WO2001092958A1 - Composition de resine photosensible, element photosensible, procede de production de motif de resist et procede de production de carte a circuit imprime - Google Patents
Composition de resine photosensible, element photosensible, procede de production de motif de resist et procede de production de carte a circuit imprime Download PDFInfo
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- WO2001092958A1 WO2001092958A1 PCT/JP2001/004496 JP0104496W WO0192958A1 WO 2001092958 A1 WO2001092958 A1 WO 2001092958A1 JP 0104496 W JP0104496 W JP 0104496W WO 0192958 A1 WO0192958 A1 WO 0192958A1
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Classifications
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- 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
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- 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
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- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/322—Aqueous alkaline compositions
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- 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
- H05K3/0094—Filling or covering plated through-holes or blind plated vias, e.g. for masking or for mechanical reinforcement
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- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0756—Uses of liquids, e.g. rinsing, coating, dissolving
- H05K2203/0769—Dissolving insulating materials, e.g. coatings, not used for developing resist after exposure
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- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
- H05K2203/0786—Using an aqueous solution, e.g. for cleaning or during drilling of holes
- H05K2203/0793—Aqueous alkaline solution, e.g. for cleaning or etching
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- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/13—Moulding and encapsulation; Deposition techniques; Protective layers
- H05K2203/1377—Protective layers
- H05K2203/1394—Covering open PTHs, e.g. by dry film resist or by metal disc
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- 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
- H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
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- 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
- H05K3/061—Etching masks
- H05K3/064—Photoresists
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/114—Initiator containing
- Y10S430/12—Nitrogen compound containing
- Y10S430/121—Nitrogen in heterocyclic ring
Definitions
- the present invention relates to a photosensitive resin composition, a photosensitive element, a method for producing a resist pattern, and a method for producing a printed wiring board.
- tenting There are two methods for manufacturing printed wiring boards: tenting and plating.
- tenting method copper through-holes for chip mounting are protected with resist, and electrical circuits are formed through etching and resist peeling.
- plating method copper is deposited in through holes by electroplating, protected by soldering, and an electric circuit is formed by resist stripping and etching.
- a photosensitive resin composition and a photosensitive element are used as a resist, and in particular, an alkali-developable resist is mainly used from the viewpoint of running cost and working environment. Then, after the resist is cured, the uncured portions are removed with an alkali developing solution and washed with a spray pressure. Therefore, the photosensitive resin composition to be used is required to have tenting properties, that is, tent reliability, which cannot be broken by a developing solution or spray pressure of washing. Also, especially in the plating method, the current density in the fine wire portion of the printed wiring board is higher than the current density in the sparse portion of the wiring, so that the plating of the thin wire portion is thicker than the resist. Peeling residue (overhang peeling residue) Therefore, the resist is required to have no peeling residue even if the plating is overhanged, that is, to have excellent peelability.
- JP-A-5-271129 discloses a photosensitive resin composition using a vinyl urethane compound and having good tent reliability.
- a photosensitive resin composition has been used to increase the density of wiring of a printed wiring board and to achieve high precision.
- Japanese Patent Application Laid-Open No. 5-232699 discloses an acrylate compound having a single polyethylene glycol chain.
- the polyethylene glycol chain is solely used, the hydrophilicity is too strong, and thus there is a problem that defects such as deterioration in tent reliability and peeling properties occur.
- An acrylate compound having a single polypropylene glycol chain has low resolution. Further, such an acrylate compound is easily separated in an alkaline developer. This causes sludge, which is insoluble in the developing solution, and if it adheres to the substrate, it may cause a short circuit or disconnection. In addition to the requirements for tent reliability and peelability described above, it was also required to shorten the manufacturing time in order to improve the productivity of printed wiring boards.
- the conventional development time required 25 seconds or more when developing a layer made of a photosensitive resin composition having a thickness of about 37 to 42 / m.
- the development time can be reduced to within 20 seconds, the development time will be significantly reduced, and the production time will be further reduced.
- it is effective to improve the hydrophilicity of the noinder polymer of the photosensitive resin composition.
- the hydrophilicity of the photosensitive resin composition is improved, the resistance of the developing solution is reduced, so that the breaking of the tent tends to increase, that is, the tent reliability tends to decrease. For this reason, there has hitherto been no photosensitive resin composition in which the development time is shortened and the tenth reliability is sufficiently satisfied. Disclosure of the invention
- An object of the present invention is to provide a photosensitive resin composition capable of shortening the development time, and having high releasability and tent reliability.
- the present invention is a photosensitive resin composition satisfying the following (1) and (2).
- (1) When a 1.0% by weight aqueous solution of sodium carbonate is sprayed on a layer of the photosensitive resin composition having a thickness of 37 to 42 tm under the following conditions, the photosensitive resin composition is formed. The object layer can be removed within 20 seconds. However, the condition is that The inner diameter of the nozzle is 1.2 mm, the spray pressure is 0.05 MPa, and the distance between the point closest to the photosensitive resin composition layer at the spray nozzle and the photosensitive resin composition layer Is 50 o. (2) A layer of the photosensitive resin composition having the above thickness is laminated on a copper-clad laminate having 18 triple holes having a length of 16 mm and three consecutive holes having six diameters.
- a cured film obtained by photo-curing with an exposure amount that cures 24 steps in a 1-step step tablet was coated with a 1.0% by weight aqueous sodium carbonate solution under the above conditions three times for 36 seconds.
- the number of broken holes is less than 5 when sprayed.
- the present invention is the photosensitive resin composition in which the layer of the photosensitive resin composition can be removed preferably within 19 seconds, more preferably within 18 seconds.
- the present invention provides a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator, wherein the component (B) contains ethylene glycol in the molecule.
