JP4885243B2 - Photosensitive resin composition and laminate - Google Patents

Description

  The present invention relates to a photosensitive resin composition that can be developed with an alkaline aqueous solution, a photosensitive resin laminate in which the photosensitive resin composition is laminated on a support, and a resist pattern on a substrate using the photosensitive resin laminate. The present invention relates to a method for forming the resist pattern and an application of the resist pattern. More specifically, the manufacture of printed wiring boards, the manufacture of flexible printed wiring boards, the manufacture of lead frames for mounting IC chips (hereinafter referred to as “lead frames”), metal foil precision processing such as metal mask manufacturing, BGA (ball grid array) ) And CSP (chip size package), etc., TAB (Tape Automated Bonding) and COF (Chip On Film: semiconductor IC mounted on a film-like fine wiring board) The present invention relates to a photosensitive resin composition that provides a resist pattern suitable for manufacturing members such as ITO bumps, address electrodes, or electromagnetic wave shields in the field of manufacturing semiconductor bumps and flat panel displays.

  Conventionally, printed wiring boards are manufactured by a photolithography method. The photolithographic method is a method in which a photosensitive resin composition is applied onto a substrate, pattern exposure is performed to polymerize and cure the exposed portion of the photosensitive resin composition, and an unexposed portion is removed with a developer to form a resist on the substrate. A method of forming a conductor pattern on a substrate by forming a pattern, forming a conductor pattern by etching or plating, and then peeling and removing the resist pattern from the substrate.

  In the photolithography method described above, in applying the photosensitive resin composition on the substrate, a method of applying the photosensitive resin composition solution to the substrate and drying, or a support, a layer made of the photosensitive resin composition ( Hereinafter, a method of laminating a photosensitive resin laminate (hereinafter referred to as a “dry film resist”) in which a “photosensitive resin layer” and a protective layer as necessary are sequentially laminated on a substrate is used. Is done. In the production of printed wiring boards, the latter dry film resist is often used.

A method for producing a printed wiring board using the dry film resist will be briefly described below.
First, when the dry film resist has a protective layer such as a polyethylene film, it is peeled off from the photosensitive resin layer. Next, the photosensitive resin layer and the support are laminated on a substrate such as a copper clad laminate using a laminator so that the substrate, the photosensitive resin layer, and the support are in this order. Next, the exposed portion is polymerized and cured by exposing the photosensitive resin layer with ultraviolet rays such as i rays (365 nm) emitted from an ultrahigh pressure mercury lamp through a photomask having a wiring pattern. Next, the support made of polyethylene terephthalate or the like is peeled off. Next, a non-exposed portion of the photosensitive resin layer is dissolved or dispersed and removed by a developing solution such as an aqueous solution having weak alkalinity to form a resist pattern on the substrate. Next, a known etching process or pattern plating process is performed using the formed resist pattern as a protective mask. An acid copper plating bath is usually used for the pattern plating process. Finally, the resist pattern is peeled from the substrate to produce a substrate having a conductor pattern, that is, a printed wiring board.

  In recent years, many plating techniques have been used for electronic components. Plating technology can impart electrical properties to non-conductive materials such as printed wiring boards and ceramic substrates, and can provide convenient functions for bonding such as bonding and soldering, and stable contact. This is because new characteristics such as resistance can be given.

  Various materials having many characteristics have been developed for plating materials. Examples include gold, silver, copper, platinum, rhodium, palladium, nickel, cobalt, chromium, zinc, tin, and alloy plating of these metals. In particular, gold plating having excellent corrosion resistance, low change in contact resistance due to change with time and excellent bonding properties, and silver plating which is easier to oxidize than gold but is inexpensive are used for electronic parts. Each of the gold plating and silver plating includes a cyan bath (alkaline bath, neutral bath, acid bath), a non-cyan bath, and the like, and the plating bath is selected according to the required characteristics of the coating.

  In particular, in the case of use for wire bonding, a soft film is required, and in this case, a neutral to alkaline noble metal cyanide plating bath is selected.

  On the other hand, the dry film resist includes a step of peeling after the patterning and plating steps. This stripping step is often an alkaline aqueous solution. This is because the carboxyl group-containing binder in the photoresist is dissolved in an alkaline aqueous solution.

  When patterning using a photoresist in a plating process using a neutral to alkaline bath, the photoresist containing the carboxyl group-containing binder that originally dissolves due to alkalinity is dissolved by the alkali, and the plating and the substrate are exposed to the photo resist. The phenomenon that the plating solution soaks through the gaps between the resists or the photoresist is peeled off and normal patterning cannot be performed easily occurs. On the other hand, in order to improve the plating resistance, the alkali solubility is lowered so that the problem that the photoresist cannot be peeled off from the substrate easily occurs in the peeling step.

  For these reasons, there is a demand for a photosensitive resin composition that can withstand neutral to alkaline noble metal cyanide plating baths, has excellent contamination of the plating bath, has excellent resolution and adhesion, and has excellent resist stripping properties. It was.

Regarding the plating resistance of the resist, Patent Document 1 discloses a terpolymer of methacrylic acid / ethyl methacrylate / styrene, a bisphenol A (meth) acrylate compound, a methacrylate compound having a urethane bond, 2, 2 ′. -Resolution, adhesion, sensitivity, plating bath contamination of photosensitive resin composition containing bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-bisimidazole , Developability and mechanical strength are discussed, but it cannot be said that it has resistance to a neutral to alkaline noble metal cyanide plating bath, and nothing is discussed about peelability.
Japanese Unexamined Patent Publication No. 2001-222106

  The present invention is a photosensitive resin composition that withstands noble metal plating in a neutral to alkaline cyan bath, and has excellent resolution, adhesion, and resist strippability, a photosensitive resin laminate using the photosensitive resin composition, It aims at providing the method of forming a resist pattern on a board | substrate using this photosensitive resin laminated body, and the use of this resist pattern.

The above object can be achieved by the following configuration of the present invention.
1. (A) carboxyl group-containing binder: 20 to 90% by mass, (b) addition polymerizable monomer having at least one terminal ethylenically unsaturated group: 5 to 75% by mass, (c) photopolymerization initiator: 0.01 A photosensitive resin composition containing ~ 30% by mass, wherein (b) an addition polymerizable monomer having at least one terminal ethylenically unsaturated group is represented by the following general formula (I) and general formula: A photosensitive resin composition comprising 1 to 50% by mass of at least one compound selected from the group consisting of compounds represented by (II) in the entire photosensitive resin composition.

