TW200949433A - Layered photosensitive-resin product - Google Patents

Abstract

A layered photosensitive-resin product which includes a photosensitive-resin layer having a thickness of 3-15 [mu]m and which, despite the small photosensitive-layer thickness, has satisfactory tenting properties even when exposed by direct writing exposure. This layered product upon development gives aggregates which are not oily. The layered photosensitive-resin product comprises superposed layers composed of a base layer and a photosensitive-resin layer. This product is characterized in that the photosensitive-resin layer is made of a photosensitive resin composition and that the photosensitive resin composition comprises (a) 25-64 mass% alkali-soluble resin, (b) a compound having a photopolymerizable unsaturated double bond, and (c) 0.1-20 mass% photopolymerization initiator. The product is further characterized by satisfying the following (i), (ii), and (iii): (i) a specific photopolymerizable unsaturated compound is contained in an amount of 30-55 mass% based on the whole photosensitive resin composition; (ii) the alkali-soluble resin (a) has a weight-average molecular weight of 70,000-220,000 and an acid equivalent of 100-600; and (iii) the photosensitive-resin layer has a thickness of 3-15 [mu]m.

Description

[Technical Field] The present invention relates to a photosensitive resin laminate formed by laminating a photosensitive resin composition which can be developed by an aqueous alkaline solution on a support layer, and using the photosensitivity A method of forming a photoresist pattern on a substrate by a resin laminate, and - the use of the photoresist pattern. More specifically, the present invention relates to a photosensitive resin composition which is suitable for the manufacture of a printed wiring board, the manufacture of a flexible printed wiring board, and the use of an ic wafer mounting guide. Fabrication of wireframes (hereinafter referred to as leadframes), precision machining of metal foils such as metal masks, semiconductor packages such as BGA (Ball Grid Array) or CSP (Chip Size Package) Manufacture of a tape substrate represented by TAB (Tape Automated Bonding) or COF (Chip On Film) in which a semiconductor 1C is disposed on a film-shaped fine wiring board, and manufacture of a semiconductor bump A photoresist pattern of a component such as an IT (Indium Tin Oxide) electrode, an address electrode, or an electromagnetic wave mask in the field of flat panel displays. [Prior Art] _ Previously, printed wiring boards were manufactured by photolithography. The photolithography method is a method in which a photosensitive resin composition is applied onto a substrate, pattern exposure is performed, and the exposed portion of the photosensitive resin composition is polymerized and cured, and the unexposed portion is removed by a developing solution to form a substrate. After the photoresist pattern is formed by etching or plating to form a conductor pattern, the photoresist pattern is stripped from the substrate to remove 136982.doc 200949433, thereby forming a wire on the substrate. In the photolithography method described above, when the photosensitive resin composition is applied onto a substrate, any of the following methods may be used: a method of applying a photoresist solution onto a substrate and drying it; or A photosensitive resin laminate having a support layer, a layer formed of a photosensitive resin composition (hereinafter also referred to as "photosensitive resin layer"), and an optional protective layer (hereinafter also referred to as "dry film photoresist") ") A method of laminating on a substrate. Further, in the manufacture of printed wiring boards, the latter dry film photoresist is often used. Hereinafter, a method of manufacturing a printed wiring board using the dry film resist described above will be briefly described. 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 are laminated on the substrate, for example, a copper foil laminate, in the order of the substrate, the photosensitive resin layer, and the support, using a laminator. Then, the photosensitive resin layer was exposed by 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. Then, a support layer such as polyethylene terephthalate is peeled off. Next, the unexposed portion of the photosensitive resin layer is dissolved or dispersed by a developing solution such as an aqueous solution having a weakity to form a photoresist pattern on the substrate. As a method of fabricating a metal wire using a photoresist pattern on a substrate formed in the above manner, there are roughly two methods, that is, a method of removing a metal portion not covered by a photoresist layer by etching and plating with plating The method of metal. In particular, the use of the former is more often taken from the simplicity of the steps. 136982.doc 200949433 Method. In the method of removing a metal portion by etching, a through-hole (through hole) of a substrate or a via hole for interlayer connection is covered with a hardened photoresist film, thereby avoiding the inside of the hole The metal is etched. This method is called the cover hole method. In the silver engraving step, for example, a vaporized copper, a gasified iron, or a copper ammonia complex solution is used. With the miniaturization of the wiring wiring intervals in the printed wiring board in recent years, the pattern of the narrow pitch is preferably produced at a good yield, and the dry film photoresist is required to have high resolution and the same capping property. As a method of improving the resolution, the resolution can be easily improved by thinning the dry film photoresist, but the following problems occur: the film has a weak resistance to physical external force due to the ejection of the development step and the etching step, thereby The through hole and the via hole cannot be protected in the developing step and the etching step (the cap hole property is not good). Patent Document 1 discloses that the photoresist is excellent in the amount of difunctional monomers in the unsaturated resin in the photosensitive resin composition. However, only the ratio of the trifunctional monomer in the unsound compound is described, and there is a problem that the capping property is poor in a certain range. Patent Document 1 will be described later in the comparative example. Patent Document 2 discloses that the photoresist is excellent in that the unsaturated compound is a tetrafunctional monomer in the photosensitive resin composition. However, in direct drawing exposure using such photoresists, there is a problem that the capping property is poor. Patent Document 3 discloses a photoresist which is excellent in trifunctional monomers in an unsaturated resin composition in a photosensitive resin composition. However, in the direct edge exposure of the film of the 5th photoresist, there is a problem that the hole porosity is not good 136982.doc 200949433. However, when a large amount of these polyfunctional monomers are contained in the photosensitive resin composition, there is also a problem that oily aggregates are generated during development. Therefore, the industry has demanded that even if the capping property is good in direct drawing exposure and the coagulation is not oily when developing, the powdery agglomerates are also less. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2000-347400 (Patent Document 3). DISCLOSURE OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION An object of the present invention is to provide a photosensitive resin laminate which is exposed even when the thickness of the photosensitive resin layer is as thin as 3 to 15 and even by direct drawing exposure. At the same time, the capping property was also good and oily aggregates were not generated during development, and powdery aggregates were also less. [Technical means for solving the problem] The above problems can be attained by the following constitution of the present invention. That is, the present invention is as follows. 1 . A photosensitive resin laminate comprising a support layer and a photosensitive resin layer, wherein the layer: the layer contains a photosensitive resin composition, and the photosensitive resin composition The composition comprises: at least (a) a solvent-soluble resin in an amount of 25 to 64% by mass; (b) a compound having a photopolymerizable unsaturated double bond; 136982.doc 200949433 (c) a photopolymerization initiator 0.1 to 20% by mass; Further, the following (i), (Π), and (m) are satisfied: (1) The compound having the photopolymerizable unsaturated double bond as the above 00, and the total amount of the photosensitive resin composition is from 3 to 55 The mass% is at least one selected from the group consisting of a compound represented by the following formula (I) and a compound represented by the following formula (1): [Chemical Formula 1]

