Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/031—Organic compounds not covered by group G03F7/029

Definitions

• the present invention relates to a photosensitive resin composition and a laminate, a method for forming a resist pattern using the same, and a method for producing a printed wiring board, a lead frame, or a semiconductor package.
• Electronic devices such as personal computers and mobile devices use printed wiring boards for mounting components and semiconductors.
• DFR dry film resist
• a photosensitive resin layer which comprises a support, a photosensitive resin layer, and a protective layer
• DFR is generally prepared by laminating a photosensitive resin layer on a support and further laminating a protective layer on the photosensitive resin layer.
• the photosensitive resin layer used here is generally of an aluminum-based development type using a weak alkaline aqueous solution as a developing solution.
• thermoplastic polymer having a carboxyl group As the photosensitive resin layer, a composition containing a thermoplastic polymer having a carboxyl group, an addition polymerizable monomer having at least one terminal ethylenically unsaturated group, and a photopolymerization initiator is generally used. Have been.
• the protective layer is first peeled off, and then a DFR is laminated using a laminator or the like on a permanent circuit making board such as a copper-clad laminate or a flexiple board. Exposure is performed through a wiring pattern mask film or the like. Next, if necessary, the support is peeled off, and the unexposed portion of the photosensitive resin layer is dissolved or dispersed and removed with a developer to form a resist pattern on the substrate.
• the process of forming circuits can be broadly classified into two methods.
• the first method is to etch away the copper surface of the copper-clad laminate, etc., which is not covered by the resist pattern, and then make the resist pattern part stronger than the developing solution. This is a method of removing with an alkaline aqueous solution.
• a copper surface such as a copper-clad laminate not covered with the resist pattern is plated with copper, solder, nickel, tin, or the like, and then, similarly to the first method.
• This is a method of removing the resist pattern portion and etching the copper surface of the copper-clad laminate or the like that has appeared after the removal.
• cupric chloride, ferric chloride, copper-ammonia complex solution and the like are used for the etching.
• the characteristics of the DFR used here require high resolution, high tenting characteristics, plating resistance, and good peelability from the viewpoint of productivity and yield.
• the present inventor has used a monomer having a urethane structure having a specific structure to provide etching resistance, plating resistance, and tenting properties (development of post-exposure DFR for closing and protecting through holes, spraying of etching solution, etc.). (Durability against pressure) and the like have been found to be extremely improved (see JP-A-63-184744).
• the present inventor has found that the use of a monofunctional monomer having a specific structure improves the fixation resistance and the releasability (see JP-A-6-161103). ).
• An object of the present invention is to provide a photosensitive resin composition and a laminate having high sensitivity while maintaining characteristics such as tenting properties, plating resistance, and peeling properties by using a plurality of monomers having a specific structure in combination.
• Another object of the present invention is to provide a method for forming a resist pattern using the photosensitive resin laminate, and a method for manufacturing a printed wiring board, a lead frame or a semiconductor package. Disclosure of the invention
• thermoplastic polymer having a hydroxyl group (a) a thermoplastic polymer having a hydroxyl group
• R 1 and R 4 are hydrogen or a methyl group.
• R 2 and R 3 are residues represented by the following formula (a)]
• R. I an alkyl group having 1 to 20 carbon atoms
• R 6 is hydrogen or a methyl group
• p is an integer from 0 to 20
• q is an integer from 0 to 20
• the sum of P and q Is an integer from 2 to 20 and these groups may be in the form of a block or in a random form.
• R 8 and R 9 are hydrogen or a methyl group, which may be the same or different, s is an integer of 320, and r and t are integers of 110 It is. ]
• the photosensitive resin laminate according to (2) is laminated on a circuit-forming substrate so that the photosensitive resin composition layer is in close contact with the circuit-forming substrate;
• Actinic rays are illuminated image-wise and the exposed areas are photo-cured;
• Unexposed areas are removed by development to form a cured resist pattern; and then etched or plated,
• a method for manufacturing a printed wiring board including steps.