(Wherein R ¹ is a linear, branched, or cyclic alkyl group having 4 to 12 carbon atoms, or an alkylaryl group having 6 to 12 carbon atoms, and R ^{2 to} R ⁵ are each independently hydrogen or a methyl group. , A is C ₂ H _4, B is CH ₂ CH (CH ₃ ), n _{1 to} n ₄ are each independently an integer of 0 to 15, and n ₁ + n ₂ + n ₃ + n ₄ is 2 or more.
The arrangement of repeating units of-(A-O)-and-(B-O)-may be random or block. In the case of a block, either-(AO)-or-(BO)-may be on the urethane bond side. )

(Here, R ⁶ and R ⁷ are each independently a linear, branched, or cyclic alkyl group having 4 to 12 carbon atoms, or an alkylaryl group having 6 to 12 carbon atoms, and R ^{8 to} R ¹¹ are each independently hydrogen or a methyl group, a is _C 2 _{H 4,} B is _{CH 2 CH (CH 3),} n 5 and _{n 6} represents an integer of 0 to _{15, n} 5+ _{n 6} represents at least one .n ₇ ~n ₁₀ is each independently an integer of _{0~15, n 7 + n 8 +} n 9 + n 10 is 2 or more.
The arrangement of repeating units of-(A-O)-and-(B-O)-may be random or block. In the case of a block, either-(AO)-or-(BO)-may be on the urethane bond side. )
2. The above (b) addition polymerizable monomer having at least one terminal ethylenically unsaturated group further contains a compound represented by the following general formula (III). The photosensitive resin composition as described.

(Wherein R ¹² is a linear, branched or cyclic alkyl group having 4 to 12 carbon atoms, or an alkylaryl group having 6 to 12 carbon atoms, and R ¹³ and R ¹⁴ are independently hydrogen or methyl group. , A is C ₂ H _4, B is CH ₂ CH (CH ₃ ), n _{11 to} n ₁₄ are each independently an integer of 0 to 15, and n ₁₁ + n ₁₂ + n ₁₃ + n ₁₄ is 2 or more.
The arrangement of repeating units of-(A-O)-and-(B-O)-may be random or block. In the case of a block, either-(AO)-or-(BO)-may be on the urethane bond side. )
3.1. Or 2. A photosensitive resin laminate comprising a photosensitive resin layer comprising the photosensitive resin composition described above and a support.
4). 2. on the substrate; A method for forming a resist pattern, comprising a lamination step of forming a photosensitive resin layer using the photosensitive resin laminate described above, an exposure step, and a development step.
5. 3. In the exposure step, direct drawing and exposure are performed. A method for forming a resist pattern as described in 1. above.
6.4. Or 5. A method for producing a printed wiring board comprising a step of etching or plating a substrate on which a resist pattern is formed by the method described in 1.
7.4. Or 5. A method for producing a substrate having a concavo-convex pattern, comprising a step of processing a substrate on which a resist pattern is formed by the method described in 1 by sandblasting.
8.4. Or 5. A method for manufacturing a semiconductor package, comprising a step of plating a substrate on which a resist pattern is formed by the method described in 1.
9.4. Or 5. The manufacturing method of bump including the process of plating the board | substrate which formed the resist pattern by the method of description.
10.4. Or 5. A method for manufacturing a lead frame, comprising a step of etching a substrate on which a resist pattern is formed by the method described in 1.
11.4. Or 5. A method for producing a printed wiring board, comprising a step of plating a substrate on which a resist pattern is formed by the method described in 1 above, wherein the plating step uses a noble metal cyanide plating bath.
12.4. Or 5. A method for producing a semiconductor package, comprising a step of plating a substrate on which a resist pattern is formed by the method described in 1 above, wherein the plating step uses a noble metal cyanide plating bath.
13.4. Or 5. A method for producing a bump, comprising a step of plating a substrate on which a resist pattern is formed by the method described in 1), wherein the plating step uses a noble metal cyanide plating bath.

  The present invention relates to a photosensitive resin composition that has resistance to a neutral to alkaline noble metal cyanide plating bath and that can be developed with an alkaline aqueous solution that is excellent in resolution, adhesion, and resist releasability, and the photosensitive resin composition. Photosensitive resin laminate used, method for forming resist pattern on substrate using photosensitive resin laminate, and application of resist pattern, printed wiring board manufacture, lead frame manufacture, semiconductor package And can be suitably used for the production of flat displays.

  Hereinafter, the present invention will be specifically described.

(A) Carboxyl group-containing binder In the photosensitive resin composition of the present invention, (a) the carboxyl group-containing binder has an acid equivalent containing a monomer containing an α, β-unsaturated carboxyl group as a copolymerization component. And those having a weight average molecular weight of 5,000 to 500,000 are preferably used.

  The carboxyl group of the carboxyl group-containing binder is necessary for the photosensitive resin composition to have developability and releasability with respect to a developer and a release solution composed of an alkaline aqueous solution. The acid equivalent is preferably 100 to 600, more preferably 250 to 450. It is 100 or more from the viewpoint of securing compatibility with other components in the solvent or the composition, particularly (b) addition polymerizable monomer described later, and 600 or less from the viewpoint of maintaining developability and peelability. Is preferred. Here, an acid equivalent means the mass (gram) of the thermoplastic copolymer which has a 1 equivalent carboxyl group in it. The acid equivalent is measured by potentiometric titration with a 0.1 mol / L NaOH aqueous solution using a Hiranuma Reporting Titrator (COM-555).

The weight average molecular weight of the carboxyl group-containing binder of the present invention is preferably 5,000 to 500,000. From the viewpoint of maintaining the thickness of the dry film resist uniformly and obtaining resistance to the developer, it is preferably 5,000 or more, and from the viewpoint of maintaining developability, 500,000 or less is preferable. More preferably, the weight average molecular weight is 20,000 to 100,000. The weight average molecular weight in this case is a standard polystyrene (Shodex manufactured by Showa Denko KK) by gel permeation chromatography (GPC).
It is a weight average molecular weight measured using a calibration curve according to STANDARD SM-105). The weight average molecular weight can be measured using gel permeation chromatography manufactured by JASCO Corporation under the following conditions.
Differential refractometer: RI-1530
Pump: PU-1580
Degasser: DG-980-50
Column oven: CO-1560
Column: KF-8025, KF-806M × 2, KF-807 in order
Eluent: THF
The carboxyl group-containing binder is preferably a copolymer composed of at least one of the first monomers described below and at least one of the second monomers described below.