(1) (where R, R2, and R3 are independent of each other; and are independently independent integers from 0 to 4,

One ~ especially double π can be 〇; w is the base of representation); [Chemical 2]

CH2—C*-CH2

136982.doc (II) 200949433 (In the formula, 'R5, R6, 厌7, and 厌8 are independent; mi, m2, m3, and singly are independent integers of 〇~4, and can also be 〇); (11) The (a) alkali-soluble resin has a weight average molecular weight of 70,000 to 220,0 Å, and an acid equivalent of 1 〇〇 to 6 〇〇; (n 〇 the thickness of the photosensitive resin layer is a 3 to 15 pm. In the photosensitive resin laminate according to the above (b), the compound having a photopolymerizable unsaturated double bond is contained in an amount of 35 to 55 mass% based on the total amount of the photosensitive resin composition, and is selected from the above formula (1). The photosensitive resin laminate according to the above 1 or 2, wherein the photopolymerization initiator is 9 or more, wherein the compound represented by the above formula (π) is at least one of the group consisting of the compound represented by the above formula (π). The photosensitive resin laminate according to any one of the above-mentioned items 1 to 3, wherein the ratio of the (4) test resin is set to A mass with respect to the total amount of the photosensitive resin composition. %, the ratio of the above (b) compound having a photopolymerizable unsaturated double bond is set to B% by mass And A/B is κι to 丨3. 5. A method for forming a photoresist pattern comprising: a photosensitive resin layer of the photosensitive resin laminate according to any one of the above 1 to 4 The dusting step, the exposure step of exposing with ultraviolet rays, and the developing step of removing the unexposed portion. 6. The method for forming a photoresist pattern according to the above 5, wherein in the exposing step, exposure is performed by direct drawing. A method of manufacturing a wire comprising the steps of: forming a substrate having a photoresist pattern of 136982.doc • 10·200949433 by a method as described in the above 5 or 6 using a copper flute laminate as a substrate. 8. A method of manufacturing a printed wiring board, characterized in that a metal-clad insulating board is used as a substrate, and light is formed by the method according to any one of the above 4 to 7. The substrate of the resist pattern is etched or plated, and the photoresist pattern is stripped. • A method of manufacturing a lead frame, characterized in that a metal plate is used as the substrate, as recorded by any one of the above 4 to 8 In the method of forming a substrate having a photoresist pattern, silver etching is performed, and the photoresist pattern is removed. [1] A method of manufacturing a semiconductor package is characterized in that a wafer on which a circuit as an LSI is formed is used as a substrate, The substrate on which the photoresist pattern is formed by the method described in any one of the above 4 to = plating is performed and the photoresist pattern is peeled off. 11. A method of manufacturing a substrate having a concave-convex pattern, characterized in that: The substrate on which the photoresist pattern was formed by the method described in any one of the above 4 to 10 was processed by a sand blasting method using a glass rib as a substrate, and the photoresist pattern was peeled off. [Effect of the Invention] The photosensitive resin laminate of the present invention has an effect that although the thickness of the photosensitive resin layer is as thin as 3 to 15 (four)', even when exposed by direct drawing exposure, the capping property is good, and development is performed. Oily aggregates are not produced, and powdery aggregates are also less. [Embodiment] Hereinafter, the present invention will be specifically described. <Photosensitive Resin Laminate> 136982.doc 200949433 The photosensitive resin laminate system of the present invention comprises at least a support layer and a photosensitive resin layer, and the photosensitive resin layer contains a photosensitive resin composition. The photosensitive resin composition contains at least (a) an alkali-soluble resin in an amount of 25 to 64% by mass; (b) a compound having a photopolymerizable unsaturated double bond; (c) a photopolymerization initiator further satisfying the following (1), Ii) and (iii): (0) The compound (b) having a photopolymerizable unsaturated double bond, which is selected from the group consisting of 3 to 55% by mass based on the total amount of the photosensitive resin composition At least one of the compound represented by the general formula (1) and the compound represented by the following general formula (I): [Chemical 3]

And the independent is H or CH3; 4 integers, can also be 0; W is CH3 or (where R!, r2, and Π4 are respectively independent of 〇OH); 136982.doc - 12· 200949433 [Chemical 4]

(wherein R5, R6, R7, and each are independently called; called, ^, 1η3, and nu are each independently an integer of 〇~4, which may also be 〇); (Π) the above (a) alkali The weight average molecular weight of the soluble resin is 7 Å to 220,000, and the acid equivalent is 1 〇〇 to 6 〇〇; (iii) The thickness of the photosensitive resin layer is 3 to 15 μm. In the case where the amount of each component in the photosensitive resin composition is described, the amount of each component is described in terms of the mass % of the solid content in the photosensitive resin composition as a standard.

