TW201232173A - Photosensitive resin composition - Google Patents

Abstract

A photosensitive resin composition which comprises (A) an alkali-soluble polymer, (B) a photopolymerization initiator, and (C) a compound having an ethylenically unsaturated double bond, wherein the photopolymerization initiator (B) is a 2,4,5-triarylimidazole dimer or an acridine compound, while a compound represented by general formula (I) is contained as the compound (C). In general formula (I), R1, R2, A, B, n1, n2 and n3 are each as defined in the description. The photosensitive resin composition is excellently and stably dispersible in a developer to minimize the generation of an aggregate. Further, the resin composition exhibits proper developability and can provide a flexible cured resist with good etching resistance.

Description

201232173 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a photosensitive resin composition and the like. [Prior Art] v Previously, precision processing of printed circuit boards or metals was made by photolithography. The photolithography method refers to applying a photosensitive resin composition onto a substrate to perform pattern exposure and polymerizing and curing the exposed portion of the photosensitive resin composition. The developing solution removes the unexposed portion to form an anti-reflection on the substrate. The etching pattern is formed by etching or plating to form a conductor pattern, and then removing the resist pattern from the substrate to form a conductor pattern on the substrate. In the photolithography method, when the photosensitive resin composition is applied onto a substrate, a method of applying a photoresist solution onto a substrate and drying it is used, or a support layer and a photosensitive layer are sequentially laminated. Any one of a layer of a resin composition (hereinafter referred to as a photosensitive resin layer) and a photosensitive resin layer of a protective layer as required on a substrate, but is often used in the production of a printed circuit board. the latter. The method and method for producing a printed circuit board using the above-mentioned photosensitive resin laminate are briefly described below. First, a protective layer such as a polyethylene film is peeled off from the photosensitive resin laminate. Then, a photosensitive resin layer and a support are laminated on the substrate such as a copper foil laminate using a laminating machine so as to be in the order of the substrate, the photosensitive resin layer, and the support. Then, the photosensitive resin layer is exposed through a photomask having a wiring pattern, whereby the exposed portion is polymerized and cured. Then, the support of 160046.doc 201232173 containing 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 resist pattern on the substrate. The step of dissolving or dispersing the photosensitive resin layer in the unexposed portion by the developing solution is referred to as a developing step, and the minimum time required for dissolving the photosensitive resin layer in the unexposed portion is taken as the minimum development time. Not all of the photosensitive resin composition is dissolved in the developer, and as the development step is repeated each time, the insoluble component having poor developer dispersibility gradually increases, and aggregates are generated. The aggregates adhere to the substrate and cause a short circuit failure. Then, the formed anti-(4) old case is used as a protective mask, and the known surname processing or pattern electric money processing is performed. Finally, the anti-small agent pattern is peeled off from the substrate to manufacture a substrate having a conductor pattern, that is, a printed circuit board. . At the time of the etch treatment, the resistance of the anti-# agent pattern is more important. If the resistance to money is poor, then the money engraved into the gap between the anti-button pattern and the substrate and the part of the top of the circuit. In terms of the appearance of the surface from the top direction, discoloration and oxidation due to penetration were observed, and the reproducibility of the width of the i-conductor pattern was deteriorated in the - portion, and the linearity was poor and the fluctuation was indefinite. Further, in the case where the etching resistance is poor, the occurrence of the absence of the conductor pattern or the finer the broken conductor pattern becomes, the more the defects become more conspicuous. The step of performing the known (four) treatment using the anti-(four) pattern formed as described above as a protective mask is referred to as (4) (4). Cut (4) (4) In the case of the lyrics, the necessary steps are to completely dissolve the conductors, so the substrate transport speed depends on (4) (4) Jim 160046.doc • 4- 201232173 The minimum development time is shorter, there is excessive exposure to the developer In the case where the adhesion between the substrate and the formed resist pattern is impaired, particularly in the case where a photosensitive resin layer having a small thickness is used in order to improve the resolution and the etching efficiency, the above-described situation becomes remarkable. Further, in the developing step and the etching step, when the flexibility of the hardened resist is insufficient, a part of the resist pattern may be damaged by contact with the transport roller or deposition of the developer or the etching solution. , resulting in the absence or disconnection of the conductor pattern. Under this circumstance, means for using polytetramethylene glycol di(meth)acrylate or using a urethane compound in order to improve the softness and chemical resistance of the hardened resist has been reported (refer to the patent literature).丨, 2). [PRIOR ART DOCUMENT] Patent Document 1 Patent Document 1 and Japanese Patent Application Publication No. JP-A No. Hei. No. Hei. No. Hei. No. Hei. The chemical resistance described in the above refers to an alkali aqueous solution or a plating solution, and does not disclose the resistance of the acidic drug used in the etching step, and does not disclose the developability or cohesiveness. There is still a need to provide a photosensitive resin composition which is excellent in dispersion stability of a developer, suppresses generation of aggregates, and has moderate developability, flexibility of a cured resist, and good etching resistance. In view of the above circumstances, the object of the present invention is to provide a developing solution which is excellent in dispersion stability, can suppress generation of aggregates, and has a developing property of moderately 16046.doc 201232173, softness of a hardening antisynthesis agent, and good resistance. A photosensitive resin composition with a surname and the like. [Means for Solving the Problems] The present inventors have diligently studied and repeated experiments in order to solve the above problems, and as a result, have found that the present invention can be solved by the following technical means, and the present invention has been completed. That is, the present invention is as follows.上述] A photosensitive resin composition comprising (4) a soluble polymer, a W photopolymerization initiator, and (C) a compound having an ethyl (tetra) bond and a double bond, and (B) photopolymerization initiation The agent is a 2,4,5•triaryl taste salivary dimer or a ruthenium complex, and the compound having the ethylenically unsaturated double bond and having the following formula (!): [Chemical Formula 1] Ο qp (I) CH2=ii丨-+女卜W Seven "'2 • · { where R, and 112 respectively represent a hydrogen atom or a methyl group, eight are. or c3H6, at - (A-0 In n, _ and _(A_0)n3_, the arrangement of the repeating units of _C2H4 〇 and _c can be random, and the 'or 4^ can also be a block, when the arrangement is block , -C2H4-0- and -C3H6-〇-中之# . τ can also be _B 0 base side ' B is a carbon number 4 to 8 of a two-valent alkyl chain, . ηι is 0 ~ 丨An integer of 〇, n3 is an integer of 0 to 10' Π| + η3 is an integer of 〇 10, * 跫, and h is an integer of 1 to 20} (2) A photosensitive resin combination as described in (1) above Object, which as the above (6) has 160046.doc -6 - 5 201232173 has ethylenic unsaturation The double bond is different from you, and the second is a redundant, and further contains the following general formula (π): [Chemical 2] R3 Ο H2C=: C ς 〇 _ {wherein RAR4 is independently a hydrogen atom Or 曱 base, ... and ~ are respectively independent of 〇~20 integer, n4+n7 "~4G integer, n5h6 are each an integer of 1~20, + w is an integer of 2~4〇, and _(匸2 The arrangement of the repeating units of ^_〇卜 and (CsHU-O)- may be random or block, and in the case where the arrangement is a block, either of them may be a bisphenol side. [3] The photosensitive resin composition according to the above [2], wherein, in the above formula (1)), h and η are each independently an integer of 丨~(9), and 〜~~ is an integer of 2 to 40. [4] The photosensitive resin composition according to any one of the above [1] to [3] wherein the (A) alkali-soluble polymer is selected from the group consisting of styrene and/or (mercapto)-propionic acid The photosensitive resin composition of any one of the above-mentioned [1] to [4], wherein 'n2 is 1 to 10 in the above formula (1). The integer, and η丨+n3 is 0. [6] The photosensitive resin composition of any one of the above [1] to [5], wherein the compound (C) having an ethylenically unsaturated double bond further contains at least one urethane bond in the molecule. The photosensitive resin composition of any one of the above-mentioned (C) which has the ethylenic unsaturated double bond, and further contains 16046.doc 201232173 Formula (III): [Chemical 3] 卩5 〇0 Re H^=^-〇^^H4-〇^C3H6_〇^__[!_i=CH2 {wherein Rs and R6 are each independently a hydrogen atom or a ruthenium Base, ... and!! 9 respectively set the bracelet to an integer of 3 to 40' and the arrangement of the repeating units of _((:2^_〇)_ and _((:3^_〇)_ can be a random 'also It can be a compound represented by block}. [8] The photosensitive resin composition according to any one of the above [1] to [7] wherein the compound (C) having an ethylenically unsaturated double bond further comprises the following formula (IV) and/or (V): [Chemical 4] h2c: R1 IV) ηι〇~η丨2 respectively (wherein R5 and & respectively are independently hydrogen atoms or methyl groups are integers of 1 to 30} [Chemical 5]