  The first monomer is a monomer containing an α, β-unsaturated carboxyl group in the molecule. Examples include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Among these, (meth) acrylic acid is particularly preferable.

  The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl ( Esters of vinyl alcohol such as (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, vinyl acetate , (Meth) acrylonitrile, styrene, and polymerizable styrene derivatives. Of these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are particularly preferable.

  (A) The carboxyl group-containing binder used in the present invention is prepared by adding a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution obtained by diluting a mixture of the above monomers with a solvent such as acetone, methyl ethyl ketone, or isopropanol. Synthesis can be carried out by adding an appropriate amount and stirring with heating. In some cases, the synthesis is performed while a part of the mixture is dropped into the reaction solution. As synthesis means, bulk polymerization, suspension polymerization and emulsion polymerization may be used in addition to solution polymerization.

  The ratio of (a) the carboxyl group-containing binder used in the present invention to the entire photopolymerizable resin composition is 20% by mass or more and 90% by mass or less, more preferably 30% by mass or more and 70% by mass or less, and 40% by mass. The amount is particularly preferably 60% by mass or less. It is 20% by mass or more from the point that the tenting film strength is improved and edge fuse is suppressed, and 90% by mass or less from the point that developability is improved.

(B) Addition polymerizable monomer having at least one terminal ethylenically unsaturated group (b) Addition polymerizable monomer having at least one terminal ethylenically unsaturated group (hereinafter, simply referred to as addition polymerizable monomer) May include at least one compound selected from the group consisting of compounds represented by the following general formula (I) and general formula (II) as an essential component.

(Wherein R ¹ is a linear, branched, or cyclic alkyl group having 4 to 12 carbon atoms, or an alkylaryl group having 6 to 12 carbon atoms, and R ^{2 to} R ⁵ are each independently hydrogen or a methyl group. , A is C ₂ H _4, B is CH ₂ CH (CH ₃ ), n _{1 to} n ₄ are each independently an integer of 0 to 15, and n ₁ + n ₂ + n ₃ + n ₄ is 2 or more.
The arrangement of repeating units of-(A-O)-and-(B-O)-may be random or block. In the case of a block, either-(AO)-or-(BO)-may be on the urethane bond side. )

(Here, R ⁶ and R ⁷ are each independently a linear, branched, or cyclic alkyl group having 4 to 12 carbon atoms, or an alkylaryl group having 6 to 12 carbon atoms, and R ^{8 to} R ¹¹ are each Independently hydrogen or methyl group, A is C ₂ H _4, B is CH ₂ CH (CH ₃ ), n ₅ and n ₆ are each independently an integer of 0 to 15 and n ₅ + n ₆ is 1 or more N _{7 to} n ₁₀ are each independently an integer of 0 to 15, and n ₇ + n ₈ + n ₉ + n ₁₀ is 2 or more.
The arrangement of repeating units of-(A-O)-and-(B-O)-may be random or block. In the case of a block, either-(AO)-or-(BO)-may be on the urethane bond side. )
The proportion of at least one compound selected from the group consisting of the compounds represented by the general formula (I) and the general formula (II) in the photosensitive resin composition of the present invention is in the entire photosensitive resin composition. 1-50 mass% is preferable, More preferably, it is 3-30 mass%. More preferably, it is 20 mass% or less. This amount is 1% by mass or more from the viewpoint of developing good plating properties, and is 50% by mass or less from the viewpoint of having good peelability.

  The compound represented by the above general formula (I) includes a polyisocyanate and a compound having a hydroxyl group and two (meth) acryl groups in one molecule (polyethylene oxide chain adduct of glycerol dimethacrylate, polypropylene of glycerol dimethacrylate). And urethane compounds with oxide chain adducts, polyethylene / polypropylene oxide chain adducts of glycerin dimethacrylate, and the like. Examples of the polyisocyanate used include tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, α, α′-. Dimethyl-o-xylylene diisocyanate, α, α′-dimethyl-m-xylylene diisocyanate, α, α′-dimethyl-p-xylylene diisocyanate, α, α, α′-trimethyl-o-xylylene diisocyanate, α , Α, α′-trimethyl-m-xylylene diisocyanate, α, α, α′-trimethyl-p-xylylene diisocyanate, α, α, α ′, α′-tetramethyl-o-xylylene diisocyanate, α, α, α ', α'- Examples thereof include tetramethyl-m-xylylene diisocyanate, α, α, α ′, α′-tetramethyl-p-xylylene diisocyanate, cyclohexane diisocyanate, and the like. A compound obtained by hydrogenating an aromatic ring of a diisocyanate compound, for example, a hydrogenated product of m-xylylene diisocyanate (Takenate 600 manufactured by Mitsui Takeda Chemical Co., Ltd.) is also included.

Specific examples of the compound represented by the general formula (I) include a reaction product of hexamethylene diisocyanate and glycerin dimethacrylate added with 5 mol of propylene oxide on average (in the general formula (I), R ¹ is hexa A methylene group, R ^{2 to} R ⁵ are methyl groups, n ₁ = n ₃ = 0, n ₂ = n ₄ = 5, Toho Chemical Industries, Ltd., UA-47), hexamethylene diisocyanate and Reaction product with glycerin dimethacrylate added with an average of 4 moles of ethylene oxide (in the above general formula (I), R ¹ is a hexamethylene group, R ^{2 to} R ⁵ are methyl groups, and n ₁ = n ₃ = 4 , N ₂ = n ₄ = 0, Toho Chemical Industries, Ltd., UA-41).

  The compound represented by the general formula (II) includes polyisocyanate, a compound having a hydroxyl group and two (meth) acrylic groups in one molecule (polyethylene oxide chain adduct of glycerin dimethacrylate, glycerin dimethacrylate). Polypropylene oxide chain adducts, polyethylene / polypropylene oxide chain adducts of glycerin dimethacrylate and the like) and (poly) alkylene glycol urethane compounds. As the polyisocyanate, those described above are used.