(a) Detective resin The so-called solvent-soluble resin means an ethylene (tetra) ester containing an m group, an acrylic acid, a (meth) acrylic acid _, a (meth) acrylonitrile, or a copolymer of methyl amide. The horse (4) test soluble resin preferably contains a radical and the acid is 100 to 600. The so-called acid equivalent of '", the mass of the compound. The acid equivalent is more than the linear polymorphism of the slow base of h It is better to raise and solve U 疋25G or more, and it is better than 1 136982.doc *13· 200949433 or more in terms of resistance and reproducibility. It is preferable that it is 600 or less. The measurement of the acid equivalent is carried out by the potentiometric titration method using the Sampron automatic titrator (COM-555) manufactured by Hiranuma Industry Co., Ltd. using 0.1 mol/L of sodium hydroxide. The weight average molecular weight of the (a) alkali-soluble resin to be used is preferably 70,000 or more and 220,000 or less. From the viewpoint of improving the developability, it is preferably 220,000 or less. From the viewpoint of the porosity of the pores and the properties of the aggregates In terms of weight average molecular weight, it is preferably 70,000 or more. Further preferably, it is 70,000 or more and 200,000 or less, more preferably 70,000 or more and 120,000 or less. The weight average molecular weight is a GPC 'Gelph Permeation Chromatography (MPC) manufactured by Japan Spectrophotometer (pump: Gulliver, PU) -15 80 type, pipe column: Shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) manufactured by Showa Denko Electric Co., Ltd. 4 in series, moving layer solvent: tetrahydrofuran, and using poly The styrene standard sample (calibration curve of Shodex STANDARD SM-105 manufactured by Showa Denko Co., Ltd.) is obtained by polystyrene conversion. The alkali-soluble resin preferably contains at least one or more of the first monomers described later. a copolymer of at least one or more of a second monomer to be described later. A carboxylic acid or an acid anhydride having a polymerizable unsaturated group in the first single-system molecule, and examples thereof include (meth)acrylic acid and fumaric acid. , cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and cis-butyl diacid half-ester. Among them, (mercapto)acrylic acid is particularly preferred. Here, (meth)acrylic acid means acrylic acid. / methacrylic acid. The same as the following. 136982.doc -14- 200949433 The mono-system is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. For example, (meth) propylene Acid methyl vinegar, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (A Acrylic acid dibutyl sulfonate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate The vinegar of vinyl alcohol such as ethyl acetate acetonate, (meth) propyl guar, #ethylene and styrene. Among them, methyl (meth) acrylate, (methyl) propylene ginseng butyl vinegar is preferred. , styrene, (mercapto) acrylic vinegar. The alkali-soluble resin contains a carboxyl group, an acid equivalent of 100 to 6 Å, and a weight average molecular weight of 70'000 to 220,000 from the viewpoint of the property of the capping property and the property of the agglomerate, and is a preferred embodiment of the present invention. U) The ratio of the alkali-soluble resin to the total of the photosensitive resin composition is in the range of 25 to 64% by mass, preferably 4 to 6 % by mass. The photoresist pattern formed by exposure and development has characteristics as a photoresist, for example, from the viewpoint of & capping, etching, and various plating steps, it is preferable that it is 25 mass ❶/❶. The above is 64% by mass or less. (b) Photopolymerizable unsaturated compound The term "photopolymerizable unsaturated compound" means a compound having at least one ethylenically unsaturated bond in the molecule. In the photosensitive resin composition of the present invention, the compound (b) having a photopolymerizable unsaturated double bond is contained in an amount of from 30 to 55% by mass based on the total amount of the photosensitive resin composition. a group of the compound represented by the formula (1) and a compound represented by the following formula (Π) to 136982.doc 15 200949433 A photopolymerizable unsaturated compound: [Chemical 5]

CH2-^〇C3H6j—

〇 (where R!, R2, and R3 are independently Η or CH3; ηι, n2, n3, and ... are each independently an integer of 0 to 4, and may be 〇 at the same time; w is represented by CHyi〇H Base), [Chem. 6]

