TW201001065A - Photosensitive resin composition and layered object obtained therewith - Google Patents

Abstract

A photosensitive-resin layered object is provided in which the photosensitive resin layer, even when having a thickness as small as 3-15 μm, has satisfactory tenting properties. The layered object includes a supporting layer, which does not peel off unintentionally, i.e., has a satisfactory peel strength. A photosensitive resin composition is also provided which comprises the following: (a) 20-90 mass% alkali-soluble resin, (b) 5-75 mass% compound having a photopolymerizable unsaturated double bond, and (c) 0.1-20 mass% photopolymerization initiator. The composition is characterized in that the compound having a photopolymerizable unsaturated double bond (b) comprises a compound represented by the following general formula (I): (I) {wherein R1, R2, R3, and R4 each independently is H or CH3; R5's each independently is propyl or butyl; n1+n2+n3+n4 is an integer of 21-50; and m1+m2+m3+m4 is an integer of 0-19 (the remainder being omitted)}.

Description

201001065 VI. [Technical Field] The present invention relates to a photosensitive i-ray tree, which can be developed by using an aqueous solution, and a mouthpiece which is formed of the photosensitive resin composition. A photosensitive resin laminate in which a light-reducing resin layer is laminated on a support layer, a method of forming a photoresist pattern on a substrate using the photosensitive resin laminate, and various uses of the photoresist pattern. More specifically, the present invention relates to a photosensitive resin composition which is suitable for the production of a printed circuit board, a flexible printed circuit board, and a lead frame for IC chip mounting (hereinafter referred to as a lead frame). Manufacturing, metal foil manufacturing and other metal foil precision processing, BGA (Baii Grid Array) or csp (chip size wafer size package) semiconductor package manufacturing, TAB (TapeAutQmated Bonding, tape and tape type) (automatic bonding) or (3) manufacturing of a strip substrate represented by "resolving 〇 n (7), film flipping: placing semiconductor 1C on a film-like micro-board), manufacture of semiconductor bumps, ITO in the field of flat panel displays (Indium Tin idexide, indium tin oxide) electrode, address electrode, or electromagnetic wave mask and other components of the photoresist pattern. [Prior Art] Previously, printed circuit boards were manufactured by photolithography. The photographic method refers to a method in which a photosensitive resin composition is applied onto a substrate, and pattern exposure is performed to thermally cure the exposed portion of the photosensitive resin composition, and development is carried out. A photoresist pattern is formed on the substrate by removing the unexposed portion, and a conductor pattern is formed by performing a residual or plating process, and then the photoresist pattern is peeled off from the substrate to form a conductor pattern on the substrate. Doc 201001065 In the above photolithography method, when the photosensitive resin composition is applied onto a substrate, any of the following methods is used: a method of applying a photoresist solution onto a substrate and drying it; Alternatively, a layer of a support layer, a layer formed of a photosensitive resin composition (hereinafter also referred to as "photosensitive resin layer"), and a photosensitive resin laminate of a protective layer as needed (hereinafter also referred to as " Dry film photoresist") A method of laminating on a substrate. Moreover, in the manufacture of printed circuit boards, the latter dry film photoresist is mostly used. Hereinafter, the method of manufacturing a printed circuit board using dry film resist will be described earlier. First, when the dry film photoresist has a protective layer such as a polyethylene film, it is peeled off from the photosensitive resin layer. Then, the photosensitive resin layer and the support layer are laminated on the substrate, for example, a copper vl laminate, in the order of the substrate, the photosensitive resin layer, and the support layer by a bonding machine. Next, the photosensitive resin layer was exposed to ultraviolet rays containing i-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. Next, a support layer such as polyethylene terephthalate is peeled off. Then, the unexposed portion of the photosensitive resin layer is dissolved or dispersed by a developing solution such as an aqueous solution having a weak alkalinity to form a photoresist pattern on the substrate. The method of fabricating a metal conductor pattern using the photoresist pattern on the substrate formed in the above manner is roughly classified into two methods: a method of removing a metal portion not covered by a photoresist, and a metal plating using a bell coating. The method. In particular, the method of the former is mostly used from the viewpoint of the simplicity of the steps. 139404.doc 201001065 In the method of removing the metal portion by using the photoresist, the photoresist is used to cover the through hole (via) of the substrate or the via hole for interlayer connection, thereby preventing the metal in the hole from being etched. . This method is called a cover hole method. In the cap hole method, it is required that the cured photoresist film is not damaged by etching, that is, it is excellent in capping property. In the etching step, for example, a copper chloride, a ferric chloride, a copper ammonia complex solution is used. With the miniaturization of wiring intervals in printed circuit boards in recent years, a narrow pitch pattern is favorably produced for good yield, and dry film photoresist is required to have high resolution and high capping property. As a method of improving the resolution, the resolution can be easily improved by reducing the thickness of the dry film photoresist, but there is a problem that the resistance to the physical external force of the film caused by the ejection in the developing step and the etching step becomes weak. Therefore, in the developing step and the surname step, the cured photoresist film cannot protect the via hole and the via hole (the cap hole property is poor). Patent Document 1 discloses a photosensitive resin composition containing four kinds of fluorenyloxypropyl groups having a specific number of oxime 1 as a photosensitive tree. Saturated compound. However, in the case of using the compound exemplified in the examples, there is a problem that the capping property is poor. Patent Document 2 discloses a photosensitive resin composition containing a photopolymerizable unsaturated compound having four (fluorenyl) acrylate groups. However, its cover porosity needs to be further improved. In the case where a large amount of the photopolymerizable unsaturated compound having a large number of (meth) acrylate groups is contained in the photosensitive resin composition, the support layer may be formed if the thickness of the photosensitive resin layer is reduced. Involuntarily easy 139404.doc 201001065 problem of peeling off. Therefore, for the thick layer of the photosensitive layer, 3⁄4 + # a ^ , U曰Η? Also, the laminated body is required to have a good cover hole and the support layer does not peel off involuntarily. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2000-347400 [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei 2 No. Hei. In the case of the case, the cap hole property is also good', and the support layer has sufficient peeling strength.