- the present invention provides an acridine compound having at least one acridinyl group in the molecule of the component (C), which is represented by the general formula (II):
- R 3 represents an alkylene group having 6 to 12 carbon atoms.
- the present invention is a photosensitive transcript composition
- a photosensitive transcript composition comprising (A) a binder polymer, (B) a photopolymerizable compound and (C) a photopolymerization initiator, wherein the component (A) has a weight average molecular weight of 3 A polymer component having a molecular weight of 0,000 to 7.0,000, wherein the component (B) is A photosensitive resin composition containing a photopolymerizable compound having at least one ethylenically unsaturated bond and having a unit number of alkylene glycol having 2 to 6 carbon atoms of 15 or more.
- the present invention provides a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator, wherein the component (A) has a weight average molecular weight Is a polymer component having a molecular weight of 300,000 to 700,000, wherein component (B) has at least one ethylenically unsaturated bond in the molecule, and has a molecular weight of 900 or more. It is a photosensitive resin composition containing a polymerizable compound.
- the present invention provides a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator, wherein the total amount of the components (A) and (B) is The amount of component (A) is 40 to 80 parts by weight, the amount of component (B) is 20 to 60 parts by weight, and the amount of component (C) is 0.1 to 100 parts by weight. 0 1 to 3 parts by weight of the photosensitive resin composition.
- the present invention is a photosensitive element obtained by coating any of the above photosensitive resin compositions on a support and drying.
- the above-described photosensitive element is laminated on a circuit-forming substrate such that the photosensitive resin composition layer is in close contact with the photosensitive element, and is irradiated with actinic rays in an image-like manner, and the exposed portion is light-cured. And a method for producing a resist pattern, wherein unexposed portions are removed by development.
- the present invention is a method for manufacturing a printed wiring board, characterized by etching or attaching a circuit-forming substrate on which a resist pattern has been manufactured by the above-described method for manufacturing a resist pattern.
- tent reliability is excellent because high-speed development can be performed, and entry of an etching solution, a plating solution, or the like into a through hole can be efficiently prevented.
- it is possible to prevent conduction failure, short-circuit failure, and the like of the printed wiring board, and thus it is possible to manufacture the printed wiring board with high yield. Therefore, the production line speed of the printed wiring board can be greatly increased, and the production time can be reduced, so that the workability and productivity can be improved.
- the present invention is useful for increasing the density and resolution of printed wiring.
- FIG. 4 is an external view of an evaluation board used to evaluate a deformed tent tear rate in a test example of the present invention.
- (meth) acrylic acid means acrylic acid and its corresponding methacrylic acid
- (meth) acrylate means acrylate and its corresponding methacrylate
- (meth) acryloyl The group means an acryloyl group and a corresponding methacryloyl group.
- the photosensitive resin composition of the present invention is a photosensitive resin composition satisfying the following (1) and (2). (1) When spraying a 1.0% by weight aqueous solution of sodium carbonate on a layer of the photosensitive resin composition having a thickness of 37-42 under the following conditions, a layer of the photosensitive resin composition is obtained. Can be removed within 20 seconds.
- the conditions are as follows: the inner diameter of the spray nozzle is 1.2 feet, the spray pressure is 0.05 MPa, the point closest to the layer of the photosensitive resin composition in the spray nozzle and the photosensitive resin.
- the recommended distance to the composition layer is 50.
- a layer of the photosensitive resin composition having the above thickness is laminated on a copper-clad laminate having 18 triple holes with a length of 16 tubes, each of which has three holes of 6 mm in diameter. Then, 24 steps were cured in a 1-step step tablet. A 1.0% by weight aqueous solution of sodium carbonate was spray-sprayed 3 times for 36 seconds under the above-mentioned conditions onto the cured film obtained by photocuring at the exposure dose. In this case, the number of hole breaks is 5 or less.
- the photosensitive resin composition includes, for example, (A) a binder polymer, and (B) a photopolymerizable polymer.
- A a binder polymer
- B a photopolymerizable polymer.
- a polyalkylene glycol di (meth) acrylate having both an ethylene glycol chain and a propylene glycol chain in the molecule of the compound
- C acridine or an acridine-based compound having at least one acridinyl group in the molecule.
- the photosensitive resin composition further includes, for example, (A) a polymer component having a weight average molecular weight of 30,000 to 700,000, (B) at least one ethylenically unsaturated compound in the molecule. It can be obtained by including a photopolymerizable compound having a bond and having 15 or more alkylene glycol units having 2 to 6 carbon atoms and (C) a photopolymerization initiator.
- A a polymer component having a weight average molecular weight of 30,000 to 700,000
- B at least one ethylenically unsaturated compound in the molecule. It can be obtained by including a photopolymerizable compound having a bond and having 15 or more alkylene glycol units having 2 to 6 carbon atoms and (C) a photopolymerization initiator.
- the photosensitive resin composition includes, for example, (A) a polymer component having a weight average molecular weight of 30,000 to 700,000, (B) at least one ethylenically unsaturated compound in a molecule. It can be obtained by including a photopolymerizable compound having a bond and a molecular weight of 900 or more and (C) a photopolymerization initiator.
- Examples of the (A) noinder polymer include an acrylic resin, a styrene resin, an epoxy resin, an amide resin, an amide epoxy resin, an alkyd resin, and a phenol resin. From the viewpoint of alkali developability, an acrylic resin is preferred. These can be used alone or in combination of two or more.
- the above (A) and the under polymer used in the present invention can be produced, for example, by subjecting a polymerizable monomer to radical polymerization.
- polymerizable monomer examples include styrene, vinyltoluene, _methylstyrene, p-methylstyrene, p-ethylstyrene, p-methoxystyrene, p-ethoxystyrene, p-chlorostyrene, and p-bromostyrene.
