TW200919085A - Photosensitive resin composition and laminate thereof - Google Patents

Abstract

Disclosed is a photosensitive resin composition containing 20-90% by mass of a binder resin (a), 5-75% by mass of an addition polymerizable monomer (b) having at least one terminal ethylenically unsaturated group, and 0.01-30% by mass of a photopolymerization initiator (c). The binder resin (a) has an acid equivalent weight of the carboxyl group content of 100-600 and a weight average molecular weight of 5,000-500,000, while containing a specific compound as a copolymerization component. This photosensitive resin composition is characterized in that the addition polymerizable monomer (b) contains a specific addition polymerizable monomer.

Description

200919085 IX. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a photosensitive resin composition which can be developed by an aqueous alkaline solution, and which is formed by laminating the photosensitive resin composition on a support. A resin laminate, a resist pattern forming method for forming a resist pattern on a substrate using the photosensitive resin laminate, and a use of the resist pattern. More specifically, the present invention relates to a photosensitive resin composition which provides a resist pattern suitable as a protective cover member, that is, a printed circuit board, a flexible printed circuit board, and an IC chip (Imegrated) Circuit Chip, integrated circuit chip) Metal foil processing such as manufacturing of lead frame (hereinafter referred to as lead frame), metal mask manufacturing, BGA (Ball Grid Array) or csp (chip ^)

Semiconductor package manufacturing such as Package (wafer size package), tab (Tape Automated Bonding) or c〇F (Chip)

On FUm, film flip-chip: manufacture of a tape substrate represented by semiconductor 1 (: mounted on a film-like micro-board), manufacture of semiconductor bumps, and IT0 (Indium Tin 〇 xide, oxidation) in the field of flat panel displays The manufacture of a member such as an indium tin) electrode or an address electrode or an electromagnetic wave shield, and a protective cover member when the substrate is processed by a sand blast method. [Prior Art] Previously, printed circuit boards were manufactured by photolithography. The photolithography method is a method in which a photosensitive resin composition is applied onto a substrate, pattern exposure is performed, and the exposed portion of the photosensitive resin composition is polymerized and cured, and the unexposed portion is removed using a developing solution. Therefore, after the resist pattern 134399.doc 200919085 is formed on the substrate to form a conductor pattern, the resist pattern is removed from the substrate, thereby forming a conductor pattern on the substrate. In the above-described money shadow method, when the photosensitive resin composition is applied onto a substrate, any of the following methods may be used: a method in which a photoresist solution is applied onto a substrate and dried; or A photosensitive resin laminate in which a support layer, a layer formed of a photosensitive resin composition (hereinafter referred to as "photosensitive resin layer"), and an optional protective layer are laminated in this order (hereinafter referred to as "dry" Film photoresist") A method of laminating on a substrate. Moreover, the latter's dry film photoresist is often used in the manufacture of printed circuit boards. Hereinafter, a method of manufacturing a printed circuit board using the above dry film photoresist will be briefly described. When the dry film photoresist has a protective layer such as a polyethylene film, it is first peeled off from the photosensitive resin layer. Then, using a laminator, a photosensitive resin layer and a support are laminated on a substrate such as a steel foil laminate, in the order of the substrate, the photosensitive resin layer, and the support (usually by poly-p-benzoic acid B) A diester or the like is formed). Then, the photosensitive resin layer was exposed by ultraviolet rays containing 1 line (365 nm) emitted from an ultrahigh pressure mercury lamp through a mask having a wiring pattern, whereby the exposed portion was polymerized and cured. Then peel off the support. Next, a developer such as a weakly alkaline aqueous solution is used to dissolve or disperse the unexposed portion of the photosensitive resin layer to form a resist pattern from the substrate. In addition, the process of forming a circuit after forming a resist pattern can be roughly divided into two methods. The first method is as follows: the steel surface of the steel foil laminate or the like which is not covered by the resist pattern is touch-etched, and then the resist pattern portion is removed using an inspectability 134399.doc 200919085 stronger than the developer. In this case, in terms of the simplicity of the steps, a method of covering the through holes (through holes) with a cured film and then performing the engraving (cover hole method) is often employed. The second method is as follows: a copper plating treatment is performed on the same copper surface as described above, and after further performing soldering, recording, and the like, as needed, the resist pattern portion is removed in the same manner and further exposed. The method of the copper surface of the copper _ laminate or the like (4) (plating method) An etching solution such as vaporized copper, vaporized iron, a copper ammonium complex solution, or a sulfurium/hydrogen peroxide aqueous solution can be used for the etching. With the miniaturization of wiring intervals of printed circuit boards in recent years, it is required to produce a pattern having a narrow pitch for good yield, and it is required that the dry film photoresist has high resolution and high density. In addition, after development, a semi-hardening resist called a foot (hardened resist foot) may be formed in the boundary portion between the hardening resist and the substrate (see FIG. 丨). If the foot is increased, the resist is added. The feet of the wires are in contact with each other to cause insufficient resolution, thereby causing a problem that the conductor pattern after the etching step is swayed. Therefore, the industry seeks a dry film photoresist having a very small footprint on the post-development hardening resist. Further, recently, the importance of the plating method has been increasing from the viewpoint of producing a narrow pitch pattern with good yield. In the plating method, the plating resistance of the photoresist is important, and if the plating resistance is insufficient, the following phenomenon is likely to occur: the treatment liquid penetrates between the resist and the substrate during the treatment before the plating is performed. The undercut is caused by the hardened resist, causing the resist to rise from the substrate. If such a phenomenon occurs, plating penetration (a phenomenon in which the plating reaches the lower portion of the resist) occurs, and therefore a resist having excellent plating resistance is expected. 134399.doc 200919085 In Patent Document 1, a quaternary copolymer containing methacrylic acid/mercaptoacrylic acid hydrazide/two dibasic acid butyl vinegar/acrylic acid 2-ethyl hexanyl ketone, and bicyclo fluorene dimethanol The resolution, adhesion, plating resistance, peeling property, and scum generation property of the photosensitive resin composition of the dimercapto acrylate are described, but the resolution, the adhesion, and the plating resistance are described. Can not fully respond to the status quo. [Problem to be Solved by the Invention] An object of the present invention is to provide a photosensitive resin composition and a photosensitive resin laminate using the same, which is photosensitive The resin composition has particularly excellent high resolution and inter-pigmentability as a resist material such as an etching resist or a plating resist, and has extremely small feet after development and is excellent in plating resistance. [Technical means for solving the problem] The above object can be achieved by the following constitution of the present invention. The present invention is as follows. A photosensitive resin composition comprising: (a) a binder resin 2〇~9〇哲县0/ _. Α Α w 贾I %, the (a) binder resin has a carboxyl group content of acid The equivalent weight is λαλλ α Τ马 100-600, and at least one compound unit selected from the group consisting of compound groups Φ, κ, and 砰 represented by the following general formulas (1) and (II) is used as a copolymerization component, and the weight average molecular weight is &; in the case of 5,000 ~ 500,000; (b) has at least one too 妓 7 weeping. 5 to 75% by mass of the addition polymerizable monomer of the wood ethylenically unsaturated group: and (4) the amount of the photopolymerization initiator 〇.G1 to 3Qf; and the addition polymerizable monomer (b) is selected from the group consisting of At least one of the addition polymerizable monomers in the compound group of 134399.doc 200919085 represented by the following formula (10), Htl] 'h2c=9

