mirc-C=CH2 (R5 and R6 are each independently a hydrogen atom or a methyl group. E and F represent The structure of the remnant unit having a carbon number of 2 to 6 may be the same or different, and in the case of the difference, the structure of the repeating unit of -(E-Ο)- and _(F_〇)_ may constitute 'may constitute a block .m9, mil and ml2 billion or more of the whole number 133895.doc -10- 200921275' m9 + ml0 and mn + mi2 〇~50 each independently an integer of m9 + ml0 + irregularly Mll+ml2 is an integer of 30~50 °) [Chemical 4]

(wherein R7 is hydrogen, alkyl, aryl, acridine, alkoxy or substituted). f

Lj (2) The photosensitive resin composition as disclosed in (1) which further contains 〇.〇1~p Berry/〇(d) N-aryl_α_amino acid compound and 〇〇1~3 〇% by mass of (6) halogen compounds. (3) A photosensitive resin laminate comprising: a support comprising a base film; and a layer comprising the photosensitive resin composition as disclosed in (1) or (2) laminated on the support. A method for forming a photoresist pattern, comprising the steps of: preparing a photosensitive resin laminate according to (3), laminating a layer of the photosensitive resin composition comprising a photosensitive resin composition on a substrate to form a photosensitive layer The photosensitive resin layer 'exposure and develop the photosensitive resin layer. (5) The method for forming a photoresist pattern as disclosed in (4), wherein in the above exposure step =: the exposure method is direct drawing, and the illumination speed is 1 〇 or more, and the scanning speed in the direction of the field sweep is 2 (10) / More than two seconds. (Step: "Manufacturing method of a substrate having a concave-convex pattern, which comprises using a glass rib as a substrate, and forming a photoresist on the substrate by using (4) or (5) Figure # 'The substrate obtained by 133895.doc 200921275 is processed by a sandblasting method to strip the photoresist pattern. (7) A method for manufacturing a conductor pattern, which comprises the following steps: using a metal plate or a metal film insulating plate as a method A substrate, a method for forming a photoresist pattern on the substrate, for: engraving or an electric clock. The method for manufacturing a substrate (8)-type printed circuit board comprises the steps of: using a metal-clad insulating board as a substrate And using the method disclosed in _(5) to form a photoresist pattern on the substrate to perform (four) or electroplating on the obtained substrate, and stripping the photoresist pattern. (9) A method for manufacturing a lead frame, which comprises the following steps: using a metal The board is used as a substrate, and a photoresist pattern is formed on the substrate by the method disclosed in (4) or (5), and the obtained substrate is left to be etched to peel off the photoresist pattern. (1) A semiconductor package is manufactured. A method, comprising the steps of: using a wafer formed of an LSI circuit as a substrate, or the use of such ⑷ ⑺

Lj ", a photoresist pattern is formed on the 4 substrate, and the obtained substrate is subjected to an electron microscope 'peeling resist pattern. [Effects of the Invention] The present invention provides a tree having a high sensitivity and a good capping property and a high resolution, a compound, a photosensitive tree using the photosensitive resin composition, and a body photosensitive property. The resin laminate is used for forming a photoresist pattern, a method, and a pattern on a substrate, and can be used for manufacturing a wire and a printed circuit board; manufacturing a main conductor, manufacturing a semiconductor package, and including

In the manufacture of a flat panel display having a substrate of the embossed > The photosensitive resin composition of the present invention has high sensitivity, high resolution of 133895.doc 200921275, good caphole property, good short circuit, short circuit, and good protection of through-holes for manufacturing printed circuit boards. The production speed and the manufacturing time are shortened. [Embodiment] Therefore, the breakage of the printed circuit board can be prevented from being broken by the photoresist film, etc., so that the yield can be greatly improved, thereby improving workability and productivity. The present invention will be specifically described below. <Photosensitive resin composition> (a) Testable polymer

In the photosensitive resin composition of the present invention, (a) the test-soluble polymer is an alkali-soluble polymer containing an acid-requiring acid having an acid equivalent of 100 to _ and a weight average molecular weight of 5,000 to 500 Å. In order for the photosensitive resin composition to have developability or releasability with respect to the developer or the release liquid containing the aqueous test solution, the alkali-soluble polymer must have a carboxyl group. The acid equivalent is preferably (10) ~ deputy, more preferably 25 〇 ~ 45 〇. From the viewpoint of ensuring compatibility with other components in the solvent or the composition, particularly the (8) ethylenically unsaturated addition polymerizable monomer described later, it is possible to maintain developability or releasability. In terms of opinion, it is 6〇〇 or less. Here, the acid equivalent means a mass (gr_) of a base having a base of a ruthenium equivalent in the photosensitive resin composition. Further, the acid equivalent was measured by a potentiometric titration method using a Reporting Titrator (C〇M_555) of m〇I/L. The weight average molecular weight of the alkali-cooling south molecule is preferably from 5, 〇〇〇 to 50,000'000. It is 5,000 or more from the viewpoint of maintaining the thickness of the dry film resist layer uniformly to obtain the resistance to the developer, and 500, from the viewpoint of maintaining the developability of I33895.doc 13 200921275. the following. More preferably, the weight average molecular weight is 20,000 to i 〇〇, _. The weight average molecular weight at this time is determined by a calibration curve of condensate permeation chromatography (GPC, gel permeati (m blood. Fushun using polystyrene (Shodex STANDARD SM-105 manufactured by Showa Denko) The weight average molecular weight can be measured using a gel permeation chromatograph manufactured by JASCO Corporation, and determined according to the following conditions: Differential Refractometer: RI-1530 Pump: PU-1580 Deaerator: DG- 9-80-50 Column oven: CO-1560 e column is KF-802.5, KF-806Mx2, KF-Stn