- Polymerizable styrene derivatives acrylamide, acrylonitrile, vinyl alcohol esters such as vinyl-n-butyl ether, alkyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate Ethyl ester, getyl aminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoro Propyl (meth) acrylate, (Meth) acrylic acid, 1-bromo (meth) acrylic acid, 1-chloro (meth) acrylic acid,] 3 Furyl (meth) acrylic acid,] 3-Styryl (meth) acrylic acid, maleic acid, maleic Maleic Maleic Acid monoesters such as acid anhydride, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate,
- alkyl (meth) acrylate examples include those represented by the general formula (I)
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents an alkyl group having 1 to 12 carbon atoms
- the alkyl group of these compounds includes a hydroxyl group, an epoxy group, And a compound substituted with a gen group.
- Examples of the alkyl group having 1 to 12 carbon atoms represented by R 2 in the general formula (I) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, Examples include octyl, nonyl, decyl, pendecyl, dodecyl and their structural isomers.
- Examples of the monomer represented by the general formula (I) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) Pentyl acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.
- the (A) pinder polymer contains a lipoxyl group.
- radical polymerization of a polymerizable monomer having a carboxyl group and another polymerizable monomer is preferable. Can be manufactured. Methacrylic acid is preferred as the polymerizable monomer having a carbonyl group.
- the binder polymer is styrene or styrene from the viewpoint of flexibility. It is preferable to include a ren derivative as a polymerizable monomer.
- the content is preferably 2 to 30% by weight, more preferably 2 to 28% by weight, and 2 to 2% by weight. It is particularly preferred to contain 7% by weight. If this content is less than 2% by weight, the adhesion tends to be poor, and if it exceeds 30% by weight, the peeled pieces tend to be large and the peeling time tends to be long.
- binder polymers are used alone or in combination of two or more.
- binder polymers for example, two or more binder polymers composed of different copolymer components, two or more binder polymers having different weight average molecular weights, and two different binder polymers are used.
- the above-mentioned binder polymers are exemplified. Further, a polymer having a multimode molecular weight distribution described in JP-A-11-327137 may be used.
- the weight average molecular weight of the binder polymer is preferably 30,000-70,000, more preferably 35,000 to 65,000, and 40,000 to 6,00. 0, 000 is particularly preferred. If the molecular weight is lower than 30,000, the film coating properties and tenting properties tend to be poor. On the other hand, when the molecular weight exceeds 70,000, the development time tends to be long.
- the weight-average molecular weight is measured by gel permeation chromatography (GPC), and is obtained by conversion based on a calibration curve using standard polystyrene.
- the weight average molecular weight of the polymer component after mixing the binder polymer having a weight average molecular weight of 600,000 and the binder polymer having a weight average molecular weight of 30,000 used in a test example of the present application described later is 55,000. Met.
- the degree of dispersion of the binder polymer when two or more binder polymers are used in combination, the dispersion degree of the entire polymer (weight average molecular weight Z number average molecular weight) is used, or the binder polymer alone is used.
- the degree of dispersion of one polymer component is preferably 1.5 to 5.0, more preferably 1.8 to 4.0, and more preferably 2.0 to 3.5. Is particularly preferred.
- the number average molecular weight is measured by GPC in the same manner as the weight molecular weight and converted into standard polystyrene.
- the (B) photopolymerizable compound used in the present invention preferably has at least one ethylenically unsaturated bond in the molecule, but more preferably 2 or more in view of tenting properties and peeling properties. It is particularly preferred to have
- a photopolymerizable compound having 15 or more alkylene glycol units having 2 to 6 carbon atoms can be used.
- the number of carbon atoms is preferably 2 to 6, more preferably 2 to 5, and particularly preferably 2 or 3. Further, the number of units, that is, the total number of repeating units is preferably from 15 to 30, more preferably from 15 to 25, and particularly preferably from 15 to 20. If the number of units is less than 15, the tenting property and sensitivity are poor, and the peeling time tends to be long. On the other hand, when the number of units exceeds 30, resolution tends to deteriorate, and the obtained resist shape tends to be brittle.
- the molecular weight of the component (B) is preferably at least 900, more preferably from 900 to 250, and particularly preferably from 100 to 150. When the molecular weight is less than 900, tenting properties and sensitivity are poor, and the peeling time tends to be long.
- the component (B) preferably contains a polyalkylene glycol di (meth) acrylate having both an ethylene glycol chain and a propylene glycol chain in the molecule.
- This (meth) acrylate is not particularly limited as long as it has both an ethylene glycol chain and a propylene glycol chain (n-propylene glycol chain or isopropylene glycol chain) as an alkylene glycol chain in the molecule.
- the (meth) acrylate further includes an alkylene glycol having about 4 to 6 carbon atoms, such as an n-butylene glycol chain, an isobutylene glycol chain, an n-pentylene glycol chain, a hexylene glycol chain, and structural isomers thereof. It may have a mono-chain.
- the plurality of ethylene glycol chains and the propylene glycol chains do not need to be present in a continuous block, but may be present at random.
- the secondary carbon of the propylene group may be bonded to an oxygen atom, or the primary carbon may be bonded to an oxygen atom.
- the alkylene glycol chain in the above has, for example, the general formula (III):
- Examples of the alkyl group having 1 to 3 carbon atoms in the general formula (111), the general formula (IV) and the general formula (V) include a methyl group, an ethyl group, an n-propyl group and an isopropyl group.
- the general formula (111), the general formula (IV) and the general formula of the repeating number of ethylene glycol one Le chain in (V) Total (1 ⁇ + 111 2, m 3 and m 4) are each independently 1 to 30 of It is an integer, preferably an integer of 1 to 10, more preferably an integer of 4 to 9, and particularly preferably an integer of 5 to 8. If the number of repetitions exceeds 30, tent reliability and resist shape tend to deteriorate.