The photosensitive resin layered body in which the thickness of the resin layer to be solved is as small as 3 to 15 and the support layer is not involuntarily produced by the present invention. [Technical means for solving the problem] The inventor of the present application has worked diligently to solve the problem and repeated the investigation, and found that the above-mentioned materials can be unexpectedly solved by the following composition. Thus, the invention of the case was finally completed. That is, the present invention is as follows. [1] - a kind of photosensitive resin and personal components: 曰,, and. The product contains the following (a) alkali-soluble resin 20 to 90% by mass; (b) compound having a photopolymerizable polyfluorene/hydrazine, and an unsaturated double bond; 5 to 75 mass (C) photopolymerization The initiator is 0.1 to 20% by mass; and contains a compound selected from the group consisting of the following formulas (to a small amount of a compound as a == compound: 乍 is a top (b) has a photopolymerizable non-139404.doc Compound of 201001065: [Chemical 1] ch2

C2h,o j—CH2—c

Ch2

In the formula, R!, R2, R3, and R4 are each independently H or CH3, and R5 is independently a propyl or a butyl group, and n!, n2, n3, ri4, m2, m3, and rru are each independently 0 or positive. The integer, n 0112+113+114 is an integer from 21 to 50, and 11^+1112 + 1113 + 1114 is an integer from 〇 to 19, where -(c2H4-0)- and -(R5-〇)_ The arrangement of the repeating units may be random or block, and the order of _((:2114_〇)_ and -(Rs-O)- may be located on the central carbon side}. [2] The photosensitive resin composition of the above-mentioned (8) is a compound which has k to the group which consists of the compound represented by the following formula, and the (v) compound which has the photo-polymerizable unsaturated double bond: [Chemical 2] 139404.doc 201001065

CH

CH2 (Π)

In the formula, R5, R6, r7 & r8 and 丨4 are each independently 〇 or a positive integer number}. [3] The layer of the photosensitive resin composition described in the photosensitive resin laminate is independently H or CH3, and 1丨, i2, 込' and 1]+12 + 13 + 14 are 0 to 20, and Including the photosensitive resin layer formed by the above [1] or [2] and the forming half of the photoresist pattern supporting [4], LA is a method comprising: laminating on a substrate

The photosensitive layer described in the above [3] is a step of concentrating the photosensitive resin layer of the lining layer, exposing with active light, and exposing the unexposed portion. [5] The method for forming a pattern of light, +, a, and a particularly resistive pattern as described in the above [4], wherein the direct exposure pattern is exposed to the exposure step. [6] A method for fabricating a conductor pattern, the method comprising the steps of: using a copper foil laminate as a substrate in a method of forming a β L 9-resist pattern as described in [4] or [5] above; A method of manufacturing a substrate having an I-resistance pattern for etching or plating 139404.doc 201001065 m-type printed circuit board, characterized in that metal is used in a method of forming light P as described in broad or m and pattern formation The substrate on which the resist pattern is formed as a substrate is etched or plated by the insulating plate as a substrate, and the photoresist pattern is peeled off. [8] A method for producing a lead frame, which is characterized in that, in the method for forming a photoresist pattern as described in the above (4) or m, a substrate in which a metal plate is used as a substrate to form a photoresist pattern is formed. The etching is advanced, and then the photoresist pattern is peeled off. [9] A method of manufacturing a semiconductor package, characterized in that:

In the method of forming a photoresist pattern according to the above [4] or (5), a substrate having a photoresist pattern formed by using a wafer formed of an LSI: 3⁄4 channel as a substrate is plated, and then the photoresist pattern is peeled off. [10] A method for producing a substrate having a concave-convex pattern, characterized in that a substrate capable of being subjected to sandblasting in a method of forming a photoresist pattern as described above is used as a substrate by a sand blasting method The substrate on which the photoresist pattern is formed is cured, and then the photoresist pattern is peeled off. [Effects of the Invention] The photosensitive resin laminate of the present invention has the following effects: Even in the case where the thickness of the photosensitive layer is as thin as 3-5 日, the cap hole property is good, and the support layer does not. Involuntarily peeling off, that is, the support layer can obtain the separation strength. [Embodiment] Hereinafter, the present invention will be specifically described. <Photosensitive resin composition> 139404.doc 201001065 The photosensitive resin composition is characterized in that it contains the following components: (a) alkali-soluble resin 20 to 9 〇 mass %, (b) 5 to 75% by mass of a compound having a photopolymerizable unsaturated double bond, and (c) a photopolymerization initiator 〇1 to 2% by mass; and containing a compound selected from the following formula (1) At least one compound of the group consisting of the compounds represented as the above (b) a compound having a photopolymerizable unsaturated double bond: [Chemical 3]

In the formula, R!, R2, heart and ruler 4 are each independently H or CHS, and the hearts are respectively propyl or butyl, and ηι, n2, n3, ~, 叱, 叱, 叫, and 叫 are independently 0 or Positive integer, ...+~+"+~ is an integer of 2i~5〇, and mi+m2+m3+m4^; » jtb 4 ' -(C2H4-0)-^-(R5-0). The arrangement of το may be random or block, and the order of -(Rs-O)- may be located on the central carbon side. 139404.doc 201001065 For each component in the photosensitive resin composition In the case where the amount of the component is described, the amount of each component is described as the mass % when the solid content in the photosensitive resin composition is used as a reference. (a) The solvent-soluble resin is an alkali-soluble resin. And means a vinyl resin containing a carboxyl group, for example, a copolymer of (mercapto)acrylic acid, (meth)acrylate, (mercapto)acrylonitrile, (meth)acrylamide, etc. & (a) The soluble resin preferably contains a carboxyl group and has an acid equivalent of from 100 to 600. The acid equivalent refers to the mass of the alkali-soluble resin containing one equivalent of a carboxyl group. It is preferably 25 Å or more and 45 Å or less. The acid equivalent is preferably improved in terms of development resistance and improvement in resolution and adhesion, and is preferable in terms of developability and peelability improvement. The measurement of the acid equivalent is carried out by a potentiometric titration method using a sodium hydroxide automatic titrator (COM-555) manufactured by Hiranuma Industries Co., Ltd. using a sodium hydroxide of 0_1 m〇l/L. The weight average molecular weight of the alkali-soluble resin is preferably 70,000 or more and 220,000 or less. The weight average molecular weight of the alkali-soluble resin is preferably 220,000 or less in terms of improvement in developability, and the pore-covering property and the property of the agglomerate are preferable. Preferably, it is 7 〇 or more. The weight average molecular weight of the alkali-soluble resin is more preferably 7 Å or more, 2 Å, 〇〇〇 or less, more preferably 70 Å. 〇〇 Above, 12〇, 〇〇〇 below. The weight average molecular weight is a gel permeation chromatograph (Gpc, Gel) manufactured by 曰本分光(股)