(where R', R6, and R7AR8 are each independently j^CH3; called, m2, m3, and nu are each independently an integer of 〇~4, which can also be 〇). Specific examples of at least one photopolymerizable unsaturated compound selected from the group consisting of the compound represented by the above formula (1) and the compound represented by the above formula 136982.doc -16-200949433 (II) For example, in the above formula (1), R!, R2 and R3 are Η, ηι, n2 and n3 are integers i, n4 is an integer 〇, and w is a compound of CH3 (Xinzhongcun Chemical Industry Co., Ltd.) Ν ester ester ester A-TMPT-3PO) manufactured by the company; also exemplified: in the above formula (1), R 丨, 化 and R3 are Η, ηι, 〜 and 〜 are integers 3, n4 is an integer 〇, and 霄 is Compound of ^^ (NK ESTER A-TMPT-9PO manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). In addition, in the above formula (π), &, &, ruler 7 and heart are Η, m2, melon 3 and m4 are integer 〇 compounds (Xin Nakamura Chemical Industry Co., Ltd. manufactures NK) ESTER A-TMMT); also in the above formula (II), 'R5, r6, 尺7 and 尺8 are Η, m丨, m2, and m4 is an integer 1 compound (Sartomer Japan) The company's sr_494). The content of at least one photopolymerizable unsaturated compound selected from the group consisting of the compound represented by the above formula (1) and the compound represented by the above formula (II) is from the viewpoint of the capping property. 35 to 55 mass%, more preferably 40 to 55 mass%. Further, the photopolymerizable unsaturated compound shown below can be used in addition to (b) the photopolymerizable unsaturated compound 'except the compound represented by the above formula (I) or the above formula (?). For example, 1,6-hexanediol di(meth)acrylate, M_cyclohexanediol di(meth)acrylate, polyethyleneglycol bis(indenyl)acrylate, 2_two (pair Phenyl)-propanone-(methyl)-propyl acetoacetate, tris(meth)acrylic acid vinegar, trimethylpropane tris(meth)acrylate, polyoxypropyltrimethylolpropane (Meth) acrylate, polyoxyethyl trihydroxy decyl propane triacrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate vine, 136982.doc -17- 200949433 Propylene diglycidyl glycerol tris(meth)acrylic acid vinegar, dioxin a diglycidyl ether di(indenyl) acrylate, p_hydroxypropyl _p, _(propylene decyloxy) propyl phthalate Acid ester, phenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polyalkylene glycol (meth) acrylate, poly Propylene glycol mono(indenyl) acrylate. Further, a urethane compound may be mentioned, and examples of the urethane compound include hexamethylene diisocyanate, toluene diisocyanate or a diisocyanate compound such as 2,2,4-trimethylhexa. A carbazate compound of decyl diisocyanate and a compound having a hydroxyl group and a (meth) propyl group in one molecule such as 2-hydroxypropyl acrylate or oligomeric propylene glycol monomethacrylate. Specifically, there is a reactant of hexamethylene diisocyanate and oligo-propylene glycol monodecyl acrylate (manufactured by Nippon Oil & Fats Co., Ltd., Blemmer ρρι〇〇〇). These urethane compounds may be used singly or in combination of two or more. At least one photopolymerizable group selected from the group consisting of the compound represented by the above formula (I) and the compound represented by the above formula („) is not contained in the total amount of the photosensitive resin composition. The total content of the (b) compound having a photopolymerizable unsaturated double bond of the saturated compound is from 3 to 55 mass%, preferably from 35 to 55 mass%, more preferably from 40 to 55 mass. And the ratio of the (a) alkali-soluble resin to A mass% and the ratio of the (b) photopolymerizable unsaturated double bond to the total amount of the photosensitive resin composition When it is 8% by mass, a/B is 1.1 M. 3 is a preferred embodiment of the present invention. From the viewpoint of capping property, it is preferred that A/B is 1.1 or more, and preferably a/B is 1-3 or less. 136982.doc *18» 200949433 (C) Photopolymerization initiator In the photosensitive resin composition, as the (e) photopolymerization initiator, a known resin can be used. The amount of the (c) photopolymerization initiator contained in the composition is in the range of 0.1 to 20% by mass, more preferably in the range of 05 to 10%. The amount of %. From the viewpoint of obtaining sufficient sensitivity, it is preferable that the mass is 0/〇 or more, and the light is sufficiently transmitted to the bottom surface of the photoresist to obtain a good high resolution. It is preferably 2% by mass or less. As such a photopolymerization initiator, 2' ethyl hydrazine, octaethyl hydrazine, hydrazine, 2 benzopyrene, 2, 3-stall蒽醌, 2_phenyl hydrazine, 2,3_diphenyl fluorene, 1- gas hydrazine, 2- gas hydrazine, 2-methyl hydrazine, iota, 4-naphthoquinone, 9,10- Phenanthrene, 2-methyl-1,4-naphthoquinone, 91〇_phenanthrenequinone, 2_methyl_14_naphthoquinone, 2,3-dimethylhydrazine, 3_gas_2_methylhydrazine Isoindoles; aromatic ketones such as benzophenone, Michelin [4,4,_bis(dimethylamino) dioxin], 4,4-bis(diethylamino) Benzophenone; benzoin or benzoin ethers, such as benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, ethyl benzoyl benzoin; dialkyl ketals, such as benzyl didecyl ketal, benzyl diethyl a sulphide; 9-oxopurines, such as diethyl _9 oxa sulfonium, gas -9 oxa sulfonium; dialkyl Kean acid esters, such as dimethylamino benzoic acid ethyl ester; oxime esters, such as 丨 phenyl phenyl hydrazine, 2 propylene glycol ketone -7 acetylene sulfhydryl hydrazine, 1-phenyl _ 1,2-propylenedione 2 - (hydrazine-ethoxycarbonyl) hydrazine; octomer dimer, such as 2-(o-phenyl)-4,5-diphenylimidazolyl dimer, 2_(o Phenyl)-4,5-bis-(m-methoxyphenyl)imidazolyl dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazolyl dimer; acridine a compound such as a pyridinium. These compounds may be used singly or in combination with two or more types of workers, 136,982.doc -19·200949433, which has improved capping property and inhibits the formation of oily aggregates. Preferably, the "biting compound" is particularly preferred as 9-phenyl acridine. Here, the oily agglomerate is a cohesive substance having a high viscosity, and is generally considered to have a compound having an unsaturated double bond as a main component. On the other hand, it is considered that the powdery agglomerates are mainly composed of an inhibitor and a starter, and are different from oily aggregates. (d) Other components In order to improve the handleability of the photosensitive resin composition of the present invention, a leuco dye or a fluoran dye or a coloring matter may be added. ❹ As the leuco dye, ginseng (4-dimethylaminophenyl)methane [colorless crystal violet], bis(4-diamidophenyl) decane [colorless malachite green] can be mentioned. Among them, in the case of using colorless crystal violet, the contrast is good and good. In the case where the photosensitive resin composition contains a leuco dye, the content thereof is preferably from 1 to 10% by mass. From the viewpoint of the performance of the contrast, it is preferably 1 mass/〇 or more, and more preferably 10% by mass or less from the viewpoint of maintaining storage stability. In the photosensitive resin composition, a combination of a leuco dye and a halogen compound described below is a preferred embodiment of the present invention in terms of adhesion and contrast. Examples of the coloring matter include magenta, phthalocyanine green, golden amine base, p-magenta, crystal violet, fluorenyl orange, Nero blue 2B, Victoria blue, and malachite green (Batu Valley Chemical Co., Ltd.) Aizen (registered trademark) Malac_ GREEN), alkaline blue 2〇, diamond green (Alzen (registered trademark) DIam〇Nd green gh manufactured by Hodogaya Chemical Co., Ltd.). In the case where the photosensitive resin group 136982.doc • 20- 200949433 contains a coloring matter, it is considered to be ~1% by mass. The content of 0·001% by mass is better in the content of 县, which is better in the county. The content of 1% by mass or less has the effect of maintaining storage stability. ▲ In the photosensitive resin composition of the present invention, from the viewpoint of sensitivity: 'N-aryl·α, a carboxylic acid compound may be contained. As the N-arylamine acid compound, it is preferred that Ν• streptoglutamic acid. Acidified with aryl-α-amine. In the case of matter, the content of 〇 〇 1 is better. ,. Above mass% or less.

