WO2011013664A1 - 感光性樹脂組成物、感光性樹脂積層体及びレジストパターン形成方法 - Google Patents
感光性樹脂組成物、感光性樹脂積層体及びレジストパターン形成方法 Download PDFInfo
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- WO2011013664A1 WO2011013664A1 PCT/JP2010/062623 JP2010062623W WO2011013664A1 WO 2011013664 A1 WO2011013664 A1 WO 2011013664A1 JP 2010062623 W JP2010062623 W JP 2010062623W WO 2011013664 A1 WO2011013664 A1 WO 2011013664A1
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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
-
- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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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- 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
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
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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
- H05K3/0076—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the composition of the mask
-
- 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
- H05K2203/12—Using specific substances
- H05K2203/122—Organic non-polymeric compounds, e.g. oil, wax, thiol
- H05K2203/124—Heterocyclic organic compounds, e.g. azole, furan
Definitions
- the present invention relates to a photosensitive resin composition that can be developed with an alkaline aqueous solution, a photosensitive resin laminate formed by laminating the photosensitive resin composition on a support, and a substrate using the photosensitive resin laminate.
- the present invention relates to a method for forming a resist pattern and a use of the resist pattern.
- the manufacture of printed wiring boards the manufacture of flexible printed wiring boards, the manufacture of lead frames for mounting IC chips (hereinafter referred to as lead frames), metal foil precision processing represented by metal mask manufacturing, BGA (ball grid array) ) And semiconductor packages such as CSP (chip size package), tapes typified by TAB (Tape Automated Bonding) and COF (Chip on Film: a semiconductor IC mounted on a film-like fine wiring board)
- lead frames metal foil precision processing represented by metal mask manufacturing
- BGA ball grid array
- semiconductor packages such as CSP (chip size package)
- tapes typified by TAB (Tape Automated Bonding) and COF (Chip on Film: a semiconductor IC mounted on a film-like fine wiring board)
- TAB Transmission Automated Bonding
- COF Chip on Film: a semiconductor IC mounted on a film-like fine wiring board
- the manufacture of substrates the manufacture of semiconductor bumps, the manufacture of barrier ribs represented by ITO electrodes, address electrodes and electromagnetic wave
- printed wiring boards are manufactured by a photolithography method.
- a photolithography method for example, in the case of a negative type, a photosensitive resin composition is applied on a substrate, pattern exposure is performed to polymerize and cure an exposed portion of the photosensitive resin composition, and an unexposed portion is removed with a developer. Then, a resist pattern is formed on the substrate, a conductor pattern is formed by etching or plating, and then the resist pattern is peeled off from the substrate to form a conductor pattern on the substrate. It is done.
- the photosensitive resin composition when the photosensitive resin composition is applied onto the substrate, the photosensitive resin composition solution is applied to the substrate as a photoresist solution and dried, or the support, the photosensitive resin composition
- a layer of photosensitive resin hereinafter also referred to as “photosensitive resin layer”
- a photosensitive resin laminate hereinafter also referred to as “dry film resist” in which a protective layer, if necessary, are sequentially stacked are laminated on a substrate. Either way is used. In the production of printed wiring boards, the latter dry film resist is often used.
- the dry film resist has a protective layer, for example, a polyethylene film
- a protective layer for example, a polyethylene film
- the photosensitive resin layer and the support are laminated on the substrate (for example, copper-clad laminate) in the order of the substrate, the photosensitive resin layer, and the support (for example, polyethylene terephthalate).
- the exposed portion is polymerized and cured by exposing the photosensitive resin layer to ultraviolet rays such as i rays (wavelength 365 nm) emitted from an ultrahigh pressure mercury lamp through a photomask having a wiring pattern.
- the support is 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.
- the metal in the hole is usually 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.
- a cupric chloride solution, a ferric chloride solution, or a copper ammonia complex solution is used.
- JP 2000-241971 A Japanese Patent Laid-Open No. 2002-056321 JP 2001-209177 A JP 2008-287227 A
- the object of the present invention is to overcome the above-mentioned problems, have a very good contrast immediately after exposure, excellent in resolution and sensitivity, and in a specific aspect, can suppress a decrease in residual film properties at the time of peeling. It aims at providing the photosensitive resin composition, the photosensitive resin laminated body using the same, and the resist pattern formation method.
- the present invention is as follows.