Rs 〇Η^=Κ!_ 〇~fc3He-〇|^C2H4_〇t^C3He-0 七4 〇Re —c=ch2 独 {中中' Rs and R0 are each independently a hydrogen atom or a sulfhydryl group, ni〇 ~ni2 respectively 16046.doc (V) 201232173 Established as an integer from 1 to 3 0. The photosensitive resin composition of any one of the above-mentioned (C), wherein the (C) compound having an ethylenically unsaturated double bond further contains an isocyanuric acid group in the molecule. Compound. [10] The photosensitive resin composition according to any one of the above [1] to [9] wherein, when the total solid content of the photosensitive resin composition is 〇〇 mass%, the above (A) The amount of the above-mentioned (B) photopolymerization initiator is adjusted when the total solid content of the photosensitive resin composition is 100% by mass. When the total solid content of the photosensitive resin composition is 100% by mass, the compounding amount of the compound having an ethylenically unsaturated double bond is 5% by mass. 50 0 quality 0 / 〇. And a photosensitive resin layer comprising the photosensitive resin composition according to any one of the above [1] to [10], which is laminated on the support film. [12] A method of producing a substrate on which a resist pattern is formed, comprising the steps of: laminating a photosensitive resin laminated layer layer as described in [11] above on a substrate, and performing the photosensitive property via a mask The exposure step of exposing the resin laminate and the developing step of removing the unexposed portion. A method of manufacturing a circuit board, which comprises forming a circuit board by etching or plating a substrate manufactured by the method of the above. [Effects of the Invention] 160046.doc 201232173 According to the present invention, it is possible to provide a developer which is excellent in dispersion stability, suppresses generation of aggregates, and has moderate developability. The softness of the hardened resist and the good touchability. A preferred photosensitive resin composition for forming a good conductor pattern; and a photosensitive resin laminate having a photosensitive denier layer containing the composition. [Embodiment] Hereinafter, a mode for carrying out the invention (hereinafter simply referred to as "the embodiment") will be described in detail. Further, the present invention is not limited to the following embodiments, and various modifications can be made without departing from the spirit and scope of the invention. <Photosensitive resin composition> In the present embodiment, the photosensitive resin composition contains an alkali-soluble polymer, (B) a photopolymerization initiator, and (c) a compound having an ethylenically unsaturated double bond. <(A) Alkali-soluble polymer> The (A) alkali-soluble polymer means a vinyl resin containing a carboxyl group, and examples thereof include (meth)acrylic acid, (mercapto) acrylate, and (meth)acrylonitrile. (f-) a copolymer of acrylamide or the like. (A) The alkali-soluble polymer preferably has a carboxyl group and has an acid equivalent of 100 to 6 Å (the acid equivalent is preferably 1 Å on the viewpoint of improving development resistance and improving resolution and adhesion. From the viewpoint of improving developability and releasability, it is preferably 6 Å or less. The acid equivalent is more preferably 250 to 450. (A) The alkali-soluble polymer preferably has a weight average molecular weight of 5 and more than 500,000 〇〇〇. (A) The weight average molecular weight of the alkali-soluble polymer is such that the properties of the coagulum are developed and the side of the photosensitive resin laminate is formed. 160046.doc 1Λ -10 - 201232173 Edge melting, slicing, etc. are not exposed. From the viewpoint of the properties of the film, it is preferably 5,000 or more. From the viewpoint of improving the developability, it is preferably 5 Å or less. Here, the edge meltability means that the photosensitive resin is laminated. When the body is curled into a roll shape, the phenomenon in which the photosensitive resin composition layer protrudes from the end surface of the roll. The so-called "slinterability" refers to a phenomenon in which the wafer scatters when the unexposed film is cut by a cutter, if the wafer is attached. Photosensitive resin product The upper surface of the layered body or the like is transferred to the mask in the subsequent exposure process or the like to cause a defect. (A) The weight average molecular weight of the alkali-soluble polymer is more preferably 5,000 or more and 3 Å, 〇 In the following, it is preferably 1 Å or more and 200 Å or less. (A) The soluble polymer can be, for example, one or more of the following two types of monomers: The first monomer is a carboxylic acid or a fatty liver having a polymerizable unsaturated group in the molecule. Examples thereof include (meth)acrylic acid, fumaric acid, cinnamic acid, barley acid, and clothing. Butic acid, maleic anhydride, maleic acid half ester, etc. More preferably (meth)acrylic acid. Here, 'the so-called (meth)acrylic acid means acrylic acid or methacrylic acid. The second monomer is a monomer which is non-acidic and has at least one polymerizable unsaturated group in the molecule, and examples thereof include decyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (methyl) Isopropyl acrylate, n-butyl (meth) acrylate, (fluorenyl) Isobutyl enoate, second butyl ketone (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate Ester, benzyl (mercapto) acrylate, ethoxylated, such as vinyl acetate, (mercapto) acrylonitrile, stupid 600046.doc 201232173 ene, styrene derivatives, etc. Methyl acrylate, n-butyl (meth) acrylate, styrene, styrene derivative, and benzyl (meth) acrylate " as (A) a copolymer component in a soluble polymer, preferably The styrene derivative or the styrene derivative preferably has a copolymerization ratio of from 2% by mass to 6% by mass. The copolymerization ratio has sufficient cohesiveness and etching resistance. The amount is preferably 20% by mass or more. From the viewpoint of moderate developability and softness of the cured film, it is preferably 60% by mass. /❶The following. The copolymerization ratio is more preferably 20% by mass to 50% by mass, still more preferably 20% by mass to 30% by mass. Further, as a copolymer component, styrene or a styrene derivative, (mercapto) is preferably used. Methyl acrylate and (meth)acrylic acid are copolymerized. Further, in order to obtain excellent resolution different from the above, the copolymerization ratio of the styrene or styrene derivative is preferably 4 Å. /〇~6〇 mass ° / 〇 'and 'as a copolymer component' is preferably a copolymer of styrene or a styrene derivative, methyl (meth) acrylate, and (meth) acrylic acid . When the total solid content of the photosensitive resin composition is 100% by mass, the amount of the (A) alkali-soluble polymer in the photosensitive resin composition is preferably in the range of 40% by mass to 80% by mass. More preferably, it is 5 〇 mass% to 70 mass%. The blending amount is preferably 40% by mass or more from the viewpoint of edge meltability, and is preferably 8% by mass or less from the viewpoint of development time. <(B) Photopolymerization initiator> The above photosensitive resin composition contains 2,4,5-triarylmyrazole dimer or 160046.doc -12-201232173 acridine compound as (B) photopolymerization The essential ingredients of the starter. Specific examples of such may, for example, be 2—(o-phenyl)-4,5-diphenylimidazole dimer, 2-(o-phenyl)-4,5-bis(methoxyphenyl). Imidazole dimer, ^(o-fluorophenyl)-4,5.diphenylimidazole dimer, 2_(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2_(pair 2,4,5-triarylimidazole dimer such as methoxyphenyl)_4,5-diphenylimidazole dimer, 9-phenyl acridine 'oxime, 7-bis (9,9-acridine) Acridine derivatives such as heptane and the like. Examples of the photopolymerization initiator which can be further contained in the photosensitive resin composition include, in addition to the 2,4,5-triarylimidazole dimer or acridine compound, dibenzophenone, N, N. '-Tetramethyl-4,4'-didecylaminodibenzophenone (Mitchler), N,N,-tetraethyl-4,4,-diaminobenzophenone, 4 _Methoxy-4'-dimethylaminodibenzophenone, 2-benzyl-2-dimethylamino. -(Carboxylinylphenyl)-butanone 丨, 2, fluorenyl (decylthio)phenyl]_2_morpholinyl-acetone-1 and other aromatic ketones, 2_ethyl fluorene, phenanthrenequinone , 2_t-butyl hydrazine, octyl hydrazine, 1,2-benzopyrene, 2,3-benzopyrene, 2_phenyl fluorene, 2,3-diphenyl fluorene, ι蒽醌 gas, 2_methyl hydrazine, hydrazine, 4_naphthoquinone, 9,10-phenanthrenequinone, 2-mercapto-1, 4-naphthoquinone, 2,3-dimethylhydrazine, etc. , benzoin, benzoin ethyl ether, benzoin phenyl ether and other benzoin ether compounds, benzoin and other benzoin derivatives, N-phenylglycine derivatives, coumarin compounds, 4, 4, bis (diethylamine) Base) diphenyl fluorenone and the like. These photopolymerization initiators may be used singly or in combination of two or more. When the total solid content of the photosensitive resin composition is 100% by mass, the amount of the photopolymerization initiator (B) in the photosensitive resin composition is preferably 0.1% by mass. /. ~20% by mass. The blending amount is 20% by mass or less to the bottom surface of the resist from the viewpoint of obtaining a sufficient light sensitivity of 160,046.doc 201232173 degrees. It is preferably 0.1% by mass or more, and is preferable from the viewpoint of sufficiently transmitting light and obtaining good high resolution. A more preferable range of the blending amount is 〇.5 mass% to 1 〇<(c) a compound having an ethylenically unsaturated double bond>; a compound having an ethylenically unsaturated double bond; Equivalently, it has an ethylenic character; and the compound 1 which is saturated with pour is (c) a compound having an ethylenically unsaturated double bond, and examples thereof include di(methyl)(tetra) acid vinegar and then so-called (meth) acrylate. , means acrylic acrylate or methacrylate. The photosensitive resin composition contains the following general formula (〖): [Chemical 6] R·) Ο Or CH24—“Bu 0仏0 yA.〇y “H2 • · * (I) {wherein, R] and I independently represents a hydrogen atom or a sulfhydryl group, and octagonal or C3H6, in -(Α-Ο)η丨- and _(A_〇)n3_, the arrangement of the repeating units of _c2h4 〇 and _C3H6 可 may be Randomly, it may be a block. When the arrangement is a block, either -QHcO- and <3 out-〇- may be _Β_〇·base side, Β is carbon number 4 to 8 of the 2 valence alkyl chain, 〇| is an integer of 〇~1〇, ~ is an integer of 〇~10, ηι+η3 is an integer of 0 to 10, and ~ is an integer of 〇2〇} The compound serves as (C) a compound having an ethylenically unsaturated double bond. Here, in the case where the bis(meth) acrylate represented by the above formula (1) is combined with the invention of the invention to prepare a photosensitive resin composition, The details of the mechanism of the photosensitive resin composition which is excellent in dispersion stability, can suppress the generation of aggregates, and has moderate developability, softening resistance (4) flexibility, and good rice-resistance resistance, is not clear, but it is speculated It is the effect as described below. The second (nodular) acrylate of the formula (1) has a group represented by -(B-0)-, compared with the oxyethylene or oxypropylene group generally used, the chain: the chain is long, and Since it has a side chain, it is estimated that the degree of freedom of the main chain is relatively large, and the flexibility of the chemical structure (sometimes referred to as capping property) is excellent. The mysterious bond has a tendency to cause a nucleophilic substitution reaction of a carbon adjacent to oxygen due to an acid and to break the bond, but the bis(methyl) propyl s 曰 通式 represented by the general formula (I) has The ratio y of the bond-breaking reaction site due to the acid represented by (Β·〇)_ is preferably an oxidized vinyl group or an oxypropylene group, and is considered to be excellent in acid resistance (sometimes referred to as etching resistance). Further, the bis(meth) acrylate represented by the formula (I) has a higher oleophilicity as a group represented by 〇)·, which is presumed to be a dispersion of a phenyl-containing initiator which is easily developed as a coagulum. It is excellent in the stability (inhibition of the generation of the agglomerates. Further, the moderate developability is also estimated to be derived from the moderate lipophilicity of the di(meth)acrylate represented by the formula (1). In the compound of the formula (1), η丨 and h are preferably an integer of 〇. That is, n, +n3 is preferably an integer of 〇. More specifically, from the viewpoints of edge meltability and ease of production, etc. In other words, the compound represented by the above formula (1) is preferably, for example, the following formula (VI): 160046.doc •••(VI) 201232173 [Chemical 7] CHz^C~~Q—Ό~^〇ηΟΗ2〇Η2〇Η2 〇Η2〇·]—