The photosensitive resin composition of the present invention may further contain a dentate compound. Examples of the dentate compound include bromopentane, desert smoldering, desertified isobutylene, desertified ethylene, diphthyl, sulphate, sulphate, and sulphate. , ginseng (2,3-di-dipropyl) acid s曰, dichloroacetamide, iodopentane, iodine isobutane, u mountain three gas_2, 2_bis (decachlorophenyl) ethylene And gasifying the di-p well compound, wherein tribromotolylhydrazine can be used particularly well. When the photosensitive resin composition contains a _-based compound, the content thereof is 0.01 to 3% by mass. Further, in order to improve the thermal stability and storage stability of the photosensitive resin composition of the present invention, a photosensitive resin composition may be added with a radical polymerization inhibitor, a benzotriazole, and a carboxybenzotriene. At least one or more compounds of the group consisting of azoles. Examples of such a radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, t-butylcatechol, chlorite, and 2,6-di. - tert-butyl-p-cresol, 2,2'-fluorenylene bis (4-methyl-6-first butyl phenol), 2,2'--fluorenylene bis (4-ethyl _6) _T-butyl phenyl porphyrin), 136982.doc • 21- 200949433 Acetophenyl (tetra) (tetra) and diphenyl nitrosamine. Also, as a benzotriazole, /χί. Examples include, for example, 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazine, 簪7 1 g , bis(yi 2_ethylhexyl)aminomethylene-123- benzoquinone di-salt, bis(Ν·2·hexyl p «, , hexyl) aminyl fluorenyl, 2,3-toluene Triazole and bis(N-2-transethylethyl)aminomethylene], 2,3-benzotriazine. Further, examples of the benzyl group:r咕1 open-type include 4-mercapto-, 5-carboxyl-1,2,3-benzotriazole, Ν-(Ν, Ν-二-2 -Ethylhexyl)aminomethylenecarboxybenzobenzodiazepine Membrane _ base m-based benzotriene, "2-ethylhexyl" amine-based extension from:: polymerization inhibitors, benzotris-sodium and (four) stupid and three-salt total addition is better 〇.01~ 3 mass%, more preferably 0.05 mass%. On the resin group. In view of the storage stability, the amount is more preferably 0.001% by mass or more, and more preferably 3% by mass or less from the viewpoint of maintaining sensitivity. ° The photosensitive tree-frequency composite towel of the present invention may be used as needed. As such an additive, for example, polyethylene glycol: polyoxypropylene polyoxyethylene, polyoxyethylene monomethyl mystery, polyoxypropylene = methyl ether, polyoxyethylene polyoxy (tetra) monomethyl (10) - R- .3« „ 6 women single-single shout, polyhydrogen hydrazine 浠 乙 、 、, polyoxyethylene ethoxylated polyoxypropylene 氧 'oxygen 戌 ¥ ¥ ¥ ¥ ¥ 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻 邻Ethyl citric acid: n-acid diethyl hydrazine, b-branched bar-like acid vinegar. 暇 正 正 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 The content of the plasticizer is preferably from 5 to 50% by mass, more preferably from 5 to 30% by mass. From the viewpoint of suppressing the delay of the development time and imparting flexibility to the cured film, it is preferred that 5 The photosensitive resin laminate of the present invention contains a photosensitive resin formed of a photosensitive resin composition, and is preferably 50% by mass or less, from the viewpoint of suppressing insufficient hardening or cold flow. a layer and a support layer. If necessary, a protective layer may be provided on the surface of the photosensitive resin layer opposite to the support layer side. Holding the layer, it is desirable to pass the light emitted from the exposure source

