TW200846825A - Photosensitive resin composition and layered product - Google Patents

Abstract

A photosensitive resin composition which has resistance to alkaline noble-metal cyanide plating baths, is excellent in resolution, adhesion, and resist strippability, and can be developed with an alkaline aqueous solution; and a layered photosensitive-resin product including the photosensitive resin composition. The photosensitive resin composition is characterized by comprising 20-90 mass% carboxylated binder (a), 5-75 mass% addition-polymerizable monomer (b) having at least one ethylenically unsaturated terminal group, and 0.01-30 mass% photopolymerization initiator (c). It is further characterized in that as the addition-polymerizable monomer (b) having at least one ethylenically unsaturated terminal group, a specific compound is contained in an amount of 1-50 mass% based on the whole photosensitive resin composition.

Description

[Technical Field] The present invention relates to a photosensitive resin composition which can be developed by using an aqueous solution, and a photosensitive resin composition and a photosensitive layer of a milk on a support. A resin laminate, a method of forming a photoresist pattern on a substrate using the photosensitive tree J-composite layer, and a use of the photoresist pattern. More specifically, the present invention relates to a lead frame for wafer mounting (hereinafter referred to as "lead frame") for manufacturing a printed circuit board, manufacturing a f-shirt, or a printed circuit board, and reintegrated circuit (integrated circuit). Manufacturing, all of them are metal box precision machining, BGA (Ball Grid Array) and Up (Chip Size Package), wafer size %f station, 牮a “ ▲ 4) semiconductor package manufacturing, TAB (Tape Automated B〇nding) and CO chat ip 0n Film, film flip chip package: where the semiconductor is mounted on a thin micro-board Manufacture of representative tape-and-reel substrate, manufacture of semiconductor bumps, manufacture of ITO (Indium Tines Indium Tin) electrodes, address electrodes or electromagnetic wave masks in the field of flat panel displays, etc. [Prior Art] The epoch circuit board is manufactured by photolithography. The photolithography method refers to a method in which a photosensitive resin composition is applied onto a substrate to perform patterning. Exposing to cause polymerization of the exposed portion of the photosensitive resin composition to remove the unexposed portion by the developer to form a photoresist pattern on the substrate, performing button etching or electric clock processing to form a conductor pattern, and then peeling off the substrate The photoresist pattern f' is used to form a conductor pattern on the substrate. 128769.doc 200846825 ^ The towel is coated on the substrate in the (four) silk tree frequency compound: ' Know any of the following methods: Photosensitive tree wax a method in which a composition solution is applied to a substrate (4), or a support layer, a layer composed of a photosensitive resin composition (hereinafter referred to as a "photosensitive resin layer"), and a layered protective layer as needed The method of laminating a layer of a photosensitive resin laminate (hereinafter referred to as "dry film photoresist") on a substrate ip uses the latter dry film photoresist in the manufacture of a printed circuit board.

Hereinafter, a method of manufacturing a printed circuit board using the above dry film photoresist will be briefly described. First, in the case where the dry film photoresist has a protective layer such as a polyethylene film, the protective layer is peeled off from the photosensitive resin layer. Then, a photosensitive resin layer and a support are laminated on the substrate such as a copper back laminate in the order of the substrate, the photosensitive resin layer, and the support by using a laminator. Then, the photosensitive resin layer is exposed by ultraviolet rays such as i-line (365 nm) emitted from a super-high mercury lamp in a mask having a wiring pattern, whereby the exposed portion is subjected to polymerization hardening. Then, the support composed of polyethylene terephthalate or the like is peeled off. Then, the unexposed portion of the photosensitive resin layer is dissolved or dispersed by a developing solution such as a weakly alkaline aqueous solution to form a photoresist pattern on the substrate. Then, the formed photoresist pattern is used as a protective mask, and a known etching treatment or pattern plating treatment is performed. Acidic copper plating baths are commonly used in pattern plating processes. Finally, the resist pattern is peeled off from the substrate to produce a substrate having a conductor pattern, i.e., a printed circuit board. In recent years, electroplating techniques have been frequently used in electronic parts. The reason is that the non-conductive material such as printed circuit board and enamel plate can be given the following new characteristics: it can have the function of bonding, welding and bonding, and can have the contact resistance value of 敎Wait. For electric (four) materials, various (4) materials are being developed. For example, there are gold, silver, copper, buttons, alloys of these metals, etc., and reading 4, especially in electronic parts. The change in contact resistance caused by the change is low, and the σ ί 生 之 之 之 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金There are nitrogen baths (test baths, cold baths) and non-cyanide baths in Jindian money and silver mines, respectively. The plating bath is selected according to the required characteristics of the film. In particular, in the case of wire bonding applications, a soft film is required, and a neutral to alkaline cyanide precious metal plating bath is selected. Alternatively, the dry film photoresist is subjected to a patterning and plating step, including a stripping step. An alkaline aqueous solution is often used in the stripping step. The reason for this is that the retardant mixture containing the photoresist is transferred to an aqueous solution. In the case of using a neutral to test bath, in the case of patterning using a photoresist, it is easy to produce a phenomenon in which a photoresist containing a silk-containing binder which is originally dissolved due to the testability is caused by a base. When dissolved, the plating solution penetrates from the gap between the substrate and the photoresist material during plating, or the photoresist material is peeled off and normal patterning cannot be performed. On the other hand, in order to improve the resistance to electric ore, the solubility is excessively lowered, so that the problem of peeling off the photoresist from the substrate is liable to occur in the peeling step. For the above reasons, the company hopes to develop a medium-to-neutral-basic 128769.doc 200846825 cyanide precious metal plating bath and electroplating bath, which is excellent in contamination, excellent in resolution and adhesion, and excellent in removability of photoresist. A photosensitive resin composition.

Further, in the case of the electric resistance of the photoresist material, Patent Document 1 contains a terpolymer of methacrylic acid/ethyl methacrylate/styrene, a bismuth A-based (fluorenyl) acrylate compound, a methacrylate compound having a urethane bond, 2,2,-bis(2,3-dichlorophenyl)-4,4,5,5,-tetraphenyl-1,2'- The resolution, adhesion, sensitivity, plating bath contamination, developability, and mechanical strength of the photosensitive resin composition of diimidazole have been described, but there is no mention of a neutral-alkaline cyanide precious metal plating bath. The tolerance 'has no explanation for the peelability. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. 21-2221 No. 6 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] This is! The purpose of the present invention is to provide a photosensitive resin composition which is excellent in resolution, adhesion, and photoresist releasability in a neutral metal-reactive cyanide bath. Photosensitive Resin Laminate A method of forming a photoresist pattern on a substrate using the photosensitive resin laminate, and use of the photoresist pattern. [Means for Solving the Problem] The above object can be attained by the following constitution of the present invention. The photo-resin composition is characterized in that it contains (4) a carboxyl group-containing binder 20 to 9 〇 mass% ^. And (b) an addition polymerizable agent containing at least one terminal ethylenically unsaturated group: _. % of quality;:! (%) The photopolymerization-initiated photosensitive resin composition contains at least one selected from the group consisting of compounds represented by the following general formula (1) and the general formula (Π), and contains 1 to 50 128769.doc 200846825 mass%. The compound is (b) an addition polymerizable monomer containing at least one terminal ethylenically unsaturated group. [Chemical 1] CH2—0—C—c—ch2 π 丨0扒N C-0-—(A-0)nr(B-0)nr~CH—CH2—〇—C—C—cu / II ! Γ R1\ OR3 (I) NC—〇—(A-0)n3-(B-0)n4-CH—CH^—O—C—C—ru I II I! I ~

H〇l{心0^2—〇—* II u 2 0 R5 (where ' R1 is a linear, branched or cyclic alkyl group having a carbon number of 4 to 12, or an alkyl group having a carbon number of 6 to 12 The bases, R2 to R5 are each independently hydrogen or methyl, a is C2H4, B is CH2CH(CH3), and each is independently an integer of 〇15, and (1) + ιΐ2+η3+η4 is 2 or more. -(A-Ο) The arrangement of the repeating units of - and - (B-Ο)- may be a random arrangement or a block arrangement. In the case of block arrangement, _(八-〇)_ and _(B_〇)_ Any order can be on the urethane bond side.) [Chemical 2] CHo OH II I -CN- -Re- HO 1 II -NC-0-{A〇)nHB-0)n9- °ΤΓΗ2 (A*0)nr(B*°)n6 ~CH~CH2~〇—q—q— II I~CH2 0 R9 R7H〇—ch~ch2—0—c—c_ 〇H HO II I ~