Permeation Chromatography) (pump: Gulliver, pu-1580, pipe column: Showa Denko (registered trademark) (KF_8〇7, KF-139404.doc 12 201001065 806M, KF_806M, KF_802_5) ^ splicing, moving The bed solvent: tetrahydrofuran, which is obtained by using a polystyrene standard sample (a calibration curve manufactured by Showa Denko Co., Ltd., "STANDARD SM-105") and converted into polystyrene. The alkali-soluble polymer is preferably from the lower side. a copolymer composed of at least one of the first monomers and at least one of the following second monomers: The first monomer is a carboxylic acid or an acid anhydride having a polymerizable unsaturated group in the molecule. (Meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Among them, particularly good (曱The term "(meth)acrylic acid" means acrylic acid and/or methacrylic acid. The same applies hereinafter. The second monomer is a monomer which is non-acidic and has at least one polymerizable unsaturated group in the molecule. Give: ( Ethyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, Dibutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxyhexyl (meth)acrylate, (meth)acrylic acid Benzyl esters, vinyl alcohol esters such as vinyl acetate, (meth)acrylonitrile, styrene, and the present invention. Among them, methyl (meth)acrylate and (meth)acrylic acid are preferred. Butyl ester, styrene, benzyl (meth) acrylate. The copolymerization ratio of the first monomer to the second monomer is preferably 1 〇 6 6 〇 / / °, the second monomer It is preferably from 4 to 90 mass%, more preferably from 15 to 35 mass% of the first monomer and from 65 to 85 mass% of the second monomer. From the viewpoint of the porosity of the cap and the properties of the aggregate (a) alkali-soluble tree hunting contains 139404.doc 13 201001065 has a carboxyl group, an acid equivalent of 100-600, and a weight average molecular weight of 70,000~22 0,000 is a preferred embodiment of the present invention. (a) The ratio of the alkali-soluble polymer to the total of the photosensitive resin composition is in the range of 20 to 90% by mass, preferably 4 to 6 % by mass. The photoresist pattern formed by exposure and development has a property as a resist, such as a capping property, and sufficient resistance in etching and various plating steps, and is preferably 20 mass 〇/〇 or more. 9 〇 mass 0 / 〇 or less. (b) Compound having an unsaturated double bond capable of photopolymerization, a compound having an unsaturated double bond capable of photopolymerization, means having at least one ethylenic unsaturated in the molecule. The compound of the bond. Further, the photosensitive resin composition contains at least one compound selected from the group consisting of compounds represented by the following general formula (1) as (b) a compound having an unsaturated double bond capable of photopolymerization: [Chemical 4]

In the formula, R, R2, R3 and R4 are each independently Η or CH3, and R5 is independently propyl or butyl, respectively, η], n2, n3, n4, m2, m3 and m4 respectively 139404.doc - 14- 201001065 Independent is 〇 or a positive integer, n1+n2+n3+n^21~50 integer, and called ten out of the stir + called 〇~19 integer 'here, _ ((: 2 private _ 〇 The arrangement of the repeating sheets 70 of _ and _ (private) _ may be random or block, and the order of -(C2H4-〇)_ and -(Rs-O)- may be located at the center. The carbon side}. From the viewpoint of the capping property, ηι+η2+η3+η4 of the above formula is further preferably 21 to 40, more preferably 30 to 40. NK Ester ATM-35E). also

Specific examples of the compound from the group consisting of the compounds represented by the above formula (1) include, for example, R丨, 2, R3 and R4H′ ηι, n2, and ~ is a positive integer, ηι+η2+η3+η435, and m1+m2+m3+m4 is a compound of 〇(Xinzhongcun Chemical κ)

The compound selected from the group consisting of the compounds represented by the above formula (I) is particularly preferably a compound wherein at least nM + n^+ms+nu is 0 in the group consisting of the compounds shown. Preferred is a photosensitive resin composition

Further, in terms of pupillability, it is preferable to further contain at least one of the selected groups 139404.doc •15-201001065 and a compound of a double bond: [Chemical 5]

