Classifications

• • 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
• • 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
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
  • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process

Definitions

• the present invention relates to a photosensitive resin laminate in which a photosensitive resin composition developable with an alkaline aqueous solution is laminated on a support layer, a method of forming a resist pattern on a substrate using the photosensitive resin laminate, and the resist It relates to the use of the pattern.
• lead frames the manufacture of printed wiring boards, the manufacture of flexible printed wiring boards, the manufacture of lead frames for IC chip mounting (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
• the present invention relates to a photosensitive resin composition that provides a resist pattern suitable for manufacturing members such as bump electrodes and ITO electrodes, address electrodes, or electromagnetic wave shields in the field of flat panel displays.
• 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 portions of the photosensitive resin composition, and unexposed portions are removed with a developer to form a resist pattern on the substrate. After forming a conductor pattern by etching or plating, the resist pattern is peeled off from the substrate to form a conductor pattern on the substrate.
• a method for producing a printed wiring board using the dry film resist will be briefly described below.
• the dry film resist has a protective layer, for example, a polyethylene film
• a photosensitive resin layer and a support layer 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 layer are in this order.
• the exposed portion is polymerized and cured by exposing the photosensitive resin layer to ultraviolet rays containing i-line (365 nm) emitted from an ultra-high pressure mercury lamp through a photomask having a wiring pattern.
• the support layer such as polyethylene terephthalate, is then peeled off.
• an unexposed portion of the photosensitive resin layer is dissolved or dispersed and removed with a developer, for example, an aqueous solution having weak alkalinity, to form a resist pattern on the substrate.
• a method of removing a metal portion not covered with a resist by etching and a method of plating There is a method to attach metal.
• the former method is frequently used recently because of the simplicity of the process.
• the metal in the hole is prevented from being etched by covering the through hole (through hole) of the substrate and the via hole for interlayer connection with a cured resist film.
• This construction method is called a tenting method.
• cupric chloride, ferric chloride, and a copper ammonia complex solution are used for the etching process.
• Patent Document 1 discloses an excellent photoresist due to a large amount of trifunctional monomers in the unsaturated compound in the photosensitive resin composition. However, only the ratio of the trifunctional monomer in the unsaturated compound is described, and there is a problem that the tent property is not excellent within a certain range. Patent Document 1 will be described later in a comparative example.
• Patent Document 2 discloses a photoresist that is superior to a tetrafunctional monomer as an unsaturated compound in the photosensitive resin composition. However, the direct drawing exposure using these has a problem that the tent property is not excellent.
• Patent Document 3 discloses an excellent photoresist using a trifunctional monomer in an unsaturated compound in a photosensitive resin composition.
• An object of the present invention is to provide a photosensitive resin laminate having little aggregates.
• the present invention is as follows. 1. It is a photosensitive resin laminate formed by laminating at least a support layer and a photosensitive resin layer, and the photosensitive resin layer is made of a photosensitive resin composition,
• the photosensitive resin composition is At least (a) 25-64% by mass of an alkali-soluble resin, (B) a compound having a photopolymerizable unsaturated double bond, (C) 0.1 to 20% by mass of a photopolymerization initiator, Furthermore, the photosensitive resin laminated body characterized by satisfy
• the compound (b) having a photopolymerizable unsaturated double bond is selected from the group consisting of a compound represented by the following general formula (I) and a compound represented by the following general formula (II) At least one photopolymerizable unsaturated compound is contained in an amount of 30 to 55% by mass based on the total amount of the photosensitive resin composition.
• the alkali-soluble resin (a) has a weight average molecular weight of 70,000 to 220,000 and an acid equivalent of 100 to 600.
• the photosensitive resin layer has a thickness of 3 to 15 ⁇ m.
• R 1 , R 2 , and R 3 are each independently H or CH 3 , n 1 , n 2 , n 3 , and n 4 are each independently an integer of 0-4, at the same time good .W be 0 CH 3, or a group represented by OH.
• R 5 , R 6 , R 7 , and R 8 are each independently H or CH 3 , and m 1 , m 2 , m 3 , and m 4 are each independently an integer of 0 to 4) And may be 0 at the same time.
• the compound (b) having a photopolymerizable unsaturated double bond is at least one selected from the group consisting of the compound represented by the general formula (I) and the compound represented by the general formula (II).