(I) (wherein R1 represents a hydrogen atom or a methyl group, ... < a free-air atom, a halogen atom, a fluorenyl group, a carbon number of 12, and a ^ a A alkoxy group having a number of 1 to 12 a group consisting of a 'carboxy group, and a group consisting of _alkyl groups, a V sulfhydryl group.) [Chemical 2] ' (B) H2C=rC—C00—CH; (wherein 'R3 represents a hydrogen atom or a methyl group' R4 represents a prime atom , the basis of the base of the carbon, the base of the carbon, the carbon number, the base of the group of the rebellious 1 and the i-M, the 70-milk [3] soil.) 0 I! 〇Η^〇Ηα-〇 ^Β-〇^〇--〇=〇Η2 -•(HI) (R Μ independently represents a hydrogen atom or a methyl group. Α and Β represent a carbon number extension group, which may be the same or different, In different cases, ~6 0)··nightmare)·The repeating unit may be a block structure or a random ^ 134399.doc 200919085 ^, m2, m3 and work 4 are 〇 or positive integers, the sum of these is 〇~4〇. r is a halogen atom or an alkyl group having a carbon number of 1 to 3, and n is an integer of 〇~4. 2. The photosensitive resin composition according to the above aspect, wherein the content of at least one of the addition polymerizable monomers represented by the above formula (Ιπ) with respect to the entire photosensitive resin group a is 5 to 35 mass. %. 3. The photosensitive resin composition starting agent (C) according to the above 1. or 2. contains a compound selected from the group consisting of the following formula (IV) to >, 2,4,5-triaryl π methane Polymer: [Chem. 4] wherein the above photopolymerization shows a group of compounds

The base and the alkoxy group and the _ group are each independently an integer of 1 to 5. ). Choose free hydrogen, the group of

1 to 5 of the alkane P, q and r 4. The photosensitive polymerizable monomer (b) of any one of the above-mentioned 1. to 3. contains a selected from the following ', ", 'and a compound, at least one addition polymerizable monomer in the compound group. (Formula (V) shown in the above formula B4399.doc -10- ••(V) 200919085 [Chemical 5] ff fHa 0 H2C=C—C—(c2H4-〇)^CH2CH-〇}—^C2H4~〇}—c- -c: :CH〇 (wherein R8 and R9 independently represent a hydrogen atom or a sulfhydryl group. ^ And 13 is an integer of 〇4, and t2 is an integer of 4 to 20.). The photosensitive resin composition of any one of the above-mentioned 1 to 4, wherein the terminally polymerizable monomer has a terminal ethylenically unsaturated group (reactive terminal group) per 10 μg of the photosensitive resin composition. For 〇.1〇~〇4〇莫耳. (6) A photosensitive resin laminate comprising a support and a photosensitive resin composition according to any one of the above 1 to 5 laminated thereon. 7. A method of forming a resist pattern comprising a laminating step, an exposing step, and a developing step. In the laminating step, a photosensitive resin layer is formed on the substrate using the photosensitive resin laminate as described above. 8. The method of forming a resist pattern according to the above 7, wherein direct writing is performed in the above exposure step. 9. A method of manufacturing a printed circuit board, comprising: a method of manufacturing a lead frame of a step of etching or plating a substrate having a resist pattern formed by the method of 7 or 8 above, comprising The step of etching the substrate having the resist pattern formed by the above 7 or the above is performed. A method of manufacturing a semiconductor package 'includes a step of etching or plating a substrate on which a resist pattern is formed by the method of 7 or 8 above. 134399, d〇c 11 200919085 12. A method of manufacturing a bump comprising the step of etching or plating a substrate having a resist pattern formed by the method described above or the like. A method of producing a substrate having a concave-convex pattern, comprising the step of processing a substrate having a resist pattern formed by the method of the above 7 or 8 by sand blasting. [Effects of the Invention] The photosensitive resin composition of the present invention, the photosensitive resin laminate, a method of forming a resist pattern using the same, and a printed circuit board, a lead frame, a package, a bump, and a substrate having a convex pattern The production method exhibits an excellent effect of high resolution and high adhesion, extremely small feet after development, and excellent resistance to mineralizing liquid. [Embodiment] Hereinafter, the present invention will be more specifically described. (a) Resin for the binder The resin for the binder (a) used in the present invention is a compound having a group content of 100 to 600 in terms of acid equivalent, and a compound group selected from the group consisting of the following formulas (1) and (ι) A resin for a binder having at least one compound as a copolymerization component and having a weight average molecular weight of 5,000 to 500,000. H2c-c-^r2 (1) R1 (wherein R1 represents a hydrogen atom or a methyl group, and r2 represents an alkyl group selected from a chlorine atom, a south atom, a hydroxyl group, a carbon number of 12, and a carbon number of a group of a group consisting of a decyl alkano group, a slow group, and an i-based group.) 134399.doc 200919085 [Chemical 7] h2c=c-coo- R4 (D)