In the formula, R5 'R6, 尺7, and r8 are each independently ch or ch3, 1, 1, 1 and U are each independently 0 or a positive integer, and il+lrH3 + 14 is 〇~2〇 敕3 number}. Specific examples of at least one compound selected from the group consisting of the compounds represented by the above formula (Π) include R5, R6, and R7, and the heart is Η, li, h, I3, and Compound (NK Ester A-TMMT manufactured by Shin-Nakamura Chemical Industry Co., Ltd.); R5, R6, R7 and Rah, ^, l2, ^ and U are each independently 〇 or a positive integer, 11+丨2+13+ 14 is a compound of 4 (4, manufactured by Sart 〇 mer japan Co., Ltd.). Further, at least one compound selected from the group consisting of compounds represented by the above formula (Π) is used. Obtained by a suitable synthesis method. For example, if Ri, R2, & and R4 are Η, ηι+η2+η3 + η4 is 28, m ** + m2+m3+m4 is a compound of 8, J "T It is obtained by reacting pentaerythritol as a starting material with 2 & 139404.doc -16-201001065 Moer Ethylene Oxide to react the obtained product with 8 mol of propylene oxide, and the resulting product is in an appropriate acid. Esterification with acrylic acid in the presence of a catalyst. Also as (b) an unsaturated compound which can be photopolymerized, except In addition to the compound represented by the above formula (1) or the above formula (Π), a compound having an unsaturated double bond capable of photopolymerization may be used. For example, photopolymerization may be carried out as an octa (b). Examples of the unsaturated compound include 1,6-hexanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, and polyethylene glycol di(methyl). Acrylate, polyethylene glycol polypropylene glycol di(meth) propylene knockout, 2_bis(p-hydroxyphenyl)propane di(meth)acrylate, 2,2-bis[(4-(methyl)) Propylene oxime-polyalkyleneoxy)phenyl]propane glycerol tri(meth) acrylate, trimethylolpropane tris(mercapto) acrylate, polyoxypropyl dimethylolpropane tri Mercapto) acrylate, polyoxyethyltrihydroxydecylpropane triacrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tris(decyl) acrylate, bisphenol A Dimethyl sulphate 1) oleyl ether di(meth) acrylate, phthalic acid-β-hydroxypropyl-β,-(propylene decyloxy)propane S 曰, phenyloxy Ethylene glycol (meth) acrylate, fluorenyl aglycol based polyethylene glycol (fluorenyl) acrylate, nonyl phenoxy polyalkylene glycol (mercapto) - acrylate, polypropylene glycol mono (fluorenyl) Further, as the other (b) photopolymerizable unsaturated compound, a urethane compound may be mentioned. Examples of the urethane compound include hexamethylene diisocyanate. , phenylene diisocyanate, or a diisocyanate compound such as 2,2,4-trimethylhexamethylene diisocyanate, and a compound having a hydroxyl group and a (fluorenyl) acrylonitrile group in one molecule, such as a diene 139404.doc - 17-201001065 Amino-esterification of acid-2-hydroxypropyl ester, oligo-propylene di-pre- early methacrylate. Specifically, there is a reaction product of 'm 〇 methylene diisocyanate and oligopropylene glycol early methacrylate (曰 油 ,, BLEMMER PP1000). (b) The total amount of the compound having an unsaturated double bond capable of photopolymerization is preferably from 5 to 75% by mass based on the total amount of the photosensitive resin composition, and the content is formed by exposure. The photoresist pattern is sufficiently exhibited as a photoresist: from the viewpoint of performance: 5 mass % is μ ^ true 〇 / 〇 or more, and from the viewpoint of cold flow, it is 75 mass % or less. The content of the +-type compound in the group consisting of the compound represented by the formula (1) is preferably from 5 to 25 % by mass based on the total amount of the photosensitive resin composition. It is preferred that the mass of at least one compound selected from the group consisting of the compounds represented by the above formula (11) is 25% by mass relative to the photosensitivity. The total amount of the resin composition is preferably 疋10 40 Berry%. From the viewpoint of the capping property, it is preferably at least % by mass, and from the viewpoint of viscosity, it is preferably 4 〇 by mass or less 疋 (c) a photopolymerization initiator photosensitive resin composition, as c) The photopolymerization initiator may be generally used. The content of (c) photopolymerization squeak contained in the photosensitive resin composition is in the range of 0.1 to 2% by mass, and further preferably in the range of ~% by mass. From the viewpoint of obtaining sufficient sensitivity, it is preferable that the 〇1 is more than /. In addition, the light is sufficiently transmitted to the bottom surface of the resist to obtain the southern resolution of the household. In other words, it is preferably 20% by mass or less. ] 39404.doc -18· 201001065 r Examples of the photopolymerization initiator include 2-ethyl oxime, octaethyl hydrazine, and 1,2-stupid Bismuth, 2,3-benzopyrene, 2-phenylindole, 2,3-diphenylphosphonium, 1-chloropurine, 2-gastrim, 2-methylhydrazine, 1, 4-naphthoquinone, 9,10-phenanthrenequinone, 2_mercapto- 14-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthene, 2,3-dimercaptopurine Anthraquinones such as 3-chloro-2-indenyl hydrazine; aromatic ketones such as benzophenone Michlerone [4,4,-bis(didecylamino)benzophenone], 4,4,-bis(diethylamino)benzophenone; benzoin or benzoin ethers, such as benzoin , benzoin ethyl bond, benzoin phenyl ether 'mercapto benzoin, ethyl benzoin; dialkyl ketal, such as benzoin decyl ketal, benzoin diethyl ketal; 9-oxopurine For example, diethyloxanthene, chloro-9-oxosulfonate; dialkylamine-based acetophenones, for example: ethyl decylaminobenzoate; oxime esters, such as 1 _Phenyl-indole, 2-propanedione-2-0-benzylidene hydrazide, phenyl], 2-propanedione-ethoxymethyl) hydrazine; lophine dimer, For example, 2_(o-chlorophenyl)_4,5_two stinky...polymer, 2-(o-phenyl)-4,5-bis(m-methoxyphenyl)mastene: p-methoxy Phenyl)·4,5-diphenyl taste salic dimer; a hydrazine compound such as 9-phenyl acridine; pyrazoline-sodium oxalate, such as 1-phenyl-3-styryl-5-phenyl· σ ratio, 1 · η - its base -phenyl)-3-styryl-5-phenyl-indole porphyrin, phenyl_3_(4_di-le-butyl-present vinyl)-5-(4-tert-butyl-benzene Pyrazole and the like. These are the same - above. The blade J is used alone in the past, and it is also possible to use two kinds of them together, for the direct drawing and exposure, as the photopolymerization initiator "make" the sensitivity and the group of the compound === (10) Species compounds. When the compound is used as a starter in the case of 139404.doc -19-201001065, the content of the compound is preferably in the range of G.1 to 20% by mass based on the total amount of the photosensitive resin composition. The good range is from 0.5 to 10% by mass. From the viewpoint of obtaining sufficient feeling, the content is preferably 〇1 詈% 7 疋 1 1 董 Dong/0 or more, and further, the light is sufficiently transmitted to the bottom surface of the resist (the contact between the resist and the substrate) From the viewpoint of obtaining good high resolution, it is preferably 丨0% by mass or less. (d) Other components In order to improve the handleability of the photosensitive resin composition, the photosensitive resin composition may further contain a leuco dye or an incineration dye or a coloring matter as (4) other components of the "historic" leuco dye, which may be exemplified by: 4-dimethylaminophenyl)decane [hidden color. 曰曰篡], bis(4-dimethylaminophenyl)phenyl decane [hidden malachite green]. In the case of a leuco dye, it is preferred to use leuco crystal violet. In the case of containing a leuco dye, the content of the ruthenium dye is preferably 〇1 to 1% by mass in the photosensitive resin composition. From the viewpoint of the performance of the contrast, it is preferably 〇1% by mass or more, and from the viewpoint of maintaining storage stability, it is preferably 丨〇 quality. Hereinafter, from the viewpoint of adhesion and contrast. The leuco dye is used in combination with the halogen compound described below for the photosensitive resin composition, which is a preferred embodiment of the present invention. Examples of the coloring matter include magenta, phthalocyanine green, golden amine base, and magenta. (para magenta) 'Crystal violet, thiol orange, Nile blue 2B, dimension Dorian Blue, Malachite Green (AIZEN (registered trademark) MALACHITE GREEN), Basic Blue 20 'Diamond Green (Zhutu Valley B9404.doc •20· 201001065)