• the photopolymerization initiator is 9-phenylacridine, Or 2.
• a method for forming a resist pattern comprising a laminating step of laminating a photosensitive resin layer of the photosensitive resin laminate according to any one of the above, an exposing step of exposing to ultraviolet rays, and a developing step of removing unexposed portions. 6). In the exposure step, the exposure is performed by direct drawing.
• a copper-clad laminate is used as the substrate, Or 6.
• the manufacturing method of a conductor pattern including the process of etching or plating the board
• a method for producing a printed wiring board comprising: etching or plating a substrate on which a resist pattern is formed by the method according to any one of the above, and peeling the resist pattern.
• a metal plate is used as the substrate, and the above 4. to 8.
• a method for producing a lead frame comprising: etching a substrate on which a resist pattern is formed by any one of the methods described above; and peeling off the resist pattern. 10.
• a method for producing a semiconductor package comprising: plating a substrate on which a resist pattern is formed by the method according to any one of the above, and peeling the resist pattern. 11. Glass ribs are used as the substrate, and the above 4.
• a method for producing a substrate having a concavo-convex pattern characterized in that a substrate on which a resist pattern is formed by any one of the methods is processed by a sandblasting method and the resist pattern is peeled off.
• the photosensitive resin laminate of the present invention has a thin photosensitive resin layer thickness of 3 to 15 ⁇ m, it has good tent properties even when exposed by direct drawing exposure, and during development.
• the oily agglomerates are not generated and the amount of powdery agglomerates is small.
• the photosensitive resin laminate of the present invention is a photosensitive resin laminate formed by laminating at least a support layer and a photosensitive resin layer, and the photosensitive resin layer is made of a photosensitive resin composition,
• the photosensitive resin composition is At least (a) 25-64% by mass of an alkali-soluble resin, (B) a compound having a photopolymerizable unsaturated double bond, (C) 0.1 to 20% by mass of a photopolymerization initiator, Furthermore, the photosensitive resin laminated body characterized by satisfy
• the compound (b) having a photopolymerizable unsaturated double bond is selected from the group consisting of a compound represented by the following general formula (I) and a compound represented by the following general formula (II) At least one photopolymerizable unsaturated compound is contained in an amount of 30 to 55% by mass based on the total amount of the photosensitive resin composition.
• the alkali-soluble resin (a) has a weight average molecular weight of 70,000 to 220,000 and an acid equivalent of 100 to 600.
• the photosensitive resin layer has a thickness of 3 to 15 ⁇ m.
• R 1 , R 2 , and R 3 are each independently H or CH 3 , n 1 , n 2 , n 3 , and n 4 are each independently an integer of 0-4, At the same time, it may be 0.
• W is a group represented by CH 3 or OH.
• R 5, R 6, R 7, and R 8 is H or CH 3 independently, m 1, m 2, m 3, and m 4 are each independently an integer of 0 to 4 And may be 0 at the same time.
• Alkali-soluble resin is a vinyl resin containing a carboxyl group, such as (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, etc. It is a copolymer.
• the alkali-soluble resin preferably contains a carboxyl group and has an acid equivalent of 100 to 600. An acid equivalent means the mass of the linear polymer which has a 1 equivalent carboxyl group in it.
• the acid equivalent is more preferably 250 or more and 450 or less. 100 or more are preferable from the viewpoint of improving development resistance and resolution and adhesion, and 600 or less is preferable from the viewpoint of improving developability and peelability.
• the acid equivalent is measured by a potentiometric titration method using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd., using 0.1 mol / L sodium hydroxide.
• the weight average molecular weight of the (a) alkali-soluble resin used in the present invention is preferably 70,000 or more and 220,000 or less. From the viewpoint of improving developability, 220,000 or less is preferable. From the viewpoint of tent properties and aggregate properties, the weight average molecular weight is preferably 70,000 or more. More preferably, it is 70,000) or more and 200,000 or less. More preferably, it is 70,000 or more and 120,000 or less.
• the weight average molecular weight was determined by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK (KF-807, KF-806M).
• the alkali-soluble resin is preferably a copolymer comprising at least one or more of the first monomers described later and at least one or more of the second monomers described below.
• the first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated 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.
• (meth) acryl refers to acryl and / or methacryl. The same applies hereinafter.
• the second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule.