- the total number of repeating propylene glycol chains (nn 2 + n 3 and n 4 ) is each independently an integer of 1 to 30. , Preferably an integer of 5 to 20, more preferably an integer of 8 to 16, and particularly preferably an integer of 10 to 14. When the number of repetitions exceeds 30, the resolution deteriorates and sludge tends to be generated.
- a photopolymerizable compound other than a polyalkylene glycol di (meth) acrylate having both an ethylene glycol chain and a propylene glycol chain in the molecule can be contained.
- examples thereof include compounds obtained by reacting alcohol with ⁇ , / 3-unsaturated carboxylic acid, 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2 , 2-bis (4I-((meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4 -Bisphenol A (meth) acrylates such as ((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-1 ((meth) acryloxypolyethoxypolypropoxy) phenyl) propane Compounds, compounds obtained by reacting monounsaturated carboxylic acids with glycidyl group-containing compounds, urethane monomers such as (meth) acrylate compounds having
- the photopolymerization initiator (C) used in the present invention it is preferable to use acridine or an acridine-based compound having at least one acridinyl group in the molecule.
- the acridine-based compound include a compound represented by the general formula (II), 9-phenylenylacridine, 9-pyridylacridine, 9-pyrazinylacridine, 1,2-bis (9-acridinyl) And bis (9-acridinyl) alkanes such as 1,4-bis (9-acridinyl) propane, 1,4-bis (9-acridinyl) butane, and 1,5-bis (9-acridinyl) pentane. These are used alone or in combination of two or more.
- alkylene group having 6 to 12 carbon atoms in the general formula (II) examples include a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a pendecylene group, a dodecylene group, and structural isomers thereof. Is mentioned.
- Specific examples of the compound represented by the general formula (II) include 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, and 1,8-bis (9-acridinyl).
- Octane 1,9-bis (9-acridinyl) nonane
- 1,10-bis (9-acridinyl) decane 1,11-bis (9-acridinyl) decane
- the above 1,7-bis (9-acridinyl) heptane is a product of Asahi Denka Kogyo Co., Ltd. Available as 17 17 These can be used in combination with two or more insects.
- the photosensitive resin composition of the present invention can contain a photopolymerization initiator other than the (C) acridine or an acridine-based compound having at least one acridinyl group in a molecule.
- a photopolymerization initiator other than the (C) acridine or an acridine-based compound having at least one acridinyl group in a molecule.
- examples thereof include benzophenone, ⁇ , ⁇ ⁇ ⁇ ′ -tetraalkyl-1,4,4′-diaminobenzophenone, such as N, ⁇ ′-tetramethyl-1,4 ′ diaminobenzophenone (Michler's ketone), and 2-benzyl-2-dimethyla Minnow 1- (4-mo ⁇ / holinophenyl) 1-butanone-1,2-methyl-1-11 [4- (methylthio) phenyl] -12-morpholinopropanone-11, etc.,
- benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, benzyl Benzyl derivatives such as dimethyl ketal, 2- ( ⁇ -chlorophenyl) -4,5-diphenylimidazomonomer, 2- ( ⁇ -chlorophenyl) -4,5-di (methoxyphenyl) ) Imidazomoni dimer, 2- ( ⁇ monofluorophenyl) —4,5-diphenylimidazole dimer, 2-( ⁇ —Methoxyphenyl) —4,5-diphenylimidazo dimer, 2 — ( 2,4-, 5-triary-imidazo-l-unimer such as 4,4-diphenylimidazo-l-ni-mer, ⁇ -phenyl-dalicin, ⁇ -phenyl-d-aricin derivative, coumarin-based compound, honium salt And the like.
- the compounding amount of the binder polymer ( ⁇ ) is preferably 40 to 80 parts by weight, more preferably 45 to 70 parts by weight, based on 100 parts by weight of the total amount of the components ( ⁇ ) and ( ⁇ ). Is more preferable.
- the amount is less than 40 parts by weight, the photo-hardened material tends to be brittle, and when used as a photosensitive element, the coating properties tend to be poor.
- the amount exceeds 80 parts by weight, the photosensitivity is insufficient. Tend to be.
- the blending amount of the ( ⁇ ) photopolymerizable compound is preferably 20 to 60 parts by weight with respect to 100 parts by weight of the total amount of the ( ⁇ ) component and the ( ⁇ ) component, and 30 to 5 parts by weight. More preferably, it is 5 parts by weight. If the amount is less than 20 parts by weight, the photosensitivity tends to be insufficient, and if it exceeds 60 parts by weight, the photocured product tends to become brittle.
- the component (B) a polyalkylene glycol di (meth) acrylate having both ethylene glycols and a propylene glycol chain in the molecule, a compound in which the number of units of the alkylene glycol having 2 to 6 carbon atoms is 15 or more, or a molecular weight.
- the blending amount of the photopolymerization initiator (C) is preferably 0.01 to 3 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B). More preferably, it is 1 to 2 parts by weight. If the amount is less than 0.01 part by weight, the photosensitivity tends to be insufficient. If the amount is more than 3 parts by weight, the absorption on the surface of the composition during exposure increases, and the internal photocuring becomes insufficient. Tends to be sufficient.
- the photosensitive resin composition may include, as necessary, a photopolymerizable compound having at least one cationically polymerizable cyclic ether group in a molecule, a cationic polymerization initiator, a dye such as malachite green, and tribromo.