(ID CHg—Q—

« R to (wherein R6 and R7 are each independently a linear, branched or cyclic group having a carbon number of 4 to 12, 128769.doc -9-200846825, or a aryl group having a carbon number of 6 to 12, R8 ~R11 is independently hydrogen or sulfhydryl, A is C2H4, B is CH2CH(CH3), 115 and 1!6 are integers from 0 to 15, and 115+116 is 1 or more. n7~n1() are independently 〇~ An integer of 15, n7 + η8 + η9 + ηι〇 is 2 or more. • The arrangement of the repeating units of (A-Ο)- and -(B-Ο)- may be a random arrangement or a block arrangement. In the case of block arrangement, either -(冬〇)_ and _(Β_〇)_ may be in the urethane bond side.) 2 ·The photosensitive resin combination of the first item Further, the compound further contains a compound represented by the following formula (III) as the above-mentioned (b) an addition polymerizable monomer containing at least one terminal ethylenically unsaturated group. [化3] Η 0

I II /NC-O~(A-0)n-|1>(B-0)n12—〇—C—pu R12 (HI) I! | CH: 〇R13 “Fly—O—(A*0) Ni3-(B"0)ni4—C—C—ch2 H 〇ϋ ^

(wherein, the linear, branched or cyclic alkyl group having a carbon number of 4 to 12, or the alkylaryl group having a carbon number of 6 to 12, R%R, independently hydrogen or methyl, and A is C2H4, B is CH2CH(CH3), ηη~ηι>ι 八..., "化4 is independently an integer of 〇~15, and 1111 + 1112+1113+1114 is 2 or more. 'Can be arranged randomly, -(A -Ο)- and -(B-0)-°) The arrangement of the repeating units of -(A-Ο)- and -(B-Ο)- as in item 1 or item 2 may be a block arrangement. In the case of the block arrangement, either of the urethane bond sides may be a photosensitive resin laminate comprising the photosensitive resin composition of 128769.doc -10- 200846825 The photosensitive resin layer and the support. A method of forming a photoresist pattern, comprising the step of forming a photosensitive resin layer on a substrate by using the photosensitive resin laminate according to item 3, an exposure step, and a developing step. 5. The method of forming a photoresist pattern according to item 4, wherein in the above exposure step, direct lithography is performed to perform exposure. A method of manufacturing a printed circuit board, comprising the steps of forming a substrate having a photoresist pattern by a method such as the method of the fourth or fifth aspect. A method of producing a substrate having a concave-convex pattern, comprising: a step of processing a substrate having a photoresist pattern formed by the method of the fourth or fifth aspect by a sand blasting method. 8. Manufacturing of a semiconductor package 顼...s + comprising forming a photoresist by a method as in item 4 or item 5. The step of the substrate of the wood into the lamp plating step 9. The method for manufacturing the bump, which comprises the step of forming the substrate of the A plate θ 帛 4 or the fifth item of the photoresist pattern by the method of the method. 10·- Manufacture method of lead frame The method of item 5 forms a step of engraving the substrate which has been patterned by the fourth or the first, and has a pattern of the first resistance. The method for manufacturing the test brush circuit board is formed by the method of item 4 or 5: 4, including the step of plating, the substrate of the electroplating step, the electric 12-T using a ratified precious metal plating bath . A manufacturing method of a bulk package is carried out by a substrate having a photoresist pattern formed by the method of the fourth aspect or the eighth aspect of the method comprising: 128769.doc 200846825 electroplating step using cyanide in the electroplating step Precious metal plating bath. A method for manufacturing a bump comprising: a step of performing a circuit on a substrate formed with a photoresist pattern by the method of the fourth or fifth aspect, and using a cyanide precious metal electric money bath in the electric ore step . [Effects of the Invention]

The present invention provides a photosensitive resin composition which is resistant to a neutral to alkaline cyanide noble metal plating bath and which is excellent in resolution, adhesion, and photo-dissociation and can be developed by using an aqueous alkaline solution. The photosensitive resin laminate of the photosensitive resin composition, a method of forming a photoresist pattern on a substrate using the photosensitive resin laminate, and the use of the photoresist pattern; the present invention is applicable to the manufacture of a printed circuit board, a wire Manufacture of frames, manufacture of semiconductor packages, and manufacture of flat panel displays. [Embodiment] Hereinafter, the present invention will be specifically described. (a) a ruthenium-based binder in the photosensitive resin composition of the present invention, as the (a) carboxyl group-containing binder, a monomer containing an α,β-unsaturated carboxyl group can be preferably used as a copolymerization component. The acid equivalent is 100 to 6 Torr, and the weight average molecular weight is 5,000 to 5 Å. In order to make the photosensitive resin composition developable and releasable to the developing solution and the peeling liquid composed of the alkaline aqueous solution, the carboxyl group of the carboxyl group-containing binder is required. The acid equivalent is preferably from 100 to 600, more preferably from 250 to 450. From the viewpoint of ensuring compatibility with other components in the solvent or composition, especially the addition polymerizable monomer described below, the acid equivalent is preferably 丨00 or more, 128769.doc • 12 - 200846825 From the viewpoint of developability and peelability, the acid equivalent is preferably 600 or less. Here, the acid equivalent means the mass (gram) of the thermoplastic copolymer containing one equivalent of a carboxyl group. Further, the measurement of the acid equivalent was carried out by a potentiometric titration method using a 0.1 mol/L NaOH aqueous solution using a Biogas Reporting Titrator (COM-555). The weight average molecular weight of the carboxyl group-containing binder of the present invention is preferably from 5,000 to 500,000. From the viewpoint of maintaining the thickness of the dry film resist uniformly and obtaining resistance to the developer, it is preferably 5,000 or more, and from the viewpoint of maintaining developability, it is preferably 500,000 or less. More preferably, the weight average molecular weight is from 20,000 to 100,000. The weight average molecular weight at this time means a weight average molecular weight measured by a gel permeation chromatography (GPC) using a standard curve of standard polystyrene (Shodex STANDARD SM-105 manufactured by Showa Denko Co., Ltd.). The weight average molecular weight can be measured by a gel permeation chromatograph manufactured by a spectrophotometer (strand) under the following conditions. Differential Refractometer: RI-1530 Pump: PU-1580 Deaerator: DG-980-50 Column oven: CO-1560

Column: KF-8025, KF-806Mx2, KF-807 Solvent: THF The carboxyl group-containing binder is preferably at least one of the following first monomers and the second monomer described below At least one or more copolymers. A monomer having an α,β-unsaturated carboxyl group in the first single system molecule. For example, 128769.doc -13- 200846825 exemplify: (mercapto)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, yacon self-supplemented maleic anhydride, and cis-butane dicarboxylic acid half ester. Of these, (meth)acrylic acid is particularly preferred. The second monomer is non-acidic and is a monomer having at least one polymerizable unsaturated group in the molecule. For example, decyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (A) Isobutyl acrylate, second butyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropionate (meth) acrylate, cyclohexyl (meth) acrylate, (methyl) Ethyl alcohol esters such as 2-ethylhexyl acrylate, benzyl (meth) acrylate, vinyl acetate, (meth) acrylonitrile, styrene, and styrene derivatives capable of generating polymerization. Among them, particularly preferred are decyl (meth)acrylate, n-butyl (meth)acrylate, styrene, and benzyl (meth)acrylate. The (a) Wei-containing binder used in the present specification can be synthesized by diluting a mixture of the above monomers into a solvent such as acetone, methyl ethyl ketone or isopropanol. A radical polymerization initiator such as benzamidine peroxide or azoisobutyronitrile is added in an appropriate amount, followed by heating and stirring. Sometimes, a part of the mixture is added dropwise to the reaction liquid for synthesis. As for the synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization can also be employed. The ratio of the (a) carboxyl group-containing binder to the photopolymerizable resin composition as used in the present invention is 20% by mass or more and 9% by mass or less, more preferably 30% by mass or more and 70% by mass or less. Particularly preferably, it is 4 〇 or more and 60% by mass or less. In view of the improvement of the strength of the cover film and the suppression of the edge melting, the age of the cup is preferably 2% by mass or more and S is preferably 9% by mass or less. The addition polymerizable monomer having at least one terminal ethylenically unsaturated group in the viewpoint of improving developability (b) 3 (8) used in the invention contains at least one terminal ethylenic unsaturated = addition polymerization single The body (hereinafter, simply referred to as an addition polymerizable single-)' contains at least one compound selected from the group consisting of compounds represented by the following general formula (1) and the general formula (π) as an essential component. [Chemical 4]