Transparency. Examples of such a support layer include polyethylene terephthalate film, polyvinyl alcohol film, polystyrene film, and gas-ethylene copolymer film, polyvinylidene gas film, and ethylene dioxide copolymerization. Membrane, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamine film, cellulose derivative film. These are the extensions. It is preferable that W 1 is advantageous in image formability and economy when it is thin, but since it is necessary to maintain strength, it is preferable to use 10 to 30 μm. In addition, the important property of the protective layer used in the photosensitive resin laminate is that the adhesion between the protective layer and the photosensitive resin layer is sufficiently small compared to the adhesion between the support layer and the photosensitive resin layer, and the adhesive layer can be easily peeled off. . For example, a polyethylene film or a polypropylene film can be preferably used as the protective layer. Further, a film excellent in peelability as shown in Japanese Laid-Open Patent Publication No. SHO 59-2() No. 2457 can be used. The film thickness of the protective layer is preferably 10 to 10 μm, more preferably 10 to 5 ton. The thickness of the photosensitive resin layer in the photosensitive resin laminate is 136982.doc -23- 200949433 depending on the application. Preferably, it is preferably 5 to 100 μm, more preferably 7 to 60 μm, and the thinner the resolution is. The more the increase, the thicker the film strength is. The method of producing the photosensitive resin laminate of the present invention by sequentially laminating the support layer, the photosensitive resin layer and, if necessary, the protective layer, may be carried out by a conventionally known method. For example, 'a photosensitive resin composition for a photosensitive resin layer is mixed with a solvent for dissolving the compositions to prepare a uniform solution, and the solution is first applied onto a support layer using a bar coater or a roll coater. It is dried to laminate a photosensitive resin layer formed of a photosensitive resin composition on a support. Then, a protective resin layer can be laminated on the photosensitive resin layer as needed to prepare a photosensitive resin laminate. Examples of the solvent include ketones represented by methyl ethyl ketone (oxime), and yeasts represented by methanol, ethanol, and isopropyl alcohol. The solvent is preferably added to the photosensitive resin composition such that the viscosity of the solution of the photosensitive resin composition applied to the support layer is 500 to 4000 mPa at 25 °C. &lt;Photoresist Pattern Forming Method&gt; The photoresist pattern using the photosensitive resin laminate of the present invention can be formed by a step including a ruthenium lamination step, an exposure step, and a development step. An example of a specific method is shown below. A copper foil laminated board is used for the purpose of producing a printed wiring board, and a glass base material such as a plasma display panel is used for the purpose of producing a textured base material. A substrate or a surface electrolytic display substrate, an organic EL sealing cover or a tantalum wafer and a ceramic substrate having through holes formed therein. The substrate for electric display is a 136982.doc •24·200949433 electrode which is coated with a dielectric layer, and then a glass paste for the partition wall is applied, and the glass paste portion of the partition wall is subjected to sandblasting. A substrate having a partition wall formed. For these substrates to be processed, the blasting step becomes an uneven substrate. First, a lamination step is performed using a laminator. In the case where the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heat-pressure-bonded to the surface of the substrate to be processed by a bonding machine to be laminated. 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 usually 4 〇 to 16 〇. (: In addition, by performing the thermo-bonding for more than two times, the adhesion and chemical resistance are improved. At this time, the two-stage laminating machine with two rollers can be used for crimping, and it is also possible to repeat Next, the pressure is applied by a roll. Next, the exposure step is performed using an exposure machine. If necessary, the support is peeled off, and exposure is performed by the photoreceptor using the active light. The exposure amount is determined according to the illuminance of the light source and the exposure time. The measurement is performed using a light meter. In addition, a direct drawing exposure method can also be used in the exposure step. Direct drawing exposure is a method of directly drawing on a substrate without using a mask. As a light source, for example, a wavelength of 35 〇 can be used. The semiconductor laser or ultra-high pressure mercury lamp ❶ pattern of 4 丨〇 nm is controlled by a computer, and the exposure amount at this time is determined according to the illuminance of the light source and the moving speed of the substrate. Then, the developing step is performed using a developing device. When there is a support on the photosensitive resin layer, it is removed as needed, and then the test is used. The developer of the raw water bath develops the unexposed portion. In addition, a photoresist image is obtained. As an alkaline aqueous solution, an aqueous solution of Na2C03 or K2C03 is used, and water/valley is selected according to the characteristics of the photosensitive resin layer, usually 136982.doc 25-200949433 uses 0·2 An aqueous solution of 2% by mass and 2Na~4〇〇c of Na2c〇3. In the alkaline aqueous solution, a surfactant, an antifoaming agent, and a small amount of an organic solvent for promoting development may be mixed. A photoresist pattern can be obtained, and a heating step of 100 to 300 ° C can be carried out as occasion demands. By performing this heating step, the chemical property can be further improved. A heating furnace of hot air, infrared rays or far infrared rays is used for heating. &lt;Manufacturing Method of Conducting Wire. Method of Manufacturing Printed Wiring Board&gt; The method of manufacturing a printed wiring board according to the present invention is followed by the method of forming a resist pattern using a copper clad laminate or a flexible substrate as a substrate, The following steps are carried out. First, a wire is formed on the copper surface of the substrate exposed by development by a known method such as a surname method or a plating method. The alkaline aqueous solution having a stronger liquid-shaping liquid is peeled off from the substrate to obtain a desired printed wiring board. The alkaline aqueous solution for peeling (hereinafter also referred to as "peeling liquid") is not particularly limited. Usually, an aqueous solution of NaOI1 and KOH having a degree of deviation of 2 to 5% by mass and a temperature of 4 to 7 cc is used. A small amount of a water-soluble solvent may be added to the stripping solution. <Method for Producing Lead Frame> The present invention The method of manufacturing the lead frame is followed by a method of forming the resist pattern using a metal plate such as copper, a steel alloy, or an iron-based alloy as a substrate, and then performing the following steps. First, etching the substrate exposed by development Then, a wire is formed. Thereafter, the light limit I36982.doc -26·200949433 is peeled off in the same manner as the above-described method of the printed wiring board, and the desired lead frame is obtained. &lt;Manufacturing Method of Semiconductor Package&gt; The method of manufacturing a semiconductor package of the present invention is carried out by the following steps after the method of forming the photoresist pattern in which a wafer as a circuit of an LSI is formed as a substrate. First, a copper or solder column is formed on the opening exposed by development, and plating is performed to form a wire. Thereafter, the photoresist pattern is peeled off in the same manner as in the above-described method of manufacturing a printed wiring board, and the thin metal layer other than the pillar-shaped plating layer is removed by etching, thereby obtaining a desired semiconductor package. . [Examples] The present invention will be described based on examples. The production methods of the samples for evaluation of the examples and the comparative examples and the evaluation methods and evaluation results of the obtained samples are shown below. Preparation of Sample for U Evaluation The photosensitive resin layered systems of the examples and the comparative examples were produced in the following manner. &lt;Production of Photosensitive Resin Laminate&gt; The solution of the composition shown in Table 1 was adjusted so that the amount of the solid matter reached 50% by mass, sufficiently stirred and mixed, and the photosensitive light shown in Table i was obtained using a knife coater. The resin composition was uniformly applied to a 16 μm thick polyethylene terephthalate film (G16 manufactured by Mitsubishi Chemical Corporation) as a support film, and dried at 95 c for 1 minute. The photosensitive resin layer after drying was 10 μχ thick. Then, a pm thick polyethylene film 136982.doc -27· 200949433 (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; A 0.4 mm thick copper foil laminate having a 35 μηι copper foil laminated on an insulating resin was used for evaluation. In addition, the following will be described when other substrates are used. &lt;Lamination&gt; The protective layer of the photosensitive resin laminate of the present invention was peeled off at a roll temperature of 105 ° C by a hot stick laminator (manufactured by Asahi-Kasei Engineering Co., Ltd., AL-700). laminated. The air pressure was set to 0.35 MPa and the lamination speed was set to 1.5 m/min. &lt;Exposure&gt; The photosensitive resin layer was exposed at an exposure amount of 12 mJ/cm 2 at 8 W using a direct drawing exposure machine (Orragon Co., Paragon 9000). &lt;Development&gt; An aqueous solution of 1.0% by mass of Na 2 CO 3 at 30 ° C was sprayed at a specific time to dissolve and remove the unexposed portion of the photosensitive resin layer. The development was carried out at an actual development time of 24 seconds, and then washed with a washing time of 36 seconds. 2) Evaluation method Various properties were evaluated by the following methods in addition to the methods described in the production of the above evaluation samples. &lt;Coverability&gt; Double-sided lamination was carried out by using the above method to fabricate a 500 mm X 5 00 mm 0.2 mm thick copper delamination plate having 2500 diameter holes of 0.3 mm. 136982.doc -28 - 200949433, a substrate is formed by exposing the substrate by the above-described exposure method to obtain a cured film, and the development is performed by using the above-described development method. After development, the number of cracks in the cured film was counted, and the number of cracks was 25 or less as follows: 〇: the number of cracks exceeded 25, less than 75 X: the number of cracks exceeded 75. &lt;Production of oily aggregates&gt; Only the photosensitive resin layer of the photosensitive resin laminate was collected, and the mixture was immersed in 200 ml of the developing solution, and stirred at 30 ° t for 2 hours. Dissolved. Thereafter, it was allowed to stand, and classification was carried out in the following manner in accordance with the state of the solution after 72 hours. 〇: No oily aggregates or powdery aggregates were produced. △: Oily aggregates and powdery aggregates are less. X ·· Oily aggregates and powdery aggregates are numerous. &lt; peel strength of support layer (PET)&gt;