• the photosensitive resin laminate according to (2) is coated on a circuit-forming substrate with a photosensitive resin composition. Laminated so that the layers of the object are in close contact;
• Actinic rays are illuminated image-wise and the exposed areas are photo-cured;
• Unexposed areas are removed by development to form a cured resist pattern; and then etched;
• a method for manufacturing a lead frame including steps.
• the photosensitive resin laminate according to (2) is laminated on a circuit-forming substrate so that a layer of the photosensitive resin composition is in close contact with the circuit-forming substrate;
• Actinic rays are illuminated image-wise and the exposed areas are photo-cured;
• Unexposed areas are removed by development to form a cured resist pattern; and then etched or plated,
• a method of manufacturing a semiconductor package including steps. BEST MODE FOR CARRYING OUT THE INVENTION
• thermoplastic polymer having a carboxyl group as the component (a) used in the present invention at least one first monomer selected from polymerizable unsaturated carboxylic acids, alkyl (meth) acrylate, Hydroxyalkyl (meth) acrylate, (meth) acrylamide and a compound in which hydrogen on nitrogen is substituted by an alkyl or alkoxy group, styrene and styrene derivatives, (meth) atalylonitrile, and (meth) Examples include compounds obtained by vinyl copolymerizing at least one second monomer selected from glycidyl acrylate.
• thermoplastic polymer having a carboxyl group examples include acrylic acid, methacrylic acid, fumaric acid, cinnamate, crotonic acid, itaconic acid, and maleic acid semi-acid. Ester and the like may be mentioned, and each may be used alone or in combination of two or more.
• the proportion of the first monomer in the thermoplastic polymer having a carboxyl group is from 15% by weight to 40% by weight, preferably from 20% by weight to 35% by weight. If the proportion is less than 15% by weight, development with an aqueous alkali solution becomes difficult. On the other hand, if the proportion exceeds 40% by weight, it becomes insoluble in the solvent during the polymerization, making synthesis difficult. It becomes difficult.
• the second monomer used in the production of a thermoplastic polymer having a propyloxyl group includes methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and cyclohexanol (meta).
• the proportion of the second monomer in the thermoplastic polymer having a carboxyl group is from 60% by weight to 85% by weight, preferably from 65% by weight to 80% by weight.
• the ratio of the second monomer is automatically determined by the ratio of the first monomer, but if the ratio is less than 60% by weight, the flexibility of the cured film deteriorates. On the other hand, if the proportion exceeds 85% by weight, the developing time is undesirably long.
• the weight average molecular weight of the thermoplastic polymer having a carboxyl group is in the range of 20,000 to 300,000, and preferably 30,000 to 150,000.
• the weight average molecular weight in this case is the weight average molecular weight measured by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene.
• the weight average molecular weight is less than 20,000, the strength of the cured film will be low. On the other hand, when the weight average molecular weight exceeds 300,000, the viscosity of the photosensitive resin composition becomes high and the applicability of the photosensitive resin composition decreases.
• thermoplastic polymer having a carboxyl group is prepared by diluting a mixture of monomers with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and then subjecting the solution to radical polymerization such as benzoyl peroxide and azoisobutyronitrile. It is preferable to synthesize by adding an appropriate amount of an initiator and stirring with heating. In some cases, synthesis is performed while a part of the mixture is dropped into the reaction solution. After the completion of the reaction, a solvent is further added to concentrate the product to a desired concentration. It may be adjusted every time. As a synthesis means, bulk polymerization, suspension polymerization, and emulsion polymerization are used in addition to solution polymerization.
• a solvent such as acetone, methyl ethyl ketone, or isopropanol
• the content of the thermoplastic polymer having a carboxyl group is preferably in the range of 30% by weight or more and 75% by weight or less, more preferably 40% by weight or more and 65% by weight or less based on the total weight of the photosensitive resin composition. If this amount is less than 30% by weight, the dispersibility of the unexposed light-sensitive resin composition in an alkaline developer is reduced, and the development time is significantly increased. If the amount exceeds 75% by weight, the photo-curing of the photosensitive resin layer becomes insufficient, and the resistance as a resist decreases.