(wherein R3 represents a hydrogen atom or a & 14 represents a group selected from the group consisting of a hydrogen atom, a meridine, a carbon group having a carbon number of 1 to 12, an alkoxy group having a carbon number of H2, a thiol group, and a (meth) group. The amount of the silk contained in the resin (4) for the binder is preferably 1 Torr or more, more preferably 25 Å or more, and 450 or less in terms of acid equivalent. The acid equivalent is the mass of the binder resin having one equivalent of a mercapto group. The prefecture in the resin for the binder is required to impart developability or releasability to the photopolymerizable resin layer with respect to the aqueous solution. In terms of development resistance, resolution, and adhesion improvement [the acid equivalent is ι 〇〇 or more, the acid equivalent is 600 or less in terms of improvement in developability and peelability. The acid equivalent was measured by a potentiometric titration method using a Hirohime automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd. to make sodium hydroxide of m〇1/L. The resin for a binder (a) used in the invention has a weight average molecular weight of 5'000 to 500,000 ^. In terms of developability and resolution, the weight average molecular weight is 500, and 〇〇〇 is suppressed. When the photosensitive resin laminate is wound into a roll shape, the photosensitive resin composition bleeds out from the end surface of the roll, that is, the edge-melting is suppressed, and the weight average molecular weight is 5 or more. In order to better exert the effect of the present invention, the weight average molecular weight of the binder resin is preferably 5,000 to 1 Torr, 〇〇〇, and more preferably 134399.doc 200919085 5,000 to 60,000 ° weight average molecular weight can be Gel permeation chromatography (GPC) manufactured by Japan Spectrophotometer (GPC) (pump: Gulliver, pu-1580; column: Shodex (registered trademark) manufactured by Showa Denko (share) (KF_8〇7, KF 8〇 6M, KF_ 806M, KF-8 〇 2.5) 4 series in series; moving bed solvent: tetrahydrofuran; using a calibration curve of polystyrene standard sample (sh〇dex STANDARD SM-105 manufactured by Showa Denko) It is obtained by the form of polystyrene conversion. (1) The binder resin (a) used in the present invention can be obtained by selecting one or more monomers from the following two monomers and copolymerizing them. The first monomer has a polymerization in the molecule. A carboxylic acid or an acid anhydride of an unsaturated group, for example, (mercapto)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester The second single system is a compound which is non-acidic and has a polymerizable unsaturated group in the molecule. The compound is selected to maintain the developability of the photosensitive resin layer, resistance in the etching and plating steps, and hardening. The compound has at least one compound selected from the group consisting of the compounds represented by the above formulas (1) and (II) as an essential component, and the compound represented by the above formula (I), For example, there are phenethyl hydrazine and a styrene derivative, and examples thereof include α-methylstyrene, p-hydroxystyrene, p-methylstyrene, p-methoxystyrene, and p-benzophenone. Expression represented by the general formula (11) For example, (meth)acrylic acid vinegar '(methyl)propionic acid 4_ via ganglion, (methic acid 4-methoxy vinegar, (meth) acrylic acid 4-methyl vinegar, (mercapto) acrylic acid 4 _ 134399.doc 14 200919085 In particular, as a compound selected from the group of compounds represented by the above formulas (1) and (8), The development of the foot is low (no foot or foot is extremely small) and t 'is better to use styrene, and in terms of resolution, 6, and foot productivity,曰 benzyl (meth) acrylate is used. ^ 1 molecule of binder is used in the amount of at least one compound selected from the group consisting of the compounds represented by the above formulas (1) and (π) copolymerized in the resin (a). The binder resin (4) is preferably 丨〇% by mass or more and 95% by mass or less. The amount is preferably from the viewpoints of resolution, adhesion, plating resistance, and foot productivity. It is 10% by mass or more, and from the viewpoint of developability, it is preferably 95 mass%/° or less. The amount is more preferably 20% by mass or more. 90% by mass or less, and more preferably 25% by mass or more and 8% by mass or less. The binder resin used in the present invention is a second monomer, except for the essential component, the above formula (I) In addition to the compound of (11), a known monomer other than 3 荨 can be used in combination as a copolymerization component, and examples thereof include decyl acrylate, ethyl (meth) acrylate, and (meth) propyl. N-propyl diester, cyclohexyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-mercapto acid 2-base Vinegar, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (decyl) acrylate, (A Alkenylamine, N-hydroxydecyl acrylamide, N-butoxymethyl acrylamide, (meth) acrylonitrile, glycidyl (meth) acrylate, these can be individually 134399.doc -15· 200919085 It is also possible to use two or more types together. The binder resin (4) used in the present invention t is preferably synthesized by mixing the above first monomer with a second monomer, and diluting with a solvent such as C-, F-ethylethyl or isopropanol. An appropriate amount of a radical polymerization initiator such as benzophenone oxime or azoisobutyronitrile is added to the resulting solution, and the mixture is heated and stirred. Sometimes, a part of the mixture is added dropwise to the reaction liquid, and the surface is synthesized. Sometimes, the solvent is added to the desired concentration after the reaction is completed. As the synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be employed. The ratio of the total of the green resin composition (solid content, the same applies hereinafter) in the range of 2 〇 to 9 〇 mass% is preferably 30 to 70% by mass. The resist pattern formed by exposure and development has a property as a resisting agent, for example, a cap hole, a money punch, and sufficient resistance in various plating steps, etc., and the ratio is preferably 20 mass. % or more and 9% by mass or less. (b) Addition polymerizable monomer The addition polymerizable monomer (b) used in the present invention is an addition polymerizable monomer having at least one terminal ethylenically unsaturated group. The addition polymerizable monomer W contains at least one addition polymerizable monomer selected from the group consisting of the following general formula (10) as an essential component. I34399.doc 16 200919085 化 - V^y r6 (r7) „ CH2-0-^A-0)^f-8-0)^c—C=CH2

II o (8) (4) ❹ represents a hydrogen atom or a methyl group. Indicates an alkyl group having a carbon number of ^, which may be the same or different. In different cases, the _(A_ 〇)- and -(B-〇)-repeat units may be block structures or random. structure. Mi, m2, m3 and „14 are 〇 or a positive integer, and the total of these is 〇~4〇. r7 is a halogen atom or an alkyl group having a carbon number of 1 to 3, and 11 is an integer of 〇~14.) In the case of at least one of the addition polymerizable monomers in the compound group represented by the above formula (111), hydrazine is preferably an ethyl group or a propyl group. Further, in terms of resolution and adhesion, Preferably, it is lower, more preferably 2 (Ηχτ, and even more preferably (4) 〇. η is preferably 0. As at least one kind of addition polymerization represented by the above formula (ΙΠ) Specific examples of the monomer include dicyclodecane dimethanol diacrylate (NK Ester A_Dcp manufactured by Shin-Nakamura Chemical Co., Ltd.) and tricyclodecane dimethanol dimercapto acrylate vine (Xinzhongcun Chemical Industry Co., Ltd.) NK Esur Dcp). In the present invention, the content of at least one of the addition polymerizable monomers selected from the group of compounds represented by the above formula (m) with respect to the entire photosensitive resin composition is 5~ 40 mass ❶ /., is a better implementation. Get the solution 134399.doc -17· 200919085 II From the viewpoint of the nature of the minerals and the mineral-resistant liquid, the content of (4) and (4) is in the form of a mass. In the above, from the viewpoint of developability, the content of the content is preferably 4% by mass or less. The addition range is from 7 to 35% by mass, and more preferably from 9 to 30% by mass. The addition-polymeric precursor (8) used in the photosensitive resin composition of the present invention is in addition to the above compounds. A known compound having at least one terminal ethylenically unsaturated group can be used. For example, 4, nonylphenyl heptaethylene glycol dipropylene glycol acrylate, (4) acid 2- County _3-phenoxy (tetra), Styrene hexaethylene glycol acrylic acid, phthalic acid liver and acrylic acid 2 propylene-based half vinegar compound and propylene oxide reaction (Japanese catalyst chemical manufacturing 'commodity name _ £ _ _ 2 〇 〇), 4_n-octylphenoxypentapropanediol propylene glycol _, 2, 2 bis [{4_(methyl) propylene oxide ethoxypoly ethoxy] phenyl] propyl, 2, 2 _ Double {(4. acetamidooxypolyethoxy)cyclohexyl}propyl, 2,2-bis U4_methylpropenyloxypolyethoxy)cyclohexyl}propane, 1,6-hexyl Glycol (methyl Acrylate, hydrazine, 4_cyclohexanediol di(meth) acrylate, polypropylene glycol di(meth) acrylate, polyethylene glycol bis-(meth) propylene fluorene oxime, polyoxyethylene polyoxypropylene a polyoxyalkylene glycol di(indenyl)acrylate such as diol di(meth)acrylate, 2_bis(p-hydroxyphenyl)propane di(meth)acrylate, glycerol tri(meth)acrylate, a polyfunctional (meth) acrylate containing a urethane group (for example, a urethane compound of hexamethylene diisocyanate and pentapropylene glycol monoester acrylate), and The polyfunctional (fluorenyl) acrylate of the cyanurate compound. These may be used alone or in combination of two or more. In view of the developability, the addition polymerizable monomer (b) contains at least one of the polymerizable monomers of the compound group represented by the following formula (v): 134399.doc -18-200919085. A preferred embodiment of the invention. , [Chemical 9] 0 ο C^~〇)^CH2CH-〇}^C2H^〇)_11_C_Ch? (wherein R and R9 represent the chlorine atom or methyl group independently. ^ and the integer, t2 is 4~20 Integer.) ' r , · (ν) As a small-sized addition polymerizable monomer selected from the group of compounds represented by the above formula (V),

For example, four propylene glycol di(methyl) two, acid hydrazine, seven propylene disulfide - γ field J zhiyi (meth) acrylate, decyl propylene diacetate diacrylate, fifteen Ύ^ 一知一(M) acrylate, added to the two-co-alcohol at the two ends of the hexamethylene disulfide, " s, a di(meth) acrylate of the yeast, in the ten _ drunk The two ends are added with two r-segments, β-d-two-bright, and white (see) di-(meth)acrylic acid vinegar is selected. In the compound group represented by the above formula (ν), the oxime, the seed-addition polymerizable monomer of the county 4 is similar to the eve- 5 3... The photosensitive resin composition as a whole i 5 to 30 mass %, is compared to the body ^ ^ ^ implementation. In terms of resolution, adhesion, and shirtiness, the addition of a polymerizable monomer is ... 1 ... The early 1 is preferably 5 temporary county.