Eluent: THF Preferably, the test polymer is a copolymer of at least one of a first monomer described later and at least one of f and a second monomer described below. The first monomer is a tickic acid or acid needle having a polymerizable unsaturated group in the molecule. For example, (meth)acrylic acid, fumaric acid, cinnamic acid, butyric acid, itaconide, maleic anhydride, and maleic acid are used. Among them, particularly preferred is (mercapto)acrylic acid. Acrylic acid refers to acrylic acid or thioglycolic acid. The same below. The second single system is non-acidic and has at least one polymerizable unsaturated group in the molecule. For example, (meth)acrylic acid methyl vinegar, (meth)acrylic acid bismuth s(meth)acrylic acid n-propyl ketone methyl) isopropyl isopropyl vinegar, 133895.doc 200921275 (meth)acrylic acid Brewing, isobutyl brewing (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid 2 Ethylhexyl ester, (meth)acrylic acid benzyl ester, ethylene glycol vinegar such as ethyl acetate acetonate, (methyl) acrylonitrile, styrene and polymerizable styrene derivatives. Among them, particularly preferred are (meth)acrylic acid methyl ketone, (meth)acrylic acid n-butyl vinegar, styrene, and (meth)acrylic acid arsenic. (a) The ratio of the alkali-soluble polymer to the total of the photosensitive resin composition is 20 to 90% by mass. /. The range is preferably from 3 〇 to 7 〇 mass%. The photoresist pattern formed by exposure and development has characteristics as a photoresist film, and is preferably 20% by mass or more from the viewpoint of sufficient resistance to capping, etching, and various plating steps. quality. /. the following. (b) Ethylene and addition polymerizable monomer In the photosensitive resin composition of the present invention, (b) ethylenic unsaturated addition is preferable from the viewpoint of analyticity and capping property. The polymerizable monomer comprises at least one compound selected from the group consisting of compounds represented by the following formula (1), at least one compound selected from the group consisting of (9), and a compound selected from the group consisting of (III) At least one compound in the population. [化5] 0—

H3C—C—CH3 Φ Ο1(A-0)m2 (B*0)n>4-C_C—CH? 133895.doc •15- 200921275 (RAR2 is independently a hydrogen atom or a methyl group. Eight and three represent carbon The number of alkylene groups of 2 to 6 may be the same or different. In these different cases, the structure of the repeating unit of 3 (A-Ο)- and -(B-〇)- may be irregularly The composition may be composed of segments. ml, m2, m3, and m4 are integers above '' mi+m2 and m3+m4 are each an integer of 〇~8, and +^ + is + is an integer of 2-8. ) [Chem. 6]

0—(C-0)mS-(D-0)m7(i-c=

H3c-c-ch3 =CH2 φ „ (II) (R3 and r4 are each independently a hydrogen atom or a methyl group, and the alkyl group having a carbon number of 2 to 6 may be the same or different, When different, the structure of the repeating unit containing -(CO)- and -(D-Ο)- may be randomly formed or block-formed. m5, m6, m7 and m8 are integers above 〇, m5 + m6 &. m7 + m8 are each independently an integer of 〇~28, m5 + m6 + m7 + m8 is an integer of 10~28) 133895.doc • 16- 200921275 [of 7] Ο _ (E-square)? *n9-(P-〇)mn-CC=CH2 H3C-C-CH3

(ΠΙ) 〇-(E-〇)mi〇-(F-〇)m12-C-cicH;