- Photo-coloring agents such as phenylsulfone and leuco-crystal violet, thermal coloring inhibitors, plasticizers such as p-toluenesulfonamide, pigments, fillers, erasers, printing, flame retardants, stabilizers, adhesion-imparting agents, Add a belling agent, exfoliation accelerator, antioxidant, fragrance, imaging agent, thermal cross-linking agent, etc.
- the photosensitive resin composition may be, if necessary, a solvent or a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl sorb, ethyl sorb, toluene, N, N-dimethylformamide, and propylene glycol monomethyl ether. It can be dissolved in these mixed solvents and applied as a solution having a solid content of about 30 to 60% by weight.
- a solvent or a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl sorb, ethyl sorb, toluene, N, N-dimethylformamide, and propylene glycol monomethyl ether. It can be dissolved in these mixed solvents and applied as a solution having a solid content of about 30 to 60% by weight.
- the photosensitive resin composition is not particularly limited, but is coated as a liquid resist on a metal surface such as copper, copper-based alloy, iron, and iron-based alloy, dried, and then coated with a protective film as necessary.
- a metal surface such as copper, copper-based alloy, iron, and iron-based alloy
- a protective film Preferably used in the form of a photosensitive element.
- the thickness of the photosensitive resin composition layer varies depending on the application, but is preferably about: 100 to 100 m in thickness after drying.
- examples of the protective film include polymer films such as polyethylene and polypropylene.
- the photosensitive element can be obtained, for example, by applying and drying a photosensitive resin composition on a polymer film such as polyethylene terephthalate, polypropylene, polyethylene, or polyester as a support.
- the coating can be performed by a known method such as, for example, Rollco overnight, Commaco night, Gravureco night, Air knife coat night, Daiko night, Barco night, and the like. Drying can be performed at 70 to 150 ° C. for about 5 to 30 minutes.
- the amount of the residual organic solvent in the photosensitive resin composition layer is preferably 2% by weight or less from the viewpoint of preventing the diffusion of the organic solvent in a later step.
- the thickness of these polymer films is preferably from 1 to 10 O ⁇ rn.
- One of these polymer films may be laminated on both sides of the photosensitive resin composition layer as a support for the photosensitive resin composition layer and the other as a protective film for the photosensitive resin composition layer.
- As the protective film those having a smaller adhesive force between the photosensitive resin composition layer and the protective film than the adhesive force between the photosensitive resin composition layer and the support are preferable, and a low fisheye film is preferable. .
- the photosensitive element may have an intermediate layer or a protective layer such as a cushion layer, an adhesive layer, a light absorbing layer, and a gas barrier layer in addition to the photosensitive resin composition layer, the support, and the protective film. Good.
- the photosensitive element is stored, for example, as it is or wound around a cylindrical core with a protective film further laminated on the other surface of the photosensitive resin composition layer. At this time, it is preferable that the support is wound up so as to be the outermost side. It is preferable to install an end surface separator from the viewpoint of protecting the end surface, and it is preferable to install a moisture-proof end surface separator from the viewpoint of edge fusion resistance on the end surface of the roll-shaped photosensitive element roll. Also, as a packing method, it is preferable to wrap it in a small moisture permeable black package.
- the core include polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, ABS Plastics such as resin (acrylonitrile-butadiene-styrene copolymer);
- the fluidity is preferably from 120 to 300 m, more preferably from 120 to 260 m, and particularly preferably from 140 to 220 m. If the fluidity is less than 120 m, the ability to follow the substrate tends to be poor, and if it exceeds 300, the storage stability tends to be poor.
- the photosensitive layer was peeled off from the support film, and bonded so that bubbles, wrinkles, foreign matter, etc. were not mixed therein until the thickness became 2 mm, and punched out with a 2 ⁇ punching dumbbell mold to obtain a test piece.
- the test piece was left on a test table of Plastome overnight that was left in a constant temperature room at 30 ° C for 10 minutes, and then a load of 5 kg was applied to the test piece, and after 15 minutes, The amount of change in the thickness of the test piece was defined as the fluidity.
- Examples of the above-mentioned plastometer include an apparatus described in Japanese Patent Application Laid-Open No. 2-54255.
- the photosensitive resin composition layer is heated to 70 to 130 ° C.
- a method of laminating may be mentioned by crimping at a pressure of extent while heating the substrate for printed circuit board 0.. 1 to 1 MPa extent (about 1 ⁇ 1 O kgf / cm 2), laminating in vacuo Is also possible.
- the surface to be laminated is usually a metal surface, but is not particularly limited.
- the photosensitive resin composition layer thus laminated is irradiated with actinic rays imagewise through a negative or positive mask pattern.
- the light source of the actinic ray a known light source, for example, a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, a xenon lamp, or the like that effectively emits ultraviolet light or visible light is used.
- a developing solution such as an alkaline aqueous solution, an aqueous developing solution, or an organic solvent, and drying. Remove the unexposed areas by developing, etc. and develop the resist pattern Can be manufactured.
- Examples of the alkaline aqueous solution include a dilute solution of 0.1 to 5% by weight of sodium carbonate, a dilute solution of 0.1 to 5% by weight of potassium carbonate, and a dilute solution of 0.1 to 5% by weight of sodium oxide.
- Can be The pH of the aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer.
- a surfactant, an antifoaming agent, an organic solvent and the like may be mixed in the alkaline aqueous solution.
- Examples of the developing method include a dip method, a spray method, brushing, and slapping.
- the resist pattern may be further cured by heating at about 60 to 250 ° C. or exposing at about 0.2 to 10 J / ci 2 as necessary. .
- a cupric chloride solution for example, a cupric chloride solution, a ferric chloride solution, an alkali etching solution, or the like can be used.
- the surface of the circuit-forming substrate is treated by a known method such as etching or plating using the developed resist pattern as a mask.
- Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating.