Chemical (version) manufacturing ΑΙΖΕΝ (registered trademark) DIAM 〇 ND GREEN GH). (3) When the coloring matter is present, the amount of addition is preferably έ()·0() 1 to 1 in the photosensitive resin group σ. In terms of operability improvement, the content is more than (%) disregarded by mass% or more, and in terms of maintaining a stable record, the content is preferably 1% by mass or less. From the viewpoint of sensitivity, the y-aryl-α-amino acid compound may also be contained in the sensible resin composition. As the Ν_aryl-α-amino acid compound, fluorene-phenylglycine is preferred. In the case where the Nna_amino acid compound is contained, the content is preferably 0.01% by mass or more and 1% by mass or less. The photosensitive resin composition may also contain a (tetra) compound. Examples of the (iv) compound include: molybdenum, lyophilized pentane, and desertified isobutylene' ^ dioxin, biphenylmethyl, benzene, m, m-methyl phenyl sulfone, tetrabromo Carbon, phosphoric acid tris(2,3-dibromo-diamine, pentylene, butyl ^(1)·three m bis (p-phenyl): alkane, chlorinated three-till compounds, etc., especially good for use The content of the material in the case of containing a halogen compound is 0. 01 to 3 mass% in the photosensitive resin composition. Further, it is heat stable of the k-photosensitive resin composition. Properties, storage stability, photosensitive resin composition can also be stepped into the right; / Α +, ν 3 攸 radical polymerization inhibitor, stupid triazole, and carboxy benzotriazole 乂 < At least one or more of the compounds selected from the group consisting of, for example, a silver salt-, a gas-based benzene, a benzoic acid, a stilbene, a naphthylamine, and a third Butyl phthalate, chlorinated copper, 2,6-di-t-butyl-p-nonylphenol, 2,2, _, and yttrium (4, methyl 139404.doc -21 . 201001065 Tributylbenzene age), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), nitrosophenylhydroxylamine aluminum salt, diphenylnitrosamine, and the like. Examples of the benzotriazoles include hydrazine, 2,3-benzotriazine, L gas-1,2,3-benzotriazole, and bis(N-2-ethylhexyl)aminone. Methyl 4,2,3. Benzotriazole, bis(N-2-ethylhexyl)aminomethylene 4,2,3-methylbenzotriazole, bis(N_2jfethylethyl)amine Methylene _i, 2, 3 benzotriazole, etc. Further, 'as a thiol benzotris, for example, a few groups -1,2,3-benzotriazole, 5-carboxyl group -1,2,3-benzotriazole, anthracene (team 1^_di_2_ethylhexyl)aminomethylenecarboxybenzotriazole, N_(N,N_:_2-hydroxyethyl)amine Methylene carboxy benzotriazole, N~(N,N-di-2-ethylhexyl)amine, ethyl thiobenzotrisene, etc. Free radical polymerization inhibitors, benzotriazoles, and carboxyl groups The benzotriazoles and the ketones of the benzotriazoles are preferably 0.01 to 3 parts by weight based on the total amount of the photosensitive resin composition. Further, G. (5) is preferably used in an amount of 5% by weight. The content is given to the photosensitive resin group From the viewpoint of storage stability, it is more preferably 5% by mass or more, and more preferably 3 mas. from the viewpoint of maintaining sensitivity. The photosensitive resin composition may also contain plastic as needed. The plasticizer may, for example, be a poly(ethylene) acid, a propylene glycol, a polyoxyethylene oxyethylene ether, a polyoxyethylene monomethyl ether or a polyoxypropylene monomethyl ether. a diol or an ester of polyoxypropylene monoterpene, polyoxyethylene (10), polyoxy(tetra)mono(di), polyoxyethylene polyoxypropylene monoethyl ether, etc.; phthalic acid diethyl ru: phthalic acid Class; o-toluene continuous amine, p-toluene continued:;: tributyl citrate, lemon brewed 2 妒, ^ ^ Wenyi B 曰, acetonitrile triethyl citrate, citric acid di-n-propyl Ester, B-tri-n-butyl citrate and the like. - 139404.doc •11· 201001065 The content of the plasticizer is preferably from 5 to 50% by mass, and more preferably from 5 to 3% by mass, based on the photosensitive resin composition. The content is suppressed, and the retardation of the film is preferably from 5% to 5% by weight from the viewpoint of imparting flexibility to the cured film, and is preferably 50% from the viewpoint of suppressing insufficient hardening or cold flow. . the following. The /photosensitive resin laminate includes a photosensitive resin layer and a support layer formed of a photosensitive resin composition. A protective layer may be provided on the surface of the photosensitive resin layer opposite to the side of the supporting layer as needed. As the support layer used herein, it is preferable that the transparent light transmitted from the exposure light source is used as such a support layer, and examples thereof include a polyethylene terephthalate film and a polyvinyl alcohol film. , polyvinyl chloride film, ethylene ethylene copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, poly-f-acrylic acid methyl acetate copolymer, polystyrene film, polyacrylonitrile film, A styrene copolymer film, a polystyrene film, a one-dimensional derivative film, and the like. These films may also be used as needed if the fog value is 5 or less. Regarding the thickness of the film, it is advantageous in terms of image formability in terms of properties and economy, but in order to maintain strength, it is preferred to use a thickness of 10 to 30 μm. The important characteristic of the protective layer used in the optical resin laminate is that the adhesion between the protective layer and the photosensitive resin layer is lower than that of the support layer and the photosensitive resin layer. For example, a polyethylene film, polypropylene:: is preferably used as a protective layer. Also, you can use this patent. A film excellent in peelability disclosed in Japanese Laid-Open Patent Publication No. 59-202457. The film thickness is better than ι〇~1, and then better... Call. The thickness of the photosensitive resin layer in the photosensitive resin laminate is preferably 139404.doc • 23- 201001065 and further preferably 7 to 60 μπι. The thicker the thickness, the more the film strength is different, preferably 5 ~100 μπι The thicker the resolution, the higher the resolution and the higher the resolution. As a method of producing a photosensitive resin laminate by laminating a support layer, a photosensitive resin layer, and an optional protective layer, a known method can be employed. 2, for example, the photosensitive resin combination used in the photosensitive resin layer can be mixed with the solvent of each of the photosensitive resin compositions to form a uniform solution: first, the solution is applied by a bar coater. The cloth is coated on the support layer and then dried, and the photosensitive resin formed of the photosensitive resin composition is laminated on the support layer. ~ The thickness of the photosensitive resin layer after drying is preferably 丨~丨, and further f2~50 _ of the f, more preferably 3~15 μηι. The thickness is preferably a pore size of 3 μηι or more, and is preferably 15 μηι or less from the viewpoint of analytical properties. Further, a protective layer is laminated on the photosensitive resin layer as needed, whereby a photosensitive resin laminate can be produced. The solvent of the cold-reactive photosensitive resin composition may, for example, be a ketone represented by a subunit ethylamine (bribet), an alcohol represented by an α f alcohol, ethanol or isopropyl alcohol. The solvent is preferably added to the photosensitive resin composition such that the viscosity of the photosensitive resin composition solution applied to the support layer is 5 〇〇 to 4 〇〇〇 mpa.s at 251. <Photoresist Pattern Forming Method> The photoresist pattern using the photosensitive resin laminate may be formed by a layer a: a step of performing a layer, an exposure step of exposing with active light, and a removal of no J39404.doc • 24 · 201001065