Specific examples of the compound represented by the general formula (II) include glycerin dimethacrylate to which hexamethylene diisocyanate and an average of 4 mol of ethylene oxide are added, an average of 6 mol of ethylene oxide and an average of 13 mol of propylene oxide. (I.e., in the above general formula (II), R ⁶ and R ⁷ are hexamethylene groups, R ^{8 to} R ¹¹ are methyl groups, and n ₇ = n ₉ = 4, n) _{8 = n 10 = 0, n} 5 = 6, n 6 = 13 , compound: manufactured by Toho chemical Industry Co., UA-42), and glycerol dimethacrylate obtained by adding average 5 moles of propylene oxide with hexamethylene diisocyanate , Polyalkylene glyco added with an average of 6 moles of ethylene oxide and an average of 13 moles of propylene oxide Reaction product between Le (i.e., the general formula (II), ^{R 6} and ^{R 7} hexamethylene ^group, R 8 to R ¹¹ is a methyl _{group, n 7 = n 9 = 0} , n 8 = n 10 = 5, n ₅ = 6, n ₆ = 13: Toho Chemical Industries, Ltd., UA-48) and the like.

  As the addition polymerizable monomer (b) used in the present invention, a known compound having at least one terminal ethylenically unsaturated group can be used in combination with the above compound.

  For example, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxyethyltrimethylolpropane tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxylated tetra (meth) acrylate, 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxyhexaethylene glycol acrylate, phthalic anhydride and 2 -Reaction product of half-ester compound with hydroxypropyl acrylate and propylene oxide (product name, manufactured by Nippon Shokubai Chemical) EA 200), 4-normal octylphenoxypentapropylene glycol acrylate, 2,2-bis [{4- (meth) acryloxypolyethoxy} phenyl] propane, 2,2-bis {(4-acryloxypolyethoxy) ) Cyclohexyl} propane or 2,2-bis {(4-methacryloxypolyethoxy) cyclohexyl} propane, 1,6-hexanediol (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, or polypropylene glycol di Polyoxyalkylene glycol di (meth) acrylate such as (meth) acrylate, polyethylene glycol di (meth) acrylate, polyoxyethylene polyoxypropylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) pro Examples include pandi (meth) acrylate, glycerol tri (meth) acrylate, 2,2-bis (4-methacryloxypentaethoxyphenyl) propane, and polyfunctional (meth) acrylates of isocyanuric acid ester compounds.

  In addition, it is preferable to include a compound represented by the following general formula (III) from the viewpoint of further improving resolution, adhesion, and resistance to noble metal plating in a neutral to alkaline cyan bath. It is an embodiment of the invention.

(Wherein R ¹² is a linear, branched or cyclic alkyl group having 4 to 12 carbon atoms, or an alkylaryl group having 6 to 12 carbon atoms, and R ¹³ and R ¹⁴ are independently hydrogen or methyl group. , A is C ₂ H _4, B is CH ₂ CH (CH ₃ ), n _{11 to} n ₁₄ are each independently an integer of 0 to 15, and n ₁₁ + n ₁₂ + n ₁₃ + n ₁₄ is 2 or more.
The arrangement of repeating units of-(A-O)-and-(B-O)-may be random or block. In the case of a block, either-(AO)-or-(BO)-may be on the urethane bond side. )
Specific examples of the compound represented by the general formula (III) include a diisocyanate compound (for example, hexamethylene diisocyanate, tolylene diisocyanate, or 2,2,4-trimethylhexamethylene diisocyanate), and a hydroxyl group in one molecule. And urethane having a (meth) acrylic group (for example, 2-hydroxypropyl acrylate, monomethacrylate having a propylene glycol chain, monomethacrylate having a polyethylene glycol chain, monomethacrylate having an ethylene oxide chain and a propylene oxide chain, etc.) Compounds.

  As for content in the case of containing the compound represented by the said general formula (III), 3-70 mass% is preferable with respect to the whole photosensitive resin composition. 3 mass% or more is preferable from the viewpoint of resolution, and 70 mass% or less is preferable from the viewpoint of the flexibility of the resist pattern.

  The amount of the (b) addition polymerizable monomer contained in the photosensitive resin composition of the present invention is in the range of 5 to 75% by mass, and more preferably in the range of 15 to 70% by mass. This amount is 5% by mass or more from the viewpoint of suppressing poor curing and a delay in development time, and is 75% by mass or less from the viewpoint of suppressing cold flow and delayed peeling of the cured resist.

(C) Photopolymerization initiator For the photosensitive resin composition of the present invention, those generally known as (c) photopolymerization initiators can be used. The amount of the (c) photopolymerization initiator contained in the photosensitive resin composition of the present invention is in the range of 0.01 to 30% by mass, and more preferably 0.05 to 10% by mass. From the viewpoint of obtaining sufficient sensitivity, it is preferably 0.01% by mass or more, and from the viewpoint of sufficiently transmitting light to the bottom surface of the resist and obtaining good high resolution, it is preferably 30% by mass or less.

  As such a photopolymerization initiator, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1, Quinones such as 4-naphthoquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone, benzophenone, Michler's ketone [4,4'-bis (dimethylamino) benzophenone], 4,4'-bis (diethylamino) Aromatic ketones such as benzophenone Benzoin, benzoin ethyl ether, benzoin phenyl ether, benzoin ethers such as methyl benzoin and ethyl benzoin, dialkyl ketals such as benzyl dimethyl ketal and benzyl diethyl ketal, thioxanthones such as diethyl thioxanthone and chloro thioxanthone, dimethylaminobenzoic acid Dialkylaminobenzoates such as ethyl, 1-phenyl-1,2-propanedione-2-O-benzoyloxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, etc. Oxime esters, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-chlorophenyl) -4,5-bis- (m-methoxyphenyl) imidazolyl dimer, 2- ( -Methoxyphenyl) -4,5-diphenylimidazolyl dimer and other dimers, acridine, 9-phenylacridine, 9- (p-methylphenyl) acridine, 9- (p-ethylphenyl) acridine, 9- (P-iso-propylphenyl) acridine, 9- (pn-butylphenyl) acridine, 9- (p-tert-butylphenyl) acridine, 9- (p-methoxyphenyl) acridine, 9- (p-ethoxy) Phenyl) acridine, 9- (p-acetylphenyl) acridine, 9- (p-dimethylaminophenyl) acridine, 9- (p-cyanophenylphenyl) acridine, 9- (p-chlorophenyl) acridine, 9- ( p-bromophenyl) acridine, 9- (m-methylphenyl) acridine, 9- (m -N-propylphenyl) acridine, 9- (m-iso-propylphenyl) acridine, 9- (mn-butylphenyl) acridine, 9- (m-tert-butylphenyl) acridine, 9- (m-methoxy) Phenyl) acridine, 9- (m-ethoxyphenyl) acridine, 9- (m-acetylphenyl) acridine, 9- (m-dimethylaminophenyl) acridine, 9- (m-diethylaminophenyl) acridine, 9- (cyanophenyl) ) Acridine, 9- (m-chlorophenyl) acridine, 9- (m-bromophenyl) acridine, 9-methylacridine, 9-ethylacridine, 9-n-propylacridine, 9-iso-propylacridine, 9-cyanoethyl Acridine, 9-hydroxyethyl acridine, 9-c Roethylacridine, 9-methoxyacridine, 9-ethoxyacridine, 9-n-propoxyacridine, 9-iso-propoxyacridine, 9-chloroethoxyacridine, N-phenylglycine, N-methyl-N-phenylglycine, N- Ethyl-N-phenylglycine, amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2 , 3-Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, 1-phenyl-3- (4-tert- Butyl-styryl) -5- (4-tert-butyl-fur Yl) - pyrazoline compounds such pyrazoline, and the like.