- the resist pattern can be peeled off, for example, with an aqueous solution that is more powerful than the alkaline aqueous solution used for development.
- the strong alkaline aqueous solution for example, an aqueous solution of 1 to 10% by weight of sodium hydroxide, an aqueous solution of 1 to 10% by weight of 7] potassium oxide and the like are used.
- the peeling method include an immersion method and a spray method.
- the printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board, and may have a small diameter through hole.
- the method for measuring the removal time of the layer of the photosensitive composition in the present invention can be performed, for example, by the following methods (1) to (4).
- the photosensitive resin composition is applied and dried on the support so that the thickness of the photosensitive resin composition layer is 37 to 42 / z rn, and a protective film is laminated as necessary. Obtain a photosensitive element.
- the surface of the support is preferably a polyethylene terephthalate film that has not been subjected to any special treatment that makes it difficult to remove the layer of the photosensitive resin composition.
- the spray nozzle with an inner diameter of 1.2 (a square full cone type spray nozzle manufactured by Spraying System Japan Co., Ltd.) is moved to the point closest to the photosensitive resin composition layer of the spray nozzle (the tip of the spray nozzle). ) And the layer of the photosensitive resin composition are arranged so as to have a distance of 50 ran.
- a 1.0% by weight aqueous solution of sodium carbonate is spray-sprayed at a spray pressure of 0.05 MPa so as to sufficiently cover the entire surface of the photosensitive resin composition layer having a square shape.
- the spray pressure it is easy to measure the pressure of a pipe for supplying a 1.0% by weight aqueous solution of sodium carbonate to the spray nozzle.
- the method for measuring the number of hole breaks in the cured film in the present invention can be performed, for example, by the following methods (1) to (4).
- the photosensitive resin composition is coated on the support so that the thickness of the photosensitive resin composition layer is 37 to 42, dried, and, if necessary, a protective film is laminated. obtain.
- the surface of the support is preferably a polyethylene terephthalate film that has not been subjected to any special treatment that makes it difficult to remove the layer of the photosensitive resin composition.
- the photosensitive element obtained in 1 is peeled off the protective film, if necessary, on one side of the substrate for measuring the number of torn holes obtained in 2.
- Laminate at a pressure of 0.4 MPa and a speed of 1.5 m / min.
- a spray nozzle with an inner diameter of 1.2 mm (spray nozzle system Japan Co., Ltd., square full cone type spray nozzle) is cured at the point closest to the cured film of the spray nozzle (the tip of the spray nozzle). Install so that the distance from the membrane is 50 images.
- ⁇ ⁇ ⁇ ⁇ Spray a 1.0% by weight aqueous solution of sodium carbonate at a spray pressure of 0.05 MPa for 3 x 36 seconds to spray the entire surface of the cured film sufficiently.
- the spray pressure it is easy to measure the pressure of a pipe for supplying a 1.0% by weight aqueous sodium carbonate solution to the spray nozzle. Further, it is preferable to use a plurality of spray nozzles or oscillating nozzles so that the 1.0% by weight aqueous solution of sodium carbonate sufficiently strikes 18 triple holes.
- UA-13 Poly (ethylene propylene dalicol) modified urethane diacrylate (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.), molecular weight 1056, carbon number 2-6
- a P G-400 Heptane propylene glycol diacrylate (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.), unit number of alkylene glycol having 532 molecular weight and 2-6 carbon atoms, 7
- 4G Tetraethylene glycol dimethacrylate (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.), number of units of alkylene glycol having a molecular weight of 330 and carbon number of 2 to 4, and then the obtained photosensitive resin composition
- the solution was applied evenly on a 16 m thick polyethylene terephthalate film (trade name: G2-16, manufactured by Teijin Limited), dried with a hot air convection dryer at 100 ° C for 10 minutes, and then made of polyethylene.
- the photosensitive element was obtained by protection with a protective film (trade name: NF-13, manufactured by Tama Poly Co., Ltd.).
- the film thickness after drying of the photosensitive motif composition layer was 40 m, and the fluidity was adjusted in the range of 140 to 220 m.
- the copper surface of a copper-clad laminate (trade name: MCL-E-61, manufactured by Hitachi Chemical Co., Ltd.), which is a glass epoxy material with copper foil (thickness: 35 m) laminated on both sides, was brushed with a brush equivalent to # 600.
- a polishing machine manufactured by Sankei Co., Ltd.
- the obtained copper-clad laminate was heated to 80 ° C., and the photosensitive resin composition layer was removed from the copper surface by using a heat roll at 120 ° C. while peeling off the protective film. Lamination was performed at a speed of 5 m / min.
- the resolution is as follows: a phototool having a 21-step step tablet of a stofer and a line width / space width of 30/200 to 200/200 (unit: m) as a resolution evaluation negative.
- a photo tool having a wiring pattern was brought into close contact, and exposure was performed with an amount of energy such that the number of remaining steps after development of the 21-step step bullet of the I-one step was 8.0.
- the exposure was performed using an exposure machine having a high-pressure mercury lamp (trade name: HMW-201B, manufactured by Oak Corporation).
- HMW-201B high-pressure mercury lamp
- the peeling property can be measured by laminating as described above, exposing at a predetermined exposure amount, and then developing with the above developer, followed by a degreasing bath (PC-455 (manufactured by Meltex Corporation)). (0% by weight) for 2 minutes and washed with water. Next, it was immersed in a soft etching bath (150 g of ammonium persulfate) for 60 seconds and washed with water. Then, pre-treatment was performed in the order of immersion in a 10% by weight sulfuric acid bath for 1 minute.