(The ruler 5 and the ruler 6 are each independently a hydrogen atom or a methyl group. £ and ? represent an alkylene group having a carbon number of 2 to 6', which may be the same or different, and in the case of the difference, -(E) The structure of the repeating unit of -Ο)- and -(F-〇)_ can be constructed irregularly, and the composition of the mourning segment 19, ml0, mll and ml2 are integers above ,, m9 + ml〇 and heart + (10) respectively Independently an integer of 〇~5〇, m9 + mi〇+ mll+ml2 is an integer of 30 to 50.) (4) as at least one compound selected from the group represented by the above formula (1) 'T enumeration: 2 '2_双{(4•Pro-oxypolyethyleneoxy)phenyl}propane or 2,2-lu-methylpropenyloxypolyethylidene)phenyl}propane. t is a good result that the polyvinyloxy group of the compound W is selected from the group consisting of monoethyloxy, divinyloxy, = ", knees per oxime, ethylene vinyl, tetravinyloxy, pentavinyloxy" a compound of any one of the group consisting of ethylene, hexaethyleneoxy and octaethyleneoxy. In addition, it can also be exemplified: 2,2_double {(4•propyl-anthraceneoxy-polyoxyalkyloxy) ketone}iron 2,2·double{(4' methacryloxy-oxyl-concentration Oxy)phenyl}propyl. As the polyoxyl group oxy group which the compound has, a propyloxy group or a mixture of an ethyloxy group and a benzyloxy group may be mentioned. Among these, 133895.doc • 17- 200921275 The most preferred is 2,2-bis U4-methacrylinyldiethyloxy)phenyl}propane. Specific examples of the at least one compound selected from the group represented by the above formula (ID) include polyethylene glycol having an average of 5 moles of ethylene oxide added to both ends of bisphenol A. Dimethacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) NK ESTER BPE_500 or an average of 6 moles of Ethylene Ethylene and an average of 2 moles of Ethylene-Polypropylene The dimethyl propylene phthalate of the diol is exemplified as a compound of at least one selected from the group represented by the above-mentioned ones. Ethylene glycol polyethylene glycol dimethacrylate or bisphenol A is added to the average of 15 moles of ethylene oxide and 2 moles of epoxy-propylene polyalkylene glycol The sensible resin composition of the present invention comprises at least one compound selected from the group consisting of the compound represented by the above formula (1), and is selected from the group consisting of the formula TO. At least a _(tetra) compound in the compound group and at least one compound selected from the group consisting of: The tenth amount is preferably 5 to 6 (% by mass) to 5: mass 曰% in the photosensitive resin composition. The viewpoint of high resolution and high capping property is good: the 疋 is 1 5% by mass or more, and it is preferable that the amount of 60% by mass or less is selected from the group of compounds represented by the above formula (1), And at least one compound selected from the group consisting of the above formula (π), i33895.doc-J8-200921275, and at least one compound selected from the group consisting of the above formula (弋) (b) The ethylenic unsatisfactory amount is preferably % by mass% of the amount of the early body, and more preferably 80% by mass to 1% by mass of 疋7〇% by mass. The amount of at least one compound selected from the group consisting of the above-mentioned two Li groups is preferably a mass/denier: bei: broadly more preferably 1 to 2% by mass, and even more preferably 2 to 1 〇 is preferable from the viewpoint of exhibiting high resolution, and the amount is preferably from the viewpoint of maintaining the softness of the cured film. In the same manner, at least one of the compound groups selected from the group of the compounds represented by the invention is contained in the sensible resin composition of the invention, and at least one of the compounds is represented by 疋〇·(4)% by mass, more preferably 〜2. 〇% by mass, and then better: °ϋ. In terms of high resolution and high capping, the 疋S罝 of the lamp is 0,5 mass. It is preferable that the amount is a view of the flexibility of the 30-mass cured film, and the same as the at least one compound selected from the group of compounds represented by the above formula _ contained in the photosensitive resin composition of the present invention. The amount is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, and still more preferably 10 to 20% by mass. It is preferable from the viewpoint of exhibiting high capping property. When the amount is 1% by mass or more, it is preferable that the amount is 30% by mass or less from the viewpoint of suppressing the peeling delay of the cold flow and the cured photoresist film. Further, in the (b) ethylenically unsaturated addition polymerizable monomer, at least one compound selected from the group consisting of the compound represented by the above formula (1) = 133895.doc -19· 200921275 The photopolymerizable unsaturated compound shown below may be used in addition to at least one compound selected from the group consisting of the compound represented by the formula (IIJ) and at least one compound selected from the group consisting of the compound represented by the above formula (IIJ). Example: k can be enumerated. 1) 6-hexanediol di(meth)acrylic acid, 1,4_cyclohexanediol) acrylate, polypropylene glycol di(meth) acrylate, polyethylene glycol one (a Acrylate, 2_bis(p-hydroxyphenyl)propane di(meth)acrylofluorene S曰, propylene glycol tri(meth)acrylate, trimethylolpropane tri(methyl)propane vinegar, poly Oxypropyl propyl trimethyl methacrylate tris(decyl) acrylate 曰 polyoxyethyl dihydroxy decyl propane triacrylate 'pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate Ester, trimethylolpropane-glycidyl ether di(meth)acrylate, Bisphenol A diglycidyl diether di(meth) acrylate, β hydroxypropyl U propylene oxy) propyl phthalate S S 曰 氧基 oxy polyethylene glycol (methyl) propyl benzoic acid Ester, nonylphenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polyalkylene glycol (meth) acrylate vinegar, polypropylene glycol mono (meth) acrylate vinegar, triethylene glycol Propylene glycol, polypropylene glycol added to aerobic propylene and then added with oxygen bake at both ends (addition of an average of 3 moles of oxyethylene to the two ends of the polypropylene glycol with an average of 12 moles of oxypropylene) Dimethacrylate of polyalkylene glycol. Further, an amino phthalate compound can also be mentioned. Examples of the urethane compound include, for example, hexamethylene diisocyanate, toluene diisocyanate or bishydroxyisocyanate 4, such as diisoxamic acid 2,2,4-trimethylhexyl Vinegar, a urethane compound formed by reacting a compound having a hydroxyl group and a (meth)acryl group in a knife, for example, 2-acryloyl acrylate to oligodiol monomethacrylate. Specifically, for example, a reaction product of diisocyanate and 133895.doc -20. 200921275 propylene glycol monomethylpropionate (manufactured by Nippon Oil & Fats Co., Ltd., B) emmer PP1000). These may be used alone or in combination of two or more. The ratio of the (b) ethylenically unsaturated addition polymerizable monomer used in the present invention to the total of the photosensitive resin composition is 5 to 70 mass. / 〇 range, preferably 10 to 60 mass. In terms of sensitivity, resolution, and adhesion improvement, it is preferably 5% by mass or more, and in terms of suppressing the peeling delay of the cold flow and the cured photoresist film, it is preferably 7 〇 mass%. the following. (c) Photopolymerization initiator In the photosensitive resin composition of the present invention, a well-known person can be used as (c) a photopolymerization initiator. The amount of the (c) photopolymerization initiator contained in the photosensitive resin composition of the present invention is in the range of 0.01 to 3 % by mass, more preferably in the range of 0.0 5 to 10% by mass. From the viewpoint of obtaining sufficient sensitivity, it is preferably 疋0,0 1% by mass or more, and it is preferable that light is sufficiently penetrated to the bottom surface of the photoresist film to obtain good high resolution. 30% by mass or less. As such a photopolymerization initiator, 2' ethyl hydrazine, octaethyl hydrazine, 1,2-benzopyrene, 2,3-benzopyrene, 2-phenyl fluorene, 2,3-Diphenyl enanium, 1_gas oxime, 2-gas oxime, 2-methylindole, 1,4-naphthoquinone, 9,1 〇 phenanthrenequinone, 2-methyl-14 »naphthoquinone, 9,1〇_phenanthrenequinone, 2_mercaptophthylquinone, 2,3-dimercaptopurine, 3-gas-2-methylindole, etc.; aromatic ketones such as Phenyl ketone, michelitone [4,4, bis(dimethylamino)diphenyl hydrazide] 4,4'-bis(diethylamino) dioxin; benzoin or benzoin ether, for example Female scent, benzoin ethyl ether, benzoin phenyl ether, decyl benzoin, ethyl benzoin; dialkyl ketals, such as benzyl didecyl ketal, benzyl di 133895.doc -21 . 200921275 ethyl ketal; Thiophenones such as diethyl thioxanthene, gas oxime oxime; dialkylamino benzoic acid esters such as dimethylamino benzoic acid ethyl ester oxime esters such as 1-phenyl-1 , 2-propanedione-2-0-alum-based hydrazine, hydrazine-stupyl-1,2-propanedifluorene-2-(0-ethoxyxoyl); phenanthrene dimer, eg (ozone benzene -4,5-diphenylmeridyl dimer, 2•(o-chlorophenyl)-bis-(m-methoxyphenyl fine fluorenyl dimer, 2_(p-methoxyphenyl)_4 '5-diphenylmipyl dimer. These compounds may be used alone or in combination of two or more. In the photosensitive resin composition of the present invention, the compound is represented by the following formula: (4) Photopolymerization initiators are the invention: preferred embodiments. In the photosensitive resin composition of the present invention, the amount of the biting compound is (MH to 30% by mass, preferably - the mass of the second is good θ, and the 乂 is correct. The value is set to 0. 〇1% by mass or more, and the light is sufficiently penetrated by the surface of the film to obtain a good high resolution. % below. [Chemistry 8]