" 〇JL CC—^C H2 {wherein the heart and the ruler 2 respectively represent a hydrogen atom or a methyl group, and n2 is preferably an integer of 1 to 20', more preferably an integer of 丨15, especially preferably 丨Polybutanediol di(meth)acrylate shown as an integer of (7). More specifically, 'for example, butanediol di (meth) acrylate, dibutyl diol di (meth) acrylate, tributyl diol di (meth) acrylate, tetrabutyl diol di ( Methyl) acrylate, pentabutyl glycol di(meth)acrylate vinegar, hexabutylene glycol di(meth) acrylate, heptabutyl diol di(meth) acrylate acid, eight butyl Diol di(meth)acrylate, nonabutylene glycol di(meth)acrylate, decabutylene glycol di(meth)acrylate, eleven butanediol di(decyl)acrylic acid vinegar, ten Dibutylene glycol di(meth)acrylate, thirteen butanediol di(meth)acrylate, tetradecanediol di(meth)acrylate, fifteen butanediol di(decyl)propene Sour and so on. In the compounds represented by the above formulas (I) and (VI), the integer is preferably an integer of from 1 to 15 and is preferably an integer of the formula From the viewpoint of the nature, it is preferably 1 or more, and on the other hand, it is preferably 2 or less in terms of resistance to surname. N2 is preferably an integer of 5 to 1 。. When the total solid content of the photosensitive resin composition is 丨〇〇% by mass, the compounding amount of the compound represented by the above formula (1) or (VI) in the photosensitive resin composition is preferably! quality. /. ~ 丨 5 mass%. The blending amount is preferably 丨% by mass or more from the viewpoint of obtaining the softness of the cured film, and is 5, preferably 5% by mass or less from the viewpoint of 160046.doc 201232173 X" A more preferable range of the blending amount is 1% by mass to 1% by mass, and a preferred range is 3% by mass. ~10% by mass. Further, from the viewpoint of further improving the flexibility, the photosensitive resin composition preferably further comprises the following formula (11): [Chemical 8] A-U-fC3He, C^tr^P^ •. Seven