CH2—0-C—〇~ch vi? | b 2 ^C-〇—(A^Q)nr^〇)n2—CH-CH2-〇-C-C-nu «X ϋ Γ 2 Ο)

IJ4 - 异 -〇 -(Α·0)π 3·(Β-0)Π4-〇Η—C Η厂 Ο— Η Ο CH2—〇一c—c—ru I! I' 2 Ο R5

(wherein R1 is a linear, branched or cyclic alkyl group having a carbon number of 4 to 12, or an alkylaryl group having a carbon number of 6 to 12, and R2 to R5 are each independently hydrogen or a fluorenyl group, and octa is C2H4, Β is CH2CH(CH3), η 〗 〖η4 are each an integer of 〇~15, and ηι + 112 + ΓΙ3 + is 2 or more. - Arrangement of repeating units of -(A-Ο)- and -(B-0)- It may be a random arrangement or a block arrangement. In the case of block arrangement, the order of _(eight-〇)_ and -(B_0)_ may be on the urethane bond side. .) 128769.doc -15- 200846825 [Α5]Π5*(Β·〇)^6

OH

Hfi C'N-Re-NCO-(Α-0)ητ-(Β-0)η&-·CH-CH2-〇-ϋ CHo 乂CM-R7-N.C_0-(AO)n0-{BO) Nt〇—CH'CH2-〇—c—C一广1_»ϋπ UIH i,7CHi CH2-〇—c__q—ru 丨丨“CH2 0 R11

(ID

(wherein R6 and R7 are each independently a linear, branched or cyclic alkyl group having 4 to 12 carbon atoms, or an alkylaryl group having 6 to 12 carbon atoms, and R8 to Rii are each independently hydrogen or methyl. A is C2H4, B is CH2CH(CH3), n5 and ~ are each independently an integer of 0 to 15, and t^+n6 is 1 or more. The illusion~niQ is independently an integer of 〇15, η7+η8+η9+ηι 〇 is 2 or more. The arrangement of repeating units of -(AO)- and -(BO)- may be a random arrangement or a block arrangement. In the case of block arrangement, -(八_〇)_ and Any of _(heart 〇)_ may be on the urethane bond side.) At least one selected from the group consisting of the compounds represented by the above formula (I) and formula (π) The proportion of the compound in the photosensitive resin composition of the present invention is preferably from 丨 to "% by mass, more preferably from 3 to 30% by mass, based on the entire photosensitive resin composition. Further preferably 2% by mass is considered to be a good electric difficulty, and the amount is preferably: from the viewpoint of having good peelability in the above-mentioned quality/〇, and the amount is preferably 50% by mass. the following. The compound represented by the above formula (1) is exemplified by (iv) an oleic acid vinegar and a compound having a thiol group and two (meth) propylene groups in one molecule (glycerol II 128769.doc -16-200846825 methacrylate) Polyethylene oxide chain adduct, polypropylene oxide chain adduct of glycerol dimethyl acrylate, polyepoxybutene-polypropylene propylene burning chain of glycerol dimethyl acrylate An adduct of a metal phthalic acid formed by an adduct or the like. Examples of the polyisocyanate to be used include anthraquinone diisocyanate, diphenylmethane-4,4'-diisocyanate, and hexa Methyl diisocyanate, isophorone diisocyanate, o-diphenylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, α,α,_didecyl-o-dimethyl phthalocyanine , α,α'-dimethyl-m-xylene diisocyanate, α'α1·dimethyl-p-diphenylene diisocyanate, α,α,α'-trimethyl-o-xylene diisocyanate, α, α,α'_tridecyl-m-xylene diisocyanate, α,α,α-monomethyl-p-nonylphenyl diisocyanate, α,α,α, α,_Tetramethyl-o-diphenylene diisocyanate, α,α,α,,α,_tetradecyl-m-diphenylene diisocyanate, α,α,α,,α'-four Methyl-p-xylene diisocyanate, cyclohexane di-cyanate, etc. It is also possible to carry out the gas ring of the diisocyanate compound, and a compound such as m-xylene diisocyanate. A hydride of vinegar (Takenate 60〇 manufactured by Mitsui Takeda Chemical Co., Ltd.), etc. As a specific example of the compound represented by the above formula (1), hexamethylene diisocyanate has an average of 5 moth earrings. The reactant of oxypropylene glycerol dimercaptopropene (IV) (in the above formula (1), r1 is hexamethylene R to R is a fluorenyl group, and ηι = η3 =. , ~^ Qiaozhi compound, manufactured by Toho Chemical Industry Co., Ltd., UA-47), 丄re Tianzhuang, a seedling & said that the arsenic-iso-cyanide I 酉曰 and the addition have an average of 4 moles of epoxy Reaction of glycerol dimethyl acrylate 6 (in the above formula (1), R1 is hexamethylene, r2 to r5 are methyl, (tetra) (tetra), n2-n4 = ruthenium, Toho Chemical Industry (8) Manufacturing, - (4)). 128769.doc -17- 200846825 As the compound represented by the above formula (Π), a polyisoxic acid and a compound having a hydroxyl group and two (meth)acryl groups in one molecule (glycerol II) may be mentioned. Polyethylene oxide chain adduct of methacrylate, polypropylene oxide chain adduct of glycerol dimethyl endoate, polyepoxy-polypropylene oxide of glycerol dimethacrylate A urethane compound formed by a chain adduct or the like and a (poly)alkylene glycol. As the polyisocyanate, the above may be used. Specific examples of the compound represented by the above formula (II) include hexamethylene diisocyanate and glycerol dimethacrylate having an average of 4 mol of ethylene oxide added thereto, and an average of addition of 6 a reaction of a molar ethylene oxide and a polyalkylene glycol having an average of 13 moles of propylene oxide (i.e., in the above formula (Η), R6 and R7 are hexamethylene, r8~r" are methyl, Η7=η9=4, n8=n1Q=〇, η5=6, η6=13 compound··Dongbang Chemical Industry Co., Ltd. ^ UA 42), /, methylene-isocyanate has its own purpose and addition An average of $ mega epoxicone glycerol dimethacrylate, and a reactant formed by addition of an alkylene diol having an average of 6 moles of ethylene oxide and an average of 13 moles of propylene oxide (ie, In the above formula („), R6&R7 is a hexamethylene group, r8~r1i is a methyl group, n8==ni〇=5, n5=6, n6=13 compound: manufactured by Toho Chemical Industry Co., Ltd. UA-48), etc. As for the (b) addition polymerizable monomer used in the present invention, in addition to the above-mentioned chemical substance, it is also known to use at least one terminal ethylenically unsaturated group in combination. Examples of the compound include tetraethylene glycol di(meth)acrylic acid vinegar, nonaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, and trishydroxycarbonyl group 128769. .doc -18- 200846825 Propane tri (meth) acrylate, polyoxyethyl trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxylated tetra (indenyl) Acrylate, 4-mercaptophenylheptaethylene glycol dipropylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxy hexaethylene glycol acrylate, phthalic anhydride and acrylic acid 2 a reaction product of a hydroxypropyl ester half ester compound and propylene oxide (manufactured by Nippon Shokubai Chemical Co., Ltd., trade name 〇E- 'A 200), 'n-octylphenoxypentapropylene glycol acrylate, 2,2- Double [{4_(fluorenyl) propylene oxime polyethoxy] phenyl] propane, 2, 2 bis {(4 propylene oxypolyethoxy) cyclohexyl} propane or 2, 2- bis {(4-Methyl propylene oxypolyethoxy)cyclohexyl}propane, 1,6-hexanediol (meth) acrylate, 〗 〖, 4_cyclohexanediol di(meth) propylene Examples of the ester include polypropylene glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate, polyoxyethylene ethyl polyoxypropyl propylene di(meth) acrylate, and the like. Polyoxyalkylene glycol di(meth)acrylate, 2-bis(p-hydroxyphenyl)propane di(meth)acrylate, tris(meth)acrylate, 2,2_double (4_ a polyfunctional (meth)acrylic acid vinegar of methacryloxy-pentaoxypentaethoxy-phenyl)propane and a heterodimeric cyanate compound. Further, the resolution, adhesion, and the like are further improved. From the viewpoint of the resistance of the noble metal plating in the neutral to alkaline cyanide* bath, the compound represented by the following formula '(ΠΙ)) is a preferred embodiment of the present invention. 128769.doc -19- 200846825 [Chem. 6]