  Particularly, from the viewpoint of high resolution, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer and Michler's ketone [4,4′-bis (dimethylamino) benzophenone] or 4,4′-bis (diethylamino) benzophenone Are preferably combined.

  In the photosensitive resin composition of the present invention, in addition to the components described above, coloring substances such as dyes and pigments can be employed. Examples of such coloring substances include phthalocyanine green, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green, basic blue 20, and diamond green.

  Moreover, you may add a color former in the photosensitive resin composition of this invention so that a visible image can be given by exposure. Examples of such a color former include a combination of a leuco dye or a fluoran dye and a halogen compound. Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2, 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, and chlorinated triazine compounds. .

  The amount of the coloring substance and the color former is preferably 0.01 to 10% by mass in the photosensitive resin composition. It is preferably 0.01% by mass or more from the viewpoint of recognizing sufficient colorability (coloring property), 10% by mass or less from the viewpoint of maintaining the contrast between the exposed part and the unexposed part and maintaining storage stability.

  Furthermore, in order to improve the thermal stability and storage stability of the photosensitive resin composition of the present invention, the photosensitive resin composition is selected from the group consisting of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles. It is preferable to contain at least one compound.

  Examples of such radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2 Examples include '-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine.

  Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, and bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzo. Examples include triazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole.

  Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl). Examples include aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole.

  The total amount of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass. This amount is preferably 0.01% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin composition, and more preferably 3% by mass or less from the viewpoint of maintaining sensitivity.

  In order to improve the hue stability of the photosensitive resin composition of the present invention, the photosensitive resin composition may contain a phosphite compound. Examples of the phosphite compound include 2,4,8,10-tetra-tert-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d. F] [1,3,2] dioxaphosphene pin, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (2,4-di-tert-butylphenyl) Pentaerythritol-diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, 4,4′-butylidenebis (3-methyl-6-tert-butylphenyl-di-tridecylphosphite, 4,4 ′ Examples thereof include isopropylidene-di-phenol alkyl phosphite or trisisodecyl phosphite. Amount when added is 0.01 to 5 mass%.

  You may make the photosensitive resin composition of this invention contain a plasticizer as needed. Examples of such plasticizers include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, and polyoxyethylene monoethyl. Glycol ethers such as ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, phthalates such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate , Triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate Le, and the like.

  When adding a plasticizer, it is preferable to contain 5-50 mass% in a photosensitive resin composition, More preferably, it is 5-30 mass%. 5 mass% or more is preferable from a viewpoint of suppressing the delay of image development time or providing a softness | flexibility to a cured film, and 50 mass% or less is preferable from a viewpoint of suppressing insufficient hardening and cold flow.

<Photosensitive resin composition preparation solution>
The photosensitive resin composition of the present invention may be a photosensitive resin composition preparation liquid to which a solvent is added. Suitable solvents include ketones represented by methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol, and isopropyl alcohol. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of the photosensitive resin composition preparation liquid is 500 to 4000 mPa · sec at 25 ° C.

<Photosensitive resin laminate>
The photosensitive resin laminate includes a photosensitive resin layer made of a photosensitive resin composition and a support. The photosensitive resin composition can be laminated on a support to form a photosensitive resin laminate. Moreover, you may have a protective layer on the surface on the opposite side to the support body of the photosensitive resin layer as needed.

  The support used here is preferably a transparent one that transmits light emitted from the exposure light source. Such supports include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate polymer film, methyl methacrylate. Examples thereof include a copolymer film, a polystyrene film, a styrene copolymer film, a polyacrylonitrile film, a polyamide film, and a cellulose derivative film. These supports can be stretched if necessary. The haze is preferably 5 or less. A thinner support is advantageous in terms of image forming properties and economic efficiency, but a substrate having a thickness of 10 to 30 μm is preferably used from the viewpoint of maintaining the strength.

  Further, an important characteristic of the protective layer used in the photosensitive resin laminate is that the protective layer is sufficiently smaller than the support and can be easily peeled with respect to the adhesion with the photosensitive resin layer. For example, a polyethylene film and a polypropylene film can be preferably used as the protective layer. Also, a film having excellent peelability disclosed in JP-A-59-202457 can be used. The thickness of the protective layer is preferably 10 to 100 μm, and more preferably 10 to 50 μm.

  The thickness of the photosensitive resin layer in the photosensitive resin laminate of the present invention is preferably 5 to 100 μm, more preferably 7 to 60 μm. As the thickness is thinner, the resolution is improved, and as the thickness is thicker, the strength of the cured film is improved.

A conventionally known method can be adopted as a method for preparing the photosensitive resin laminate of the present invention by sequentially laminating a support, a photosensitive resin layer, and if necessary, a protective layer.
For example, the photosensitive resin composition used for the photosensitive resin layer is made into the above-mentioned photosensitive resin composition preparation liquid, first applied onto a support using a bar coater or a roll coater, and dried, and then on the support. A photosensitive resin layer made of the photosensitive resin composition is laminated on the substrate.

  Next, if necessary, a photosensitive resin laminate can be prepared by laminating a protective layer on the photosensitive resin layer using a laminator.

<Resist pattern formation method>
A resist pattern using the photosensitive resin laminate of the present invention can be formed by a process including a laminating process, an exposing process, and a developing process. An example of a specific method is shown.