- Alkali-soluble polymer containing (a) carboxylic acid, having an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000: 20 to 80% by mass, (b) Acrylic group Ethylenically unsaturated addition-polymerizable monomer containing at least one compound having: 5 to 60% by mass, (c) photopolymerization initiator containing N-aryl- ⁇ -amino acid compound: 0.1 to 20% by mass (D) leuco dye: 0.1 to 10% by mass, and (e) the following general formula (I): ⁇ In the formula, R 1 represents an alkyl group having 1 to 9 carbon atoms, an alkoxyl group having 1 to 9 carbon atoms, an alkylthio group having 1 to 16 carbon atoms, a mercapto group, an amino group, and an alkylamino group having 1 to 9 carbon atoms.
- the compound having an acrylic group in the ethylenically unsaturated addition polymerizable monomer containing at least one compound having the acrylic group (b) is represented by the following general formula (II): ⁇ Wherein R 2 , R 3 , R 4 , and R 5 represent H, X and Y each independently represent an alkylene group having 2 to 4 carbon atoms, and X and Y are different from each other; 1 , p 2 , p 3 , p 4 , p 5 , p 6 , p 7 and p 8 are each independently 0 or a positive integer, and p 1 , p 2 , p 3 , p 4 , p 5 , The sum of p 6 , p 7 and p 8 is an integer from 0 to 20.
- the photosensitive resin composition as described in said (1) which is a compound represented by these.
- the (e) mercaptothiadiazole compound is selected from the group consisting of 5-methylthio-2-mercapto-1,3,4-thiadiazole, 2-amino-5-mercapto-1,3,4-thiadiazole, and 5-methylamino-2.
- -Photosensitivity according to (1) or (2) above which is at least one compound selected from the group consisting of mercapto-1,3,4-thiadiazole and 2,5-dimercapto-1,3,4-thiadiazole Resin composition.
- a laminating step of laminating the photosensitive resin laminate according to (6) above on a substrate A resist pattern forming method comprising an exposure step of exposing a photosensitive resin layer in a photosensitive resin laminate, and a development step of developing and removing an unexposed portion of the photosensitive resin layer.
- a photosensitive resin composition that has a very good contrast immediately after exposure, is excellent in resolution and sensitivity, and in a specific embodiment can suppress a decrease in residual film properties at the time of peeling, and A photosensitive resin laminate and a resist pattern forming method using the same are provided.
- the present invention relates to (a) an alkali-soluble polymer containing a carboxylic acid, having an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000 (in this specification, (a) an alkali-soluble polymer.
- R 1 represents an alkyl group having 1 to 9 carbon atoms, an alkoxyl group having 1 to 9 carbon atoms, an alkylthio group having 1 to 16 carbon atoms, a mercapto group, an amino group, and an alkylamino group having 1 to 9 carbon atoms. It represents one group selected from the group consisting of groups.
- Alkali-soluble polymer (a) The alkali-soluble polymer in the photosensitive resin composition of the present invention contains a carboxylic acid, has an acid equivalent of 100 to 600, and a weight average molecular weight of 5,000 to 500, 000 alkali-soluble polymer.
- the carboxyl group of the alkali-soluble polymer is necessary for the photosensitive resin composition to have developability and peelability with respect to a developer and a stripper composed of an aqueous alkali solution.
- the acid equivalent of the alkali-soluble polymer is 100 to 600, preferably 250 to 450. The acid equivalent ensures compatibility with the solvent or other component in the photosensitive resin composition, particularly with an ethylenically unsaturated addition polymerizable monomer containing at least one compound (b) having an acrylic group described later. From the viewpoint of maintaining the developing property and the peelability.
- the acid equivalent means the mass (gram) of the alkali-soluble polymer having 1 equivalent of a carboxyl group therein. The acid equivalent is measured by a potentiometric titration method using a Hiranuma Reporting Titrator (COM-555) with a 0.1 mol / L NaOH aqueous solution.
- the weight average molecular weight of the alkali-soluble polymer is 5,000 to 500,000. It is 5,000 or more from the viewpoint of maintaining the thickness of the photosensitive resin layer uniform and obtaining resistance to the developing solution, and 500,000 or less from the viewpoint of maintaining developability. More preferably, the weight average molecular weight is from 20,000 to 100,000.
- the weight average molecular weight means a weight average molecular weight measured by gel permeation chromatography (GPC) using a calibration curve of polystyrene (for example, Shodex STANDARD SM-105 manufactured by Showa Denko KK). More typically, the weight average molecular weight can be measured using gel permeation chromatography manufactured by JASCO Corporation under the following conditions.