The step of the developing step of the exposure portion is formed. Hereinafter, a case in which a small lift method is used as a substrate 'is a copper case laminate for manufacturing a printed circuit board, and a glass substrate for manufacturing an uneven substrate, for example, electropolymerization. A substrate for a display panel or a surface conduction electron emission display (Conduction Electron-emitter Display) substrate, an organic EL (Electroluminescent) sealing cover, or a stone substrate formed with a through hole, a ceramic substrate, or the like. The substrate for plasma display refers to a substrate on which a dielectric layer is formed by forming an electrode on a glass, and then a glass paste for a partition wall is applied to a glass paste portion for partition walls to form a partition wall. These sandblasted glass substrates are used as the uneven base material. First, the lamination step is carried out using a bonding machine. When the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is pressure-bonded to the surface of the substrate by a bonding machine to laminate. In this case, the photosensitive resin layer may be laminated only on one surface of the substrate surface, or may be laminated on both surfaces. The heating temperature at this time is generally about 40 to 1 60. (: In addition, by performing the thermocompression bonding twice or more, the adhesion and the chemical resistance are improved. The two-stage laminating machine having the two-roller can be used for the heating and crimping, and the roller can be repeatedly passed several times. Then, the pressure is applied. Then, the exposure step is performed by the exposure machine. If necessary, the support layer is exposed by the active light for exposure. The exposure amount is determined by the illumination of the light source and the exposure time. The exposure amount can be measured by the light meter. The measurement is performed. In the exposure step, a direct drawing exposure method can be used. The so-called direct, meta-exposure refers to the method of directly drawing on the substrate without using a mask to expose the light 139404.doc -25- 201001065. For the light source, for example, a semiconductor laser or an ultra-high pressure mercury lamp having a wavelength of 35 〇 to 4 〇 can be used. The drawing pattern is controlled by a computer, and the exposure amount is determined by the illumination of the light source and the moving speed of the substrate. Next, (4) The developing device performs a development step. When the support layer is present on the photosensitive resin layer after the exposure, it is removed as needed, and then the developer using the alkali water solution is not exposed. The developing portion is removed to obtain a resist image. As the aqueous alkali solution, a hydrazine... or an aqueous solution of 2: (3) is used, and the aqueous alkali solution can be appropriately selected in accordance with the characteristics of the photosensitive resin layer, and the concentration is usually about 0.2. ~2% by mass, a temperature of about 2〇~4〇〇c iNa2C〇3 aqueous solution. The aqueous solution may also be mixed with a surfactant, a foaming agent, a small amount of an organic solvent for promoting development, etc. '' Second, the photoresist pattern can be obtained by the above steps, and can be carried out stepwise by about 100 to 300. (: The heating step can be further improved by performing the heating step. Hot air can be used for heating, Infrared and far-infrared heating furnaces. <Method for manufacturing body pattern and method for manufacturing printed circuit board> The printed circuit board can be formed by using a copper foil laminate or a flexible substrate as a substrate. The formation method is obtained by the following steps. First, a conductor pattern is formed on the copper surface of the substrate exposed by development by a known method such as etching or plating. An aqueous solution stronger than the developer removes the photoresist pattern from the substrate to obtain a desired printed circuit board. The aqueous alkali solution for stripping (hereinafter also referred to as "peeling liquid") is also not particularly limited, and the concentration is generally about 2~5% 、%, Na〇H, koh aqueous solution with a temperature of about 4〇~7〇〇c. 139404.doc •26· 201001065 A small amount of water-soluble solvent can also be added to the stripping solution. Manufacturing Method &gt; Wire wood can be obtained by using a metal plate such as copper as a substrate. Gold, an iron-based alloy, and a method of forming a first-resistance pattern are obtained by the following steps: The exposed substrate is surface-etched to form a pure pattern of the conductor pattern (10). The first resist pattern is peeled off to obtain the desired lead frame. &lt;Manufacturing method of semiconductor package&gt;

The semiconductor package can be obtained by performing the method of forming the photoresist pattern obtained by using the wafer which has been formed as an LSI, and then performing the following steps to obtain copper or solder in the opening exposed by _ The pillar u forms a conductor pattern. Thereafter, the photoresist pattern is peeled off by the method of the above-mentioned printed circuit board, and the thin metal layer of the portion other than the weight = is removed by (4), thereby obtaining the desired semiconductor package. &lt;Manufacturing Method of Substrate Having Concavo-Convex Pattern&gt; The photosensitive lip layer body is laminated on a substrate capable of performing sand blasting and the like, for example, a glass substrate, in the same manner as in the above-mentioned <resist pattern forming method> The glass substrate coated with the glass rib pulp, the metal substrate such as the ceramic substrate, the stainless steel, the ore, the sapphire or the like, the synthetic resin layer or the like, is subjected to exposure and development. Thereafter, the blasting step is performed by spraying the blast material from above the formed photoresist 5 to the target depth, and the resin portion remaining on the substrate is 139404.doc -27-201001065 And a stripping step of removing the material, thereby forming a fine pattern on the substrate. The spray material used in the above blasting step can be used by a known person, for example, it can be used.