• · · (I (wherein, R3 and R4 are each independently a hydrogen atom or a sulfhydryl group, ... and n? are each independently an integer of 〇~20, ... + shame is an integer of '仙,' and ... are independently 1 An integer of 〜2〇, n5 + n6 is an integer of 2 to 4 ,, and the arrangement of repeating units of -(C2H4-〇)· and (CM-O)· may be random or block, When 忒 is arranged as a block, _(C2H4_〇)_& _((:3Η6_〇)_ may be a bisphenol group side as a compound having ethylenic unsaturation In the case where the compound represented by the above formula (1) or (VI) is used in combination with the compound represented by the above formula (11), the photosensitive resin composition for further improving softness is disclosed. Although the details of the mechanism are not clear, it is presumed to be as follows. That is, it is presumed that when the compound represented by the formula (1) or (VI) is used in combination with the compound represented by the above formula (11) , to enhance the reactivity of photopolymerization. And 'the cured film after this exposure becomes stronger, and is presumed to be 16046.doc 201232173 In the above formula (II), ru and η? are each independently an integer of 〇~20, and ήβη7 is an integer of 0 to 40' ns and η6 are each independently an integer of 1 to 20, and ήβη6 is 2~ Further, it is preferable that the lower limit of η4 + η5 + η6 + η7 is 2 or more, and the upper limit is 40 or less. n4 + ns + n6 + n7 from the viewpoint of the softness of the cured film, It is preferably 2 or more. On the other hand, from the viewpoint of resolution, it is preferably 40 or less. Further, from the viewpoint of etching resistance, the lower limit of the range of ru+k+r^+n7 is better. 4 or more, the upper limit is (10) or less, and the lower limit of the range is more preferably 6 or more, and the upper limit is 12 or less. Further, from the viewpoint of supportability, the lower limit of the range of ...+~+...+shame is 16 or more. The upper limit is 40 or less, and the lower limit of the more preferable range is 40 or less. Further preferably, ... and η are each independently an integer of 1 to 1 ,, more preferably an integer of Wn 7 2 to 20, and more preferably, The specific example of the compound represented by the above formula (11) is exemplified by the addition of both ends of the double A Ethylene glycol methacrylate with 2 moles of ethylene oxide, or ethylene glycol with an average of 5 moles of ethylene oxide at both ends of the double ages The acrylate and the two bisphenol A are bis-acrylic vinegars which are added with an average of 6 moles of ethylene oxide, and the oxidized propylene of the ear is 15 苴 and π π, The both ends are added with an average of ethylene oxide of the ear and an average of 2 moles of oxygen methacrylate, etc. One of the alcohols is a photosensitive resin or a solid component when the amount of the photosensitive resin composition is %. The compounding amount of the compound 160046.doc 201232173 represented by the above formula (Π) in the mass is set to HK) is preferably 5f% by mass to 2% by mass. The amount of the blending is preferably 5% by mass or more, and from the viewpoint of the softness of the cured film, the blending amount is preferably 20% by mass or less. A more preferable range of the blending amount is 5% by mass to 5%, and the amount is preferably from 7% by mass to 5% by mass. The photosensitive resin composition preferably further comprises the following general formula (III) from the viewpoint of the softness of the iUI-lifting film: [Chemical Formula 9]. —. Such as the power of coffee. ..., · . · (丨丨丨) 5 and R_6 are independent of hydrogen or sulfhydryl groups, w and & are respectively independent integers from 3 to 40, and _(C2H4-〇)- and _(C3H6-0 The arrangement of the repeating units may be random or block compounds as (c) compounds having ethylenically unsaturated double bonds. In the compound represented by the above formula (111), from the viewpoint of improving the flexibility of the cured film, it is preferred that W and Μ are each independently an integer of 3 or more, and more preferably an integer of 5 or more. Specific examples of the compound represented by the above formula (ΠΙ) include, for example, a polyalkylene glycol in which an average of 1 mole of ethylene oxide is added to a polypropylene glycol having an average of 9 moles of propylene oxide. Methacrylate and the like. The total solid content of the photosensitive resin composition was set to 丨00 mass 0/. In the photosensitive resin composition, the compounding amount of the compound 160046.doc 19 201232173 represented by the above formula (ΠΙ) is preferably from i% by mass to 20% by mass. The blending amount is preferably 丨% by mass or more from the viewpoint of obtaining the softness of the cured film, and is preferably 20% by mass or less from the viewpoint of etching resistance. A more preferable range of the blending amount is 3% by mass to 15% by mass, and further preferably a range of 5% by mass to 1% by mass. The photosensitive resin composition preferably further comprises the following general formula (IV) and/or (v) from the viewpoint of improving the flexibility of the cured film: [Chemical 10] r5 ο 〇 % H2C = ic - 〇 ^ C2H4 -〇^c3He-〇^c2H4-〇^—!!--i=CH2 2 . ( IV) {wherein, Rs and R6 are each independently a hydrogen atom or a sulfhydryl group, and ni〇~ni2 are independently 1 An integer of ~30} [化11]

Rs Ο 〇R H2C_c—c—〇—(-C3H6-〇-)—(-c2H4-〇|—(-c3He-〇-)—c—C=CH2 Πι° °11 n12 * · · (V) { In the formula, Rs and Re are each independently a hydrogen atom or a methyl group, and ni〇~ni2 are each independently an integer of from 1 to 30. The compound shown is (C) a compound having an ethylenically unsaturated double bond. In the compound represented by (IV) or (V), from the viewpoint of enhancing the flexibility of the hardening enthalpy, it is preferred that n1G to ni2 are each independently an integer of i or more, and more preferably an integer of three or more. 160046.doc • 20- 201232173 A specific example of a compound of (Γ) or (V) heart, for example, may have an average of 18 moles of propylene oxide on the polypropylene glycol, and then add an average of 7 moles of oxidation B at both ends. Dilute diol methacrylate-methyl acrylate vinegar; in addition to an average of 18 moles of propylene oxide polypropylene: yeast, 9 and add an average of 3 moles of ethylene oxide at each end The diol-methyl acrylate acid is added to the polypropylene glycol with an average of 12 moles of propylene oxide, and the average of 3 moles of ethylene is added to the ping on the ping. An alcohol-burning dimethyl acrylate vinegar; on the addition of an average of 6 moles of ethylene oxide on the polyethylene glycol, and then add an average of 6 moles of propylene oxide on both ends of the polyalkylene Alcoholic dimethacrylate vinegar and the like. When the total solid content of the photosensitive resin composition is set to 5% by mass, the compounding amount of the compound represented by the above formula (ιν) or (7) in the 'gremental resin composition is preferably 1 quality. quality. /. . The blending amount is preferably 1% by mass or more from the viewpoint of resistance to (four), and is preferably 3% by mass or less from the viewpoint of the flexibility of the cured film. More preferably, the blending amount is in the range of 5% by mass to 25% by mass, and further preferably in the range of 5% by mass to 23% by mass. The photosensitive resin composition preferably further contains a compound having at least one urethane bond in the molecule as a compound having an ethylenically unsaturated double bond. Specifically, it can be exemplified by a hexamethylene group. Monoisocyanate compound such as diisocyanate, toluene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2-hydroxypropyl (f-) acrylate, oligomeric B a urethane compound obtained by reacting a hydroxy (meth) acrylate compound such as a diol (meth) acrylate or an oligomeric propylene glycol (meth) acrylate, 160046.doc -21 - 201232173 has a knives The at least one urethane-bonded compound is preferably hexamethylene diisocyanate, toluene monoisocyanate, 2,2,4-trimethylhexaarene, for example, from the viewpoint of 14-grain. A urethane compound obtained by a reaction of a diisocyanate (tetra) compound such as a bis-isocyanate with an oligopropylene glycol (meth) acrylic acid. The total solid content of the photosensitive resin composition is set to 1 〇. 〇 mass / 〇, in the photosensitive resin composition The compounding amount of the compound having at least one amino group 曱g曰 bond in the above molecule is preferably 5 mass% / 〇. The amount of the compound is preferably 5% by mass or more in terms of etch resistance. From the viewpoint of the nature, it is preferably 2% by mass or less. A more preferable range of the blending amount is 8 mass% / 2 〇 mass. / 〇, and further preferably, the range is 8 mass% to 17 mass% β photosensitive The resin composition preferably further contains a compound having an isocyanuric acid group in the molecule as (C) a compound having an ethylenically unsaturated double bond. Specifically, as a compound having an isocyanuric acid group in the molecule, for example, Ethyl ethoxylated isocyanuric acid triacrylate, ε-caprolactone modified mono-(2-propenyloxyethyl) isocyanurate, modified by ε_caprolactone Bis-(2-propanyloxyethyl)isocyanurate, tris(2-propenyloxyethyl)isocyanurate modified by ε_hexyl vinegar, isocyanuric acid Ethylene oxide modified acrylate, ethylene diacetate modified by isocyanuric acid oxyethylene, isocyanuric acid Ethylene-modified triacrylate, acrylate modified by isocyanuric acid propylene oxide, diacrylic acid ester modified by propylene oxide isocyanurate, propylene oxide modified triacrylate by isocyanuric acid, etc. The total solid content of the photosensitive resin composition is set to 1〇〇f -22-160046.doc