- the alkali-soluble polymer is preferably a copolymer of one or more first monomers described below and one or more second monomers described later.
- the first monomer is a carboxylic acid or carboxylic 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.
- (meth) acrylic acid is particularly preferable.
- the second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule.
- (meth) acryl means acryl and / or methacryl.
- the content of the alkali-soluble polymer in the photosensitive resin composition is in the range of 20 to 80% by mass, preferably in the range of 30 to 70% by mass. From the viewpoint that the resist pattern formed by exposure and development has sufficient resist properties, such as tenting, etching, and various plating processes, the content is 20% by mass or more and 80% by mass or less. .
- the polymerizable monomer is a monomer having one or more ethylenically unsaturated bonds.
- Examples of the compound having an acrylic group include 1,6-hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, polypropylene glycol diacrylate, polyethylene glycol diacrylate, 2-di (p-hydroxyphenyl) propanedi Acrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxypropyltrimethylolpropane triacrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, Trimethylolpropane triglycidyl ether triacrylate, bisphenol A diglycidyl ether diacrylate, ⁇ -hydroxypropyl- ⁇ '-(a Liloyloxy) propyl phthalate, phenoxy polyethylene glycol acrylate, nonyl phenoxy polyethylene glycol acrylate, nonyl phenoxy
- polyalkylene glycol diacrylate An average of 3 moles of ethylene oxide is added to both ends of propylene glycol.
- Polyalkylene glycol diacrylate include pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, bisphenol A diglycidyl ether diacrylate, and diacrylate of bisphenol A alkylene oxide adduct are preferable.
- R 2 , R 3 , R 4 , and R 5 represent H, X and Y each independently represent an alkylene group having 2 to 4 carbon atoms, and X and Y are different from each other; 1 , p 2 , p 3 , p 4 , p 5 , p 6 , p 7 and p 8 are each independently 0 or a positive integer, and p 1 , p 2 , p 3 , p 4 , p 5 , The sum of p 6 , p 7 and p 8 is an integer from 0 to 20.
- the content of the compound having an acrylic group in the photosensitive resin composition of the present invention is preferably 1 to 45% by mass, more preferably 1 to 30% by mass, and further preferably 5 to 20% by mass. .
- the content is preferably 1% by mass or more, more preferably 5% by mass or more from the viewpoint of having good contrast immediately after exposure. Moreover, it is preferable that it is 45 mass% or less from a viewpoint of suppressing the fall of the remaining film property at the time of peeling, and 30 mass% or less is more preferable.
- R 6 and R 7 each independently represent H or CH 3
- A represents C 2 H 4
- B represents C 3 H 6
- n1 + n2 is an integer of 2 to 30
- n3 + n4 Is an integer from 0 to 30, n1 and n2 are each independently an integer from 1 to 29, n3 and n4 are each independently an integer from 0 to 30, and-(AO)-and-(
- the arrangement of the B—O) — repeating unit may be random or block.
- Examples of the compound represented by the general formula (III) include 2,2-bis ⁇ (4-acryloxypolyethyleneoxy) phenyl ⁇ propane and 2,2-bis ⁇ (4-methacryloxypolyethyleneoxy) phenyl ⁇ propane. Is mentioned.
- the polyethyleneoxy group of the compound represented by the general formula (III) is monoethyleneoxy group, diethyleneoxy group, triethyleneoxy group, tetraethyleneoxy group, pentaethyleneoxy group, hexaethyleneoxy group, heptaethyleneoxy group.
- octaethyleneoxy group nonaethyleneoxy group, decaethyleneoxy group, undecaethyleneoxy group, dodecaethyleneoxy group, tridecaethyleneoxy group, tetradecaethyleneoxy group, and pentadecaethyleneoxy group It is preferably any group selected.
- Examples of the compound represented by the general formula (III) include 2,2-bis ⁇ (4-acryloxypolyalkyleneoxy) phenyl ⁇ propane and 2,2-bis ⁇ (4-methacryloxypolyalkyleneoxy). Phenyl ⁇ propane and the like are also included.
- Examples of the polyalkyleneoxy group possessed by the compound represented by the general formula (III) include a mixture of an ethyleneoxy group and a propyleneoxy group, and an adduct having a block structure of an octaethyleneoxy group and a dipropyleneoxy group.