SiC Sl〇2, A12〇3, CaC〇3, Zr〇2, glass, stainless steel, etc. 2~; particles of about 100 μηι. [Examples] Hereinafter, the present invention will be described based on non-limiting examples. The preparation method of the sample for evaluation of the examples and the comparative examples, and the evaluation methods and evaluation results of the obtained samples are as follows. 1) Preparation of sample for evaluation The photosensitive resin layered system in the examples of the shell and the comparative example was produced in the following manner. &lt;Preparation of Photosensitive Resin Laminate&gt; The composition solution shown in the following Table 2 was adjusted so that the amount of the solid matter was 50% by mass, and the mixture was sufficiently stirred and mixed, and the table 1 was used by a doctor blade coater. The photosensitive resin composition shown above was uniformly applied to a 16 μη thick polyethylene terephthalate film (R340-G16 manufactured by Mitsubishi Chemical Corporation) as a support film, and dried at 95 t for several minutes. The film thickness of the photosensitive resin layer after drying was 10 μm. Then, a 35 μm thick polyethylene film (GF_858 manufactured by Tamapoly Co., Ltd.) as a protective layer was bonded to the surface of the photosensitive resin layer to obtain a photosensitive resin laminate. &lt;Substrate&gt; Evaluation was carried out using a 〇4 thick steel $ laminated board having a 35 μηι copper foil laminated on an insulating resin. Furthermore, in the following description, the contents are described only when other substrates of 139404.doc • 28-201001065 are used. &lt;Lamination&gt; While peeling off the protective layer of the photosensitive resin laminate, it was produced by Asahi Kasei Engineering Co., Ltd. by a hot roll, and the temperature was 丨〇5. Set to 〇35 Mpa and set the stacking speed to 1 ·5 m/min. &lt;Exposure&gt;

The photosensitive resin layer was exposed by a direct edge image exposure machine (manufactured by 〇rbotech, Para) to expose the photosensitive resin layer at a power of 8 W and with an exposure amount of 16 m&quot;em2. &lt;Development&gt; The 1.G mass of the jet 30C is called an aqueous solution for a predetermined time, and the unexposed portion of the light-reducing resin layer is dissolved and removed. The development was carried out for an actual development time (four) seconds, and then washed with a water washing time of 36 seconds. 2) Evaluation method Each of the properties was evaluated by the following method, except for the method of the above 1) production of the sample for evaluation and the method of the clothing F Y. &lt;Capperity&gt; The above-mentioned square robes are called a hole with a hole diameter of ^ mm _500 匪 0, 2 _ thick copper enamel layer on both sides of the slab, how to use the above exposure method The entire surface of the obtained substrate was directly subjected to (four) (four) film 'after the development method was carried out by the above development method, and the crack of the hardened photoresist film was classified: 仃 (4) 1 in the following manner 139404.doc -29- 201001065 A : rupture The number is 25 or less B: the number of cracks exceeds 25, and is 75 or less C: the number of cracks exceeds 75, and is 150 or less D: the number of cracks exceeds 150. &lt;Peel strength of support layer (PET)&gt; A substrate on which a photosensitive resin layer of a photosensitive resin laminate was laminated on one surface by the above method was produced, and the substrate was placed under 23 art and 5% relative humidity. Hours' then 18 〇 for the 1 吋 wide support layer (pet). After peeling, the strength was measured using TENSILON RTM-500 (manufactured by Toyo Seiki Co., Ltd.), and classification was carried out in the following manner: A: The maximum average peel strength was 3 gf or more B: The maximum average peel strength was less than 3 gf. 3) Evaluation results The evaluation results of the examples and comparative examples are shown in Table 1 below. The parts by mass of B-1 to B-3 in Table 1 are parts by mass of the solid matter, excluding the solvent. Preparing a solution of each of B-1 to B-3 in such a manner that the solid content of B-1 to B-3 having a solid content of 50% by mass was prepared in such a manner as to be a solid matter of Table 1, thereby adjusting the photosensitivity The content of each of the above components in the resin composition. 139404.doc •30· 201001065 til Comparative Example 1 (N in 1-Η &lt;s 〇0.07 Tf c&gt; Os 〇\ a\ a\ u Example 8 fS ID 1-Η &lt;s ο 0.07 ON C\ a \ ON c Example 7 (N in ΙΛ ri rs ο 0.07 rf 〇 100 o Example 6 (S in 〇% τΗ &lt;s ο 0.07 o ON 〇\ OS C\ &lt;&lt; Example 5 fS 1/5 〇ΙΛ fS ο 0.07 rr oa\ Cv Os 〇\ &lt;&lt; Example 4 fS tn un fN Ο 0.07 oa\ ON a\ a\ CQ &lt; Example 3 uo ?*Η &lt;s ο 0.07 兮o ON C\ a\ On &lt;Example 2 ΙΛ rj ο 0.07 o ON ON ON OS &lt; Example 1 fS in !2 fS ο 0.07 o Q\ 〇\ ON OS &lt; Bl Β-2 Β-3 Μ-1 Μ-2 Μ-3 Μ-4 Μ-5 τ»Η (S Μ Η ^t Η Dl D-2 Grade|Level 4μ ® ^ CQ 1 β Total solvent (parts by mass) Peel strength of capping support layer • 31 · 139404.doc 201001065 &lt;Description of Symbols&gt; B-1 : a terpolymer of 25% by mass of mercaptoacrylic acid, 65% by mass of decyl methacrylate, and 10% by mass of butyl acrylate (weight average molecular weight 100,000, Acid equivalent 344) B-2: ternary copolymer of 25% by mass of methacrylic acid, 65% by mass of methyl methacrylate, and 10% by mass of butyl acrylate (weight average molecular weight: 200,000, acid equivalent 344) B-3 : 曱a terpolymer of 25% by mass of acrylic acid, 50% by mass of decyl methacrylate, and 25% by mass of styrene (weight average molecular weight: 5 Å, hydrazine, acid equivalent 344) M-1: at the four ends of pentaerythritol A total of 35 moles of ethylene oxide tetraacrylate (atm_35E, manufactured by Shin-Nakamura Chemical Co., Ltd.) M-2 was added to the four ends of pentaerythritol to form a tetraacrylate with oxime ethylene oxide (Sartomer). Sr_494 manufactured by Japan Co., Ltd. M-3: A total of 4 moles of pentaerythritol and a total of 8 moles of ethylene acrylate 12 moles of propylene oxide polypropylene glycol further added to each end of the average of 3 moles of ethylene oxide to form a polyalkylene glycol dimethyl acrylate acid g Each of the above-mentioned addition of an average of 5 moles of ethylene bromide-forming polyethylene glycol dimethacrylate ( Hitachi Chemical (shares) of producing FA-321M) I -1: 9 - phenyl.丫cr 1-2 : N-phenylglycine 139404.doc -32- 201001065 1-3 · 2-(ozone-based)-4,5-diphenyl η-methane dimer 1-4 : 1-phenyl-3-(4-t-butyl-styryl)_5_(4_t-butyl-phenyl)η ratio σ sitle D-1 : diamond green D-2 : leuco crystal Violet F-1: mercaptoethyl ketone, in Comparative Example i 'Because the compound represented by the above formula (1) is not used