When the amount of S 201232173 is %, the compounding amount of the compound having an isocyanuric acid group in the molecule in the photosensitive resin composition is preferably from 1% by mass to 2% by mass. The amount of the coating is preferably from 1% by mass in terms of the etch resistance, and is preferably from 2% by mass or less from the viewpoint of the flexibility of the cured film. The blended amount is preferably in the range of 1% by mass to 15% by mass, and further preferably in the range of 2% by mass. ~10% by mass. In addition to a compound selected from the group consisting of the compounds represented by the above formulas (I) to (VI), a compound having at least one amine phthalate bond in the molecule, and a compound having an isocyanuric acid group in the molecule. The photosensitive resin composition other than the compound may further comprise a photopolymerizable ethylenically unsaturated compound as (C) a compound having an ethylenically unsaturated double bond as follows: Specifically, as a photopolymerizable ethylene Examples of the unsaturated compound include polypropanol di(meth)acrylate, polyethylene glycol (meth)acrylate, 2-di(p-hydroxyphenyl)propane (f-) acrylate, and glycerin ( Mercapto) acrylate, trimethylol tris(mercapto) acrylate, polyoxypropyl dimethylolpropane tri(meth) acrylate, polyoxyethyl trimethylolpropane di(meth)acrylic acid Ester, pentaerythritol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylpropane triglycidyl ether tri(meth) acrylate, phenoxy polyethylene glycol (fluorenyl) acrylate Mercaptobenzene Polyethylene glycol (Yue-yl) acrylate. These may be used alone or in combination of two or more. The mass of the total solid component of the photosensitive dendritic composition is set to 1 〇 ° mass ° /. In the case of the photosensitive resin composition, the compounding amount of the (C) ethylenically unsaturated double bond in the photosensitive resin composition is preferably from 5% by mass to 5% by mass. . The deployment is 160046.doc -23- 201232173. The amount is preferably 5 mass/〇 or more in terms of sensitivity, resolution, and adhesion, and is preferably 50% by mass or less from the viewpoint of suppressing the peeling delay of the cold flow and the hardened resist. The blending amount is more preferably "% by mass to 45% by mass. <leuco dye, fluorin dye, coloring matter> The photosensitive resin composition may further contain a leuco dye, a fluorin dye or a coloring matter. These dyes make the exposed portion develop color, so that it is preferable in terms of visibility, and the contrast between the exposed portion and the unexposed portion when the inspection machine or the like reads the position for exposure to show the situation. The larger one is easier to identify and is more advantageous. As the leuco dye, tris(4-dimethylaminophenyl)methane [leuco crystal violet], bis(4-dimethylaminophenyl)benzene The base methane [hidden malachite green] ° is particularly preferably a leuco crystal dye as a leuco dye from the viewpoint of a good contrast. As a fluorin dye, a 2-(dibenzylamino group) is exemplified. ) fluorin, 2-anilino-3-methyl-6-diethylamino fluorane, 2-anilino-3-methyl-6-dibutylamino fluorane, 2-anilino-3- Methyl-6-N-ethyl-N-isoamylamino fluorane, 2-anilino-3-methyl-6-N-indenyl-N-cyclohexylamino fluorane, 2-anilinyl 3- gas-6-diethylamine Fluorane, 2-anilino-3-indolyl-6-N-ethyl-N-isobutylamino fluorane, 2-anilino-6-dibutylamino fluorane, 2-anilino- 3-mercapto-6-N-ethyl-N-tetrahydrofurfurylamino fluorane, 2-anilino-3-methyl-6-piperidinylamino fluorane, 2-(o-anilinoyl) - 6-diethylamino fluorane, 2-(3,4-dianiline)-6-diethylamino fluorane, etc. The total solid content of the photosensitive resin composition is set to 100. The content of the leuco dye or the fluorescein dye in the photosensitive resin composition is preferably 0.1% by mass to 1% by mass. The content is the exposed portion and the unexposed portion. The viewpoint of the contrast is preferably 〇1% by mass or more, and is preferably 1% by mass or less from the viewpoint of maintaining storage stability. Examples of the coloring matter include magenta and phthalocyanine green. Golden amine base, p-magenta, crystal violet, methyl orange, Nero blue 2B, Victoria blue, malachite green (Aizen (registered trademark) manufactured by Hodogaya Chemical Industry Co., Ltd., MALACmTE GREEN), alkaline blue 2〇 Diamond green Aizen (registered trademark), diam〇nd GREEN GH) manufactured by Kasei Kogyo Co., Ltd.. When the total solid content of the photosensitive resin composition is 100 mass%, the photosensitive resin composition is a coloring substance. The content is preferably 质量.〇〇1% by mass to 丨% by mass. The content is preferably 0.001% by mass or more from the viewpoint of operability improvement, and is preferably 1 mass from the viewpoint of maintaining storage stability. In the embodiment of the present invention, it is preferable to use a leuco dye and the following halogen compound in the photosensitive resin composition in view of adhesion and contrast. As the functional compound, for example, bromopentane, bromoisopentane, brominated isobutylene, bromide #, diphenyl bromide & benzyl bromide, dibromodecane, tribromomethylphenylsulfone , carbon tetrabromide, tris(2,3·dibromopropyl)phosphate, trimethylacetamide, iodopentane, iodoisobutane, u, trichloro-2,2•bis(p-chlorobenzene) Ethyl bromide, gasified trimorphine compound, etc., especially tribromomethylphenylhydrazine. When the total solid content of the photosensitive resin composition is 100 160046.doc -25 to 201232173% by mass, the content of the halogen compound in the photosensitive resin composition is preferably 0.01% by mass to 3% by mass. The blending amount is preferably 0.01% by mass or more from the viewpoint of obtaining adhesion and contrast, and is preferably 3 mass in terms of storage stability. /❶The following. <Radical polymerization inhibitor, benzotriazole, carboxybenzotriazole> Further, in order to improve the thermal stability and storage stability of the photosensitive resin composition, the photosensitive resin composition may further contain a selected from At least one or more compounds selected from the group consisting of a radical polymerization inhibitor, an intrinsic trisalt, and a sulphonic trisalt. Examples of the radical polymerization inhibitor include p-methoxy group, p-benzoic acid, o-benzotrizene, cedaramine, t-butyl catechin, vaporized cuprous, and 2'6-di- Tributyl-p-methyl, 2,2,-methylenebis(4)methyl-tert-tert-butylenemethylenebis(4-ethyl-6-t-butylene), arginylphenylhydroxylamine aluminum salt, Diphenylnitrosamine and the like. Examples of the benzotriazoles include 1,2,3-benzotriazole, Buqi-1,2,3-benzotriazine, and bis(Ν'2.ethylhexyl)aminone. Benzo-benzotriazine, bis(tetra)ethylhexyl)aminomethylene·123 methylbenzotrisene, bis(N_2-traethylethyl)aminomethylene·benzotrisene, and the like. As a basic and three. Sitting class, for example, may be exemplified by: 4 side groups], benzotriazole, 5-carboxy_丨2 3_ lean, the present oxadiazole, N_(N,N_:_2-ethylhexyl)aminomethylene group Kexiao 41-, oxadiazole, N_(N,N-di-2-hydroxyethyl)aminomethylene sulfhydryl benzotriene, sitting, ·^ r —, Ν·(Ν,Ν-diethyl Hexyl) amine group ethyl carboxy benzotriazole and the like. Radical polymerization inhibitor, benzene 160046.doc relative to the entire photosensitive resin composition

-26· 201232173 The total content of the whole class and the slow-base benzotriazoles is preferably 〇.〇丨quality. More preferably, it is 5 mass% to 1 mass%. In view of the storage stability of the photosensitive resin composition, the content is preferably 3% by mass or more from the viewpoint of maintaining sensitivity and suppressing discoloration of the dye. . <Plasticizer> The photosensitive resin composition may optionally contain a plasticizer. Examples of such a plasticizer include phthalic acid esters such as diethyl phthalate, o-f-benzenesulfonamide, p-toluenesulfonamide, tributyl citrate, and citric acid diethylbenzene. Stuffed, triethyl citrate triacetate, triterpene citrate tri-n-propyl ester, acetaminophen citrate tri-positive, polyethylene glycol, polypropylene glycol, polyethylene glycol terephthalyl ether, polypropylene glycol Alkyl ether and the like. When the total solid content of the photosensitive resin composition is J 〇〇% by mass, the content of the plasticizer in the photosensitive resin composition is preferably from 质 5% to 50% by mass. /◦, better for 丨~ child quality. The content is preferably 1% by mass or more from the viewpoint of imparting flexibility to the cured film, and is preferably 50% by mass or less from the viewpoint of suppressing insufficient hardening or cold flow from the viewpoint of imparting flexibility to the cured film. <Solvent> The solvent for dissolving the photosensitive resin composition may, for example, be a ketone represented by MEK 'methyl ethyl ketone, and represented by decyl alcohol, ethanol or isopropanol. Alcohols, etc. The solvent is preferably added to the photosensitive resin composition 16046.doc -27 so that the viscosity of the solution of the photosensitive resin composition coated on the support film becomes 500 mPa·s to 4000 mPa·s at 25 Å. - 201232173. <Photosensitive Resin Laminate> In the present embodiment, the photosensitive resin laminate includes a photosensitive resin layer containing a photosensitive resin composition and a support film. Further, it is preferable to laminate the photosensitive resin layer on the support film as needed, or to provide a protective layer on the surface opposite to the support film side of the photosensitive resin layer. As the branch film, a transparent person that transmits light emitted from the exposure light source is preferable. Examples of such a wrap film include a polyethylene terephthalate film, a polyethylene glycol film, a polystyrene film, a gas ethylene copolymer film, a polyvinylidene chloride film, and a gas-off ethylene copolymer film. , polymethyl methacrylate copolymer film 'polystyrene film, polyacrylonitrile film, styrene-bake copolymer film, poly-branched film 'fiber (four) biofilm, and the like. These films may also be used as an extension, preferably haze 5, as desired. The thinner the thickness of the thin enamel, the more advantageous it is in terms of image formation and economy, but in order to maintain the strength, it is preferable to use 10 μm to 30 μm. An important characteristic of the protective layer used in the photosensitive resin laminate is that the protective layer is sufficiently smaller than the support film to be easily peeled off from the contact with the photosensitive resin layer. For example, a polyethylene film, a poly(tetra) film or the like can be preferably used as the protective layer. Further, it is also possible to use a film excellent in peeling property disclosed in Japanese Laid-Open Patent Publication No. 59-59. The film thickness of the protective layer is preferably 1 〇 μ 1 〇〇 μιη ‘ more preferably 1 〇 μιη 〜 5 〇. The thickness of the photosensitive 11-tree layer in the photosensitive resin laminate is different depending on the application, but it is preferably $μ1〇〇μιη', more preferably 7 μm to 6〇 (four), and the thinner the resolution is, the more The thicker the film strength. Furthermore, without the need for higher depressions, 160046.doc