• thermoplastic polymers having a carboxyl group may be used alone or in combination of two or more.
• Examples of the ethylenically unsaturated addition polymerizable monomer (b) used in the present invention include a compound represented by the following general formula 1, a compound represented by the following general formula 2, and a compound represented by the following general formula 3.
• R 5 is an alkyl group having 1 to 20 carbon atoms
• R 6 is hydrogen or a methyl group
• p is an integer of 0 to 20
• q is an integer of 0 to 20
• p The sum of and q is an integer from 2 to 20, and these groups can be in block or random form.
• R s and R J are hydrogen or a methyl group, which may be the same or different, s is an integer of 3 to 20, r and t are 1 to 10 It is an integer. ]
• the compound of the above general formula 1 is a urethanated product of a disubstituted isocyanate compound and a hydroxy (meth) atalylate compound having an alkyloxide repeating unit.
• W is a divalent alkyl group having 2 to 20 carbon atoms, and is hydrogen or a methyl group.
• R 2 and R 3 are residues represented by the above formula (a), m is an integer from 2 to 25, n is an integer from 0 to 15, and these groups are random. It may be in the form of a block or a block.
• Examples of the above-mentioned disubstituted isocyanate compounds include hexamethylene diisocyanate, tolylene diisocyanate, and isophorone diisocyanate. Hexamethylene diisocyanate is more preferable.
• Examples of the hydroxy (meth) acrylate compound having an alkyloxide repeating unit include, for example, Examples of the compound include hydroxypropyl (meth) acrylate and hydroxyethyl (meth) acrylate with alkylene oxide added thereto.
• Examples of the alkylene oxide to be added include propylene oxide and ethylene oxide, which may be used alone, two or more kinds may be used in a random form, or may be used in a block form. Absent.
• Preferable examples include compounds obtained by adding propylene oxide to 2-hydroxypropyl methacrylate, such as Plenmer PP 100 (manufactured by NOF Corporation).
• the compound of the above general formula 2 is an esterified product of a monol obtained by adding ethylene oxide and / or Z or propylene oxide to an alkyl-substituted phenol and methacrylic acid or acrylic acid.
• R is an alkyl group having 1 to 20 carbon atoms
• RD is hydrogen or a methyl group
• p is an integer of 0 to 20
• q is an integer of 0 to 20
• the sum of p and q is an integer from 2 to 20.
• the compound of the above-mentioned general formula 3 is a compound which can be synthesized by a force of causing a (meth) acrylic acid to undergo an esterification reaction or a transesterification reaction with a polyol obtained by adding ethylene oxide to polypropylene oxide.
• R 8 and R 9 are hydrogen or a methyl group
• the number s of repeating units of propylene oxide is 3 to 20 and preferably 8 to 15.
• the number of repeating units r and t of ethylene oxide is from 1 to 10, preferably from 2 to 5.
• the component (b) used in the present invention may contain a compound other than the compounds of the above general formulas 1 to 3.
• Such compounds include, for example, 2-hydroxy-3-phenoxypropyl acrylate, phenoxytetraethylene glycol acrylate, ⁇ -hydroxypropyl mono ((attaliloyloxy) propyl phthalate) , 1,4-tetramethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexane diol (T) Atarilate, heptapropylene glycol di (meth) atarilate, glycerol (meth) atarilate, 2-di (p-hydroxyphenyl) propane di (meth) atarilate, glyceronoletri (meta) atarilate, trimethylol propanetri (Meth) acrylate, polyoxypropyltrimethylolpropanetri (meth) acrylate, polyoxye
• the ratio (weight 0 ) of the compound of the above general formula 1 / the compound of the above general formula 2 to the compound of the above general formula 3 is preferably 10 to 80/10 to 80/10 to 80, preferably. Is from 15 to 7 ⁇ OZl 5 to 7 OZl 5 to 70.