(IV) a pyridyl group, an alkoxy group or a substituted group: acridine, 9-phenylindole (p-ethylphenyl) acridine, 9_(different

(wherein, r7 is an alkyl group of hydrogen, an alkyl group, an aryl group or a DI.) As the acridine compound described above, for example, pyridine, 9-(p-nonylphenyl)acridine, 9-133895.doc -22-200921275 Propyl phenyl) acridine, 9-(p-n-butylphenyl) acridine, 9-(p-tert-butylphenyl) acridine, 9-(p-methylphenyl) acridine, 9- (for ethoxylated stupyl). Acridine, 9-(p-ethoxyphenyl) acridine, 9-(p-diaminophenyl) acridine, 9-(p-cyanophenylphenyl) acridine, 9-(p-diphenyl) Acridine, 9-(p-diylphenyl) σ acridine, 9-(m-methylphenyl) acridine, 9-(meta-propylphenyl) sputum, 9-(m-isopropylphenyl) Acridine, 9-(m-butylphenyl)acridine, 9-(m-butylphenyl)acridine, 9-(m-methoxyphenyl)acridine, 9-(m-ethoxyphenyl) Acridine, 9-(m-decylphenyl) acridine, 9-(m-diaminoamino)phenyl 9-(m-ethylamine basic) bite, 9-(cyanophenyl) 0丫0, 9-(m-chlorophenyl)acridine, 9-(m-bromophenyl)acridine, 9-fluorenyl acridine, 9-ethyl. Acridine, 9-n-propyl acridine, 9-isopropyl acridine, 9-cyanoethyl acridine, 9-hydroxyethyl acridine, 9-ethylethyl acridine, 9-methoxy acridine 9-ethoxy hydrazine, 9-n-propoxy acridine, 9-isopropoxy acridine, 9-chloroethoxy oxime. Among them, 9-phenyl acridine is preferred. (d) Ν-aryl-α-amino acid compound ’ is preferably a photosensitive resin group

It is preferably 3% by mass or less. In the photosensitive resin composition of the present invention, the compound contains 0.01 to 3% by mass of fluorenyl-α-yl-OC-face/μ Α® a 曰.