s has the disadvantage that the polymerization of unsaturated double bonds (10) results in poor peel strength of PET. [Industrial Applicability] The present invention can be applied to a printed circuit board. ^ c Rugged lIk, manufacture of a flexible printed circuit board, and post-conduction of an IC chip (to win, and to stay in Zhu) For the manufacture of lead frames, metal mask manufacturing, etc., metal smelting, smelting, processing, Β (} Α (spherical grid array or CSP (wafer size packaging), etc. TABaape

Automated Bonding, 棬 々 ώ A 8棬f-type automatic joint) or COF (Chip 〇11

Film: The manufacture of the body bumps of the semiconductor 1 (: the manufacture of the n-belt substrate, the 4 boards), the plane ΙΤΟ electrode, the 宕讪 炻 , , , , , , , Manufacturing of components such as bungee poles and electromagnetic wave masks, etc. 139404.doc • 33 -

Claims (1)

201001065 VII. Patent application scope: 1 . A photosensitive resin composition comprising the following components: (a) 20 to 90% by mass of an alkali-soluble resin, (b) having an unsaturated double bond capable of photopolymerization The compound is 5 to 75 mass%, and 1 (C) photopolymerization initiator is 0.1 to 20% by mass; and contains at least one compound selected from the group consisting of compounds represented by the following formula (I). As the above (b) a compound having an unsaturated double bond capable of photopolymerization: [Chemical 1] In the formula, R, R2, R3 and R4 are each independently H or CH3, respectively η!, Π2, n3, n4, m丨, 叫, m3 and m4 are independently propyl or butyl, independently A positive integer, ηι+η2+η3+η4 is an integer of 21~5〇, and is called the tenth 叱+叫+ is an integer of 卜^, where _(c2H4〇)_ ”(Rs-o)- is repeated The arrangement of the units may be random or block, and 139404.doc 201001065 and -(c2h4-o) winter (R5_0)_ may be located on the central carbon side}. 2. If requested The photosensitive resin composition further comprising at least a compound selected from the group consisting of compounds represented by the following formula (11) as the above (b) having a side sheet h, sentence J into the first unsaturated compound of the double bond compound: [Chemical 2] CH, -c2h4o 0 R5 0- e2H4〇 -C —CH2-(c2H40 \—〇 0 CH2—4-C2H40 )ir0, a o (Π) R7 Re {where r5, r6, and R7aR8 are each independently h or (3) 3, U2, i3, and u are divided into G or a positive integer ' and ii + i2 + (four) is 〇 ~ another integer}. 3. 4. Photosensitive Resin Laminate </ RTI> A photosensitive resin layer and a support layer formed of the sensitization of the sensitizing tree of the claim U2. A method for forming a photoresist pattern, comprising: laminating a photosensitive resin layer of a photosensitive J. raw resin laminated body of a member, a exposure step of exposing with active light, and removing the substrate; The shadowing step of the unexposed part. 139404.doc 201001065 5. The method of forming the silk pattern of claim 4, wherein the exposure is performed by direct drawing in the exposure.乂6. A "pattern" of a conductor pattern, a method of the invention, comprising the following steps: using a copper-stacked core substrate for forming a photoresist pattern as in Test No. 4 or 5 The substrate on which the photoresist pattern is formed is subjected to money engraving or money application. The method for manufacturing a printed circuit board is characterized in that it is used in the method for opening up the photo-resistance diagram of item 4 or 5. The metal-coated insulating sheet is used as a substrate on which a photoresist pattern is formed for surging or mineralizing, and the photoresist pattern is peeled off. 8. 9. A method for manufacturing a lead frame, characterized in that: In the method for forming a first resist pattern, a metal plate is used as a substrate, and a substrate of a light-emitting pattern is silver-etched, and then the photoresist pattern is peeled off. A semiconductor package H manufacturing method, wherein (4) is in a method of forming a photoresist pattern A substrate having a photoresist pattern as a substrate is used as a substrate, and a resist pattern is formed by plating, and then the photoresist pattern is peeled off. Further, a method of manufacturing a substrate having a concave-convex pattern is characterized in that :Using real In the method of forming a photoresist pattern according to claim 4 or 5, a substrate having a photoresist pattern formed by using a substrate which can be subjected to sandblasting as a substrate is processed, and then the photoresist pattern is peeled off. 139404.doc 201001065 IV. Designation of Representative Representatives (1) The representative representative of the case is: (none) (2) A brief description of the symbol of the representative figure: 〆5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention. : 139404.doc