• the content of the ethylenically unsaturated addition polymerizable monomer (b) is preferably from 20% by weight to 65% by weight based on the total weight of the photosensitive resin composition. More preferably, the content is 30% by weight or more and 60% by weight or less. If the proportion is less than 20% by weight, the light-sensitive resin is not sufficiently cured, and the strength as a resist is insufficient. On the other hand, When the total amount exceeds 65% by weight, when the photosensitive resin laminate is stored in the form of a roll, the phenomenon that the photosensitive resin layer gradually protrudes from the end face, that is, the edge fusion deteriorates.
• 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer is used as the photopolymerization initiator of the component (c).
• This compound is known by the trivial name Rofinnimer.
• photopolymerization initiators can be used in combination.
• photopolymerization initiators include, for example, benzyldimethyl ketal, benzyljetinole ketanore, benzinoresipropinoleketanore, benzinoresipheninoleketanore, benzozinmethinoleatenore, and benzoinechinore.
• Athenole benzoinpropynoleatenole, benzoinpheninoleatenole, thioxanthone, 2,4-dimethinolethioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropinolethioxanthone, 2 , 4 diisopropynolethioxanthone, 2 monofluorobenzene, 4 fluoroisoxanthone, 2 chlorothioxanthone, 4 monoclox thioxanthone, 1 chloro-4-propoxythioxanthone, benzophenone, 4, 4, one screw Aromatic ketones such as reamino) benzophenone [Michler's ketone], 4,4,1-bis (getinoleamino) benzophenone, 2,2-dimethoxy-12-phenylacetophenone; 2- (o-chlorophenyl) -4,5 —Bimi
• the content of the photopolymerization initiator as the component (c) of the present invention is preferably 0.01% by mass or more and 20% by mass or less based on the total mass of the photosensitive resin composition. More preferably, the content is 1% by mass or more and 10% by mass or less. If the amount is less than 0.01% by mass, the sensitivity is not sufficient. On the other hand, if this amount is more than 20% by mass, the ultraviolet ray absorption rate becomes high, and the curing at the bottom of the photosensitive resin layer becomes insufficient.
• the photosensitive resin composition of the present invention contains a compound represented by the following formula 4 as the component (d) dye.
• This compound is classified as B a s i c in the C I (Color Index) classification.
• Gle en 1 A compound called Gle en 1 whose formal chemical name is bis (p-ethylaminophenyl) phenylmethylimsulfate.
• Diamond Green (trade name), which is a kind of Basic Green 1, is sold as Aizen Diamond Green GH (product name, manufactured by Hodogaya Chemical Co., Ltd.).
• the amount of diamond green added is preferably from 0.01% by mass to less than 0.1% by mass, more preferably from 0.03% by mass to less than 0.07% by mass, based on the total mass of the photosensitive resin composition. If the amount is less than 0.01% by mass, the coloration after development is small, so that the inspection is difficult. If the amount exceeds 0.1% by mass, it is difficult to align with the pattern of the substrate when exposing with a mask, which is not preferable. In general, when a dye is added, the sensitivity tends to decrease.
• the photosensitive resin composition of the present invention may contain coloring substances other than diamond green, such as dyes and pigments.
• coloring substances include, for example, fuchsin, phthalocyanine green, auramine base, carboxide green S, paramagenta, crystal violet, methinole orange, nile venolay 2B, Victoria blue, malachite green, and pey Thick blue 20 and the like.
• radical polymerization inhibitors include, for example, p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, t-butylcatechol, cuprous chloride, 2,6-di-t-butyl-p-cresonol, Examples include 2,2, methylenebis (4-ethynole 6-t-butynolephenol) and 2,2 'methylenebis (4-methyl-6-t-butylphenol).
• the photosensitive resin composition of the present invention may contain a coloring dye which develops a color upon irradiation with light.
• a coloring dye a combination of a leuco dye and a halogen compound is well known.
• leuco dyes include tris (4-dimethylamino-2-methylphenyl) methane [leucocrystal violet], tris (4-dimethylamino-12-methylphenyl) methane [leucomalachite green], and the like.
• examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, butylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tripromomethylphenylsulfone, carbon tetrabromide, and carbon tetrabromide.
• the photosensitive resin composition of the present invention may contain an additive such as a plasticizer, if necessary.
• additives include, for example, estanolates such as getyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, triptyl citrate, triethyl atenate, and triacetate citrate.
• estanolates such as getyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, triptyl citrate, triethyl atenate, and triacetate citrate.
• the thickness of the photosensitive resin layer in the photosensitive resin laminate of the present invention is preferably 1 ⁇ um or more and 150 m or less, more preferably 3 // m or more and 80 m or less, .
• the thickness of the photosensitive resin layer is preferably 1 ⁇ or more from the viewpoint of film-forming coatability, and is preferably 15 ⁇ or less from the viewpoint of the resolution and adhesion of the image after development.
• the method for producing the photosensitive resin laminate of the present invention can be performed by a conventionally known method.
• the photosensitive resin composition of the present invention is mixed with a solvent to form a uniform solution, and the solution is applied to a support using a bar coater or a roll coater and dried to form a uniform solution.
• a photosensitive resin laminate of the present invention in which a photosensitive resin layer is laminated.
• the support used in the photosensitive resin laminate of the present invention is desirably a transparent substrate that transmits active light.
• a transparent substrate that transmits active light.
• the thickness of the support used in the photosensitive resin laminate of the present invention is preferably from 1 ⁇ to 40 ⁇ , and more preferably from 12 ⁇ to 30 ⁇ .
• the thickness of the support is preferably 10 m or more from the viewpoint of handling, and is preferably 40 ⁇ or less from the viewpoint of resolution.
• a protective layer may be laminated on the photosensitive resin of the photosensitive resin laminate of the present invention to produce a three-layer photosensitive resin laminate.
• the thickness of the protective layer is preferably from 15 ⁇ to 50 ⁇ , and more preferably from 25 m to 45 m. It is preferably 15 m or more from the viewpoint of the yield of the final product, and is preferably 5 O ⁇ um or less from the viewpoint of the production cost.
• the film used for the protective layer include a polyolefin film such as a polyethylene film and a polypropylene finolem, a polyestenorefinolem, and a polyester film whose releasability has been improved by silicone treatment or alkyd treatment. Particularly, a polyethylene film is preferable.
• the printed wiring board is manufactured through the following steps.
• a stripping step of removing the resist pattern from the substrate using an alkali stripper examples include a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an ultraviolet fluorescent lamp, a carbon arc lamp, a xenon lamp, and the like.
• a parallel light source In order to obtain a finer resist pattern, it is more preferable to use a parallel light source.
• exposure may be performed with the photomask floating above the support by several tens / zm to several hundred / m.
• alkali developer used in the developing step examples include aqueous solutions of sodium carbonate, carbon dioxide lime, and the like. These alkaline aqueous solutions are selected according to the characteristics of the photosensitive resin layer, but are generally in the range of 0.51% to 3% ⁇ 1. A real aqueous solution is used.
• the etching step is performed by a method suitable for the DFR to be used, such as acid etching or alkali etching.
• the alkaline stripping solution used in the stripping step is generally an aqueous solution having a stronger strength than the aqueous solution used in the development, for example, 1 wt% or more and 5 wt% or less of sodium hydroxide or water.
• An aqueous solution of an oxidizing realm is used.
• the copper surface that appears under the resist pattern may be etched after the resist pattern is stripped.
• a lead frame is manufactured using the photosensitive resin laminate of the present invention, instead of the copper-clad laminate or the flexible substrate described above, instead of the copper-clad laminate or the flexible substrate, a copper, copper alloy, iron-based alloy, or other metal plate is used. Laminate the photosensitive resin layer, perform exposure and development, and then etch. Finally, the cured resist is removed to obtain the desired lead frame. Furthermore, when manufacturing a semiconductor package, a photosensitive resin layer is laminated on a wafer for which circuit formation as an LSI has been completed, exposed and developed, and the opening is plated with copper or solder in a columnar shape. Next, the hardened resist is peeled off, and the thin metal layer other than the columnar plating is removed by etching to obtain a desired semiconductor package.