N*C-0'~(A-0)nlr(B-0)n-i2〇—c—CH 13 2 (ΠΙ )

N~C—0~(Α-Ο)η^3-(Β-0)Πΐ4—C

—?=CH a O R1

(here, R12 is a linear, branched or cyclic alkyl group having a carbon number of 4 to 12, or an alkylaryl group having a carbon number of 6 to 12, and R13 and R14 are each independently hydrogen or methyl, and A is QH4. 'B is CH2CH(CH3)' nil~nH are each independently an integer of 〇~15' ηιι + η〗 2+ηΐ3+η4 is 2 or more. -(A-Ο)-and-(B-0)- The arrangement of the repeating units may be a random arrangement or a block arrangement. In the case of block arrangement, the order of _(eight_〇)_ and _(Β·〇)_ may be The amino phthalate bond side.) Specific examples of the compound represented by the above formula (III) include a diisocyanate compound (for example, hexamethylene diisocyanate, toluene diisocyanate, or 2, 2, 4-trimethylhexamethylene diisocyanate) and a compound having a hydroxyl group and a (meth)acryl group in one molecule (for example, 2-hydroxypropyl acrylate, monodecyl acrylate having a propylene glycol chain, having polyethyl b A urethane compound formed by a monomethacrylate of a glycol chain, a monomethacrylate having an ethylene oxide chain or a propylene oxide chain, or the like. The content of the photosensitive resin composition as a whole is preferably from 3 to 7 % by mass based on the compound represented by the above formula (1), and a is preferably from 3% by mass in terms of resolution. The above is preferably 70% by mass or less from the viewpoint of the flexibility of the resist pattern. 128769.doc -20. 200846825 (b) Contained in the photosensitive resin composition of the present invention The amount of the addition polymerizable precursor is in the range of 5 to 75% by mass, and more preferably in the range of WO% by mass: from the viewpoint of suppressing the hardening failure and the development time delay, the amount is 5 Berry% or more, and The amount is 75 mass% or less from the viewpoint of suppressing the peeling retardation of the cold flow (c) and the curing photoresist. (c) Photopolymerization initiator In the photosensitive resin composition of the present invention, as (4) light The amount of the (C) photopolymerization initiator contained in the photosensitive resin composition of the present invention is in the range of 〇. 〇1 to 3 〇% by mass, and a better range. It is 0.05 to 10% by mass. In terms of obtaining sufficient sensitivity, it is better to ask for quality. From the viewpoint of sufficiently transmitting light to the bottom surface of the photoresist and obtaining good high resolution, it is preferably 3% by mass or less. As for the photopolymerization initiator, there are mentioned: Base, octaethylguanidine, 1,2-benzopyrene, 2,3-benzopyrene, 2-phenylindole, 2, hongdiphenyl enan, 1-chloroindole, 2 -Chloropurine, 2-methylhydrazine, anthracene, 4_naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-i,4-naphthoquinone, 9,1 quinone phenanthrenequinone, 2-mercaptopurine Anthraquinones such as naphthoquinone, 2,3·diindenylhydrazine, 3-chloro-2-indolylhydrazine, etc.; diphenyl fluorenone, Michler's ketone, 4,4f-bis(didecyl) Aromatic ketones such as amino)diphenyl fluorenone], 4,4 bis(diethylamino)benzophenone; benzoin, benzoin ethyl ether, benzoin phenyl ether, benzoin ether, benzoin ethyl ether, etc. Benzoin ethers; dialkyl ketals such as benzyl dimethyl ketal and benzyl diethyl ketal; thioxanthone such as diethyl thioxanthone and chlorothioxanthone, dinonylamine Dialkylamino benzoate such as ethyl benzoate; 128769.doc • 21- 200846825 Class; 1- Base-1,2-propanedione o-benzidine, l-phenyl n-propenyl-2-(o-ethoxyl) will be the same as JIANG; class 2. chlorophenyl) c diphenyl Imidazole dimer, 2-(o-chlorophenyl)-4,5-bis("oxyphenyl": azole dimer, 2-(p-methoxyphenyl m, 5: diphenyl taste 4 dimerization Lophine dimer, acridine, 9-phenyl acridine, 9-(p-methylphenyl) acridine, 9... (p-ethylphenyl) acridine, 9-(isopropyl Phenyl phenyl acridine, 9-(p-n-butylphenyl) acridine, 9-(p-tert-butylphenyl) acridine, & methoxy-p-methoxyphenyl) acridine, 9-(pair Ethoxyphenyl)acridine, (p-ethylphenyl) acridine, 9-(p-trimethylaminophenyl) oxime, 9-(p-cyanophenylphenyl) acridine , 9-(p-chlorophenyl)acridine, 9-(p-bromophenyl)acridine, 9-m-methylphenyl)acridine, 9-(iso-propylphenyl)acridine, (different) Propyl phenyl) acridine, 9-(meth-butylphenyl) acridine, 9-(m-butylphenyl) acridine, m-methoxyphenyl) acridine, 9-(oxyethoxy) Phenyl) acridine, 9-(m-ethylphenyl) acridine, 9-(m-dimethyl Aminophenyl) acridine, 9-(m-ethylaminophenyl) acridine, 9-(cyanophenyl)acridine, 9-(m-chlorophenyl)acridine, 9-(m-bromophenyl) Acridine, 9-methyl acridine, 9-ethyl acridine, n-propyl % bite, 9-isopropyl acridine, 9-cyanoethyl acridine, 9-hydroxyethyl acridine, 9-chloroethyl acridine, 9-methoxyacridine, 9-ethoxy acridine, 9-n-propoxy acridine, 9-isopropoxy acridine, 9-chloroethoxy acridine , small phenylglycine' Ν-methyl Ν-phenylglycine, Ν-ethyl phenylglycine, pentyl bromide, isoamyl bromide, brominated isobutylene, dibromoethylene, two Benzyl bromide, benzyl > odor, one, / smoldering, three desert methyl phenyl stone, carbon tetrabromide, tris(2,3-dibromopropyl) phosphate, trichloroacetamide, Iodopentane, isobutane, 1,1,1·trichloro-2,2·bis(p-chlorophenyl)ethane, phenyl_3·(4-tert-butyl·128769.doc •22 - 200846825 Pyrazoline compound such as styryl)-5-(4-t-butyl-phenyl)pyrazoline. Especially from the viewpoint of high resolution, it is preferred to use 2_(o-chlorophenyl)-4,5-mono-based miso-polymer with Michelin g [^,^|_double (two Mercaptoamino)diphenyl fluorenone or 4,4 bis(diethylamino)benzophenone is combined. In the photosensitive resin composition of the present invention, a coloring matter such as a dye or a pigment may be used in addition to the above components. As such a coloring material, for example, indigo green, crystal violet, methyl orange, nile blue 2B, Victoria blue, malachite green, basic blue 2, and diamond green Wait. Further, a color developer may be added to the photosensitive resin composition of the present invention to provide a visible image by exposure. As such a color developing agent, a combination of a leuco dye or a fluorane dye and a halogen compound can be mentioned. As far away halogen compounds, bromopentane, bromoisopentane, brominated isobutylene, ethylene bromide, diphenylmethyl bromide, benzyl bromide, dibromomethane, tribromomethylphenylsulfone, tetrabromo Carbon, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, iodopentane, iodine isobutane, trichloro-2,2_bis(p-phenyl)ethane, six Ethyl chloride, chlorinated triazine compounds, and the like. The amount of the coloring matter and the color developing agent is preferably 0.01 to 1% by mass in the photosensitive resin composition. From the viewpoint of recognizing sufficient coloring property (color rendering property), it is preferably 〇〇1% by mass or more, and it is preferable from the viewpoint of maintaining the contrast between the exposed portion and the unexposed portion and maintaining storage stability. It is 1 〇 mass% or less. Further, in order to improve the thermal stability of the photosensitive resin composition of the present invention, 128769.doc -23-200846825, storage stability, it is preferred that the photosensitive resin composition contains a free radical polymerization inhibitor and benzene. And at least one or more compounds selected from the group consisting of triazoles and carboxybenzotriazoles. As for such a radical polymerization inhibitor, for example, p-methoxyl 35, p-benzoic acid, o-benzotriene, naphthylamine, and t-butyl phthalate are desired: cuprous chloride, 2, 6-di(t-butyl)-p-A Chu-butyl f-methylene bis(4-methyl-.6-dibutyl butyl), 2,2,-methylenebis(4-ethyl -"Sancha), subvorcyl phenyl amide amine salt, and diphenyl nitrosamine. Further, as for the benzotris, for example, 1,2,3-benzotrienyl, 2,3-benzotris, bis(tetra)ethyl-benzotriazole, and bis (N_2_B) It? I, * Earth-based T-based-1, 2, 3-cardiac 2-ethylhexyl) aminomethylene triterpenoid, and bis(N-2-carbylethyl), methylopen, and the like. ·Meso soil_1,2,3-benzotrisole and 'for carboxybenzotriazoles, benzotris-m,2,3-benzene exemplified: contigs-1,2,3· A benzylidene benzotrisole, and a ν, ν (_' Ν di-diethyl) amine ethyl carboxy benzotriazole, and the like. , monoethylhexyl) amine radical polymerization inhibitor, benzotriene addition amount, better, and several groups of benzotrisole "" on the photosensitive tree wax group, the amount is better It is the viewpoint of 〇〇1 旦%%, storage stability: the amount is preferably 3; the amount: =, the sensitivity is maintained in order to improve the color tone stability of the photosensitive sensation composition of the present invention. Also, 128769.doc -24- 200846825 A phosphite hydrate compound can be contained in the photosensitive resin composition. As for the phosphite citrate compound, for example, 2, 4, 8 is calculated as a fourth (t-butyl group), 6 cases are 3_methyl_4_hydroxy_5_second, and its butyl group is a butyl group. Diphenyl[d,f][l,3,2]: apo-phosphonium, 2 2-methylene 雔μ 6 / ώ 暴 (4,6_2 (t-butyl) Phenyl)octyl ylide, bis (2 4 _ r 筮 = η - #, μ t , mono- butyl) benzyl) pentaerythritol - diazoic acid 8 曰, two (2, 4 _ Di(t-butyl)phenyl)phosphite vinegar, 4,4,-butylene bis(3-methyl-6-t-butylphenyl-bis(tridecyl)phosphite, different