(N-propyl) phenylglycine and N-S, for example, N-phenylglycine, N-ethyl-N-phenylglycine, N_, N_(n-butyl)· Phenylglycine, Zheng (2_ 133895.doc -23· 200921275 oxiranylethyl)-N-phenylglycine, N_methyl_N_phenylalanine, N_ethyl-N-benzene Alanine, N-(n-propyl)phenylalanine, N-(n-butyl)-N-phenylalanine, N-nonylphenylproline, N-fluorenyl-N-phenyl Aleucine, N-methyl(p-tolyl)glycine, N_ethyl_N_(p-phenylene)glycine, N-(n-propyl)(p-tolyl)glycine, N -(n-butyl)-N-(p-tolyl)glycine, N-methyl_N_(p-chlorophenyl)glycine, N-ethyl-N-(p-phenyl)glycine , N_(n-propyl)_N_(p-chlorophenyl)glycine, N-(n-butyl)_N_(p-chlorophenyl)glycine, N-methyl_N_(p-bromophenyl)glycine Acid, N-ethyl-N-(p-bromophenyl)glycine, N_(n-propyl)_N-(p-bromo)glycine, N-(n-butyl)_N_(p-bromophenyl) Glycine, N, NI_diphenylglycine, N-(p-chlorophenyl)glycine, N-(p-bromophenyl) Kowloon amine, N- (o-chlorophenyl) glycine. Among them, N-phenylglycine is particularly preferred. In the photosensitive resin composition of the present invention, it is preferred that the photosensitive resin composition contains γ1 to 3f% of the compound. The _ _ compound has 3 in the range of 0 · 1 to 15 mass %. The content of the bismuth-based compound which is preferable from the viewpoint of photocurability is G.G1% by mass or more, and it is preferable that the content of the ii-based compound is 3 mass from the viewpoint of storage stability of the photoresist film. %the following. Examples of the dentate compound include: dimethyl pentoxide, isoamyl desert, brominated isobutylene, ethylene bromide, triphenylsulfonyl bromide, benzyl bromide, dibromomethane, di, sigma Carbon bromide, tris(2,3-dibromopropyl) phosphate, tris-hexane with amine, amyl iodide, isobutyl iodide (is〇butyl 133895.doc •24- 200921275 iodide) Trichloro-2,2-bis(p-phenylphenyl)ethane, chlorinated triazine compound', among which tribromotolylsulfone can be used particularly well. (0 Other components In order to improve the handleability of the photosensitive resin composition of the present invention, a leuco dye or a coloring matter may be added. As the leuco dye, tris(4-diaminoguanyl-2-methylphenyl) hydrazine may be mentioned. Alkane (alias: colorless crystal violet), tris(4-diaminoguanyl-2-methylphenyl)methane (alias: colorless malachite green), fluoran dye, in which case the contrast is good when using colorless crystal violet Preferably, when the photosensitive resin composition contains a leuco dye, the content thereof is preferably from 01 to 10% by mass. ::: From the viewpoint of contrast, it is preferred that the content of the leuco dye is 01. From the viewpoint of maintaining the storage stability, it is preferable that the content of the leuco dye is 〇 〇 by mass or less. In the photosensitive resin composition, a leuco dye is used in combination with the above preferred embodiment. 'E. From the viewpoint of adhesion and contrast, (e) a functional compound is a comparative example of A and 2 of the present invention: magenta, cyanine green, and gold amine salt; and fry::, Γ crystal violet 1 base Dial, Nero Blue 2B, Victoria Blue, Γ AiZen (registered trademark) crane C-cut N), blue tester 2, diamond green (protective soil A) (registered trademark) DIAm〇Nd coffee (version) gas &amp; compound contains coloring matter ). In the photosensitive resin group o.oow quality. /. . . ,. When the quality is 01, the added amount is better, 1 mass. The content of Αβ has an effect of improving the operability. The following contents have the effect of maintaining storage stability. 133895.doc -25· 200921275 Yanyang, about improving the thermal stability and storage stability of the photosensitive resin composition of the present invention, and adding a radical polymerization inhibitor, benzene to the photosensitive resin composition. And at least one or more compounds selected from the group consisting of triazoles and carboxybenzotriazoles. 'As such a radical polymerization inhibitor, for example, succinyloxybenzene, p-benzoic acid, o-benzotriene, cedaramine, t-butyl catechin, gas: cuprous, 2, 6 - di-t-butyl _ 曱 age, 2, 2, _ methylene bis(1) methyl 6 butyl benzene age), 2, 2: methylene bis (4_ethyl _6 • Tert-butylbenzene^), nitrosophenylhydroxylamine aluminum salt and diphenylnitrosamine. Further, 'as a benzotrisole, for example, i 2 3 benzene, monoazole, 1-gas-12,3-benzotrimethylene, bis (N-amine, 2 1 1 1 ϋ - , ^基基)Aminohydrazinyl _ , '3-本开二唾, bis(Ν·2_ethylhexyl)aminomethylene] oxazole and bis(indol-2-hydroxyethyl)amino A 1 book opened two. Wait and wait. In addition, as a few benzotris, for example, 2,3-benzotriazole, 5-carboxyl. carboxy - its u, recorded I2,3 · open three saliva, N-(N,N- II.2_Hexahexyl)Aminomethylidene-based sylvestris, succinylcarboxyl-opened oxadiazole, N-(N, squad 2, hydroxymethyl-polymethylidene carboxy benzophenone Trisodium and N_ soil-based ethyl carboxybenzotriazole, etc., an __ethylhexyl) amine radical polymerization inhibitor, cage ^ c &,, θ open diazole and carboxybenzotriazole The addition of human juice I is preferably 0.01~3 quality Jinci / s page 5 of the clock god; 'Better is 0.05 to 1 mass 〇 /. It is preferable that the amount is 0.01% by mass or more, and it is preferable that the amount is 3% by mass or less. From the viewpoint of i-sensitivity, the photosensitive resin composition of the present invention may also contain plasticizing 133895.doc •26-200921275 as needed. As such an additive, for example, polyalcohol, polyoxypropylene polyoxyethylene, polyoxyethylene monoterpene, polyoxypropylene:: methyl bond, polyoxyethylene oxypropylene monomethyl ether, polyoxyethylene B Diluted single sulphur, = propylene single-six scale, polyoxyethylene polyoxypropylene single-single singer and other diols screaming: phthalic acid, such as diethyl phthalate, phthalic acid, toluene : Γ 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒 棒The amount of the additive such as a plasticizer contained in the photosensitive resin composition is preferably from 5 to 50% by mass, more preferably from 5 to 3% by mass. From the viewpoint of suppressing the L time of the development time to the softness of the cured film, it is preferable that the mass % or more is further less than the mass% or less from the viewpoint of suppressing hardening or cold flow. The photosensitive resin laminate of the present invention comprising a photosensitive resin layer and a support for supporting the layer may also be required to form a protective layer on the side of the support with the photosensitive resin layer. As the support used herein, it is preferable to make the transparency of the light emitted from the exposure light source transparent. Examples of such a support include, for example, a polyethylene terephthalate film, a polyglycol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene gas film, and a vinylidene chloride. Polymerized ruthenium, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamine film, cellulose derivative film. § 荨 荨 film can also be used as needed. It is preferred that the haze is 5 or less. The thickness of the thin film of the image forming property and advantageous in terms of economy 'must maintain strength, so this is preferred to use I33895.doc -27 · 200921275 1 0~30 μηι persons. Further, the important property of the protective layer used in the photosensitive resin laminate is that the adhesion between the support and the photosensitive resin layer is smaller than that of the photosensitive resin layer, and the adhesion between the protective layer and the photosensitive resin layer is sufficiently small. For example, a polyethylene crucible or a polypropylene film can be preferably used as the protective fork 3, and a film having a peeling property as shown in Japanese Laid-Open Patent Publication No. SHO 59-202457 can be used. The film thickness of the protective layer is preferably W μιη, and the thickness of the photosensitive resin layer in the photosensitive resin laminate of