- an adduct of random structure an adduct of block structure of tetraethyleneoxy group and tetrapropyleneoxy group or an adduct of random structure, an adduct of block structure of pentadecaethyleneoxy group and dipropyleneoxy group or random Structure additions are preferred.
- 2,2-bis ⁇ (4-methacryloxypentaethyleneoxy) phenyl ⁇ propane is most preferred.
- the compound represented by the general formula (III) in the photosensitive resin composition of the present invention contains the compound represented by the general formula (III), the compound represented by the general formula (III) in the photosensitive resin composition of the present invention
- the content is preferably 1 to 40% by mass, more preferably 5 to 30% by mass.
- the content is preferably 1% by mass or more from the viewpoint of having good contrast immediately after exposure, and is preferably 40% by mass or less from the viewpoint of suppressing a decrease in resolution and adhesion. .
- urethane compounds may also be mentioned.
- urethane compounds include hexamethylene diisocyanate, tolylene diisocyanate, and 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 may be used alone or in combination of two or more.
- the content of the (b) ethylenically unsaturated addition polymerizable monomer used in the present invention in the photosensitive resin composition is in the range of 5 to 60% by mass, preferably in the range of 10 to 50% by mass.
- the said content rate is 5 mass% or more from a viewpoint which a sensitivity, a resolution, and adhesiveness improve, and it is 60 mass% or less from a viewpoint from which an edge fuse is suppressed.
- the (c) photopolymerization initiator in the photosensitive resin composition of the present invention contains an N-aryl- ⁇ -amino acid compound as an essential component.
- an N-aryl- ⁇ -amino acid compound By including an N-aryl- ⁇ -amino acid compound, good sensitivity is ensured.
- the N-aryl- ⁇ -amino acid compound is particularly preferably N-phenylglycine from the viewpoint of sensitivity.
- the (c) photopolymerization initiator used in the present invention is preferably a system in which an N-aryl- ⁇ -amino acid compound and an acridine derivative are used in combination.
- acridine derivatives include 9-phenylacridine, 9-pyridylacridine, 9-pyrazinylacridine, 1,2-bis (9-acridinyl) ethane, 1,3-bis (9-acridinyl) propane, 1,4- Bis (9-acridinyl) butane, 1,5-bis (9-acridinyl) pentane, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane (Asahi Denka Kogyo Co., Ltd.) N-1717), 1,8-bis (9-acridinyl) octane, 1,9-bis (9-acridinyl) nonane, 1,10-bis (9-acridinyl)
- photopolymerization initiator means a compound that is activated by various actinic rays, such as ultraviolet rays, and starts polymerization.
- Examples of the other photopolymerization initiators include pyrazolines such as 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, quinones such as 2-ethylanthraquinone and 2-tert-butylanthraquinone, aromatic ketones such as benzophenone and benzoin, benzoin ethers such as benzoin methyl ether and benzoin ethyl ether, acridine compounds such as 9-phenylacridine, benzyl ketals Examples include benzyl dimethyl ketal and benzyl diethyl ketal.
- thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, or 2-chlorothioxanthone can be used in combination with a tertiary amine compound such as a dimethylaminobenzoic acid alkyl ester compound. It is.
- Examples of the other photopolymerization initiator include oxime esters such as 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 1-phenyl-1,2-propanedione-2- (O Also included is -ethoxycarbonyl) oxime.
- the content of the photopolymerization initiator in the photosensitive resin composition is in the range of 0.1% by mass to 20% by mass. If the content is less than 0.1% by mass, sufficient sensitivity cannot be obtained. On the other hand, when the content ratio exceeds 20% by mass, fog due to diffraction of light passing through the photomask at the time of exposure tends to occur, and as a result, resolution is deteriorated.
- the content is more preferably in the range of 0.1 to 15% by mass, and still more preferably in the range of 0.1 to 10% by mass.
- (D) Leuco dye examples of (d) leuco dye in the photosensitive resin composition of the present invention include leuco crystal violet and fluoran dye. Among these, when leuco crystal violet is used, the contrast immediately after exposure is good, which is preferable.
- the fluorane dye examples include 3-diethylamino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, and 2- (2-chloroanilino) -6-dibutylamino.
- Fluorane 2-bromo-3-methyl-6-dibutylaminofluorane, 2-N, N-dibenzylamino-6-diethylaminofluorane, 3-diethylamino-7-chloroaminofluorane, 3,6-dimethoxy Examples include fluorane, 3-diethylamino-6-methoxy-7-aminofluorane, and the like.