A substrate on which a photosensitive resin layer of a photosensitive resin laminate is laminated on one surface by the above method is prepared, and this is carried out at 23. (:, after standing at 50% relative humidity for 24 hours, 吋8〇 was applied to the support layer of 1 吋 wide (here PET), peeled off, and the strength was measured using Tensilon RTM-500 (manufactured by Toyo Seiki) The classification was as follows: 〇: The maximum average value of the peel strength was 3 gf or more. Δ. The maximum average value of the peel strength was less than 3 gf. 3) Evaluation results The evaluation results of the examples and comparative examples are shown in Table 1. In Table 1, 136982.doc -29- 200949433 4 parts by mass are solid parts by mass and do not contain a solvent. In the preparation of the photosensitive resin composition, a methyl ethyl ketone solution having a solid content of B-Bu B-4 of 50% by mass was prepared in advance, and each B-1 to B- was prepared in such a manner as to achieve the solid matter of Table 1. 4 solution. 136982.doc •30- 200949433 [11 S.S6 66 2 ειΌ 〇 d- X ?ΓΤ &quot;IF Η

K 00-

9R inch - inch inch • ε s i inch Ό 001 -Ό01 911 〇 〇 卜 0.0 inch Ό I-

S 6 inch · Ϊ

V 卜 9 s 00 · 0 -- 卜 90- Ζ.9 8-0 〇 〇 τ 5 馨 - 01 $ 驷 驷 6 inch 136982.doc %ι β s

I inch Ό 66 卜 9S6

SZ 9Π 〇 〇

K Γ0 i inch Ό 66 i6 9 inch 9 Π ◎ 〇 ΓΟ inch Ό 66 -·- 9Π 〇 v 〇

K - ·0 •Μ

I inch Ό 00- -Όοι 9Π 〇 v 〇

K s

K

K

R

K - 09 &quot; - oe s - ζ s i inch Ό 0°1 -ΌΟΙ S inch 9Π 〇

V 〇

S 0

S 卜 0Ό 2 inch Π 921 - 09 i 〇 〇 〇

I inch

S 卜 9.ε8 - oe ε·Ι 〇 〇

V 卜 0.0 0 901

卜 9SI ε inch s inch ΙΠ ◎ 〇

V - ΓΟ

I inch Ό 66 卜 9.86 9 inch 9 Π ◎ 〇 〇 - -

S Bu 0Ό 2 66 Bu 9=°'6

9-'-I ◎ 〇 d— ·0 Ζ.0Ό

S 66 卜 9-6 9 inch 9Π ◎ 〇 〇 ·0 00 ·0 66 -^6 § 9ι·Ι ◎ 〇 〇 s - ΓΟ

I inch Ό 66 卜 9*6 9 inch 9 Π ◎ 〇 'a 'm s '8 I_2 '2 ε-2

I • 2 9-2

'I 2 2 2

I ϊ.α

S 2 ίι-审®θ&lt;ε-Η-ώ) $ *丨^叫$4&gt;軚&gt;哒刼茫矣&lt;0-&gt; ^^^-ϋ^ιϊ^τνίΓ^^φ- (q (e/s •&quot;¥w#年杂荽·«.&lt; -31 - 200949433 ' ^ &lt;symbol description&gt; Bl : 25% by mass of mercaptoacrylic acid, 65 mass% of methacrylate, acrylic 10% by mass of ternary copolymer of butyl ester (weight average molecular weight is 100,000, acid equivalent is 344) B-2: 25 mass% of methacrylic acid '65% by mass of methyl methacrylate and 10% by mass of butyl acrylate Copolymer (weight average molecular weight is '200,000, acid equivalent is 370) B-3: 25% by weight of mercaptoacrylic acid, 50% by mass of methyl methacrylate, and 25% by mass of styrene (weight average molecular weight) 50,000, acid equivalent: 344) B-4: 25% by mass of methacrylic acid, 5% by mass of methacrylate, and 25% by mass of butyl acrylate (weight average molecular weight: 70,000, acid equivalent) 344) B-5: dimethyl methacrylate 80% by mass, methacrylic acid 2 〇 mass 0 / 〇 binary copolymer (weight average molecular weight is 1 〇〇, hydrazine, acid Equivalent to 43〇) M-1: Tetraacrylate formed by adding 1 mole of ethylene oxide to four ends of pentaerythritol (SR-494, manufactured by Sartomer Japan Co., Ltd.) ❹ M-2 The tetrapropyl acid formed by acrylation of the four ends of pentaerythritol is M-3. The triacrylate formed by adding an average of 3 moles of ethylene oxide to dimethylolpropane (new Nakamura Chemical Manufacturing A-TMPT-3EO) M4. Addition of trimethacrylate M-5 with an average of 3 moles of propylene oxide on monomethylolpropane: at both ends of the double-prepared A Code 77 is added separately with an average of 2 moles of ethylene oxide I36982.doc • 32· 200949433 formed polyethylene glycol dimethacrylate M-6: polypropylene glycol diacrylate I-1 : 9-phenyl. Bite 1-2 : N-phenylglycine 1-3 · 2-(o-chlorophenyl)_4,5-phenyl-based β-sitting dimer' 1-4: 1 -Phenyl-3_(4_t-butyl-styryl)5(4-tert-butylphenyl)-β than salicin 1-5. 2-(o-chlorophenyl)_4,5-bis- (m-methoxyphenyl)imidazolyl dimer © D-1 : diamond green D-2 : colorless crystal violet F-1 : methyl ethyl ketone ratio In Example 1, when a polymer having an average molecular weight of less than 70,000 was used as the test-soluble resin, oily aggregates were generated during development to cause a problem. In Comparative Example 2, the above-mentioned formula was used in the photosensitive resin composition. The proportion of the compound represented by (11) is less than 30% by mass, and as a result, the capping property is deteriorated. In Comparative Example 3, the ratio of the compound represented by the above formula (jj) in the photosensitive resin composition is more than 55% by mass, and the above (a) is added to the total amount of the photosensitive resin composition. When the ratio of the alkali-soluble resin is Α% by mass and the ratio of the compound (b) having a photopolymerizable unsaturated double bond is B mass, A/B is less than 1.1, and the capping property is deteriorated. Comparative Example 4 is an additional test of JP-A-11-119422. In Comparative Example 4, since a polyfunctional photopolymerizable unsaturated compound which does not correspond to the compound represented by the above formula (I) and the compound represented by the above formula (π) is not used, the result is a cap hole. Sexual deterioration 'and produces oily aggregates. 136982.doc •33- 9 200949433 [Industrial Applicability] The photosensitive resin laminate of the present invention is protected by exposure on a substrate on which the photosensitive resin laminate is laminated. The hole is not affected by the developer, the etch of the liquid, and the sound is simplified, and since the oil-like agglomerates in the developer are less, not only the cleaning of the device is reduced, but also the utilization is utilized. It is useful in the manufacture of an alkaline developed printed wiring board. 136982.doc -34·