From the viewpoint of developability, a good range of L is preferably 5 to 25% by mass, and is less than or equal to % by weight. Further, the photosensitive resin of the present invention has a coarseness = a good range of 5 to 2% by mass. (9) The amount is relative to the photosensitive tree wax: eight substances: the addition polymerization polymer monomer contains a better range of 15 to 7 〇 mass; the body is 5 to 75 mass. /. From the viewpoint of the time delay, the "benefit" suppresses the hardening failure and the development & is 5% by mass or more, and in addition, the viewpoint of the peeling delay of the cooling flow and the hardening resist is 134399.doc 19. 200919085 In the photosensitive resin composition of the present invention, the addition polymerizable monomer (8) is contained per 100 g of the photosensitive resin composition from the viewpoint of resolution and etching liquid resistance. The molar number of the terminal ethylenically unsaturated group (reactive terminal group) is 0.10 to 〇.4 〇, which is a preferred embodiment. Here, the terminal ethylenically unsaturated group (reactive terminal group) , the active group which generates photopolymerization by the photopolymerization initiation in the structure of the addition polymerizable monomer, and represents a propenyl group and a mercaptopropenyl group. The value is preferably 0.10 or more, so that The cross-linking density after exposure is kept high, the swelling during development is suppressed, the resolution and the adhesion are maintained, and the etching liquid does not cause the penetration of the etching liquid on the bottom surface of the resist line, causing the copper wire to sway, and the like. The above values are preferably below 0 40 to crosslink The density is maintained at a moderate height, and the softness of the cured film is not lowered. The above range of values is preferably G.12 to G_35, and more preferably G 15 to 〇3 〇. (c) Photopolymerization initiation The photopolymerization initiator (c) used in the present invention contains at least one 2,4,5-triarylimidazole dimer represented by the following formula (IV) from the viewpoint of high resolution. A better implementation. 134399.doc •20. 200919085 [化ίο]

f The group consisting of a base and a methoxy group, and an i! group, wherein a % is 1 to 5, r is independently an integer of 1 to 5). The seed group, P, q and the covalent bond of the compound (IV) represented by the above formula (IV) can be bonded to 1, 1, -, i 2, _, 7, bond, and . Preferably, the two conjugated groups are covalently bonded to oxime, 2, a position, ... 2'4'- or 4,4,-position aryl imidazole dimer, for example, 2_(o. Compound. 2,4,5-tri-u, 2-(o-chlorophenyl)_4 5 field _4,5·diphenylimidazodimeric (tetra)phenyl)-di-methoxyphenyl such as dimerization At least one of 2,45__, which is represented by the photosensitive tree rider of the present invention, is preferably (Μ~20% by mass of the base taste salic dimer) The ratio is 0.1% by mass or more in terms of the ratio (in the viewpoint of resolution and adhesion), the example is 20 mass% or less. ', shoulders such as cohesiveness, the ratio is preferably 0.5. ~15% by mass, and further 134399.doc >21. 200919085 The preferred range is 1 to 1 0 mass 〇 / 〇. As the present invention, i#, S 〜 is preferably used as The 2,4,5-triaryldione dimer represented by the combination is used in combination with a p-aminophenyl ketone. As the p-aminophenyl group, for example, p-amino ketone or p-butylamine can be mentioned. Alkyl phenyl net, p-dimethylamino acetophenone,::; Bis-Butyl', P, P'-bis(ethylamino)benzophenone, p,p, bis(dimethylamino)benzophenone (alias: mazakirone), p, p, _ bis (indolyl: yl) benzophenone, p, p' bis (dibutylamino) benzophenone _. In addition, with pyrazoline compounds, such as 丨 phenyl _ 3 _ ( 4_Tertiary-styryl)-5-(4·Terylene-phenyl)--------------------------------------------------------- In addition to the initiator, other photopolymerization initiators may be used in combination. The photopolymerization initiator herein refers to a compound which can be activated by various active light rays such as ultraviolet rays to start the dimerization. Starting agents are: anthracene, such as ethyl hydrazine, 2_t-butyl hydrazine; aromatic ketones, such as benzophenone, benzoin; amphibians, such as benzoin 30, benzoin ethyl ether; Acridine compound, such as: 9-phenyl acridine, benzyl dimethyl ketal, benzyl diethyl ketal. Further, for example, thioxanthone, 2,4-diethyl thioxan _, Thiophene oxime such as 2-chlorothioxanthone Combination with a tertiary amine compound such as an alkyl dimethyl benzoate compound. Further, an oxime ester such as 丨 phenyl propyl diketone 2 _2 _ 醯 醯 肟 肟 肟, 1-phenyl- can be used. : 1,2-propanedione_2_(〇-ethoxycarbonyl). In addition, I34399.doc •22- 200919085 can also use N-aryl-α-amino acid compounds, among which special Preferably, the ratio of the photopolymerization initiator (c) in the present invention is 0.01 to 30% by mass. If the ratio is less than 质量·〇1, the product cannot be sufficiently obtained. Sensitivity. Further, when the ratio exceeds 30% by mass, fogging is likely to occur due to diffraction of light passing through the photomask during exposure, and as a result, the resolution is deteriorated. The content of the photopolymerization initiator (e) is more preferably 0.1 to 15% by mass, still more preferably 0.1 to 10% by mass.

(d) Other components In order to exhibit the contrast after exposure (the difference between the exposed portion and the unexposed portion), the photosensitive resin composition of the present invention may contain a leuco dye. When the colorless dye is contained, the content is preferably 〇"~"〇% by mass. As such a leuco dye, tris(4-dimethylamino-2-mercaptophenyl)methane (alias: colorless crystal violet), tris(4-dimethylaminodecylphenyl)anthracene Alkane (alias: colorless hole cancer green), smoldering dye. Among them, when M is used as a colorless crystal violet, the contrast is good, so that it is preferable. In combination with the adhesion and the contrast of the contrast, it is preferred to use the above-mentioned benefits in combination with the above-mentioned benefits in the photosensitive resin composition. Halides, such as $丨I ^ > 〉 odor pentane, exemplification of isopentane, desertification of isobutylene, ethylene bromide, bismuth, methylation, dioxin, dioxin, methane, tris Base stone wind, tetrabromo-mediated scorpion strontium / strontium sulphate, tris(2,3-dibromopropyl) phosphate, triethylene acetamide, eugenol, saponin I α .W , z, butyl iodine, Indole, 1,1-trichloro-2,2-bis(p-benzoquinone)ethane, hexachloroethane, hydrazine a diazine compound. As the 1,3-triazine 134399.doc -23· 200919085 azine: _ (4-methoxy compound, may be mentioned: 2,4,6-tris(trichloromethyl)_homoylphenyl)-4,6- Bis(trichloromethyl)-s-triazine. When the content of the compound in the photosensitive resin composition is contained, it is preferably 〇1 to 1% by mass. In order to improve the handleability of the photosensitive resin composition, a coloring matter may be added in addition to the above leuco dye. As such a coloring material, for example, poinsettia, acesulfame green, golden amine test, p-magenta, crystal violet, methyl dial, Nero blue 2, Victoria blue, malachite green (Budong Valley Chemistry (4) ^