In the case of the use of the photosensitive resin layer, the thickness of the photosensitive resin layer in the photosensitive resin laminate is preferably 10 μm to 20 μm. In terms of the surname, it is more than 1 〇, and in terms of resolution, it is 20 μηι or less. &lt;Production Method of Photosensitive Resin Laminate&gt; A method of producing a photosensitive resin laminate by sequentially laminating a support film, a photosensitive resin layer, and optionally a protective layer can be carried out by a known method. For example, a photosensitive resin composition used for a photosensitive resin layer can be mixed with a solvent which dissolves them to form a uniform solution. First, the solution is applied to the solution using a bar coater or a roll coater. The support film is then dried to laminate a photosensitive resin containing the photosensitive resin composition on the support film. Then, if necessary, a protective layer is laminated on the photosensitive resin layer, whereby a photosensitive resin laminate can be produced. &lt;Manufacturing Method of Substrate Having Resist Pattern&gt; Hereinafter, an example of a method of manufacturing a substrate on which an anti-contact agent pattern is formed using a photosensitive resin laminate will be described. The substrate thus fabricated is etched or plated as needed, whereby a circuit substrate or a printed circuit board can be manufactured. The method of manufacturing a substrate on which a resist pattern is formed using a photosensitive resin laminate, and a circuit substrate or a printed circuit board using the substrate include the following steps. Further, either of the steps (4) and (4') may use either or both of these. (1) Laminating step The protective layer of the photosensitive resin laminate is peeled off, and the photosensitive resin laminate is adhered to a substrate such as a copper foil laminate or a flexible substrate by using a heat spreader. 160046.doc -29- 201232173 (2) The exposure step allows the mask film having the desired wiring pattern to be adhered to the support (for example, a support film or the like) and exposed using an active light source, or by direct drawing. The wiring pattern performs the step of exposure. (3) Developing step After the exposure, the step of peeling off the support on the photosensitive resin layer, and then developing the unexposed portion by using a developing solution of 絵:water&gt; gluten solution to form an anti-surname pattern on the substrate . As the aqueous solution, for example, an aqueous solution of Na2c〇3 or k2C03 can be used. The aqueous solution can be appropriately selected depending on the characteristics of the photosensitive resin layer, and is usually a Na2CO3 aqueous solution having a concentration of about 0.2% by mass to 2% by mass and about 2 〇 ° c to 4 °C. The resist pattern can be obtained through the above steps, and a heating step at about 100 ° C to 300 ° C can be carried out as the case may be. The chemical resistance can be further improved by carrying out the heating step. A heating furnace that uses hot air, infrared rays, or far infrared rays can be used for heating. (4) etching step: spraying the etching solution from the formed resist pattern to etch the copper surface not covered by the resist pattern. The surname step can be applied to acid etching, inspecting, etc. This is carried out by the method of using the photosensitive resin laminated body. (4.) Electroplating step A step of plating on a substrate on which a resist pattern is formed is performed using copper plating, tin-plated lead or the like. 160046.doc 30·201232173 A method of electroplating using a substrate as an electrode, and the like. (5) After peeling off, the resist pattern is peeled off from the substrate by using an aqueous solution having a stronger proof than the developer. The alkali aqueous solution for peeling is also not particularly limited, and the use concentration is about 2% by mass to 5% by mass, and the temperature is about 4 Torr. 〇~7〇. An aqueous solution of NaOH, KOH or the like. A small amount of a water-soluble solvent may also be added to the stripping solution. As described above, the present embodiment relates to a photosensitive resin composition which can be developed by using an aqueous alkaline solution, a photosensitive resin laminate which laminates the photosensitive resin composition on a support, and a laminate of the photosensitive resin. A method of forming a resist pattern on a substrate, a use of the resist pattern, and the like. These photosensitive resin compositions and the like can provide a printed circuit board, a lead-like printed circuit board, and an IC (integrated circuit) wafer mounting lead frame (hereinafter referred to as a lead frame). Manufacturing, metal mask manufacturing and other metal foil precision processing, BGA (Ball Grid Array), CSP (Chip Scale Package), semiconductor package manufacturing, TAB (Tape Automated Bonding, volume. Manufacture of semiconductor tape bumps, including the manufacture of semiconductor tapes, and the manufacture of semiconductor bumps, which are represented by "Chip On Film" (Chip On Film: a semiconductor wafer, IC mounted on a thin film-like circuit board) A resist pattern produced by a member such as an IT (Indium Tin Oxides) electrode, an address electrode, or an electromagnetic wave mask in the field of display is preferable. [Examples] 160046.doc • 31 - 201232173 Hereinafter, the examples 1 to 14 and the comparative examples 1 and 2 will be more specifically described. First, the method for producing the sample for evaluation of the examples and the comparative examples will be described, and then the evaluation method for the obtained sample and the evaluation result thereof will be described. (1) Method for producing sample for evaluation The samples for evaluation in the examples and comparative examples were produced as follows. &lt;Production of Photosensitive Resin Laminate&gt; A photosensitive resin composition and a solvent filling agent having the composition shown in the following Table 1 (wherein the number of each component indicates the amount (parts by mass) of the solid content component) The mixture was stirred and mixed to prepare a photosensitive resin composition preparation solution, and the preparation liquid was uniformly applied to a l6 pm thick poly-p-ethyl methacrylate film (Mitsubishi p〇丨yes) as a support by a bar coater. Him Co., Ltd. manufactures the surface of 'R130-16) and drys it in a 95 〇c dryer for 1.5 knives to form a photosensitive resin composition layer. The photosensitive resin layer has a thickness of 15 μm. Then, a 19 μπ thick polyethylene film which is a protective layer on the surface of the unstacked polyethylene terephthalate film of the photosensitive resin composition layer (manufactured by Tamap〇ly Co., Ltd., GF_8丨8) A photosensitive resin laminate was obtained. In the following Table 2, the names of the material components of the photosensitive resin composition preparation liquid indicated by the abbreviation are shown. <Overall surface of the substrate> As an evaluation substrate for developability and etching resistance, a laminate of 35 i60046.doc is used.

&quot;S -32- 201232173 1.6 mm thick copper foil laminate with rolled copper foil. The surface of the substrate was subjected to wet polishing roll polishing (manufactured by 3M Co., Ltd., Sc〇tch_Bdte (registered trademark) HD #600, passed twice). &lt;Laminating&gt; The polyethylene film of the photosensitive resin laminate was peeled off, and the laminate was heated at a roll temperature of 105 ° C by a heating roll laminator (AL_7〇〇 manufactured by Asahi Kasei Co., Ltd.) to preheat the surface. To 60 〇c copper foil laminate. The air pressure was set to 0.35 MPa 'The lamination speed was set to 2.0 m/min » &lt;Exposure&gt; The mask film required for the evaluation of the photosensitive resin constituent layer was placed on the polyethylene terephthalate as a support. On the film, for Example 6, Example 9 to 14, and a comparative example, exposure was performed at an exposure amount of 70 mJ/cm 2 using an ultrahigh pressure mercury lamp (manufactured by 〇^ Manufacture Co., Ltd. 'HMW-801). 7 and 8, using a direct drawing exposure device (Hitachi

Manufactured by Via Mechanics, Inc., DI exposure machine dejdh, light source: GaN blue-violet diode 'main wavelength 4 〇 5 ± 5 nm) was exposed at an exposure of 15 mJ/cm 2 . In the evaluation sample of the softness of the cured film, the mask film required for the evaluation was placed on a polyethylene terephthalate film as a support of the photosensitive resin laminate produced as described above, and Examples 1 to 6, Examples 9 to 14, and Comparative Examples 1 and 2' were exposed by an exposure amount of 70 mJ/cm 2 using an ultrahigh pressure mercury lamp (manufactured by 〇rc Manufacturing Co., Ltd., HMW-801). For Examples 7 and 8, a direct drawing exposure apparatus (manufactured by Hitachi Via Mechanics Co., Ltd., di exposure machine DE-1DH, light source: 160046.doc • 33-201232173) was used.