• the alkali-soluble resin contains a carboxyl group, has an acid equivalent of 100 to 600, and a weight average molecular weight of 70,000 to 220,000 from the viewpoint of tent properties and aggregate properties. It is a preferred embodiment of the invention.
• the ratio of the alkali-soluble resin to the total of the photosensitive resin composition is in the range of 25 to 64% by mass, preferably 40 to 60% by mass.
• the resist pattern formed by exposure and development is preferably 25% by mass or more and 64% by mass or less from the viewpoint that the resist pattern has sufficient resistance in resist properties such as tenting, etching, and various plating processes.
• the photopolymerizable unsaturated compound is a compound having at least one ethylenically unsaturated bond in the molecule.
• the compound having a photopolymerizable unsaturated double bond is represented by the following general formula (I) and the following general formula (II). 30 to 55% by mass of at least one photopolymerizable unsaturated compound selected from the group consisting of compounds is contained with respect to the total amount of the photosensitive resin composition.
• R 1 , R 2 , and R 3 are each independently H or CH 3 , n 1 , n 2 , n 3 , and n 4 are each independently an integer of 0-4, At the same time, it may be 0.
• W is a group represented by CH 3 or OH.
• R 5 , R 6 , R 7 , and R 8 are each independently H or CH 3 , and m 1 , m 2 , m 3 , and m 4 are each independently an integer of 0 to 4) And may be 0 at the same time.
• the at least one photopolymerizable unsaturated compound selected from the group consisting of the compound represented by the general formula (I) and the compound represented by the general formula (II) include, for example, the general formula In (I), R 1 , R 2 , and R 3 are H, n 1 , n 2 , and n 3 are integers of 1, n 4 is an integer of 0, and W is CH 3 A compound (NK ester A-TMPT-3PO manufactured by Shin-Nakamura Chemical Co., Ltd.), and in the same general formula (I), R 1 , R 2 , and R 3 are H, and n 1 , n 2 And n 3 is an integer of 3, n 4 is an integer of 0, and W is CH 3 (such as NK ester A-TMPT-9PO manufactured by Shin-Nakamura Chemical Co., Ltd.) It is done.
• R 1 , R 2 , and R 3 are H
• n 1 , n 2 , and n 3 are integers of 1
• R 5 , R 6 , R 7 , and R 8 are H, and m 1 , m 2 , m 3 , and m 4 are integers of 0 (Shin Nakamura Chemical Industry Co., Ltd. NK Ester A-TMMT), also in the above general formula (II), R 5 , R 6 , R 7 and R 8 are H, m 1 , m 2 , m 3 , and m 4 is an integer greater than 1, compound (Sartomer Japan Co., Ltd. SR-494) and the like.
• the content of at least one photopolymerizable unsaturated compound selected from the group consisting of the compound represented by the general formula (I) and the compound represented by the general formula (II) is 35 to 35 from the viewpoint of tent properties. It is 55% by mass, more preferably 40 to 55% by mass.
• the photopolymerizable unsaturated compound shown below is used in addition to the compounds represented by the general formula (I) and the general formula (II). I can do it.
• urethane compounds can be mentioned.
• urethane compounds include hexamethylene diisocyanate, tolylene diisocyanate, or diisocyanate compounds such as 2,2,4-trimethylhexamethylene diisocyanate, and compounds having a hydroxyl group and a (meth) acryl group in one molecule, such as , Urethane compounds with 2-hydroxypropyl acrylate and oligopropylene glycol monomethacrylate.
• Urethane compounds with 2-hydroxypropyl acrylate and oligopropylene glycol monomethacrylate there is a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (Nippon Yushi Co., Ltd., Blenmer PP1000). These may be used alone or in combination of two or more.
• (B) photopolymerizable unsaturation comprising at least one photopolymerizable unsaturated compound selected from the group consisting of the compound represented by general formula (I) and the compound represented by general formula (II)
• the content of the entire compound having a double bond is 30 to 55% by mass, preferably 35% to 55% by mass, based on the total amount of the photosensitive resin composition. More preferably, it is 40 to 55% by mass.
• a mass% when the ratio of the (a) alkali-soluble resin to the total amount of the photosensitive resin composition is A mass%, and the ratio of the compound (b) having a photopolymerizable unsaturated double bond is B mass%, A It is a preferred embodiment of the present invention that / B is 1.1 to 1.3. From the viewpoint of tent properties, A / B is preferably 1.1 or more, and A / B is preferably 1.3 or less.