MAL (registered trademark) MALACHITE green), blue test 〇 2, diamond green (AIZEN (registered trademark) mAM 〇 ND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.). When the coloring matter is contained, the amount of the coloring matter f added to the photosensitive resin composition is preferably G.GG1 to lf%. When the content of the coloring matter is 0.001% by weight or more, the effect of improving the workability is obtained, and when the content is 1% by mass or less, the storage stability is maintained. Among them, the combination of 'Sanxi methyl phenyl sulfone and a leuco dye, and a combination of a triazine compound and a leuco dye are useful. In addition, in order to improve the thermal stability of the photosensitive resin composition of the present invention, it is preferred that the photosensitive resin composition contains at least one or more compounds selected from the group consisting of the following groups. It consists of a free radical polymerization inhibitor, benzotri(tetra), and an benzopyrene. Examples of such a radical polymerization inhibitor include p-methoxy phenol, hydroquinone, pyrogallol, naphthylamine, t-butyl catechol, cuprous chloride, 2'6- 2. Ternary butyl _ 曱 、, 2, 2, methylene bis (4) methyl i 134399.doc -24 · 200919085 third butyl phenol), 2, 2 '- methylene double (4 · B Base_6_t-butylphenol), nitrosophenyl group by imide salt, and diphenylnitrosamine. Further, examples of the benzotriazoles include ruthenium, 2,3-stuppyrene, 1-gas-I'2,3-benzotriazine, and bis(N_2-ethylhexyl)aminone. Methyl-1,2'3-benzotriazole, bis(N-2-ethylhexyl)aminoindenyl], 2,3-methylphenyltriazole, and bis(N-2-yl) Ethyl)aminomethylene _], 2,3_benzotriazine 〇 〇 〇 〇 作为 〇 〇 〇 羧基 羧基 羧基 羧基 羧基 羧基 羧基 赭 赭 赭 , , , , , , , , , , , , , , , , , , , , , , , , 2,3 - benzotriene. Sit, 5-rebel-1 2 3-poor ugly, AJ benzodiazole, Ν-(Ν,Ν·2--2-ethylhexyl)aminomethylene carboxy benzo benzopyrene-Li -(Ν,Ν-di-2-hydroxyethyl)aminomethylenecarboxyl stupid and triazole, and Ν-(Ν,Ν-di-2-ethyl-yl)amine-based ethyl carboxybenzotrien saliva. u The free radical polymerization inhibitor, benzo-, L, sitin, and carboxybenzotriazole are better than the 〇〇1 θ texture/〇, more preferably 0 05~1罝%. In the case of the photosensitive resin composition, it is better to give a storage stability. The amount is preferably 〇.〇1 quality" ', and from the point of view, the amount is better than the 曰3 outside, the sensitivity is good.疋 3 mass% or less. Combination of Photosensitive Resin of the Present Invention Such a plasticizer may, for example, contain a plasticizer. As a bovine polyethylene glycol, it is a polyoxyethylene ether, a polyoxyl ether, a polypropylene glycol, a polyoxypropylene gamma pore G 旆 early methyl ether, an ethylene polyoxypropylene monomethyl ether, a milk propylene early methyl ether, Polyoxyethylene ether, polyoxyethylene polyoxypropylene hydrazine 早 early diethyl ether, polyoxypropylene monoethyl diethyl ester and other phthalic acid-alcohol, ester, phthalic acid brewing, acetonitrile triacetate, amine , tributyl citrate, citric acid = ethyl decanoate, p-toluene sulfonate J34399.doc -25- 200919085 tri-n-propyl citrate, tri-n-butyl citrate. The amount of the plasticizer in the case of containing a plasticizer is preferably from 5 to 50% by mass, more preferably from 5 to 3% by mass, based on the photosensitive resin composition. From the viewpoint of suppressing the development time delay or imparting flexibility to the cured film, it is preferably 5% by mass or more, and more preferably 50% by mass or less from the viewpoint of suppressing insufficient hardening or cold flow. <Photosensitive resin composition preparation liquid> A photosensitive resin composition preparation liquid can be formed by adding a solvent to the photosensitive resin composition of the present invention. The solvent to be used is, for example, a ketone represented by methyl ethyl ketone (MEK), an alcohol such as methanol, ethanol or isopropyl alcohol. Preferably, the viscosity of the photosensitive resin composition preparation liquid is 25. The underside is 500 to 4000 mPa. The seCi method adds a solvent to the photosensitive resin composition. <Photosensitive Resin Laminate> The photosensitive resin laminate system of the present invention is composed of a photosensitive resin layer and a support supporting the layer, and may be provided on the surface of the photosensitive resin layer opposite to the support as needed. There is a protective layer on it. The support used herein is preferably a transparent support which can transmit light emitted from the light source for exposure. Such a support may, for example, be a polyethylene terephthalate film, a vinyl alcohol film, a polyvinyl chloride film, a gas ethylene copolymer, a poly(vinylidene chloride) film, a vinylidene chloride copolymer film, a #methyl group. A methyl acrylate copolymer ruthenium, a polystyrene film, a polyacrylonitrile film, an #ethylene copolymer film, a polyamide film, and a cellulose derivative film. These films may also be extended as needed. The haze is preferably 5 or less. As for the film 134399.doc •26- 200919085 Thick and thin film is more advantageous in terms of image formation and economy, but since it is necessary to maintain strength, etc., it is preferably 1〇~3〇(4). In addition, the important characteristic of the (four) layer of the light-sensitive resin product is that the adhesion between the protective layer and the photosensitive resin layer is sufficiently small to be easily peeled off. For example, a polyethylene film, a polypropylene film or the like can be preferably used as the protective layer. Further, a film having excellent releasability as described in JP-A-59-202457 can be used. The film thickness of the protective layer is preferably 1 G to 5 G_. θ The thickness of the photosensitive resin layer in the photosensitive resin laminate of the present invention is preferably 疋5 to 1 〇〇 ', more preferably 5 to 5 Å. The thinner the thickness of the photosensitive resin layer, the higher the resolution, and the thicker the thickness, the higher the film strength, so that the thickness can be appropriately selected depending on the application. A method of producing the photosensitive resin laminate of the present invention by sequentially laminating a support, a photosensitive resin layer, and an optional protective layer can be carried out by a conventionally known method. For example, the photosensitive resin composition used for the photosensitive resin layer can be prepared in advance as the photosensitive resin composition preparation liquid, and the preparation liquid is first applied to a support and dried by a bar coater or a light coater. Thus, a photosensitive resin layer formed of the "photosensitive resin composition" is laminated on the support. Then, a layer of the protective layer is laminated on the photosensitive resin layer as needed to form a photosensitive resin laminate. <Resist Pattern Formation Method> The resist 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. 134399.doc -27- 200919085 First, the lamination step is performed using a laminator. When the photosensitive resin laminate has a protective layer, after the protective layer is peeled off, the photosensitive resin layer is heated and pressure-bonded to the surface of the substrate by a bonding machine and laminated. At this time, the photosensitive resin layer may be laminated only on a single surface of the substrate, and may be laminated on both sides as needed. The heating temperature at this time is usually 40M 60. Further, by performing the thermocompression bonding twice or more, the adhesion of the obtained resist pattern to the substrate is improved. At this time, the pressure can be applied by using a two-stage laminator having a double roll. The photosensitive resin layer can also be pressed against the roll several times by pressure. Next, an exposure step is performed using an exposure machine. The support can be peeled off as needed and exposed by active light through a photomask. The amount of exposure is determined by the illumination of the light source and the exposure time. The amount of exposure can be measured using a light meter. In the exposure step, a maskless exposure method can also be employed. Maskless Exposure Exposure is performed on a substrate using a direct writing device without using a mask. As the light source, a semiconductor laser or an ultra-high pressure mercury lamp having a wavelength of 35 〇 to 41 〇 nm can be used. The pattern to be written is controlled by a computer, and the exposure amount at this time is determined by the illumination of the light source for exposure and the moving speed of the substrate. Then, the developing step is performed using a developing device. If a support is present on the photosensitive resin layer after exposure, the support is removed. Next, the unexposed portion was developed and removed using a developing solution composed of an aqueous alkaline solution to obtain a resist image. As the alkaline aqueous solution, it is preferred that the aqueous solution 4 such as Na2C〇34K2C〇3 can be selected in combination with the characteristics of the photosensitive resin layer, and an aqueous solution of Na2C〇3 having a concentration of 0.2 to 2% by mass is usually used. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of organic/exciting agent for promoting development, etc. may be added. Further, the temperature of the developing solution in the developing step is preferably i34399.doc • 28· 200919085 Maintain it at a fixed temperature in the range of 20 to 40 °C. The resist pattern can be obtained by the above steps, and a heating step of 1 〇 0 〜 3 〇〇 ° C can be carried out as needed. By carrying out the heating step, it is possible to enhance the chemical resistance by heating (4) a hot air, infrared, or far infrared ray type heating furnace. <Manufacturing Method of Printed Circuit Board> The method of manufacturing a printed circuit board according to the present invention, after forming a resist pattern on a copper box laminate or a flexible substrate as a substrate by the above-described resist pattern forming method A printed circuit board is manufactured through the following steps. First, the following steps are carried out: a conductor pattern is formed on the copper surface of the substrate exposed by development using a known method such as a surname method or a mineral deposit method.