• a photosensitive resin composition having the composition shown in Table 1 was mixed, applied uniformly to a polyethylene terephthalate film having a thickness of 16 ⁇ using a bar coater, and dried in a dryer at 90 ° C for 2 minutes. After drying, a photosensitive resin layer was formed. The thickness of the photosensitive resin layer was 40 ⁇ .
• the component compositions in Table 1 represent parts by mass of the solid content.
• a polyethylene film was laminated on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated to obtain a photosensitive resin laminate. (Surface of board)
• Jet scrub polishing of a copper-clad laminate with a copper foil thickness of 35 // m using Sakurandam R # 220 abrasive (Nippon Carlit Co., Ltd.) 7
• the pre-treated copper alloy substrate was subjected to a two-stage hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation) at a former roll of 100 ° C and a latter roll of 100 ° C. Laminated.
• the laminator outlet pressure was 0.3 OMPa in air gauge and the laminating speed was 2. Om / min.
• the photosensitive resin layer without a mask film, or through a mask film required in evaluation, ultra-high pressure mercury lamp (manufactured by ORC Manufacturing: HMW-80 1) were exposed at 6 0 mJ Z cm 2 by.
• the sensitivity When the sensitivity is 12 steps or more, it is in a practically effective range. When the sensitivity is 11 steps or less, the exposure amount needs to be further increased due to lack of sensitivity, and productivity decreases.
• the line space is 10/300 ⁇ for the substrate completed up to the laminating process, which is the basic condition for preparing the sample of 1). ⁇ 100/300 / m (in 5 ⁇ m increments)
• a photomask film was placed in a polyethylene terephthalate tallate film side as a support of the photosensitive resin laminate was exposed with an exposure amount of 6 OmjZcm 2 through a photomask film, removing the polyethylene terephthalate film, LWT% 30 aqueous sodium carbonate solution.
• the unexposed portion was removed by spraying at a spray pressure of 0.15 MPa for 80 seconds to obtain an image pattern.
• the resolution was defined as the minimum line width of the obtained image that was separated and did not flow (that is, there was no meandering of the image pattern, no part that was not in close contact with the substrate, etc.).
• the substrate exposed and developed on a 3 cm X 5 cm area with an exposure of 60 mJ / cm 2 is immersed in a 3 wt% sodium hydroxide aqueous solution maintained at 50 ° C, and the cured photosensitive resin layer is peeled from the substrate The time required for this was defined as the peeling time.
• the substrate that was exposed and developed using a circuit pattern-shaped photomask at an exposure amount of 6 OmjZ cm 2 was pre-processed through the following steps.
• ⁇ The resist adheres to the tape with a width of 100 ⁇ or more along the pattern.
• the photosensitive resin laminate was laminated sequentially on both sides of the substrate, and without passing through the pattern mask from both sides. Exposure was performed at an exposure amount where the number of step tablet steps described above was 13 steps. This was developed for 3 times the minimum developing time, and further washed with water at a spray pressure of 0.3 MPa for 1 minute. At least one side of the cured film in the hole was torn, and the number of holes was counted and ranked as follows.
• ⁇ tear rate 10% or more and less than 30%
• composition each component amount unit: part by weight
• abbreviation of the support shown in Table 1 are shown below.
• M-2 bis (triethylene glycol methacrylate) nonapropylene glycol
• M—5 phenoxytetraethylene glycol acrylate
• M—6 Avian-aged kissetinoletrimethylolpropane triatalylate
• M-7 Hexamethylene diisocyanate and oligopropylene glycol ethylene glycol monomethacrylate (Nippon Yushi Co., Ltd. Blenmer 70 P '
• the photosensitive resin composition according to the present invention has high sensitivity, excellent tenting properties, adhesion resistance, and peelability of a cured film, and is extremely useful for producing a printed wiring board, a lead frame or a semiconductor package.

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