Propylene-bis(phenol alkyl) phosphite vinegar or triisodecyl phosphite. The amount of addition of the phosphite compound is 0.01 to 5% by mass. The photosensitive resin composition of the present invention may further contain a plasticizer as needed. As such a plasticizer, for example, f ethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monothiol (10), polyoxyethylene polymerization can be mentioned. Two or four kinds of oxypropylene monomethyl scale, polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, etc.; Stupid bismuth citrate; o-toluene sulfonamide, p-toluene sulfonamide; tributyl citrate, triethyl citrate, ethyl citrate triacetate, ethyl citrate tri-n-propyl vinegar,醯 citric acid tri-n-butyl | The amount of addition in the case of adding a plasticizer is preferably from 5 to 50% by mass of the photosensitive resin composition, and preferably from 5 to 3% by mass. From the viewpoint of suppressing the delay of the development time or imparting flexibility to the cured film, it is preferred that 5% by mass or more is further suppressed from the viewpoint of insufficient hardening or cold flow ("fi〇w"). It is 50% by mass or less. <Photosensitive Resin Composition Conditioning Liquid> 128769.doc -25- 200846825 The photosensitive resin composition of the present invention may be prepared by mixing a photosensitive resin composition-containing solution containing a solvent. As for the suitable conjugates, the ketones represented by methyl ethyl ketone I (ΜΕΚ); and the alcohols such as methyl alcohol, ethanol and isopropyl alcohol. Preferably, a solvent is added to the minus-nine resin composition to adjust the photosensitive resin composition to a liquid solution < viscosity at 25 ° C of 500 to 4000 mPa·sec 〇 < photosensitive resin laminate Body The photosensitive resin laminate includes a photosensitive resin layer and a support composed of a photosensitive resin composition. The photosensitive resin composition can be laminated on a support to form a photosensitive resin laminate. χ, depending on the surface of the resin layer, the surface opposite to the support has a protective layer. As the support used herein, it is preferable to transparently transmit the light emitted from the exposure light source. As such a support, a polyethylene terephthalate film, a polyglycol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymerization may be mentioned. Film, polymethyl methacrylate polymer film, methyl methacrylate copolymer film, polystyrene film, stupid ethylene copolymer film, polyacrylonitrile; film, polyamine film, cellulose derivative film, etc. . These supporters may also use extensions as needed. It is preferred that the haze is 5 or less. When the thickness of the support is thin, it is advantageous in terms of image formation property and economic efficiency, and it is preferable to use thickness = 1 〇 30 30 μm. An important characteristic of the protective layer used in the photosensitive resin laminate is that the adhesion between the protective layer and the photosensitive resin layer is sufficiently smaller than the adhesion of the support to the photosensitive resin layer of 128769.doc -26- 200846825 Therefore, it can be easily peeled off. For example, a polyethylene film, a polypropylene film or the like can be preferably used as the protective layer. Further, the film thickness of the film protective layer which is excellent in the etchability as disclosed in Japanese Laid-Open Patent Publication No. SHO-59-2() No. 2457 is preferably 10 to 10 G μη, more preferably 10 to 50 μm. The thickness of the photosensitive resin layer in the photosensitive resin laminate of the present invention is preferably from 5 to 10, more preferably from 7 to 6 Å. The thinner the thickness, the resolution

The higher the degree, the higher the thickness, the higher the strength of the cured film, so that it can be appropriately selected for visual use. A method of forming the photosensitive resin layer of the present invention by sequentially supporting the support, the photosensitive resin layer, and, if necessary, the protective layer, may be carried out by a conventional method. For example, the photosensitive resin composition used in the photosensitive resin layer is prepared as the above-mentioned photosensitive resin composition conditioning liquid, and first, the preparation liquid is applied onto the support using a bar coater or a roll coater. Further, the photosensitive resin composed of the photosensitive resin composition is laminated on the support.曰', a person can form a photosensitive resin laminate by laminating a protective layer on the photosensitive resin layer by using a laminator. <Photoresist Pattern Forming Method> The photoresist pattern 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. First, the lamination step is carried out using a laminator. In the case where the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then a layered machine is used to laminate the sensitized 128769.doc -27-200846825 optical resin layer onto the surface of the substrate. At this time, the photosensitive layer can only be laminated on one surface of the substrate surface, and can be laminated on both sides as needed. The heating temperature at this time is generally 40 to 160 °C. Further, by ordering the heating and pressure bonding of one or more persons, the poetic property of the obtained photoresist pattern and the base is improved. In this case, the crimping can be carried out using a two-stage laminator with a two-stage report, or it can be repeated by repeating the report several times. Next, an exposure step is performed using an exposure machine. If necessary, the support strips φ _ and exposes it with active light through a photomask. The exposure amount is determined by the illumination of the light source and the exposure time. The amount of exposure can also be measured using a light meter. In the exposure step, an exposure method for direct lithography can be employed. In the direct lithography exposure method, exposure is performed on a substrate by a direct lithography apparatus without using a photomask. As for the light source, a half-body laser or an ultra-high pressure mercury lamp having a wavelength of 35 〇 to 4 〇 can be used. The lithography pattern is controlled by a computer, and the exposure amount at this time is determined by the illuminance of the exposure light source and the moving speed of the substrate. #的'人' performs a developing step using a developing device. After exposure, it is removed when there is a support on the photosensitive tree layer. Further, the unexposed portion was developed and removed using a developing solution composed of an aqueous test solution to obtain a photoresist pattern. As the alkaline aqueous solution, water such as NaWO3 or K2C〇3 or the like is preferred. These are selected according to the characteristics of the photosensitive resin layer, and a Na2C〇3 aqueous solution of 0·2 2 Berry/0/time is generally used. 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 added. Further, it is preferable that the temperature of the developer in the developing step is maintained at a fixed temperature within the range of 20 to 40 °C. 128769.doc -28 - 200846825 By the above steps, the photoresist pattern is obtained, and the heating step of H) 〇~3m: can be further carried out depending on the condition. The heating time is better...clock ~ age clock. The chemical resistance can be further improved by carrying out the heating step'. When heating, a hot air, infrared, or far infrared ray can be used. Further, depending on the case, the exposure step after the patterning of the 沦 / / Beishi can be further advanced. The chemical resistance can be further improved by performing the exposure step. <Manufacturing method of printed circuit board>