  First, a laminating process is performed using a laminator. When the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heat-pressed and laminated on the substrate surface with a laminator. In this case, the photosensitive resin layer may be laminated on only one surface of the substrate surface, or may be laminated on both surfaces as necessary. The heating temperature at this time is generally 40 to 160 ° C. Moreover, the adhesiveness with respect to the board | substrate of the obtained resist pattern improves by performing this thermocompression bonding twice or more. At this time, for the crimping, a two-stage laminator having two rolls may be used, or it may be repeatedly crimped through the roll several times.

  Next, an exposure process is performed using an exposure machine. If necessary, the support is peeled off and exposed to active light through a photomask. The exposure amount is determined from the light source illuminance and the exposure time. You may measure using a photometer.

  In the exposure process, an exposure method of drawing directly may be used. In the exposure method for direct drawing, exposure is performed directly on the substrate by a drawing apparatus without using a photomask. As the light source, a semiconductor laser having a wavelength of 350 to 410 nm, an ultrahigh pressure mercury lamp, or the like is used. The drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the illuminance of the exposure light source and the moving speed of the substrate.

Next, a developing process is performed using a developing device. After exposure, if a support is present on the photosensitive resin layer, this is excluded. Subsequently, the unexposed portion is developed and removed using a developer composed of an alkaline aqueous solution to obtain a resist image. As the alkaline aqueous solution, an aqueous solution of Na ₂ CO ₃ , K ₂ CO ₃ or the like is preferable. These are selected according to the characteristics of the photosensitive resin layer, but an aqueous Na ₂ CO ₃ solution having a concentration of 0.2 to 2% by mass is generally used. A surface active agent, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution. In addition, it is preferable to maintain the temperature of this developing solution in a development process at the constant temperature in the range of 20-40 degreeC.

  Although a resist pattern is obtained by the above-mentioned process, a heating process at 100 to 300 ° C. can be further performed depending on the case. The heating time is preferably 1 minute to 30 minutes. By carrying out this heating step, chemical resistance can be further improved. For heating, a heating furnace of a hot air, infrared ray, far infrared ray, or the like can be used.

  Moreover, depending on the case, the process by the exposure after patterning can also be implemented. By performing this exposure step, further chemical resistance can be improved.

<Method for manufacturing printed wiring board>
The method for producing a printed wiring board of the present invention is performed by performing the following steps after forming a resist pattern on a copper-clad laminate or flexible substrate as a substrate by the above-described resist pattern forming method.

  First, a step of forming a conductor pattern using a known method such as a step of etching the copper surface of the substrate exposed by development or a step of plating is performed.

  In the plating step, a copper plating bath or a noble metal cyanide plating bath may be used.

  Examples of the noble metal for cyanide noble metal plating include gold and silver.

  In the present invention, a gold cyanide plating bath can be preferably used.

  In the case of gold cyanide plating, the plating solution contains a cyanide complex, and is classified into an alkaline cyanide bath (pH 8.5 to 13), a neutral cyanide bath (pH 6 to 8.5), and an acidic cyanide bath (pH 3 to 6). Is done. These plating solutions can use what is marketed.

  The photosensitive resin composition of the present invention can withstand neutral to alkaline noble metal cyanide plating.

  Thereafter, the resist pattern is peeled off from the substrate with an aqueous solution having alkalinity stronger than that of the developer to obtain a desired printed wiring board. The alkaline aqueous solution for peeling (hereinafter also referred to as “peeling solution”) is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of 2 to 5% by mass is generally used. It is possible to add a small amount of a water-soluble solvent to the stripping solution. In addition, it is preferable that the temperature of this peeling liquid in a peeling process is the range of 40-70 degreeC.

<Manufacturing method of substrate having concave / convex pattern>
The resist pattern can be used as a protective mask member when the substrate is processed by the sandblasting method by the resist pattern forming method described above.

Examples of the substrate include glass, silicon wafer, amorphous silicon, polycrystalline silicon, ceramic, sapphire, and metal material. A resist pattern is formed on the substrate such as glass by the same method as the resist pattern forming method described above. After that, a blasting material is sprayed on the formed resist pattern to be cut to a desired depth, and a resist pattern portion remaining on the substrate is removed from the substrate with an alkali stripping solution or the like, and then on the substrate. It can be set as the base material which has a fine uneven | corrugated pattern. The blasting material used in the above-mentioned sandblasting process may be a known material, for example, fine particles of about ₂ to 100 μm such as SiC, SiO ₂ , Al ₂ O ₃ , CaCO ₃ , ZrO ₂ , glass and stainless steel.

  The above-described method for producing a substrate having a concavo-convex pattern by the sandblasting method can be used for production of flat panel display partition walls, organic EL glass cap processing, silicon wafer drilling processing, ceramic pinning processing, and the like. it can. Moreover, it can utilize for manufacture of the electrode of a metal material layer chosen from the group which consists of a ferroelectric film and a noble metal, a noble metal alloy, a refractory metal, and a refractory metal compound.

<Semiconductor package manufacturing method>
The semiconductor package manufacturing method of the present invention manufactures a semiconductor package by mounting a chip on which circuit formation as an LSI has been completed through the following steps.
First, copper sulfate plating or the above-mentioned noble metal cyanide plating is applied to the exposed portion of the base metal in the resist pattern-attached base material obtained by development to form a conductor pattern. Thereafter, a peeling process for peeling the resist pattern by the same method as the printed wiring board manufacturing method described above is performed, and further, etching is performed to remove a thin metal layer for portions other than the columnar plating, and the chip is formed. A desired semiconductor package is obtained by mounting.

<Bump manufacturing method>
The bump manufacturing method of the present invention is performed for mounting a chip on which circuit formation as an LSI has been completed, and is manufactured by the following steps.
First, copper sulfate plating or the above-mentioned noble metal cyanide plating is applied to the exposed portion of the base metal in the resist pattern-attached base material obtained by development to form a conductor pattern. Thereafter, a peeling process for peeling the resist pattern by the same method as the above-described method for manufacturing a printed wiring board is performed, and further, a thin metal layer other than the columnar plating is removed by etching. Get a bump.

<Lead frame manufacturing method>
The lead frame manufacturing method of the present invention is performed by performing the following steps after forming a resist pattern on a metal plate, for example, copper, copper alloy, or iron-based alloy as a substrate by the resist pattern forming method described above. Is called.