Claims (1)

200949433 X. Patent application scope: 1) A photosensitive resin laminate which is obtained by laminating at least a support layer and a photosensitive resin layer, and the photosensitive resin layer contains a photosensitive resin composition. The photosensitive resin composition contains at least: (a) 25 to 64% by mass of an alkali-soluble resin; (b) a compound having a photopolymerizable unsaturated double bond; (c) a photopolymerization initiator 〇.1 to 20 mass %; and Φ further satisfies the following (i), (Π), and (iii): (0) as the total amount of the compound package 3 having the photopolymerizable unsaturated double bond described above (b) relative to the photosensitive resin composition It is at least one selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (11): 3 〇 5 5 5 % by mass: [Chemical Formula 1] 3, η!, n2, hit 3 and can also be 0., w is in ch3 or (where R', r2, and R3 are independent of Η or ch3, respectively; η4 is independently an integer of 〇~4, It can also be the base of 〇. ΟΗ); 136982.doc 200949433 [Chemical 2] (wherein R5, R6, R7 and Rs are each independently Η or CH3; mi, m2, ΠΙ3 and m4 are each independently an integer of 0 to 4, and may also be 〇); (ii) the above (a) alkali solubility The weight average molecular weight of the resin is 70,000 to 220,000, and the acid equivalent weight is 1 〇〇 to 6 〇〇; (iii) The thickness of the photosensitive resin layer is 3 to 15 μη. 2. The photosensitive resin laminate according to claim 1, wherein the compound (b) having a photopolymerizable unsaturated double bond comprises 35 to 55 mass% based on the total amount of the photosensitive resin composition. At least one of the group consisting of the compound represented by the above formula (1) and the compound represented by the above formula (II). 3. The photosensitive resin laminate according to claim 1 or 2, wherein (c) the photopolymerization initiator is 9-phenyl acridine. 4. The photosensitive resin laminate according to claim 1 or 2, wherein the ratio of the (a) alkali-soluble resin is set to A mass% with respect to the total amount of the photosensitive resin composition, and the (b) has light When the ratio of the compound of the polymerizable unsaturated double bond is B mass%, a/B is 1.1 to 1.3. 136982.doc • 2 - 200949433 5. A method of forming a resist pattern, a photosensitive resin layer of the item 1 or 2, and a developing step of exposing the portion by ultraviolet rays. The method comprises the steps of: laminating a photosensitive resin layer such as a coating on a substrate, exposing steps, and removing unexposed 8. A method of manufacturing a lead frame, characterized in that a substrate formed with a photoresist pattern by the method of claim 5 or 6 is subjected to a meal using a metal plate as a substrate, and the photoresist pattern is peeled off. 6. The method of forming a plurality of teas as claimed in claim 5, wherein t is exposed by direct drawing in the above exposure step. A method of manufacturing an in-conductor pattern, comprising the steps of: dicing or clocking a substrate on which a photoresist pattern is formed by the method of claim (4) using a copper-clad laminate as a substrate. A method of manufacturing a printed wiring board, characterized in that a metal-clad insulating board is used as a substrate, and a substrate having a photoresist pattern formed by the method of claim 6 is subjected to engraving or recording, and stripped Resistive pattern. 10. A method of manufacturing a semiconductor package, characterized in that a substrate on which a photoresist pattern is formed by a method of the method of claim 6 is used for plating a wafer on which a circuit as an LSI has been formed. And peel off the photoresist pattern. A method for producing a substrate having a concave-convex pattern, wherein a substrate having a photoresist pattern formed by the method of claim 5 or 6 is processed by a sand blast method using a glass rib as a substrate, and Stripping the photoresist case. ® 136982.doc 200949433 VII. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 8. If there is a chemical formula in this case, please reveal the characteristics that can best show the invention. Chemical formula: 136982.doc