The GaN blue-violet diode 'main wavelength 405 Å 5 nm) was exposed at an exposure of 15 mj/cm 2 . &lt;Development&gt; The substrate for the evaluation of the developability and the resistance (four) was used in an experimental polymerizer (manufactured by Fuji Machine Co., Ltd., a dry film developing machine) after the polyethylene terephthalate film. The % mass %iNa2C〇3 aqueous solution is sprayed for a specific time' to dissolve and remove the unexposed portion of the photosensitive resin layer. At this time, development was carried out at twice the minimum development time to prepare a hardened anti-surname pattern. In addition, the minimum development time means the shortest time required to dissolve the photosensitive resin layer of the unexposed portion as described above. In the evaluation sample of the softness of the cured film, after the polyethylene film was peeled off, development was carried out under the same conditions twice under the condition of f small development time to obtain a hardening anti-money agent. &lt;Etching&gt; A steel salt etching apparatus (manufactured by Tokyo Chemical Machinery Co., Ltd., copper salt etching device) was used to develop a vaporized cuprous copper concentration of 250 g/L on the evaluation substrate on which the resist pattern was formed by development. The vaporized cuprous (4) liquid of the hydrochloric acid concentration of 3 m〇1/Li5〇t is sprayed between the four (four) to dissolve and remove the copper foil which is not covered by the anti-narrant pattern on the (4) laminate. &lt;Peeling&gt; After the etching, the substrate was sprayed with a 3% by mass aqueous solution of sodium hydroxide heated to 5 〇〇c to peel off the hardened anti-money agent. (2) Evaluation method of the sample Next, the evaluation method of the sample will be described. Doc -34·201232173 (1) Developability According to the above (1) Evaluation sample layering and development to obtain an anti-surname method, a substrate is produced and divided as described above. Based on the minimum "time, such as A: minimum development time 14 seconds or more b: minimum development time is 1 〇 second or more and less than 14 seconds C: minimum development time is less than 1 〇 second (ii) etch resistance According to the above (1) method for producing a sample for sweat price, Passing the substrate for the _ evaluation of the substrate through the exposed portion Exposure width ratio of 1 = 1 · Court Ann recognize Result

The line pattern mask of the hand is used to perform the exposure H twice the development time twice, and the time required to remove the copper f white is taken as the minimum etching time... J JL is the smallest The time of the engraving time is K4 times. The hardening anti-surname agent is peeled off with an aqueous solution of sodium hydroxide, and the conductor pattern is observed by an optical microscope. The basis is classified as follows:

BC Α: a conductor pattern was formed linearly. A conductor pattern was formed in a straight line without observing the penetration of the etching liquid, and the conductor pattern was not formed linearly by observing the penetration of the dragon etch liquid, and the flexibility of the cured film was observed. The photosensitive resin laminate produced by the above-described (1) method for producing a sample was developed by a length of 5 mm x 4 () mm and developed at a time twice the minimum development time to form an anti-silver agent. The 5 mm x 4 mm hardened resist was stretched at a speed of 100 mm/min using a tensile tester (manufactured by 0rientec Co., Ltd., 160046.doc • 35-201232173 RTM-500), based on the time The elongation of the hardened resist is classified as follows: A+: The elongation of the hardened resist is 45 mm or more A: The elongation of the hardened resist is 4 mm or more and less than 45 mm B: Hardening The elongation of the resist is 15 mm or more and less than 4 mm. C: The elongation of the hardened resist is less than 5 mm (iv) The cohesiveness makes the thickness of the photosensitive resin laminate 15 μηι, area 2〇 The photosensitive layer of m2 was dissolved in 200 ml of a 1 mass% iNa2C〇3 aqueous solution, and sprayed at a spray pressure of 0.1 MPa for 3 hours using a circulating spray apparatus. Thereafter, the developer was allowed to stand for 1 day and the generation of aggregates was observed. If a large amount of the aggregate is produced, a powdery or oily person is observed on the bottom surface and the side surface of the spraying device. The composition in which the developer has good cohesiveness does not generate such agglomerates ❶ based on the state of formation of the agglomerates, and the cohesiveness is classified as follows: A: Coagulum B is not generated at all: one part of the bottom or side of the spraying device Condensate C was observed on the whole. The aggregate was observed on the whole spray device. (v) The acid equivalent of the soluble polymer was determined as the acid when t, which means that it has! Equivalent silk test The determination of the mass of the soluble polymer h acid equivalent is based on the Pingyu automatic titrator (COM_555) manufactured by Hiranuma Industry Co., Ltd., using 氢氧化钠"m〇l/L sodium hydroxide and by potentiometric titration And proceed. 160046.doc

S • 36· 201232173 (Vi) Weight average molecular weight Weight average molecular weight can be obtained by GPC, Gel Permeation Chromatography (GPC, Gulliver, PU-1580, column: Showa Shodex (registered trademark) (1 &lt;^-807, 〖?-806]^, 1^-806M, KF-802.5) manufactured by Electric Co., Ltd., in series, moving layer solvent: tetrahydrofuran, using polystyrene A standard sample (a calibration curve obtained by Shodex STANDARD SM-105 manufactured by Showa Denko Co., Ltd.) was obtained in terms of polystyrene. (3) Evaluation results The evaluation results of the examples and comparative examples are shown in Table 1 160046.doc 37-201232173 £inch l 01 (Nr〇g»nr^ ο OH oo 1.0 so V —^Ί uu 0'-88 Oe οι 01 01 01 01 -·0 inch ·0 so so.o so υ ffl ma S'-16 inch one - -Ό For SOO 2 so.o so avv 1-1.1-' 0 pairs - - - Ό inch · 0 so so.o so ffl va ffl 99T6 SO inch - - οι οι 01 -Ό inch·0 so

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P^ r**» ^ »r&gt; νΛ NN NM NM wlwl ^1'5'1*1^1 13⁄4 iv 9-V 'V 3 'V 'V Iv 160046.doc •38· s 201232173[Table 2] The symbol component P, has a composition of styrene/methyl methacrylate/methacrylic acid (25/50/25 by weight), an acid equivalent of 344, and 35% of a copolymer having a weight average molecular weight of 51⁄4. The MEK solution p_2 (solid content) has a composition of methacrylic acid/styrene/n-butyl methacrylate/(30/20/50 by weight), an acid equivalent of 287, and a weight average molecular weight of 60,000. 47% (solids component) of the copolymer MEK solution p_3 has a composition of methacrylic acid / methyl methacrylate / stupid ethylene (weight ratio of 29/19 / 52), j man equivalent of 297 ' and weight average MEK solution P-4 having a molecular weight of 50,000 ^ copolymer of 38% (solid content) has a composition of mercapto methacrylate / methacrylic acid / n-butyl acrylate (weight ratio of 67 / 23/10), acid The MEK solution p_5 having an equivalent weight of 344 and a weight average molecular weight of 30% (solid content) of 200,000 liters of copolymer has a composition of methacrylic acid/benzyl methacrylate (weight ratio of 20/80), acid equivalent Is 430, and The MEK solution of 42% (solid content) of a copolymer having a weight average molecular weight of 55,000 has a mercaptoacrylic acid/2-ethylhexyl acrylate/benzyl methacrylate (weight ratio 25/10/) 65) The composition of the MEK solution having a cap equivalent of 350 and a copolymer of 41% (solid content) having a weight average molecular weight of 55,000 is methacrylic acid/benzyl methacrylate (weight ratio 20/) 80) The composition, the acid equivalent weight is 430, and the weight average molecular weight is 70% of the copolymer of 50% (solid content) of the MEK solution, 9-butanediol dipropionate M-2, & The two ends (four) are added with an average of 5 moles of oxidized 6 punctured polyacrylic acid vinegar ~~ (BPE-i〇f, ▲ product name made by Xinzhongcun Chemical Co., Ltd.)_ M-3 $双盼A The two ends are respectively added with an average of 6 moles of ethylene oxide and 2 moles of propylene oxide. Polyalkyl Xuezhi dimethacrylate P-6 P-7 M-1 M-4 From the reaction of hexamethylene diisocyanate with pentapropylene glycol monomethyl methacrylate to obtain dimethyl methacrylate amide M-5 | 4-mercaptosyl heptaethylene glycol dipropylene disulfide榇酩陆_Με-内内Ester-modified tris-(2-propene oxime-based) 羼齓 醅 醅 $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ Manufactured by the company, SR-494, M-6 M-7 1-8 _ tetraacrylate at the 4th end of isopentaerythritol with an average of 1 mole of argon ethylene has an average of 12 in the afternoon. Mohr's propylene oxide on polypropylene glycol, and then at both ends - such as an average of 3 moles of ethylene oxide of the polyphenols of the dimethicone, bred M-10 tetrabutyl diol diacrylate &quot; - M-11 Thirteen butanediol diacrylate m·13 sir B y from (iv) flattened to fear oxidized propylene with an average of 15 m M-14 2 polypyrene ratio 60/40 double powder type A Mixture of epoxy acrylate and tripropyl decyl ester obtained by esterification of trishydroxypropyl propane 1-1 1-2