• (C) Photopolymerization initiator For the photosensitive resin composition, those generally known as (c) photopolymerization initiators can be used.
• the amount of the photopolymerization initiator (c) contained in the photosensitive resin composition is in the range of 0.1 to 20% by mass, and more preferably in the range of 0.5 to 10% by mass. From the viewpoint of obtaining sufficient sensitivity, it is preferably 0.1% 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 20% by mass or less.
• photopolymerization initiators examples include 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, aromatic ketones such as benzophenone, Michler's ketone [4,4'-bis (dimethylamino) be
• the oily agglomerate here is a highly viscous agglomerate and is considered to be mainly composed of a compound having an unsaturated double bond.
• the powdery aggregate is considered to be mainly composed of an inhibitor / initiator and is different from the oily aggregate.
• a leuco dye examples include tris (4-dimethylaminophenyl) methane [leuco crystal violet] and bis (4-dimethylaminophenyl) phenylmethane [leucomalachite green].
• the contrast is good and preferable.
• the leuco dye is contained, the content is preferably 0.1 to 10% by mass in the photosensitive resin composition. From the viewpoint of developing contrast, it is preferably 0.1% by mass or more, and from the viewpoint of maintaining storage stability, it is preferably 10% by mass or less.
• a combination of a leuco dye and the following halogen compound is a preferred embodiment of the present invention from the viewpoint of adhesion and contrast.
• coloring substances include fuchsin, phthalocyanine, olamine base, paramadienta, crystal violet, methyl orange, Nile Bull-2B, Victoria Bull, Malachite Green (Eisen (registered trademark) manufactured by Hodogaya Chemical Co., Ltd.) MALACHITE GREEN), Basic Bull-20, and Diamond Green (Eizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.).
• the addition amount is preferably 0.001 to 1% by mass in the photosensitive resin composition.
• a content of 0.001% by mass or more has an effect of improving handleability, and a content of 1% by mass or less has an effect of maintaining storage stability.
• the photosensitive resin composition of the present invention may contain an N-aryl- ⁇ -amino acid compound from the viewpoint of sensitivity.
• N-aryl- ⁇ -amino acid compound N-phenylglycine is preferable.
• the content in the case of containing the N-aryl- ⁇ -amino acid compound is preferably 0.01% by mass or more and 30% by mass or less.
• the photosensitive resin composition of the present invention may contain a halogen compound.
• halogen compound examples include 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, and chlorinated triazine compounds. Bromomethylphenylsulfone is preferably used. When the halogen compound is contained, the content is 0.01 to 3% by mass in the photosensitive resin composition.
• the photosensitive resin composition is selected from the group consisting of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles. It is also possible to include at least one compound.
• radical polymerization inhibitors examples 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.
• 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.
• 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 addition amount of the radical polymerization inhibitor, 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.
• additives include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene monoethyl Glycol esters such as ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, citric acid Tributyl, triethyl citrate, acetyl triethyl citrate, acetyl tri-n-propyl citrate, tri-n-acetyl citrate Chill, and the like.
• the content of the plasticizer is preferably 5 to 50% by mass, more preferably 5 to 30% by mass in the photosensitive resin composition. 5 mass% or more is preferable from the viewpoint of suppressing delay in development time and imparting flexibility to the cured film, and 50 mass% or less is preferable from the viewpoint of suppressing insufficient curing and cold flow.
• the photosensitive resin laminate of the present invention includes a photosensitive resin layer made of a photosensitive resin composition and a support layer. If necessary, a protective layer may be provided on the surface of the photosensitive resin layer opposite to the support layer side.
• the support layer used here is preferably a transparent layer that transmits light emitted from the exposure light source.
• a support layer for example, a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film
• a polyethylene terephthalate film for example, a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film
• examples include polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. These films can be stretched if necessary.
• the haze is preferably 5 or less.
• a thinner film is advantageous in terms
• an important characteristic of the protective layer used in the photosensitive resin laminate is that the protective layer is sufficiently smaller than the support layer in terms of adhesion to the photosensitive resin layer and can be easily peeled off.
• a polyethylene film or a polypropylene film can be preferably used as the protective layer.
• 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 ⁇ m, more preferably 10 to 50 ⁇ m.