The method for producing a printed wiring board according to the present invention is carried out by forming a photoresist pattern on a (4) laminated board or a flexible substrate as a substrate by the above-described photoresist pattern forming method. First, a step of performing a step of etching a copper surface of a substrate exposed by development or a step of performing electroplating is carried out by using a known method to form a conductor pattern by a known method.

In the electroplating step, a copper electroplating bath can be used. It is also possible to use a cyanidation precious metal as a precious metal for cyanidation of precious metal plating, such as gold or silver. In the invention of the present invention, a cyanide gold electric ore bath can be preferably used. In the case of the ratification of gold and electric ore, the electromineral liquid contains a cyanide complex, and the electroplating solution is classified into an experimental cyanide bath (from (1) 3), a neutral cyanide bath (ρΗ6 to 8 5), and an acidic bath. _~6). These plating solutions can be used commercially. The photosensitive resin composition of the present invention is resistant to neutral to alkaline cyanide precious metal electricity. The eight' shell line utilizes a stripping step in which the photoresist pattern is peeled off from the 128769.doc -29-200846825 substrate by an aqueous solution stronger than the developer to obtain the desired printed circuit board. The alkaline aqueous solution for peeling (hereinafter also referred to as "peeling liquid") is not particularly limited, and an aqueous solution of NaOH or KOH having a concentration of 2 to 5% by mass is generally used. A small amount of a water-soluble solvent may also be added to the stripping solution. Further, it is preferred that the temperature of the stripping liquid in the stripping step is 40 to 70. The scope of 〇. <Method for producing a substrate having a concave-convex pattern>

According to the above-described photoresist pattern forming method, the photoresist pattern can be used as a protective mask member when the substrate is processed by a sandblasting method. Examples of the substrate include a glass, a germanium wafer, an amorphous germanium, a polycrystalline germanium, a ceramic germanium, a sapphire, and a metal material m, which are formed in the same manner as the above-described photoresist pattern forming method, and a resist pattern is formed on the substrate such as the glass. . Thereafter, a stripping step is performed by spraying the blast material onto the formed resist pattern and cutting it into a 'target depth blasting treatment (4), and money (4) is removed from the substrate by the liquid-pattern portion remaining on the substrate. A substrate on the substrate-(9)# concave-convex pattern. The spray material used in the above blasting step is a known one, for example, Sic, SiO 2 , Al 2 〇 3,

CaC〇3, Zr〇2, auxilial—. — 2~100 μηι of particles such as stainless steel. The method for producing a substrate having a embossed surface, a cover sheet, and a concave-convex pattern can be used for the manufacture of a separator for a flat panel, a mussel, a glass cover for an organic EL, and a stone eve. Wafer opening: τ ^ 17 , and ceramic needle processing. Also, it can be used for strong dielectric films and

Manufactured from the electrode of the metal material layer in the group of the genus, the noble metal alloy, and the high-melting-point metal. <Manufacturing Method of Semiconductor Package> 128769.doc -30. 200846825 In the method of manufacturing a semiconductor package of the present invention, a wafer for forming a circuit is packaged by the following steps, thereby manufacturing a semiconductor package. $

First, a portion of the substrate metal to which the resist pattern attached to the substrate obtained by development is exposed is subjected to copper sulfate ore or the above-mentioned cyanated noble metal to form a conductor pattern. Thereafter, a peeling step of peeling the photoresist pattern in the same manner as in the above-described method of manufacturing a printed circuit board is carried out, and further, a part of the residual plating material is subjected to a core removal of the thin metal layer (4), and the wafer is obtained by the woman. A semiconductor package is required. <Manufacturing Method of Bumps> The manufacture of the bumps of the invention is carried out by mounting a wafer as a circuit of 1si to form a completed wafer, and is manufactured by the following procedure. In the first place, the portion of the substrate metal to which the photoresist pattern obtained by development is adhered is subjected to copper sulfate plating or the above-described cyanated noble metal plating to form a conductor pattern. Thereafter, a peeling step of peeling off the photoresist pattern in the same manner as in the method of fabricating a printed circuit board is performed, and further, a step of removing a thin metal layer other than the columnar plating by etching is performed. Required bumps. ^ <Method of Manufacturing Lead Frame> The lead frame of the present invention is manufactured by forming a photoresist pattern on a metal plate such as copper, a steel alloy, or an iron-based alloy as a substrate by the above-described green pattern forming method. The following steps are taken. First, the step of engraving the substrate exposed by development to form a conductor pattern is carried out. Thereafter, the photoresist pattern (4) is peeled off from the lead frame in the same manner as in the above-mentioned method of manufacturing the printed circuit board, 128769.doc - 31 - 200846825. [Examples of the Invention] Hereinafter, examples of the embodiments of the present invention will be specifically described. (Examples 1 to 11 and Comparative Example J) f First, the production of the samples for evaluation of the examples and the comparative examples will be described. Next, the evaluation methods of the obtained samples and the evaluation results thereof are shown in Table/,