  First, a step of etching the substrate exposed by development to form a conductor pattern is performed. Then, the peeling process which peels a resist pattern with the method similar to the manufacturing method of the above-mentioned printed wiring board is performed, and a desired lead frame is obtained.

Hereinafter, examples of embodiments of the present invention will be specifically described.
(Examples 1-11, Comparative Example 1)
First, a method for producing samples for evaluation of Examples and Comparative Examples will be described, and then an evaluation method for the obtained samples and the evaluation results are shown in Table 1.

  Table 2 shows the names of the material components B-1 to K-1 in the photosensitive resin composition preparation liquid represented by the abbreviations in Table 1.

1. Production of Evaluation Samples The photosensitive resin laminates in Examples and Comparative Examples were produced as follows.

<Preparation of carboxyl group-containing binder>
First, the binder shown below was prepared.
(Synthesis example)
In a 1000 cc four-necked flask equipped with a nitrogen inlet, stirring blades, Dimroth, and thermometer, 300 g of methyl ethyl ketone was placed under a nitrogen atmosphere, and the temperature of the hot water bath was raised to 80 ° C. Next, a solid solution of 400 g in total was prepared at a composition ratio of methacrylic acid / styrene / benzyl methacrylate of 30/20/50 (mass ratio). A solution prepared by dissolving 3 g of azobisisobutyronitryl in 30 g of methyl ethyl ketone was prepared in this preparation solution, and the solution was added dropwise over 2 hours with stirring. Thereafter, the mixture was heated and stirred for 6 hours (primary polymerization). Thereafter, a solution prepared by dissolving 6 g of azobisisobutyronitrile in 30 g of methyl ethyl ketone was added dropwise in 3 portions every 4 hours, followed by heating and stirring for 5 hours (secondary polymerization). Next, 240 g of methyl ethyl ketone was added and the polymerization reaction product was taken out of the flask to obtain a binder solution B-1. At this time, the weight average molecular weight was 55,000, the dispersity was 2.6, and the acid equivalent was 290. Resin solid content in the obtained binder solution B-1 was 41 mass%.

  Similarly, the binder solution B-2 was synthesized so that methacrylic acid / styrene / methyl methacrylate = 25/25/50 (weight ratio). The composition ratio of the polymerizable substance and the resin solid content, weight average molecular weight, dispersity, and acid equivalent of the obtained binder solution are shown below.

  Binder solution-B-1: methacrylic acid / styrene / benzyl methacrylate = 30/20/50 (weight ratio) (weight average molecular weight 55,000, dispersity 2.6, acid equivalent 290, solid content concentration 41 mass% Of methyl ethyl ketone).

  Binder solution B-2: methacrylic acid / styrene / methyl methacrylate = 25/25/50 (weight ratio) (weight average molecular weight 50,000, dispersity 2.8, acid equivalent 344, solid content concentration 41 mass% Methyl ethyl ketone solution).

<Preparation of photosensitive resin laminate>
The photosensitive resin composition and solvent having the composition shown in Table 1 are thoroughly stirred and mixed to obtain a photosensitive resin composition preparation solution, and uniformly applied to the surface of a 16 μm-thick polyethylene terephthalate film as a support using a bar coater. And dried in a dryer at 95 ° C. for 4 minutes to form a photosensitive resin layer. The thickness of the photosensitive resin layer was 40 μm.
Next, a 23 μm thick polyethylene film was laminated as a protective layer on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated to obtain a photosensitive resin laminate.

<Board surface preparation>
A substrate for resolution evaluation, a substrate for evaluation of adhesion, a substrate for evaluation of resist peelability, and a substrate for evaluation of resistance to an alkaline noble metal cyanide plating bath use a 1.6 mm thick copper clad laminate laminated with 35 μm rolled copper foil. The surface was subjected to wet buffalo polishing (manufactured by 3M, Scotch Bright (registered trademark) HD # 600, twice).

<Laminate>
While peeling the polyethylene film of the photosensitive resin laminate, it was laminated at a roll temperature of 105 ° C. with a hot roll laminator (Asahi Kasei Electronics Co., Ltd., AL-70) on a copper clad laminate that had been leveled and preheated to 60 ° C. . The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.

<Exposure>
A pattern mask necessary for the evaluation of the photosensitive resin layer was placed on a polyethylene terephthalate film as a support, and was exposed with an ultrahigh pressure mercury lamp (OMW Seisakusho, HMW-201KB) at an exposure amount of 50 mJ / cm ² .
<Development>
After the polyethylene terephthalate film was peeled off, a 1 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. was sprayed for a predetermined time to dissolve and remove the unexposed portion of the photosensitive resin layer. At this time, the minimum time required for completely dissolving the photosensitive resin layer in the unexposed portion was defined as the minimum development time.
<Plating pretreatment>
The substrate for evaluating the resistance to an alkaline cyanide noble metal plating bath after development was immersed in an acid degreasing FRX (10% aqueous solution, manufactured by Atotex Japan Co., Ltd.) bath at 40 ° C. for 4 minutes. After washing with water, it was immersed in a 10% aqueous sulfuric acid solution at room temperature for 2 minutes.
<Gold cyanide plating bath>
Plating was performed at a current density of 0.5 A / m ² and 70 ° C. for 10 minutes using a plating bath having a composition of potassium gold cyanide 20 g / L, monosodium phosphate 15 g / L, and disodium phosphate 20 g / L.
<Peeling>
The evaluation board | substrate which carried out the plating process was sprayed in 50 degreeC and 3 mass% caustic soda aqueous solution, and the resist film was peeled and removed.
2. Evaluation Method (1) Resolution Evaluation A substrate for resolution evaluation that had passed 15 minutes after lamination was exposed through a line pattern mask in which the width of the exposed area and the unexposed area was 1: 1. Development was performed with a development time twice as long as the minimum development time, and the minimum mask line width in which a cured resist line was normally formed was ranked as a resolution value as follows.
A: The resolution value is 20 μm or less.
○: The resolution value exceeds 20 μm and is 25 μm or less.
X: The resolution value exceeds 25 μm.