• the thickness of the photosensitive resin layer in the photosensitive resin laminate varies depending on the application, but is preferably 5 to 100 ⁇ m, more preferably 7 to 60 ⁇ m. The thinner the thickness, the higher the resolution, and the thicker the film strength.
• a conventionally known method can be adopted as a method of sequentially laminating a support layer, a photosensitive resin layer, and if necessary, a protective layer to produce the photosensitive resin laminate of the present invention.
• the photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent that dissolves them into a uniform solution, and is first applied onto the support layer using a bar coater or a roll coater and dried, and then on the support layer.
• a photosensitive resin layer made of a photosensitive resin composition is laminated.
• a photosensitive resin laminate can be prepared by laminating a protective layer on the photosensitive resin layer.
• the solvent examples include ketones represented by methyl ethyl ketone (MEK), and alcohols represented by methanol, ethanol, and isopropanol. It is preferable to add to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition applied on the support layer is 500 to 4000 mPa at 25 ° C.
• MEK methyl ethyl ketone
• alcohols represented by methanol, ethanol, and isopropanol.
• a resist pattern using the photosensitive resin laminate of the present invention can be formed by a process including a lamination process, an exposure process, and a development process.
• An example of a specific method is shown below.
• a substrate to be processed a copper-clad laminate is used for the purpose of manufacturing a printed wiring board, and a glass substrate, for example, a substrate for a plasma display panel or a surface electrolytic display substrate, Examples thereof include an organic EL sealing cap, a silicone wafer having a through hole, and a ceramic substrate.
• a plasma display substrate is a substrate in which an electrode is formed on glass, a dielectric layer is applied, a partition wall glass paste is then applied, and a partition wall glass paste portion is subjected to sandblasting to form a partition wall. . What passed through the sandblasting process about these to-be-processed base materials becomes an uneven base material.
• the laminating process is performed using a laminator.
• 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 surface of the substrate to be processed with a laminator.
• the photosensitive resin layer may be laminated only on one side of the substrate surface or on both sides.
• the heating temperature at this time is generally 40 to 160 ° C.
• adhesion and chemical resistance are improved by performing the thermocompression bonding twice or more.
• a two-stage laminator having two rolls may be used, or it may be repeatedly crimped through the roll several times.
• 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 by the light source illuminance and the exposure time. You may measure using a photometer.
• a direct drawing exposure method may be used. Direct drawing exposure is a method in which exposure is performed by directly drawing on a substrate without using a photomask.
• the light source for example, a semiconductor laser having a wavelength of 350 to 410 nm or an ultrahigh pressure mercury lamp is used.
• the drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the light source illuminance and the moving speed of the substrate.
• a developing process is performed using a developing device. After the exposure, if there is a support on the photosensitive resin layer, it is removed if necessary, and then the unexposed portion is developed and removed using a developer of an alkaline aqueous solution to obtain a resist image.
• an alkaline aqueous solution an aqueous solution of Na 2 CO 3 or K 2 CO 3 is used. These are selected according to the characteristics of the photosensitive resin layer, but a Na 2 CO 3 aqueous solution having a concentration of 0.2 to 2% by mass and 20 to 40 ° C. is generally used.
• a surface active agent, an antifoaming agent, and a small amount of an organic solvent for accelerating development may be mixed in the alkaline aqueous solution.
• a heating step at 100 to 300 ° C. can be further performed in some cases. By carrying out this heating step, chemical resistance can be further improved.
• a hot air, infrared, or far infrared heating furnace is used for heating.
• the method for producing a printed wiring board according to the present invention is performed through the following steps following the above-described resist pattern forming method using a copper clad laminate or a flexible substrate as a substrate.
• a conductive pattern is formed on the copper surface of the substrate exposed by development using a known method such as etching or plating.
• the resist pattern is peeled 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 stripping (hereinafter also referred to as “stripping solution”) is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of 2 to 5% by mass and a temperature of 40 to 70 ° C. is generally used. It is possible to add a small amount of a water-soluble solvent to the stripping solution.
• the lead frame manufacturing method of the present invention is performed through the following steps following the above-described resist pattern forming method using a metal plate such as copper, a copper alloy, or an iron-based alloy as a substrate. First, the substrate exposed by development is etched to form a conductor pattern. Thereafter, the resist pattern is peeled off by a method similar to the method for manufacturing a printed wiring board described above to obtain a desired lead frame.