- the content of the leuco dye in the photosensitive resin composition is in the range of 0.1 to 10% by mass, preferably in the range of 0.1 to 5% by mass, more preferably 0.5 to The range is 3% by mass.
- the content is 0.1% by mass or more from the viewpoint of developing a contrast immediately after exposure, and is 10% by mass or less from the viewpoint of maintaining storage stability.
- R 1 represents an alkyl group having 1 to 9 carbon atoms, an alkoxyl group having 1 to 9 carbon atoms, an alkylthio group having 1 to 16 carbon atoms, a mercapto group, an amino group, and an alkylamino group having 1 to 9 carbon atoms. It represents one group selected from the group consisting of groups. ⁇ It is a compound represented.
- Examples of the mercaptothiadiazole compound include 5-methyl-2-mercapto-1,3,4-thiadiazole, 5-ethyl-2-mercapto-1,3,4-thiadiazole, and 5-n-propyl-2.
- 5-methylthio-2-mercapto-1,3,4-thiadiazole, 2-amino-5-mercapto-1,3,4-thiadiazole, 5-methylamino-2-mercapto-1,3,4-thiadiazole And 2,5-dimercapto-1,3,4-thiadiazole are preferably used because of their high sensitivity, adhesion and contrast performance immediately after exposure. These can be used alone or in combination of two or more.
- the content ratio of the mercaptothiadiazole compound in the photosensitive resin composition is in the range of 0.01 to 5% by mass, preferably in the range of 0.05 to 3% by mass, and most preferably 0.00. It is in the range of 1 to 2% by mass.
- the content is 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity and adhesion, and contrast, and is 5% by mass or less from the viewpoint of maintaining storage stability.
- the (e) mercaptothiadiazole compound is a powder at normal temperature, the above-mentioned content ratio is typically a solid content ratio.
- a halogen compound in the photosensitive resin composition.
- a leuco dye and a halogen compound are used in combination, and adhesion and contrast immediately after exposure are further improved.
- halogen compound examples include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2 , 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, halogenated triazine compounds, etc. .
- the content of the halogen compound in the photosensitive resin composition is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass.
- a coloring substance may be contained in the photosensitive resin composition.
- coloring substances include fuchsin, phthalocyanine, olamine base, paramadienta, crystal violet, methyl orange, Nile Bull-2B, Victoria Bull, malachite green (for example, Eisen (registered trademark) manufactured by Hodogaya Chemical Co., Ltd.) ) MALACHITE GREEN, Basic Bull-20, Diamond Green (for example, Eizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.) and the like.
- the content ratio of the coloring substance in the photosensitive resin composition is preferably 0.001 to 1% by mass, and more preferably 0.01 to 0.1% by mass.
- the content rate is 0.001 mass% or more, the effect of a handleability improvement is favorable, and when it is 1 mass% or less, the effect of maintaining storage stability is favorable.
- the photosensitive resin composition in the present invention it is possible to contain a stabilizer in the photosensitive resin composition.
- the stabilizer include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis (4- Ethyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), diphenylnitrosamine and the like.
- benzotriazole carboxybenzotriazole, 1- (2-dialkylamino) carboxybenzotriazole, pentaerythritol-3,5-di-t-butyl-4-hydroxyphenylpropionic acid tetraester, and the like.
- the content of the stabilizer in the photosensitive resin composition is preferably 0.01 to 3% by mass, and more preferably 0.05 to 1% by mass.
- the content is 0.01% by mass or more, the effect of imparting storage stability to the photosensitive resin composition is good, and when it is 3% by mass or less, the effect of maintaining sensitivity is good. is there.
- the photosensitive resin composition of the present invention can contain a plasticizer as necessary.
- the plasticizer include phthalates such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl tricitrate tri-n-propyl, Examples include tri-n-butyl acetyl citrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether.
- the content of the plasticizer in the photosensitive resin composition is preferably 5 to 50% by mass, more preferably 5 to 30% by mass.
- the content ratio is 50% by mass or less, the effect of suppressing the delay of development time and imparting flexibility to the cured film is good, and when it is 5% by mass or more, insufficient curing and cold flow are suppressed. The effect of doing is good.
- This invention also provides the photosensitive resin laminated body formed by laminating
- the photosensitive resin laminate of the present invention has a photosensitive resin layer and a support made of a base film that supports the photosensitive resin layer, and if necessary, a surface of the photosensitive resin layer opposite to the support. May have a protective layer.