U then proceeds to a stripping step, i.e., (d) inspection (d) to remove the resist pattern from the substrate in an aqueous solution of the sputum sputum to obtain the desired printed circuit board. (4) The alkaline aqueous solution (hereinafter also referred to as "peeling liquid") is not particularly limited, and it is usually used in a concentration of 2 to 5 mass% (^ or K〇H in water, night. The peeling liquid may also be added. Further, the temperature of the stripping liquid in the stripping step is preferably 4 〇 to 7 〇 (>c. <Production method of lead frame>, manufacture of lead frame of the present invention) In the method, after the resist pattern is formed on the metal plate of copper, copper alloy, or iron-based alloy as the substrate by the above-described resist pattern forming method, the lead frame is manufactured through the following steps. a step of forming a conductor pattern by developing the exposed substrate, and then performing a peeling step of peeling off the resist pattern in the same manner as in the above-described method of manufacturing the printed circuit board, thereby obtaining 134399.doc 29· 200919085 <Manufacturing Method of Semiconductor Package> The semiconductor package of the present invention is manufactured by the following steps: LSI (large integrated circuit 'large_) The wafer of the circuit of the scaie integration is packaged. First, the exposed portion of the base metal on the substrate to which the photoresist pattern is attached by development is subjected to copper sulfate plating to form a conductor pattern. Then, a peeling step is performed. That is, in accordance with the manufacturing method of the above printed circuit board

In the same manner, the resist pattern is peeled off, and further, a portion other than the columnar plating is etched to remove the thin metal layer, and the above-mentioned crystal # is packaged to obtain a desired semiconductor package. <Manufacturing Method of Bump> The bump of the present invention is used for encapsulating a wafer in which a circuit as an LSI has been formed, which can be manufactured by the following steps. First, a portion where the base metal on the substrate to which the resist pattern is attached by development is exposed is subjected to copper sulfate plating to form a conductor pattern. Of course