the present invention varies depending on the use, and is preferably 5 to 100 μM, more preferably 7~6〇(4), and the more the resolution is increased, the thicker the film strength is. The method of producing the photosensitive resin laminate of the present invention by sequentially laminating the support, the photosensitive resin layer and, if necessary, the protective layer can be carried out by a conventional method. For example, a photosensitive resin composition used in a photosensitive resin layer is mixed with a solvent in which these solvents are dissolved to prepare a solution of the same sentence, and the solution is first applied to the solution using a bar coater or a roll coater. The support is dried and a photosensitive resin layer containing a photosensitive resin composition is laminated on the support. Then, a protective resin layered body can be produced by laminating a protective layer on a photosensitive resin layer as needed. Examples of the solvent include ketones represented by methyl ethyl ketone (oxime) and alcohols represented by methanol, ethanol and isopropyl alcohol. It is preferred to add the above solvent to the photosensitive resin so that the solution viscosity of the photosensitive resin composition coated on the support is 500 to 4000 mPa at 25 C. 133. doc • 28· 200921275 Composition in. &lt;Photoresist Pattern Forming Method&gt; The light-contacting method using the photosensitive resin laminate of the present invention can be formed by a step including a lamination step, an exposure step, and a development step. The following shows an example of a specific method. As a substrate (substrate to be processed), a (4) laminated board is used for the purpose of manufacturing a printed circuit board, and a glass substrate is used for the purpose of producing a textured base material, for example, a t-ray display is mentioned. The base material for the panel or the surface electroplating display substrate, and the rough sealing cover (4) form the through-hole stone wafer and the ceramic substrate. The substrate for a plasma display refers to a method in which an electrode is formed on a glass, and a dielectric layer is applied to coat a glass paste for a partition wall, and a glass paste portion for the partition wall is subjected to sandblasting to form an isolation. The substrate of the wall. These substrates are embossed after the blasting step. First, the lamination step is carried out using a laminator. When the photosensitive resin laminate has a protective layer, after the protective layer is peeled off, the layer containing the photosensitive resin composition of the photosensitive resin laminate is heated and packed on the surface of the substrate by a laminator to form a photosensitive layer. Resin layer. In this case, the photosensitive resin layer may be formed only on one side of the surface of the substrate or on both sides. In this case, the heating temperature is usually 40 to 16 (rc. Further, by performing the heating press twice or more, the adhesion and the chemical resistance can be improved. In this case, a roller having two stages of interlocking can also be used. The segment laminator is pressed, and it can be pressed by a few passes through the roller. Then the exposure step is performed using an exposure machine. If necessary, the support is stripped 133895.doc -29- 200921275, using active light Exposure through the mask. The amount of exposure is determined by the illumination of the light source and the exposure time. It can also be measured using a light meter. In addition, the direct riding exposure method can also be used for the exposure step. The direct drawing exposure is performed on the substrate without using a mask. The direct edge image is used for exposure. As the light source, for example, a semiconductor laser or an ultra-high pressure mercury lamp having a wavelength of 35 〇 to 41 〇 nm can be used. The drawing pattern is controlled by a computer, and the exposure amount is obtained by the illumination of the light source and the movement of the substrate. The speed is determined. Then, the developing step is carried out using a developing device. When the photosensitive resin layer has a support after the exposure, it is removed as needed, and then it is used for water solubility. The developing solution develops and removes the unexposed portion to obtain a resist image. An aqueous solution of Na2C〇4K2C03 is used as an aqueous test solution. The aqueous solution is selected according to the characteristics of the photosensitive resin layer, and usually 〇: mass% is used. 2G~(4) is called an aqueous solution. In the experimental water night, a surfactant, an antifoaming agent, and a small amount of an organic solvent for promoting development may be mixed. The photoresist pattern may be obtained by using the steps described, and may be further carried out depending on the situation. Heating step of 1曰00 300 C. By performing this heating step, the chemical resistance can be further improved. Heating furnaces that produce hot air, infrared rays or far infrared rays are used. <Photoresist pattern formation using direct drawing exposure method In a method of applying a photosensitive resin composition to a support and drying the photosensitive resin composition, the photosensitive resin composition is coated with a photosensitive resin composition. The layer is then laminated on the (four) optical resin layer to form a photosensitive resin laminate 133895.doc • 30· 200921275. After the protective layer of the photosensitive resin laminate obtained by the step is peeled off, 'The layer of the photosensitive resin layer is heated by a laminator to be sandblasted (Sakamotodam A (registered trademark)# F220P) A copper foil laminate with a copper thickness of 35 μηι to obtain a copper foil laminate with a photosensitive resin layer attached thereto. Using a direct drawing exposure apparatus (manufactured by Via Mechanics Co., Ltd., DI exposure machine DE-1AH) ) 'With the h line (405 nm), the scanning speed of the laser scanning direction of 1 〇mw/cm2 or more is 2 cm/sec or more. More preferably, the illuminance is 15 mw/cm2 or more, and the scanning speed of the laser scanning direction is 3 cm / sec or more, and more preferably, the illuminance of the copper foil laminated board to which the photosensitive resin layer is attached is obtained under the condition that the illuminance is 25 mW/cm 2 or more and the scanning speed in the scanning direction of the laser is 4 cm / sec or more. The resin layer was exposed. The exposure can be improved by exposing at a speed of 10 mW/cm2 or more and a scanning speed of 2 (10)/sec or more in the scanning direction of the laser. Then, after the support was peeled off, an alkali developing machine (manufactured by Fuji Electric Co., Ltd., a dry film developing machine) was used and a mass of 30 ° C was sprayed at twice the minimum development time. /. It is called an aqueous solution (spraying magic: 〇22 Μρ^, and the unexposed photosensitive resin layer is dissolved and removed, and is washed with water (spray pressure: G.2 MPa) at the same time as the minimum development time, and dried to form light. &lt;Production Method of Conductor, Method of Manufacturing Printed Circuit Board&gt; The method of manufacturing a printed circuit board according to the present invention is after the above-described resist pattern forming method using a copper backed laminate or a flexible substrate as a substrate The following steps are carried out via 133895.doc 31 200921275. First, a wire is formed on the copper surface of a substrate which is known to be exposed by etching or plating, etc. &amp; u “See strong alkaline solution to strip the photoresist pattern from the soil plate to obtain the desired aqueous solution for printing (hereinafter also referred to as “peeling solution”) and =•S /± « ώ ” ) is not particularly limited.