- PC-455 manufactured by Meltex Corporation
- a copper sulfate plating bath (75 gZl of copper sulfate, 190 g of sulfuric acid, 50 ppm of chloride ion, 50 ppm of power perglyme PCM) (Manufactured by Meltex Corporation) at 5 ml / liter), followed by copper sulfate plating at 1.2 A / dm2 for 60 minutes at room temperature.
- the reliability of the tent is determined by the sensitivity of the substrate (see Fig. 1), which has irregular holes in which 1.6 mm thick copper-clad laminates have three holes of 4 mm, 5 mm and 6 thighs each connected to three holes. A laminate of the resin composition was laminated on both sides, exposed at a predetermined exposure amount, and developed for 36 seconds three times. After the development, the number of broken holes in the total of 2 16 holes in FIG.
- Deformation tent tear rate (%) (number of hole breaks (pieces) / 2 16 (pieces)) X 100 (1)
- the removal property of the developing sludge is determined by the photosensitive resin composition of the photosensitive element obtained.
- the material layer was taken out in an amount of 0.4 m 2 , added to a 1.0% by weight aqueous solution of sodium carbonate, stirred at 30 ° C. for 90 minutes using a stirrer, and left for one week.
- sludge deposited on the bottom of the container and adhered thereto was again removed by stirring, and the amount of sludge remaining and adhered to the bottom was observed.
- the sludge removal was evaluated as the following equation (2).
- Examples 1, 2 and 3 have excellent overhang peeling properties, excellent deformed tent tear rates, and good resolution and sludge removal properties.
- Solution 105 g (solid content 64 g), FA-024M36 g, 1,7-bis (9-acridinyl heptane) 0.4 g, N, N'-tetraethyl-4,4 'diaminobenzophenone 0.04 g, leuco crystal violet 0.9 g, tribromomethylphenylsulfone 1.3 g, malachite green 0.05 g, acetone 12.0 g, toluene 5. A solution was obtained by blending 3.0 g of Og and methanol.
- the obtained solution of the photosensitive resin composition was uniformly coated on a 16 m-thick polyethylene terephthalate film (trade name: G2-16, manufactured by Teijin Limited) and dried by hot air convection at 100 ° C. After drying for 10 minutes with a machine, the photosensitive resin composition laminate was obtained by protection with a polyethylene protective film (trade name: NF-13, manufactured by Yumapori Co., Ltd.). The film thickness of the photosensitive resin composition layer after drying was 40 m.
- the obtained solution of the photosensitive resin composition was uniformly coated on a 16-im-thick polyethylene terephthalate film (trade name: G2-16, manufactured by Teijin Limited) and dried by hot air convection at 100 ° C. After drying with a machine for 10 minutes, the film was protected with a polyethylene protective film (brand name: NF-13, manufactured by Tamapoli Co., Ltd.) to obtain a photosensitive observation composition laminate.
- the dried film thickness of the photosensitive resin composition layer was 40 / m.
- Example 1 the photosensitive element obtained in Example 1, Example 2, Example 6, Example 8, Example 9, and Example 10 was cut into 3 OmmX 30 squares, and the photosensitive element polyethylene After attaching the terephthalate film surface to the glass substrate, the polyethylene protective film was peeled off to obtain a laminate in which the glass substrate Z, the polyethylene terephthalate film Z, and the photosensitive resin composition were adhered in this order.
- a spray nozzle having a 1.2-inch inner diameter (a square full cone type spray nozzle manufactured by Spraying System Japan Co., Ltd.) was placed at the point closest to the photosensitive resin composition layer of the spray nozzle (the spray nozzle). It was set so that the distance between the tip) and the layer of the photosensitive resin composition was 50 images.
- An aqueous solution of 1.0% by weight of sodium carbonate is sprayed at a spray pressure of 0.05 MPa so that the photosensitive resin composition is sufficiently applied to the entire surface of the layer of the photosensitive resin composition of 30 ⁇ 30 squares, so that the photosensitive resin composition is complete.
- the time at which the photosensitive resin composition layer was removed was taken as the removal time of the photosensitive resin composition layer, and the results are shown in Table 6.
- a 1.6 mm thick copper-clad laminate made by Ain Co., Ltd.
- 35 m thick copper foil on both sides is connected with three holes of 6 mm in diameter and has a length of 16 mm.
- Using a die-cutting machine create 18 triple holes so that the triple holes shown in Fig. 1 are created.
- the Paris generated when the triple holes are created is polished with a brush equivalent to # 600. (Manufactured by Kei Co., Ltd.) and used as a substrate for measuring the number of broken holes.
- the triple hole and the triple hole were created side by side at a distance of 10 waking.
- Example 1 the photosensitive element obtained in Example 1, Example 2, Example 6, Example 8, Example 9, and Example 10 was removed from the photosensitive resin composition layer while peeling off the polyethylene protective film.
- lamination was performed at a pressure of 0.4 MPa at a speed of 1.5 m / min.
- the layer of the photosensitive resin composition laminated on the substrate for measuring the number of hole breaks was applied to a 41-step tablet using an exposure machine equipped with a high-pressure mercury lamp (trade name: HMW—201B manufactured by Oak Co., Ltd.).
- the photocuring was carried out at a light exposure of 24 steps of a glass (trade name: Hitachi 4 1 step step bullet made by Fuji Photo Film Co., Ltd.) to obtain a cured film, and then the support was peeled off.
- a spray nozzle with an inner diameter of 1.2 ran square full cone type spray nozzle manufactured by Spraying System Japan Co., Ltd.
- the distance was set at 50 hires.
- a 1.0% by weight aqueous solution of sodium carbonate was sprayed 3 times at a spray pressure of 0.05 MPa for 36 seconds for 3 seconds so that the entire surface of the cured film was sufficiently sprayed. was observed, and the number of torn portions to the hole tear number, Table 6 results It was shown to.