Thereafter, the stripping step is performed, that is, the resist pattern is peeled off in the same manner as in the above-described method of manufacturing the printed circuit board by the disk μ H 进而, and then the thin gold (4) other than the columnar ore is removed by (4) I. , obtain the bump of f. &lt;Manufacturing Method of Substrate Having Concavo-Convex Pattern&gt; The resist formed by the above-described resist pattern forming method can be used as a squeegee H-shield member. Examples of the substrate include glass, Shih-ray wafer, Amorpha, polycrystalline stone, ceramic, i34399.doc • 30-200919085 J = metal material, etc., in combination with the above-described resist pattern forming method. A resist pattern is formed on the substrate of glass, etc. Then, the spray material is sprayed on the resist pattern to cut the substrate to the blasting step of the ice, and the residual resist on the substrate is removed using an alkaline stripping solution or the like. The agent pattern portion may be formed into a substrate having a fine concavo-convex pattern on the substrate from the stripping step of the base Chen Yun. The spray material used in the above blasting step may be a known material, for example, a batch, a12〇3, CaC03 may be used. , ZrO, plaque, τ ^ glass stainless steel 4 particle size of about 2 ~ 1 之 particles. The above method of manufacturing a substrate having a concave-convex pattern by sand blasting can be applied to the manufacture of partition walls of flat panel displays, Organic anal (10) (10) ce, electroluminescence) glass cover processing, stone etched wafer processing, and ceramic pinning plus king. In addition, this method can be used to manufacture ferroelectric film and Electrode 0 of a metal material layer in a group consisting of a noble metal, a noble metal alloy, a high-point metal, and a high-melting-point metal compound [Examples] Hereinafter, examples of embodiments of the present invention will be specifically described. (Examples 1 to 8) Comparative Examples 1 to 3) First, the method and description of the sample for evaluation of the examples and the comparative examples, and then the evaluation method of the obtained sample and the evaluation result thereof 1. Preparation of the sample for evaluation ° was produced as follows Example σ &lt;Production of Photosensitive Resin Laminates&gt; 134399.doc -31 · 200919085 The numerical values of the components θ and θ of the έ Λ 所示 shown in Table 1 below are shown. The photosensitive resin composition and the solvent are sufficiently mixed with a β/(f component)) to obtain a photosensitive resin composition preparation liquid, and a bar coating is used: one is applied to the support as a support. On the surface of the 16 (four) thick poly 2nd dicarboxylate film, a dry coal knife was formed in a dryer of 95°° to form a photosensitive resin layer. The thickness of the photosensitive resin layer was 25 μm. Then, the photosensitivity Resin layer On the surface of the laminated polyethylene terephthalate film, a 21 (four) thick polyethylene film of the protective layer is bonded to obtain a photosensitive resin laminate. The photosensitive resin composition represented by the symbol in Table 1 is used in the formulation liquid. The name of the material component B-NDj is shown in the following Table 2. &lt;Substrate surface modification&gt; The surface of the 〇4 mm thick copper foil laminate having a rolled copper foil of 35 μηι laminated was sprayed at 0.20 MPa. The pressure was subjected to jet brushing (manufactured by Carm Co., Ltd., Japan, Sakurundum R (registered trademark) #22〇), thereby preparing a substrate for evaluation of resolution, adhesion, foot productivity, and plating resistance. &lt;Lamination&gt; The polyethylene film of the photosensitive resin laminate was peeled off, and a heat-bonding machine (manufactured by Asahi Kasei Electronics Co., Ltd., AL-70) was used for 1〇5. (: The affinity temperature was surface-modified and preheated to 6 (a photosensitive resin laminate was laminated on a copper foil laminate on TC. The air pressure was set to 〇·35 MPa, and the lamination speed was set to i 5 m/min. 〇134399.doc •32- 200919085 Using a chrome glass reticle, using an ultra-high pressure mercury lamp (manufactured by Ushi〇 Electric Co., Ltd., projection exposure unit UX2〇〇3SM-MS〇4), with an exposure of 120 mJ/cm2 Line monochromatic exposure. &lt;Development&gt; After peeling off the polyethylene terephthalate film, 3 〇. i mass% Na2C〇3 aqueous solution was sprayed for a specific time to dissolve and remove the photosensitive resin layer. At this time, the minimum time required to completely dissolve the photosensitive resin layer in the unexposed portion is set as the minimum development time. <Pre-plating treatment> The plating resistance evaluation substrate after development is subjected to acid degreasing FRX (丨〇% aqueous solution 'made by Atotech Japan Co., Ltd.) was immersed in a bath for 4 minutes under water. After washing, it was immersed in a 10% sulfuric acid aqueous solution at room temperature for 2 minutes. <Mineral copper sulfate> 19 wt ° /. Sulfuric acid copper sulfate concentrate (Meltex) The product was diluted to 3.6 times, and concentrated hydrochloric acid 2〇〇卯111 was added. Then, Cupraeid HL and Cupracid GS as brightening agents were added to 〇41111/1, 2〇1111/1, respectively, and the prepared copper sulfate plating solution was used. Using a Haring Ceil uniform plating apparatus (manufactured by Yamamoto Gold Plating Tester Co., Ltd.), the plating resistance evaluation substrate after pre-plating treatment (6 cmx 12_5 at an applied current of 0.4 A) Cm) plating for 65 minutes. At this time, the thickness of the copper-plated film is 21 μm 〇 &lt;peeling&gt; Spraying and peeling the substrate subjected to the plating treatment with 5 (TC, 3 wt% caustic soda aqueous solution) Detachment film 134399.doc -33- 200919085 2. Evaluation method Each evaluation method is as follows: (1) Resolution of the line pattern mask (chrome glass mask) with a ratio of the ratio of the exposed portion to the unexposed portion of 1:1 The substrate for exposure evaluation after lamination is laminated for 15 minutes. Development is performed with a development time twice the minimum development time, and the minimum mask line width of the hardened resist line is normally formed as the resolution value. Classify as follows. p ◎ (excellent): The resolution value is 7.5 μηη or less. 〇 (good): The resolution value exceeds 7.5 μηη and is 8.5 μπι or less. x (not): the resolution value exceeds 8.5 μηι. (2) Adhesion pass The ratio of the width of the exposed portion to the unexposed portion was a line pattern mask (chrome glass mask) of 丨: 1 ,, and the substrate for adhesion evaluation was exposed for 15 minutes after lamination. The development was carried out with a development time twice as long as the development time, and the minimum mask line width which normally formed the hardened resist line was taken as the value of the adhesion, and was classified as follows. ◎ (excellent): The value of the adhesion is 13 μπι or less. 〇(良). The value of adhesion is more than 13μηι and is 14μηι or less. X (not available): The value of the adhesion is more than 14μίη. (3) A base pattern mask (chrome glass mask) whose ratio of the width of the exposed portion to the unexposed portion is 1:1, and the substrate for evaluation of the foot generation after 15 minutes of lamination Exposure was carried out with a development time of 2 times the minimum development time for 134399.doc •34- 200919085. The foot generated by the foot of the obtained resist line of 1 5 μη! was observed, and the foot was graded as follows. ◎ (Excellent): No foot is produced at all. 〇 (good). A foot with a width of less than 1 is produced on one side of the line. X (not available): A foot with a width of 1 μηι or more is produced on one side of the line. (4) Plating resistance • A pattern mask (chrome glass mask) with a ratio of the width of the exposed portion to the unexposed portion of 1:100, which is evaluated for plating resistance after 15 minutes of lamination. The substrate is exposed. The development was carried out with a development time twice as long as the development time, and then copper sulfate was applied, and the hardening resist was peeled off. The copper sulfate plating line of 15 μm portion after the peeling of the resist was observed, and the plating resistance was classified as follows. 〇 (good): copper sulphate plating does not sneak at all. △ (may): On the one side of the line, the immersion width of copper sulfate plating is less than 丨μηι. x (not available): The immersion width of the copper sulphate plating on the one side of the line is 1 μΐΏ & 3. Evaluation results The evaluation results of Examples 1 to 8 and Comparative Examples 1 to 3 are shown in Table i. 134399.doc 200919085 Comparative Example 3 κη in oo IT) (N co 0.05 r〇〇o 0.15 X m ◎ O 〇Vl ο &lt;3 Comparative Example 2 wn (N oo 0.05 m 〇o 0.17 00 〇 XX Ο 〇 Comparative Example 1 ! in 〇o 2 ro 0.05 mdo 0.20 〇X rt 〇CN X i/Ί X Example 8 IT) »r^ oo 〇m 0.05 oo 0.21 ◎ rn ◎ 〇◎ Ο 〇 Example 7 IT) ooo ro Ϊ— ^ 0.05 oo 0.20 ◎ ◎ o ◎ Ο 〇 Example 6 ^T) 00 o Bu om 0.05 r^&gt; oo 0.21 ιο 〆 ◎ m ◎ o ◎ ο 〇 Example 5 ro 0.05 rn o 0,23 vn ◎ ro ◎ o 〇ο 〇 Example 4 沄CN in in m 0.05 mdo 0.23 U~) oo 〇ΓΛ ◎ *n O 〇ο 〇 Example 3 ^T) to ro 0.05 mdo 0.23 ◎ 〇 〇 o ◎ ο 〇 Example 2 ( 〇d 0.05 do 0.23 oo 〇·_— ◎ o ◎ ο 〇 Example 1 in ir&gt; md 0.05 mdo 0.23 iT) oo 〇rn ◎ KT) d 〇ο 〇ώ Β-2 rn ώ B-4 1 2 M- 2 M-3 M-4 M-5 r-^ (N Dl D-2 methyl ethyl ketone Mo G zL grade ε = L grade 6 n grade ε =1 grade i Photosensitive resin composition (parts by mass) (Bl to B-4 is a solid content) Solvent (parts by mass) Resolution: Adhesive footing resistance plating liquid alkali: ^Saw&lt;tiw^ Forgot Umbrella 铋哒矣 茫 茫 δ δ δ δ 荽 δ 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 43% by mass of a copolymer of methyl ester/styrene (mass ratio of 25/50/25), an acid equivalent of 344, and a copolymer having a weight average molecular weight of 50,000 (solid content) mercaptoethyl ketone solution B-2 41 having a composition of a benzoic acid/stupidyl vinyl/benzyl methacrylate (mass ratio of 3〇/2〇/5〇), an acid equivalent of 290, and a weight average molecular weight of 550,000 Mass 0/〇 (solid fraction) methyl ethyl ketone solution B-3 ^ mercapto acrylate / methyl acrylate acid ester (mass ratio 2 _) composition, acid equivalent is 43 〇, and the baryon weight is 50 mass copolymer of 50 mass 〇 / 〇 (solid content) thiol ethyl ketone solution B-4 ΐΐ昃 ΐΐ昃 acrylic acid / methyl glycerin acid brewing / acrylic acid butyl vinegar (mass ratio of 25 / 60/10) composition, acid is 374, and heavy 34 mass 0-form methyl ethyl ketone solution of copolymer with a mass average molecular weight of 80,000 M-1 decane monomethyl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.; product name: NK Ester M- 2 more than one methanol-enylic acid ester (manufactured by Shin-Nakamura Chemical Co., Ltd.; product name: nkEster A_DCP) M-3 seven-indolyl dimercapto acrylate ___ -------- M-4 7:3, a mixture of alcohol diacetic acid vinegar and pentaerythritol tetraacetic acid vinegar (manufactured by East Asia Synthetic Co., Ltd., M-5 methylene olefin oxime pentoxide) phenyl]propane (Xinzhongcun Chemical Co., Ltd.) (stock) manufacturing; product name: 1-1 2,2·-double (2-gas base)-4,4,,5,5,-four stupid '-1,1,- oxazolium _ _ &quot ; 1-2 4,4'-bis(diethylamino)benzophenone D-1 3^ A1ZEN (registered trademark G8) is a colorless product made by Tugu Chemical Co., Ltd. D-2 colorless Crystal Violet-- It is clear from Table 1 that in Examples 1 to 8, the composition of the present invention is excellent in resolution, adhesion, foot productivity, and plating liquid resistance. In Comparative Example 1, the resin for a binder does not contain at least one compound selected from the group consisting of the compounds represented by the above formulas (1) and (Π) as a copolymerization component, and in Comparative Examples 2 and 3, the photosensitive resin composition is It does not contain at least one addition polymerizable monomer selected from the group of compounds represented by the above formula (ΙΠ) as the addition polymerizable monomer (b). Therefore, it is understood that the resolution, the adhesion, the foot productivity, and the plating resistance are not excellent. [Industrial Applicability] 134399.doc -37- 200919085 The present invention can be applied to the manufacture of printed circuit boards, the manufacture of ic wafer mounting bow frames, and the fabrication of metal masks, and the like. Or manufacturing of a package such as CSP, manufacture of a tape substrate such as COF or TAB, manufacture of a semiconductor bump, manufacture of a partition wall of a flat panel display such as an ITO electrode or an address electrode or an electromagnetic wave shield, and manufacture of a concave-convex pattern by sandblasting In the method of the substrate. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic explanatory view of a foot (hardened resist foot) of a boundary portion between a hard resist and a substrate. [Main component symbol description] 1 Hardened resist pattern 2 Substrate 3 Foot 134399.doc