• the semiconductor package manufacturing method of the present invention is performed by performing the following steps following the above-described resist pattern forming method using a wafer on which a circuit as an LSI has been formed as a substrate. First, the opening exposed by development is subjected to columnar plating with copper or solder to form a conductor pattern. Thereafter, the resist pattern is peeled off by the same method as the above-described printed wiring board manufacturing method, and a thin metal layer other than the columnar plating is removed by etching to obtain a desired semiconductor package.
• ⁇ Preparation of photosensitive resin laminate> The solution of the composition shown in Table 1 was adjusted so that the solid content was 50% by mass, well stirred and mixed, and on a polyethylene terephthalate film (R340-G16 manufactured by Mitsubishi Chemical Corporation) having a thickness of 16 ⁇ m as a support film.
• the photosensitive resin composition shown in Table 1 was uniformly applied using a blade coater and dried at 95 ° C. for 1 minute. The film thickness of the photosensitive resin layer after drying was 10 ⁇ m.
• a 35 ⁇ m thick polyethylene film (GF-858 manufactured by Tamapoly Co., Ltd.) was laminated as a protective layer on the surface of the photosensitive resin layer to obtain a photosensitive resin laminate.
• ⁇ Board> The evaluation was made using a 0.4 mm thick copper clad laminate in which a 35 ⁇ m copper foil was laminated on an insulating resin. It should be noted that when other substrates are used, this is described.
• ⁇ Laminate> While peeling off the protective layer of the photosensitive resin laminate of the present invention, the laminate was laminated at a roll temperature of 105 ° C. with a hot roll laminator (Asahi Kasei Engineering Co., Ltd., AL-700). The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.
• ⁇ Exposure> The photosensitive resin layer was exposed at 8 W with an exposure amount of 12 mJ / cm 2 using a direct drawing exposure machine (Paragon 9000, manufactured by Orbotech).
• Table 1 shows the evaluation results of Examples and Comparative Examples.
• the mass parts of B-1 to B-4 in Table 1 are mass parts of solid content and do not contain a solvent.
• a methyl ethyl ketone solution having a solid content concentration of B-1 to B-4 of 50% by mass was prepared in advance, and each of the B-1 to B-4 was adjusted so as to have the solid content shown in Table 1. The solution of was formulated.
• B-1 Ternary copolymer (methacrylic acid 25% by mass, methyl methacrylate 65% by mass, butyl acrylate 10% by mass (weight average molecular weight 100,000, acid equivalent 344)
• B-2 Ternary copolymer (methacrylic acid 25% by mass, methyl methacrylate 65% by mass, butyl acrylate 10% by mass (weight average molecular weight 200,000, acid equivalent 370)
• B-3 Ternary copolymer (methacrylic acid 25% by mass, methyl methacrylate 50% by mass, styrene 25% by mass (weight average molecular weight 50,000, acid equivalent 344)
• B-4 Ternary copolymer (methacrylic acid 25% by mass, methyl methacrylate 50% by mass, butyl acrylate 25% by mass (weight average molecular weight 70,000, acid equivalent 344)
• B-5 Binary copolymer of benzyl methacrylate 80% by mass and methacrylic acid 20% by mass (weight average molecular weight
• Comparative Example 1 when a polymer having an average molecular weight of less than 70,000 was used as the alkali-soluble resin, an oily agglomerate was generated during development, resulting in a defect.
• Comparative Example 2 the ratio of the compound represented by the general formula (II) in the photosensitive resin composition was less than 30% by mass, and the tent property was deteriorated.
• Comparative Example 3 the proportion of the compound represented by the general formula (II) in the photosensitive resin composition is more than 55% by mass, and the amount of the (a) alkali-soluble resin relative to the total amount of the photosensitive resin composition.
• Comparative Example 4 is a supplementary test of JP-A-11-119422. In Comparative Example 4, since a polyfunctional photopolymerizable unsaturated compound that does not correspond to the compound represented by the general formula (I) and the compound represented by the general formula (II) was not used, the tent property was increased. This resulted in the formation of oily aggregates.
• the photosensitive resin laminate of the present invention can simplify subsequent processes by protecting a through hole from an alkaline developer and an etching solution by exposing on a laminated substrate, and developing solution. Since the oily agglomerates are small, the cleaning of the apparatus is reduced, and it is useful for the production of printed circuit boards by alkali development.

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