- six spray nozzles were arranged side by side at intervals of 30 ° so that 18 triple holes were sufficiently exposed to a 1.0% by weight aqueous solution of sodium carbonate. Table 6
- the photosensitive elements obtained in Example 1 As described above, using the photosensitive elements obtained in Example 1, Example 2, Example 6, Example 8, Example 9, and Example 10, the production line of a printed wiring board was improved.
- the photosensitive elements obtained in Examples 1 and 2 can efficiently prevent entry of an etching solution, a plating solution, or the like into the through-holes, and poor conduction of the printed wiring board. As a result, it was possible to prevent short-circuit defects and the like, and it was possible to manufacture printed wiring boards with high yield. Industrial applicability
- the present invention is useful for increasing the density and resolution of printed wiring.
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- Spectroscopy & Molecular Physics (AREA)
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- Manufacturing Of Printed Circuit Boards (AREA)
Description
Claims
Priority Applications (3)
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JP2002501106A JP3855929B2 (ja) | 2000-05-29 | 2001-05-29 | 感光性樹脂組成物、感光性エレメント、レジストパターンの製造法及びプリント配線板の製造法 |
US10/296,911 US7517636B2 (en) | 2000-05-29 | 2001-05-29 | Photosensitive resin composition, photosensitive element, production method of resist pattern and production method for printed circuit board |
AU60639/01A AU6063901A (en) | 2000-05-29 | 2001-05-29 | Photosensitive resin composition, photosensitive element, production method for resist pattern and production method for printed circuit board |
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JP2000-157530 | 2000-05-29 | ||
JP2000157530 | 2000-05-29 | ||
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PCT/JP2001/004496 WO2001092958A1 (fr) | 2000-05-29 | 2001-05-29 | Composition de resine photosensible, element photosensible, procede de production de motif de resist et procede de production de carte a circuit imprime |
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US (1) | US7517636B2 (ja) |
JP (1) | JP3855929B2 (ja) |
KR (1) | KR100537084B1 (ja) |
CN (1) | CN1228688C (ja) |
AU (1) | AU6063901A (ja) |
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JP3939402B2 (ja) | 1997-09-08 | 2007-07-04 | 日本合成化学工業株式会社 | レジストパターン形成方法 |
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2001
- 2001-05-29 KR KR10-2002-7015775A patent/KR100537084B1/ko active IP Right Grant
- 2001-05-29 AU AU60639/01A patent/AU6063901A/en not_active Abandoned
- 2001-05-29 US US10/296,911 patent/US7517636B2/en not_active Expired - Fee Related
- 2001-05-29 CN CNB018102395A patent/CN1228688C/zh not_active Expired - Lifetime
- 2001-05-29 TW TW090112863A patent/TWI306546B/zh not_active IP Right Cessation
- 2001-05-29 WO PCT/JP2001/004496 patent/WO2001092958A1/ja active IP Right Grant
- 2001-05-29 JP JP2002501106A patent/JP3855929B2/ja not_active Expired - Lifetime
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006039193A (ja) * | 2004-07-27 | 2006-02-09 | Hitachi Chem Co Ltd | 感光性樹脂組成物、これを用いた感光性エレメント、レジストパターンの製造法及びプリント配線板の製造法 |
JP4632117B2 (ja) * | 2004-07-27 | 2011-02-16 | 日立化成工業株式会社 | 感光性樹脂組成物、これを用いた感光性エレメント、レジストパターンの製造法及びプリント配線板の製造法 |
JP2006106287A (ja) * | 2004-10-04 | 2006-04-20 | Hitachi Chem Co Ltd | 感光性樹脂組成物、感光性エレメント及び感光性エレメントの製造方法 |
US8101339B2 (en) | 2005-10-25 | 2012-01-24 | Hitachi Chemical Company, Ltd. | Photosensitive resin composition, photosensitive element comprising the same, method of forming resist pattern, and process for producing printed wiring board |
WO2008032674A1 (fr) | 2006-09-13 | 2008-03-20 | Hitachi Chemical Company, Ltd. | Composition de résine photosensible, élément photosensible, procédé servant à former une impression de réserve et procédé servant à produire des cartes de câblage imprimé |
JP2010217399A (ja) * | 2009-03-16 | 2010-09-30 | Hitachi Chem Co Ltd | 感光性エレメント、並びにこれを用いたレジストパターンの形成方法及びプリント配線板の製造方法 |
JP2010256775A (ja) * | 2009-04-28 | 2010-11-11 | Hitachi Chem Co Ltd | 感光性樹脂組成物、これを用いた感光性エレメント、画像表示装置の隔壁の形成方法及び画像表示装置の製造方法 |
JP2013117581A (ja) * | 2011-12-01 | 2013-06-13 | Asahi Kasei E-Materials Corp | 感光性樹脂組成物 |
JP2013257596A (ja) * | 2013-09-17 | 2013-12-26 | Hitachi Chemical Co Ltd | 感光性エレメント、並びにこれを用いたレジストパターンの形成方法及びプリント配線板の製造方法 |
JP2015135482A (ja) * | 2013-12-20 | 2015-07-27 | 旭化成イーマテリアルズ株式会社 | 感光性エレメント、及びその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
CN1228688C (zh) | 2005-11-23 |
TWI306546B (ja) | 2009-02-21 |
US20030186166A1 (en) | 2003-10-02 |
JP3855929B2 (ja) | 2006-12-13 |
KR100537084B1 (ko) | 2005-12-16 |
KR20030076223A (ko) | 2003-09-26 |
AU6063901A (en) | 2001-12-11 |
CN1432141A (zh) | 2003-07-23 |
US7517636B2 (en) | 2009-04-14 |
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