Claims (1)

200919085 Ten 1. Patent application: A photosensitive resin composition containing: (a) Resin for adhesive 2〇~9〇. 钕其冬旦, ν缺上负负/. 'U' of the binder in the resin, wherein the carboxyl group contains, in acid equivalents, (10) 0, containing at least one compound selected from the group consisting of the compounds represented by the following general formulae (I) and (II) as a water-repellent The composition 'and the weight of the flat ib, the right 5 丨 10 averal &quot; sub I is 5,000~500,000; (b) having at least one all # 7 α ,, the unsaturated unsaturated monomer 5~75% by mass: And the addition of the earthworms to the public (c) photopolymerization initiator 〇〇1 to 3 〇 mass%; and the addition of the polymerizable monomer (8) to the group of compounds to the underarms (10) Represents 叩 to 乂 - kind of addition polymerizable monomer. [^tl] flat body, h2c=9 (!) (wherein 'R〗 indicates a hydrogen atom or a methyl group'. The sound is not selected from the hydrogen atom, the halogen atom, and the alkyl group having a carbon number of 1 to 12. ^ Μ. 1~12 of the burnt soil, 1 and a group of haloalkyl groups. [H2C=C-COO--CH. (wherein R3 represents a hydrogen atom) Or a methyl group, a phenanthrene atom, a hydroxyl group, an alkyl group having a carbon number of 12, a base group, a thiol group, and a group consisting of a group of 12 to 12 oxo groups, I34399.doc 200919085 [Chemical 3] Ο CHi-O-fA-O^BO^C—C=CH2 A ...(10) (Rt^^-O^AO^BO^C—C=CH2 o (R and R are independent representations Wind atom or sulfhydryl group; A and B represent an alkylene group having a carbon number of 2 to 6 and the like may be the same or different. When different, -(AO)- and -(B-〇)-repeat units The block structure may also be a random structure; m 1 , m 2 , m 3 and m 4 are 〇 or a positive integer, and the total is 〇 40; R 7 is a dentate atom or an alkyl group having 1 to 3 carbon atoms; , η is the number of meals of 〇~14. 2. The photosensitive composition of the sensitizing tree of the request, wherein the above-mentioned general formula is not known) an addition polymerizable monomer relative to the photosensitive resin group The content of the entire material A is 5 to 35 mass%. ,. • ί · such as the clear item 1 or the starter (C) containing at least a 2'4,5-triarylimidazole dimer of the following formula (IV), wherein the photopolymerization is carried out in the compound group I34399.doc 200919085[化4] The alkyl group and the alkoxy group, and r in the group consisting of the dentate groups are each independently an integer of 1 to 5). The group having a carbon number of 1 to 5, p, 卩4. wherein the above-mentioned additive group represents a photosensitive resin composition according to claim 1 or 2, and the monomer (b) contains a group selected from the following At least one addition polymerizable monomer of the formula (v): [Chemical 5] H CH3 〇ch2 ..-(V) (wherein R8 and R9 each independently represent a hydrogen original thickness of ten or methyl ;tl and t3 are integers of 0 to 4, and 〖2 is an integer of 4 to 20). 5. The photosensitive resin composition of claim U12, wherein the terminal ethylenically unsaturated group (reactive terminal group) of the addition polymerizable monomer (8) is 〇 in each (10) § photosensitive resin composition. .1〇~〇4〇莫耳. A photosensitive resin laminate which is a photosensitive resin composition according to any one of claims 1 to 5, which is a composite material of the present invention. A method of forming a resist pattern comprising a laminating step, an exposing step, and a developing step of forming a photosensitive resin layer on the substrate using the photosensitive resin laminate according to claim 6. The method of forming a resist pattern according to claim 7, wherein the direct writing is performed in the above exposure step. A method of manufacturing a printed circuit board comprising the step of engraving or mineralizing a substrate having a resist pattern formed by a resist pattern forming method as claimed in claim 7 or 8. A method of manufacturing a lead frame, comprising the step of forming a substrate having a P and a pattern of a pattern using a resist formation method as claimed in claim 7 or 8. U. A method of fabricating a semiconductor package, comprising the step of implanting, etching or depositing a substrate having a resist pattern formed by the barrier pattern forming method of claim 7 or 8. 〆 · · - - - - - - - - - - - - - - - - - - - - - - - - - ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' A method of manufacturing a substrate having a resist pattern and a concave-convex pattern by a sand blasting method, a step of processing a substrate formed with a resist pattern as claimed in claim 7 or 8. 134399.doc