A wide liquid mouth with a temperature of 2 to 5 mass% and a temperature of 4 〇W. A small amount of a water-soluble solvent may also be added to the stripping solution. &lt;Manufacturing Method of V-Line Frame&gt; The lead frame of the present invention is manufactured by using the following steps using a metal plate such as a copper-copper alloy or an iron-based alloy as the substrate. Μ / , Method 1 First = The substrate exposed by development is subjected to (4) to form a wire. The photoresist pattern is peeled off in the same manner as in the above-described method of manufacturing a printed circuit board, thereby obtaining a desired lead frame. &lt;Manufacturing Method of Semiconductor Package&gt; The method of manufacturing a semiconductor package of the present invention is carried out by the following steps after a method of forming the above-described photoresist pattern using a wafer on which a circuit as an LSI is formed as a substrate. First, a wire is formed by performing a columnar electric ore of copper or solder on the opening exposed by development. Thereafter, the photoresist pattern is peeled off in the same manner as in the above-described method of manufacturing a printed circuit board, and a thin metal layer other than the columnar electric ore is removed by etching to obtain a desired conductor package. 133895.doc -32· 200921275 &lt;&lt;Production method of substrate having concave-convex pattern When the substrate is processed by using the photosensitive resin layer body of the present invention as a dry film by a sand-proof method, The Lifa layer factory is firmly sensitive to the tree and is exposed and developed. = The side of the well formed by the P-day $ formed by the spraying of the spray material on the photoresist pattern, the process of cutting the sand, the use of the experimental stripping solution will be left in: the stripping step removed from the substrate, For the spray material used in the step of adding b to the substrate, it is known to use, for example, Sio, Si〇2, A(4), CaC〇"Zr〇, broken glass, stainless steel, and the like. Microparticles. The second embodiment of the present invention will be described in detail by way of examples. [Examples] 1. Preparation of samples for evaluation The photosensitive resins of Examples i to 7 and Comparative Examples i to 4 were produced in the following manner. &lt;Production of Photosensitive Resin Laminate&gt; 'Preparation of Compounds shown in Table 1' The photosensitive resin composition of the composition ratio shown in Table 2 was sufficiently mixed, mixed, and bar coating was used. The machine was uniformly applied to a 16 μη thick polyethylene terephthalate film as a support body, and dried in a dryer of 95 ° C for 3 minutes to form a photosensitive resin layer. The thickness of the layer is 3〇μιη. A 22 μm thick polyethylene crucible of the sheath is attached to the surface of the unstacked polyethylene terephthalate film of the photosensitive resin layer, thereby obtaining a photosensitive resin laminate. 133895.doc •33· 200921275 The mass parts of P1, P-2, and P-3 in Table 2 are values containing methyl ethyl ketone. &lt;substrate surface&gt; Prepared by sandblasting at a spray pressure of 0.20 MPa (Japanese ground 砥In the case of the granules, the Sakurandam A (registered trademark) #F220P is used as a substrate for sensitivity, resolution, and capping evaluation. &lt;Lamination&gt; The polyethylene film of the photosensitive resin laminate is peeled off while using a heat roller. Laminator (manufactured by Asahi Kasei Co., Ltd., AL-70), laminated photosensitive resin laminate on a substrate preheated to 6 于 at a roll temperature of 1 〇 5 ° C, and set the gas pressure to 0.35 MPa. The lamination speed is set to 丨5 m/min. &lt;Exposure&gt; Using a direct drawing exposure apparatus (manufactured by Hitachi Via Mechanics Co., Ltd., exposure machine DE_1AH), and using the h line (4〇5(10)), with illumination 25 When m W/cm is exposed, it is used for St〇uffer 2 ^ stage stage exposure meter (ste Exposure exposure of 5-stage hardening in p tablet) &lt;Development&gt; After peeling off the polyethylene terephthalate film, an exponential developing machine (manufactured by Fuji Machine Co., Ltd., dry film developing machine) was used for a specific time. Spraying (10)^% by mass of Na2C〇3 aqueous solution (spray pressure: 〇22, and the unexposed portion of the photosensitive resin layer is dissolved and removed at twice the minimum development time, and is the same as the minimum development time. The time is washed with water (spray mb) and dried. At this time, the minimum time required for the photosensitive resin layer of the unexposed portion to completely dissolve 133895.doc -34 - 200921275 was taken as the minimum development time. 2. Evaluation method The exposure speed was evaluated in order to evaluate the yield at the time of exposure, and the film crack was evaluated in order to evaluate the yield. (1) Exposure speed using a direct drawing exposure device (manufactured by Hitachi Via Mechanics Co., Ltd., DI exposure machine DE-1AH), according to the condition of calling him), illumination 25, the 21-stage staged exposure towel The exposure speed is classified in the following manner by the time required for exposure of the 5-stage hardening, that is, the exposure amount defined in Note 1 of Table 2, to 3 〇 (10) in the laser scanning direction. 〇 (good): less than 7 seconds x (poor): 7 seconds or more (2) 臈 breaking rate double-sided lamination of the photosensitive resin laminate to 1&gt;6 mmt thick copper foil laminate with a diameter of 6 mm On the substrate of the opening, the exposure was carried out in the exposure defined by the mark of Table 2, and development was carried out at twice the development time of the minimum development time, and washed with water and dried. Then, the number of hole breaks was measured, and the nose breakage rate was calculated according to the following mathematical formula. Film rupture rate (%) = [number of holes broken (number) / total number of holes (number)] χ 1 〇〇 According to the film breakage rate (%), the grade was classified as follows. ◎(Excellent): Less than 1% 〇(good): 1% or more, less than 3% X (poor): 3% or more (3) Resolution 133895.doc •35- 200921275 Using exposed and unexposed parts The line pattern mask having a width of 1:1 is exposed to the substrate for sensitivity evaluation and resolution evaluation after lamination for 15 minutes by the exposure amount defined in Note 1 of Table 2. The development was carried out at a development time twice the minimum development time, and washed with water and dried. The width of the minimum mask line that normally forms the hardened photoresist line is taken as the resolution. Table 2 below shows the results of Examples 1 to 7 and Comparative Examples 1 to 5. [Table 1]