The names of the photosensitive resin composition blending liquid components B-1 to K-1 indicated by the abbreviation in Table 1 are shown in Table 2. (1) Preparation of Samples for Evaluation The photosensitive resin layered systems of the examples and the comparative examples were produced as follows: &lt;Production of a base-containing adhesive; &gt; First, the following adhesives were prepared. (Synthesis Example) 300 g of methyl ethyl ketone was added to a 4-neck (6) four-necked flask equipped with a nitrogen gas introduction port, a stirring blade, a Dimroth condenser, and a thermometer in a nitrogen atmosphere, and hot water was added. The bath temperature was increased to 80. &lt;3. Then, a solution having a total solid content of methacrylic acid/styrene/mercapto benzyl acrylate of 4 〇〇 g was prepared at a composition ratio of 30/20/50 (mass ratio). A solution of 3 g of azobisisobutyronitrile dissolved in 30 g of mercaptoethyl ketone was prepared, and the solution was added dropwise to the above preparation solution over 2 hours while stirring. Thereafter, the mixture was heated and stirred for 6 hours (primary polymerization). Then, a solution of 6 g of azobisisobutyronitrile dissolved in mercaptoethyl_30 g was added dropwise three times every 4 hours, and stirred under heating for 128 769.doc -32 - 200846825 for 5 hours (secondary polymerization). Then, methyl ethyl ketone 24 〇 &amp; was added, and the polymerization reactant was taken out from the flask to obtain a binder solution. At this time, the weight average molecular weight was 55,000', the degree of dispersion was 2.6, and the acid equivalent was 29 (). The resin solid content in the obtained binder solution B-1 was 41% by mass. Similarly, the binder solution was synthesized in such a manner that methacrylic acid/styrene/methylpropionic acid methyl vinegar 25/25/50 (weight ratio). The composition ratio of the polymerizable substance and the resin solid content, weight average molecular weight, degree of dispersion, and acid equivalent of the obtained binder solution are shown below. Binder solution B-1: methacrylic acid / styrene / methacrylic acid vinegar = 30 / period 0 (weight ratio) (weight average molecular weight 550,000, dispersion u, acid equivalent, solid content concentration of 41% by mass Glutamine ethyl ketone solution binder solution B_2: methyl acrylate / styrene / methyl methacrylate = 25 / 25 / 50 (weight ratio) (weight average molecular weight 5 () million, dispersion η, acid Equivalent 344, a methyl ethyl hydrazine solution having a solid content concentration of 41% by mass. &lt;Production of photosensitive resin laminate&gt; The photosensitive resin composition having the composition shown in Table 1 and a solvent were sufficiently stirred and mixed. The photosensitive resin composition is blended, and the solution is applied to the surface of a 16-th thick polyethylene terephthalate film as a support by a bar coater. The photosensitive resin layer was formed by drying for 4 minutes, and the thickness of the photosensitive resin layer was subsequently laminated on the surface of the uncovered polyethylene terephthalate film of the photosensitive resin layer. Protective layer of 23 μη thick polyethylene film to obtain a photosensitive tree <Layer layer surface treatment> &lt;Substrate surface treatment&gt; 128769.doc -33- 200846825 The substrate for evaluation evaluation, the substrate for adhesion evaluation, the substrate for evaluation of peeling property of photoresist, and the alkaline cyanide noble metal electric ore bath The substrate for resistance evaluation was a wet-rolled roll-polished (3M (manufactured), Scotch-Brite (registered trademark) HD# 600, using a 1.6 mm-thick copper foil laminate laminated with 35 μm of rolled copper foil. When the polyethylene film of the photosensitive resin laminate is peeled off, the laminate is laminated at a temperature of 105 ° C by a hot roll laminator (Al-70 manufactured by Asahi Kasei Electronics Co., Ltd.). After the whole surface treatment and preheating to 6 〇. The copper foil laminate board. The air pressure is set to 0.3 5 MPa, and the lamination speed is set to 丨.5 m/min. &lt;Exposure&gt; The photosensitive resin layer is The pattern mask required for the evaluation was placed on a water-to-nanoethylene glycol film as a support, and exposed to an exposure amount of 5 〇mJ/cm 2 using an ultrahigh pressure mercury lamp (manufactured by ORC, HMW 2 〇 1 KB). Developing &gt; peeling polyethylene terephthalate film Thereafter, the aqueous solution of 1% by mass of Na2C〇3 was sprayed for a specific period of time to dissolve and remove the unexposed portion of the photosensitive resin layer. At this time, the minimum time required to completely dissolve the photosensitive resin layer of the unexposed portion was obtained. As the minimum development time. &lt;Pre-plating treatment&gt; at 40. (:, after the development of the alkaline cyanide precious metal plating bath, the substrate is evaluated for acid degreasing 1 ^; ^ (1% aqueous solution, Made by ADTEX Japan (share)) soaked in the bath for 4 minutes. After washing with water, it was immersed in an aqueous solution of 1 〇% sulfuric acid 128769.doc -34-200846825 for 2 minutes at room temperature. &lt;Cyanide gold plating bath&gt; Electroplating bath using a composition of 20 g/L of potassium cyanide, 5 g/L of sodium dihydrogen phosphate, and 20 g/L of disodium hydrogen phosphate at a current density of 5·5 A /m2, 70 ° C conditions for 10 minutes plating. &lt;Peeling&gt; The substrate was sprayed with (10) and 3 masses by electron beam treatment. /() Aqueous sodium hydroxide solution, peeling off the photoresist film. 2. Evaluation method (1) Evaluation of the resolution The substrate for the resolution evaluation was carried out for 15 minutes after the lamination by the line pattern mask having the ratio of the width of the exposed portion and the unexposed portion to one. The development was carried out by taking a development time twice as long as the development time, and the minimum mask line width at which the hardened photoresist line was normally formed was taken as the value of the resolution, and classification was carried out in the following manner. ◎ · The value of % resolution is 20 μπι or less. 〇 : The resolution value exceeds 20μηι and is 25 μπι or less. χ ··The resolution value exceeds 25 μηη. (2) Adhesion evaluation • Line pattern of ratio of 1〇〇

128769.doc The width of the exposed part and the unexposed part is i: the mask, and the light is sealed for 15 minutes after the lamination. The minimum mask with a hardened photoresist line is developed with a development time of 2 times the minimum development time. ^ -35- 200846825 ◎• The value of the adhesion is 20 μηη or less. The value of 岔·岔 is more than 20 μηη, which is 25 μηη or less. χ : The value of the adhesion is more than 25 μηη. (3) Evaluation of photoresist peeling property After passing through a laminate having a pattern of 6 cm x 6 cm, it was laminated. The substrate for the photoresist peeling evaluation of the minute was exposed. After developing with a development time of 2 times of the minimum development time, the film was immersed in a 50T:, 3% by mass aqueous sodium oxide solution, and the time during which the photoresist film was peeled off was measured, and classified in the following manner. 〇: peeling time is 60 seconds or less △. peeling time exceeds 60 seconds, is less than 120 seconds x: peeling time exceeds 120 seconds (4) Evaluation of the tolerance of the test cyanide precious metal electric shovel bath through the exposure part and not A line pattern mask having a width of 曝光:5 in the ratio of the exposure portion is exposed to the substrate for evaluation of the alkaline cyanide precious metal for 15 minutes after lamination, and the development time is 2 times the minimum development time. Development is carried out to obtain a hardened resist pattern. Thereafter, gold cyanide plating was carried out under the above conditions, and the hardened resist pattern was peeled off. The resistance of the plating solution was graded in the following manner by observing the gold wire of the 1 〇〇 μπι portion by the optical peeling optical microscope. ◎: The completely electroless plating solution sneaked in and infiltrated, showing a good line. 〇: The electroless plating solution is sneaked in, and the penetration width is less than 5 μιη. △: The electroless plating solution was infiltrated, and the infiltration width was 5 μπι or more. χ · Produce electric mineral liquid to sneak into. 128769.doc -36 - 200846825 3. Evaluation results The evaluation results of the examples and comparative examples are shown in Table 1. [Table 1]

-37- 128769.doc 200846825

〇 1-4 1-4 ^ S S S S η &lt;〇»η 04 Ο msd »〇doo ◎ ◎ 〇◎ ON 5 〇F—* ^η &gt;η *〇(Ν C&gt; msd &gt;r&gt; d &gt;'&lt; oo ◎ ◎ 〇 ◎ 〇 〇螗Ί&lt; 〇rH »〇1C *η »〇CN Ο cn so »〇ooo ◎ ◎ 〇◎ 卜填〇1—1 ?-*H ο Ο ιη CN Ο mso »〇ooo ◎ ◎ 〇◎ Ό 〇rH ψ wo wo dd dd dd dd dd dd dd dd Msd »nodo 〇5Q 〇〇〇m Ο Ο ο »η (Ν Ο r^) so »〇ooo 〇〇〇〇(N Ο τ-Η τ—Η ο ο JO &gt;〇in CN Ο msoooo »n cs 〇〇〇〇T i Ο r-t ο ο «ο (Ν Ο msddf—^ oo 〇〇〇〇ώ C N ώ τ—Η 1 S (Ν m 〇ν〇卜00 〇\ έ ο 1 ^-Η } S (Ν » S CN Q (NQ ώ ii Φ Φ Φ per #冢采+ _ _ 效^ | 铡.·衡趄M, W系$黎^ &gt;pr ΐΐ ^ 128769.doc -38- 200846825