(2) Adhesion Evaluation The substrate for adhesion evaluation 15 minutes after lamination was exposed through a line pattern mask in which the width of the exposed area and the unexposed area was 1: 100. Development was performed with a development time twice as long as the minimum development time, and the minimum mask line width in which a cured resist line was normally formed was ranked as the adhesion value as follows.
A: Adhesion value is 20 μm or less.
○: Adhesion value exceeds 20 μm and 25 μm or less.
X: Adhesion value exceeds 25 μm.
(3) Evaluation of resist peelability The substrate for resist peelability evaluation after 15 minutes from lamination was exposed through a mask having a 6 cm × 6 cm pattern. After developing with a development time twice as long as the minimum development time, the film was immersed in a 3% by weight aqueous caustic soda solution at 50 ° C., and the time taken for the resist film to peel was measured and ranked as follows.
○: Peeling time of 60 seconds or less Δ: Peeling time exceeding 60 seconds and 120 seconds or less ×: Peeling time exceeds 120 seconds (4) Evaluation of resistance to alkaline noble metal cyanide plating bath A substrate for evaluating resistance to a precious metal cyanide plating bath is exposed through a line pattern mask having a ratio of the exposed area to the unexposed area of 1: 5, and is developed with a development time twice as long as the minimum development time. Got a pattern. Thereafter, gold cyanide plating was performed under the above-described conditions, and the cured resist pattern was peeled off. After removing the resist, the 100 μm gold plating line was observed with an optical microscope, and the plating solution resistance was ranked as follows.
(Double-circle): There is no peeling of a plating and a penetration, and the favorable line is shown.
○: There is no peeling of the plating, and the width of the penetration is less than 5 μm.
(Triangle | delta): There is no plating peeling and the width | variety of a penetration is 5 micrometers or more.
X: Peeling occurred.

3. Evaluation results Table 1 shows the evaluation results of Examples and Comparative Examples.

  The present invention relates to the manufacture of printed wiring boards, flexible printed wiring boards, IC chip mounting lead frames (hereinafter referred to as lead frames), metal foil precision processing such as metal mask manufacturing, BGA (ball grid array), Manufacture of semiconductor packages such as CSP (chip size package), manufacture of tape substrates represented by TAB (Tape Automated Bonding) and COF (Chip On Film: a semiconductor IC mounted on a film-like fine wiring board), semiconductor It can be used for manufacturing members such as bumps, ITO electrodes, address electrodes, or electromagnetic wave shields in the field of flat panel displays.

Claims (13)

(A) carboxyl group-containing binder: 20 to 90% by mass, (b) addition polymerizable monomer having at least one terminal ethylenically unsaturated group: 5 to 75% by mass, (c) photopolymerization initiator: 0.01 A photosensitive resin composition containing -30 mass%,
(B) As an addition polymerizable monomer having at least one terminal ethylenically unsaturated group, at least one compound selected from the group consisting of compounds represented by the following general formula (I) and general formula (II) is photosensitive. The photosensitive resin composition characterized by containing 1-50 mass% in the whole resin composition.

(Wherein R ¹ is a linear, branched, or cyclic alkyl group having 4 to 12 carbon atoms, or an alkylaryl group having 6 to 12 carbon atoms, and R ^{2 to} R ⁵ are each independently hydrogen or a methyl group. , A is C ₂ H _4, B is CH ₂ CH (CH ₃ ), n _{1 to} n ₄ are each independently an integer of 0 to 15, and n ₁ + n ₂ + n ₃ + n ₄ is 2 or more.
The arrangement of repeating units of-(A-O)-and-(B-O)-may be random or block. In the case of a block, either-(AO)-or-(BO)-may be on the urethane bond side. )

(Here, R ⁶ and R ⁷ are each independently a linear, branched, or cyclic alkyl group having 4 to 12 carbon atoms, or an alkylaryl group having 6 to 12 carbon atoms, and R ^{8 to} R ¹¹ are each independently hydrogen or a methyl group, a is _C 2 _{H 4,} B is _{CH 2 CH (CH 3),} n 5 and _{n 6} represents an integer of 0 to _{15, n} 5+ _{n 6} represents at least one .n ₇ ~n ₁₀ is each independently an integer of _{0~15, n 7 + n 8 +} n 9 + n 10 is 2 or more.
The arrangement of repeating units of-(A-O)-and-(B-O)-may be random or block. In the case of a block, either-(AO)-or-(BO)-may be on the urethane bond side. ) The photosensitive resin composition according to claim 1, further comprising a compound represented by the following general formula (III) as the addition polymerizable monomer (b) having at least one terminal ethylenically unsaturated group.

(Wherein R ¹² is a linear, branched or cyclic alkyl group having 4 to 12 carbon atoms, or an alkylaryl group having 6 to 12 carbon atoms, and R ¹³ and R ¹⁴ are independently hydrogen or methyl group. , A is C ₂ H _4, B is CH ₂ CH (CH ₃ ), n _{11 to} n ₁₄ are each independently an integer of 0 to 15, and n ₁₁ + n ₁₂ + n ₁₃ + n ₁₄ is 2 or more.
The arrangement of repeating units of-(A-O)-and-(B-O)-may be random or block. In the case of a block, either-(AO)-or-(BO)-may be on the urethane bond side. )   The photosensitive resin laminated body which consists of the photosensitive resin layer which consists of the photosensitive resin composition of Claim 1 or 2, and a support body.   A method for forming a resist pattern, comprising: a lamination step of forming a photosensitive resin layer on a substrate using the photosensitive resin laminate according to claim 3, an exposure step, and a development step.   5. The method of forming a resist pattern according to claim 4, wherein in the exposure step, exposure is performed by direct drawing.   A method for producing a printed wiring board, comprising a step of etching or plating a substrate on which a resist pattern has been formed by the method according to claim 4.   A method for producing a substrate having a concavo-convex pattern, comprising a step of processing a substrate on which a resist pattern is formed by the method according to claim 4 or 5 by sandblasting.   A method for manufacturing a semiconductor package, comprising a step of plating a substrate on which a resist pattern is formed by the method according to claim 4.   A method for manufacturing a bump, comprising a step of plating a substrate on which a resist pattern is formed by the method according to claim 4.   A method for manufacturing a lead frame, comprising a step of etching a substrate on which a resist pattern is formed by the method according to claim 4.   A method for producing a printed wiring board, comprising a step of plating a substrate on which a resist pattern is formed by the method according to claim 4 or 5, wherein the plating step uses a noble metal cyanide plating bath.   6. A method of manufacturing a semiconductor package, comprising a step of plating a substrate on which a resist pattern is formed by the method according to claim 4 or 5, wherein the plating step uses a noble metal cyanide plating bath.   A method for producing a bump, comprising a step of plating a substrate on which a resist pattern has been formed by the method according to claim 4, wherein the plating step uses a noble metal cyanide plating bath.