1-3 TT 1-5 D-1 D-2

D-3 &quot;5T A-1 A-2 _2-(o-gas base)-4,5-di-peptidyl imidazole dimer 4,4'-bis(diethylamine) dicodone 9-stupid Acridine N-stupyl bite 2,4·diethylthiazinone 4-dimethylaminobenzoic acid ethyl ester diamond green leuco crystal violet. Bromomethyl stupyl hydrazine

Aizen Vitra brakes pure blue weight average molecular weight of 2000 polyacrylic acid bisphenol A on both sides of the addition of an average of 2 Xiaer -- a-3 I benzotriazine _ di-n-butylamino group A Base) - A-4 addition has 3 moles of nitroso-hydroxylamine aluminum 眵--- A-5 52|=|^4 field squid oxygen ^ fine cakes ifT A-6 | y Stupid sulfonate "Amine ------- a-7 base _4- via phenyl group] propionic acid 2 molar and triethylene glycol 1 molar 16046.doc -39· 201232173 [Industrially available The photosensitive resin composition and the laminate are preferably used for precision processing of a metal foil such as a printed circuit board, a flexible printed circuit board, a lead frame, or a metal mask, and a semiconductor such as BGA or CSP. Manufacture of packaged substrates, tape substrates such as TAB or COF, manufacture of semiconductor bumps, fabrication of ITO electrodes or address electrodes, electromagnetic wave masks, etc.

160046.doc • 40· S

Claims (1)

201232173 VII. Patent application scope: A photosensitive resin composition comprising (A) an alkali-soluble polymer, (B) a photopolymerization initiator, and (C) a compound having a ethylenically unsaturated double bond, And the (B) photopolymerization initiator is a 2,4,5·triarylimidazole dimer or an anthracene compound, and the (C) compound having an ethylenically unsaturated double bond includes the following formula ( The compound shown in I): [Chemical 1] 〇II CH2=CC-〇-f AO^BO ^A.〇)^~^=CH2 (I) {wherein, the heart and the ruler 2 respectively represent hydrogen atoms or Methyl, A is or C3H6 'in · (Α_〇) ηι and _(A_〇) n3•, the arrangement of repeating units of _c2H4 〇- and _c3H6_〇_ can be random or embedded In the case where the arrangement is a mourning stage, and any one of the C3H6 〇 may be a 〇·base side 'B is a valence bond of carbon number 4 to 8, and the number is (1). The integer, ~ is an integer of 〇~H) ηι+η3_~1(), and is an integer of 〇2〇. 2. The photosensitive resin composition of the present invention, wherein the compound (6) having an ethylenically unsaturated double bond further comprises a compound represented by the following formula (Π): [Chemical 2] Rj Ο H2C=c —c_〇. • · · (I 160046.doc 201232173 {wherein R3 and R4 are each independently a hydrogen atom or a methyl group, ... and n7 are each independently an integer of 0 to 20, and n4+n? is 〇~40 The integers, ~ and ... are each independently an integer from 1 to 20' n5+n6 is an integer from 2 to 40, and the arrangement of the repeating units of _(c2H4-0)- and _((:3 ratio-〇)- can be In the case of random, it may be a block, and in the case where the arrangement is a block, either of -(C2H4-〇)- and -(c3H6-0)- may be a bisphenol side}. The photosensitive resin composition of claim 2, wherein the above formula (11) is such that 'IU and η· are each independently an integer of from 1 to 20, and n4 + n7 is an integer of from 2 to 4 。. The photosensitive resin composition according to any one of claims 1 to 3, wherein the (A) alkali-soluble polymer is selected from the group consisting of styrene and/or (mercapto)acrylic acid benzyl ester as a copolymer component. In the molecule. The photosensitive resin composition according to any one of claims 1 to 4, wherein in the above formula (I), 'help is an integer from 1 to 10, and n1 + n3 is 〇. 6. If the request is 丨 to 5 The photosensitive resin composition according to any one of the above, wherein the compound (C) having an ethylenically unsaturated double bond further contains a compound having at least one amino phthalate bond in the molecule. The photosensitive resin composition of any one of the above-mentioned (C) which has the ethylenically unsaturated double bond, and further comprises the compound represented by the following formula (III): [Chemical 3] r5 〇, II I Η—c—c=ch2 n9 H2C—C—C— 160046.doc 201232173 (wherein R5ARA is independently a hydrogen atom or a sulfhydryl group, and ~ and ~ are each independently an integer of 3 to 40, and _((^4 The photosensitive resin composition according to any one of the items 1 to 7, wherein the photosensitive resin composition of any one of items 1 to 7 is the same as the photosensitive resin composition of any one of items 1 to 7, wherein The compound (C) having an ethylenically unsaturated double bond further includes a compound represented by the following formula (IV) and/or (V): [Chemical 4] R5 〇 H2C==C—C-O—(-C2H4-〇-)-(c3H6-〇)- n10 ^-C2H4-〇-j-C ni2 IV) {wherein R5 and R_6 are independent hydrogen atoms or methyl groups, respectively, n1〇~ni2 are independent integers from 1 to 30} [H5] H °\ Re H2C=C - C-0-fc3H6-〇t (c2H4-〇tfc3H6-〇7-U-i=CH2 (7) {wherein R5 and R6 are each independently a hydrogen atom or a sulfhydryl group, and η! 0~n! 2 are each independently an integer of 1 to 30}. The photosensitive resin composition according to any one of claims 1 to 8, wherein the compound having the ethylenically unsaturated double bond as the above (C) further contains a compound having an isocyanuric acid group in the molecule. The photosensitive resin composition according to any one of claims 1 to 9, wherein the amount of the (A) alkali-soluble polymer is adjusted when the total solid content of the photosensitive resin composition is 100 mass 〇/0. When the mass of the total solid content of the photosensitive resin composition is 100% by mass, the amount of the photopolymerization initiator (B) is 0.1% by mass, and the amount of the photopolymerization initiator is 0.1% by mass. ~20% by mass, and when the total solid content of the photosensitive resin composition is set to 1% by mass, the above (C) has B The compounding amount of the compound of the unsaturated double bond is 5 mass% / 〇 〜 50% by mass. 11. A photosensitive resin laminate which will contain the photosensitive resin combination according to any one of claims 1 to 10. A photosensitive resin layer is laminated on a support film. 12. A method of manufacturing a substrate having a resist pattern, comprising the steps of: laminating a photosensitive resin layer as claimed in claim 11 on a substrate a step of laminating, an exposing step of exposing the photosensitive resin laminate to a mask, and a developing step of removing the unexposed portion. 13. A method of using a circuit board by using the method of claim 12 The manufactured substrate is etched or plated to form a circuit substrate. 160046.doc 4 S 201232173 IV. Designation of representative drawings: (1) The representative figure of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: 0 r2 II I CH2=C—C -0-(-AO^—(-B-0 )^f A-0 C—C=CH2 160046.doc