[CN&lt;] 41% by mass of a copolymer of methacrylic acid/styrene/benzyl methacrylate (polymerization ratio: 30/20/50), a composition of an acid equivalent of 290, and a weight average molecular weight of 55,000. (solid form) methyl ethyl ketone solution inch engeng. Φ lean φ ΐ Jfthj ψΒη fm _ ♦ tian. (η CN ϊη jj 41 ¥ δ t tO You draw hexamethylene diisocyanate with an average of 4 moles Reaction of hexamethyl diisocyanate, a reaction of glycerol dimethacrylate of ethylene oxide, with glycerol dimethacrylate having an average of 5 moles of propylene oxide H- 裨m τ-Η 〇η ν〇¢- Μ tO Η- Η inch feeds, 1 , | take S- ^ Η* spine m 1—Η ό Η ν〇 S- Ί 5 tnf η feed 、, 1 \\ 4 δ S-^ k hexamethylene diisocyanate with an amino phthalate ester of hexamethylene diisocyanate having an average of 5 moles of propylene glycol chain with an average of 5 moles of ethylene glycol chain Monomethacrylate urethane compound hexamethylene diisocyanate with an average of 5 moles of ethylene glycol monomethacrylate chain and flat 9 molar propylene glycol monomethyl acrylate chain urethane compound is added to both ends of the double A to form an average of 5 moles of ethylene oxide polyethylene glycol dimethacrylate Ester (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.) Adds diethylene acrylate of polyethylene glycol with an average of 2 moles of ethylene oxide at both ends of Shuangshui A (Xinzhongcun Chemical Co., Ltd.) Manufacture of BPE-200, product name) Polypropylene glycol having an average of 12 moles of propylene oxide added to the dimethyl group of an alkylene glycol having an average of 3 moles of ethylene oxide added to both ends Acrylate to trimethylolpropane has an average of 3 moles of ethylene oxide triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd. A-TMPT-3E0, product name) 4-mercaptophenylheptaethylene glycol Propylene glycol acrylate (manufactured by Nippon Oil & Fats Co., Ltd., LS-100A) 4,4'-bis(diethylamino)benzophenone 2-(o-chlorophenyl)-4,5-diphenylimidazole Polymer diamond green colorless crystal violet 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole with 1-(2-di-n-butylaminomethyl)-6-carboxybenzo Triazole 1 ·· 1 mixture T—^ PQ B-2 1 M-2 Μ-3 M-4 M-5 M-6 M-7 M-8 M-9 M-10 丨Μ-11 Μ-12 τ-Η (Ν |di 1 1 D-2 1 r— &lt;128769.doc -39- 200846825 [Industrial Applicability] The present invention can be applied to the manufacture of a printed circuit board, the manufacture of a flexible printed circuit board, and the lead frame for ic chip mounting (hereinafter referred to as a lead frame). Manufacturing of metal foils such as metal foil manufacturing, manufacturing of semiconductor packages such as BGA (spherical grid array) and CSP (wafer size packaging), TAB (Tape Automated Bonding) and COF ( Chip On, Film: The manufacture of a tape substrate, which is represented by a semiconductor chip 1C on a thin film board, the manufacture of semiconductor bumps, the ITO electrode of a flat panel display, the address electrode, or the electromagnetic wave mask. Manufacturing of parts.

128769.doc -40·

Claims (1)

200846825 X. Patent application scope: 1. A photosensitive resin composition characterized by comprising (a) a carboxyl group-containing binder: 20 to 90% by mass, and (b) having at least one terminal ethylenically unsaturated group. Polymerizable monomer: 5 to 75% by mass, (c) Photopolymerization initiator: 0.01 to 30% by mass; M The photosensitive resin composition as a whole contains 1 to 50% by mass of the following formula (1) at least one compound of the group consisting of the compounds represented by the formula (II) as (b) an addition polymerizable monomer having at least one terminal ethylenically unsaturated group; [Chemical 1] CHg-0 —C—C—rw vii IW 2 NC—0—(A-0)nr(B-0)n2--CH—CH2—〇—π—C—ru / II 丫一CH2 r1\ OR3 (1) NC—O ——(A-0&gt;nr(B-0)n4-CH—CHj-〇—n—C—ru HO II 1Γ 2 0 R4 CH2_〇—c_C_c II |~CH2 o R5 φ (where R1 Is a linear, branched or cyclic alkyl group having a number of 4 to 12, or an alkylaryl group having a carbon number of 6 to 12, and R2 to R5 are each independently hydrogen or a fluorenyl group, A is C2H4, and B is CH2CH ( CH3), ηι~η4 are independently 〇~15 The integer, η 1 + ιΐ2 + η; + η# is 2 or more; • The arrangement of the repeating units of -(A-0)- and -(B_0)- may be a random arrangement or a block arrangement; In the case of a segment arrangement, the order of -(A-Ο)- and &lt;3_〇)_ can be either on the amine side of the amino phthalic acid S; 128769.doc 200846825 [Chemical 2] CH2 — Q—C·〇—pu li |~CH2 0 Re CM—R6—NCO—{Α-〇)ητ-(Β〇)ηθ—CH—CH2-〇—c—C—CH2 (Α-0)γ) 5-(Β-0)π§ ϋ CN—R7—NCO—(A*O)n9-(B-0)n10—〇Η-〇η2~〇—〇—C—CH (U) ϋΗ HO 2. II O R1U CH 广〇一c cςς-M丨; Γ 0 R1' (where 'R6 and R7 are independently a direct bond of 4 to 12 carbon atoms, a branched or cyclic group, or carbon Number 6~12 of the alkylaryl group, R8~r&quot; are independently hydrogen or methyl, A is C2H4, B is CH2CH(CH3), n5 and n6 are integers of 〇15, and h+n6 is 1 or more. N7~n1() are independently integers of 〇~15' n7+n8+n9+ni〇 is 2 or more; -(A-Ο)- and -(B-0)- repeating units can be arranged as random The arrangement may also be a block arrangement; in the case of block arrangement, the order of -(Α·〇)_ and _(Β_〇)· may be on the urethane bond side). The photosensitive resin composition of claim 1, which further contains a compound represented by the following formula (III) as the above-mentioned (addition-polymerizable monomer having at least one terminal ethylenically unsaturated group: [ 3] HO i II NC - -(A-OirviHB-O)!^—C—C II: CB (wherein R1 is a linear, branched or cyclic alkyl group having a carbon number of 4 to 12, 128769.doc -2 - 200846825 or an alkylaryl group having a carbon number of 6 to 12, and R13 and R14 are each independently hydrogen or曱, A is C2H4, B is CH2CH(CH3), ηη^ιΐΗ is independently an integer of 0~15, and ]111 + 1112+]113+1114 is 2 or more; -(AO)-and-(B-0 The arrangement of the repeating units may be a random arrangement or a block arrangement; in the case of a block arrangement, the order of -(A-Ο)- and -(B-0)- may be On the urethane bond side). 3. A photosensitive resin laminate comprising a photosensitive resin layer and a support, the photosensitive resin comprising the photosensitive resin composition of claim 1 or 2, a method for forming a photoresist pattern, characterized in that A step of laminating, a step of exposing, and a developing step of forming a photosensitive resin layer using the photosensitive resin laminate of claim 3 on a substrate. 5. The method of forming a photoresist pattern according to claim 4, wherein in the exposing step, direct lithography is performed to perform exposure. 6. A method of manufacturing a printed circuit board, comprising: forming a substrate having a photoresist pattern by a method of: = (4): or 7. A method of manufacturing a substrate having a concave-convex pattern, characterized in that The method of forming a '/, I | board binding process is formed by the method of claim 4 or 5. 8. A method of fabricating a semiconductor package, wherein the method of forming a photoresist pattern is performed by a method such as requesting 9^. And a manufacturing method comprising the steps of performing a plating process on a substrate on which a photoresist having a photoresist pattern of 4 or 5 is formed by a conventional method. 128769.doc 200846825 A method of manufacturing a lead frame, the method is formed with a photoresist pattern, and the right and wrong steps are performed by one of the printed circuit boards of claim 4 or 5. The method of claim 4 or 5 is characterized in that it comprises: a plating bath for deuterated precious metal from which the substrate of the pattern is used for electroplating by means of a step; A method of manufacturing a semiconductor package according to the invention of claim 4 or 5, wherein: the substrate having the photoresist pattern formed by the method of claim 4 or 5 is subjected to electricity: a cyanide precious metal plating bath is used in the plating step. &lt;13&gt; - A method of manufacturing a bump comprising: a step of electroplating a substrate formed with a photoresist pattern by the method of claim 4 or 5, using a cyanide noble metal plating in the electro-mine procedure bath. 128769.doc 200846825 VII. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 8. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: CH2〇—C— IH 12 2 II OR2 N^C—0—(A-0)ni-(B-0)n2-CH—CH2—Ο—C—CzzzCH (I) a NC {Α-0)Π3-(Β-0)Π4~ Η Ο CH—CH厂0——C—Cz=CH CH2一ο—c—C=〇h9 II l5 2 OR5 -4- 128769.doc