P-1 __^1____ Composition with methyl methacrylate/methacrylic acid/styrene (mass ratio 50/25/25) 'acid equivalent 344, weight average molecular weight 5 〇, 〇〇〇 copolymer 43% by mass (solid content) methyl ethyl ketone solution P-2 having a composition of methyl mercapto acrylate/mercapto acrylate/butyl acrylate (mass ratio 50/25/25) 'acid equivalent is 37 〇, the weight average molecular weight is 2 〇〇, and the copolymer of 〇〇〇 is 30 mass. /〇(solid content) mercaptoethyl ketone solution P-3

M-2 M-3 M-4 M-5 with methacrylic acid/styrene/phenyl methacrylate (mass ratio 3〇/2〇/5〇) test solid == B zhongzi zizi amount is 55 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 9-phenyl acridine 1-2 N-phenylglycine Dl diamond green D-2 colorless crystal violet D-3 tribromotolylhydrazine

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Sri% (umbrella ¥ 1) 133895.doc -38- 200921275 [Applicability on the Industry] The present invention can be used in the manufacture of a printed circuit board, ic wafer mounting a lead frame manufactured &amp; metal mask made as representative for Metal foil precision processing, in the manufacture of the package represented by (10) or the manufacture of a flexible substrate represented by the employee, the electrode or the electromagnetic wave mask is represented by the flat electrode, and the site is made by the sandblasting method, 1&quot; In the method of manufacturing a barrier wall and a substrate having a concave-convex pattern. 133895.doc -39-

Claims (1)

200921275 X. Application for Patent Park: 1. A photosensitive resin combination*, which contains: 2Q shoulder mass% (4) Bath-type southern molecule 'The above-mentioned test-soluble polymer contains several acids, and its acid equivalent is 1〇0 600, The average molecular weight in the weight is 5,000~500,000; 5~70 mass. /. (8) a ethylenically unsaturated addition polymerizable monomer; and (d) (i) 0% by mass of (4) a photopolymerization initiator, and the photosensitive resin composition contains at least one selected from the group consisting of compounds represented by the following formula (1) The compound, at least one compound selected from the group consisting of the following general formula (Π), and at least one compound selected from the group consisting of the following general formula (111) as the (b) The unsaturated addition polymerizable monomer contains 0.01 to 30% by mass of the compound represented by the following formula (IV) as the (C) photopolymerization initiator; [Chemical Formula 1] 0 0-(A- 〇)m1-(B-〇)m3-CC=CH2 φ H3C-C-CH3 (1) ό . T o r2 (Ri and R2 are each independently a hydrogen atom or a methyl group; Α & Β represents an alkylene group having a carbon number of 2 to 6, which may be the same or different, and in these different cases 'including-( The structure of the repeating unit of A-Ο)- and _(Β_0)_ may be randomly or block-structured; ηι 1, m2, m3 and m4 are integers of 0 or more, and ml+m2 and m3 + m4 are independent For an integer of 〇8, 133895.doc 200921275 ml+m2+m3+m4 is an integer from 2 to 8); [Chemical 2] 0 r3 O—(C-0)m5-(D-0)m7 C~C =CH2 Φ H3C-C-CH3 (II) φ 0—&lt;0·0}(10)-(0·Ο)πΛ«·&quot;0Η2 (R3 and R_4 are each independently a hydrogen atom or a methyl group; C and d represent The stretching group having a carbon number of 2 to 6 may be the same or different. In such a different case, the structure of the repeating unit containing -(CO)- and -(D-Ο)- may be randomly formed. 'Also can be block structure; m5, m6, m7 and m8 are 0 or more of the number 'm5+m6 and m7+m8 are each independently an integer of 〇~28, m5+m6+m7+m8 is an integer of 10~28 ); [Chemical 3] 〇R5 0—(E-0)m9—(FO)ml1-C—C=CH2 Φ H3C-C-CH3 (ill) 0-'{E-0)mi〇^(F-〇)m12-Cc=CH2 (R5 and IU are each independently a hydrogen atom or a methyl group; E and F represent a carbon number of 2 The composition of the repeating unit containing -(E-Ο)- and -(F-Ο)- may be irregularly 133895. In these different cases, the structure of the repeating unit containing -(E-Ο)- and -(F-Ο)- may be irregularly 133895. Doc 200921275 成 ' can also be block structure; m9, mi〇, and ml2 are integers above 〇, m9+ml0 and mii+ml2 are respectively independent 〇~5〇 integer, m9+ml0+mll+mi2 is 30~ (Integer of 50); wherein R7 is hydrogen, alkyl, aryl, pyridyl, alkoxy or substituted alkyl. 2. The photosensitive resin composition of claim 1, which further comprises (d) an N-arylamino acid compound of 〇〇1 to 3 parts by mass, and 0.01 to 30% by mass of the (e) halogen compound. A photosensitive resin laminate comprising: a support comprising a substrate film; and a layer comprising the photosensitive resin composition of claim 2 or 2 laminated on the support. 4. A method for forming a photoresist pattern, comprising the steps of: preparing a photosensitive resin laminate according to claim 3, and laminating a layer of the photosensitive resin composition on the substrate to form a photosensitive layer The resin layer is exposed and developed to the photosensitive resin layer. 5. The method of forming a photoresist pattern of claim 4, wherein the exposure method is direct drawing, and the illuminance is 1 〇 mW/cm 2 or more, and the scanning speed in the laser scanning direction is 2 cm / sec or more. A method for producing a substrate having a concave-convex pattern, comprising the steps of using a glass rib as a substrate, and forming a photoresist pattern on the substrate obtained by the method of claim 3 or 5 on the substrate obtained in I33895.doc 200921275 , using a sandblaster for processing, stripping the photoresist pattern. Forming a photoresist pattern on the substrate by using the method of metal claim 4 or 5, and etching the substrate of the sound 彳β &gt;&quot;&quot; Or a metal film insulation board as a substrate, using, for example, or plating 8, a method of manufacturing a printed circuit board, comprising: using a metal-clad insulating board as a substrate, using The method of VIII or 4 forms a photoresist pattern on the substrate, and the obtained substrate is etched or plated to strip the photoresist pattern. 9. 10. A method of manufacturing a lead frame comprising the steps of: using a metal plate as a substrate, and (4) forming a photoresist pattern on the substrate as in the method of claim 4 or 5 (4), _ Resistive pattern. A method of manufacturing a semiconductor package, comprising the steps of: forming a photoresist pattern on a shoulder substrate by using a method of forming a circuit as an LSI, using a method of forming a circuit as an LSI, and plating the obtained substrate. Resistive pattern. 133895.doc 200921275 seven, FIG designated representative: (a) :( no case designated representative graph) (ii) of the present symbol elements representative diagram of a brief description: eight, when the case if the formula, please reveal the best display characteristics invention Chemical formula: 0 Rt 〇-(AO)m1-(BO)m3-CC=〇H2 Φ H3C-C-CH3 (I) Φ O—(AOk-(BO^-C - C-CH? 133895.doc