- the base film is preferably a transparent film that transmits light emitted from the exposure light source.
- a base film include 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, and a polymethyl methacrylate copolymer film.
- the haze of the base film is preferably 5 or less.
- a thinner film is advantageous in terms of image forming property and economic efficiency, but is preferably 10 to 30 ⁇ m in order to maintain strength.
- an important characteristic of the protective layer used as necessary for the photosensitive resin laminate is that the protective layer is sufficiently smaller than the support in terms of adhesion to the photosensitive resin layer and can be easily peeled off.
- a polyethylene film and 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 of the present invention varies depending on the application, but is preferably 5 to 100 ⁇ m, more preferably 7 to 60 ⁇ m. The thinner the film, the higher the resolution, and the thicker the film strength. improves.
- a conventionally known method can be adopted as a method for producing the photosensitive resin laminate of the present invention by sequentially laminating a support, a photosensitive resin layer, and, if necessary, a protective layer.
- the photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent that dissolves the photosensitive resin composition to form a uniform solution.
- the solution is applied onto a support using a bar coater or a roll coater and dried.
- a photosensitive resin layer made of a photosensitive resin composition is laminated on the body.
- a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.
- the solvent examples include ketones typified by methyl ethyl ketone (MEK), and alcohols typified by methanol, ethanol, and isopropanol. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition applied onto the support is 500 to 4000 mPa ⁇ s at 25 ° C.
- the above-described photosensitive resin composition and photosensitive resin laminate according to the present invention can be used for forming a negative resist pattern.
- the present invention includes a laminating step of laminating the above-described photosensitive resin laminate of the present invention on a substrate, an exposure step of exposing the photosensitive resin layer in the photosensitive resin laminate, and developing an unexposed portion of the photosensitive resin layer.
- a resist pattern forming method including a developing step of removing. An example of a specific method is shown below.
- the substrate examples include a copper-clad laminate for the purpose of manufacturing a printed wiring board, and a glass substrate coated with a glass rib paste for the purpose of manufacturing an uneven substrate, for example, a substrate for a plasma display panel, a surface electrolytic display Examples include a substrate, a substrate for an organic EL sealing cap, a silicone wafer having a through hole, and a ceramic substrate.
- the 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 for these substrates becomes an uneven substrate.
- a photosensitive resin laminate is laminated on the substrate using a laminator or the like.
- the protective layer is peeled off, and then the photosensitive resin layer is heat-pressed and laminated on the substrate surface 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 for pressure bonding, or the photosensitive resin laminate and the substrate may be repeatedly passed through the roll and pressure bonded.
- the photosensitive resin layer in the photosensitive resin laminate is exposed using an exposure machine. If necessary, the support is peeled off before exposure and exposed to active light through a photomask.
- the exposure amount is determined by the illuminance of the light source and the exposure time, and may be measured using a light meter.
- the exposure process may be performed by direct drawing of a drawing pattern.
- the direct drawing exposure method 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.
- the unexposed portion of the photosensitive resin layer is developed and removed using a developing device. After exposure, when there is a support on the photosensitive resin layer, this is removed as necessary, and then the unexposed portion is developed and removed using a developer of an alkaline aqueous solution to obtain a resist pattern.
- an alkaline aqueous solution for example, an aqueous solution of Na 2 CO 3 or K 2 CO 3 is used. These are selected in accordance with the characteristics of the photosensitive resin layer, and 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 surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed.
- a heating process 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 can be used.
- a conductor pattern manufacturing method and a printed wiring board manufacturing method can be suitably applied to a conductor pattern manufacturing method and a printed wiring board manufacturing method.
- a conductor pattern and a printed wiring board can be manufactured by using a copper-clad laminate or a flexible substrate as a substrate and performing the following steps following the resist pattern forming method described above.
- a copper pattern of a substrate exposed by development in the resist forming method of the present invention described above is etched or plated by a conventionally known method to form a conductor pattern.
- 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 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.
- a lead frame can be manufactured by using a metal plate, for example, a copper, copper alloy, or iron-based alloy plate as a substrate and following the above-described resist pattern forming method through the following steps.
- a metal plate for example, a copper, copper alloy, or iron-based alloy plate
- the substrate exposed by development in the resist pattern forming method 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.
- a semiconductor package manufacturing method can also be suitably applied to a semiconductor package manufacturing method.
- a semiconductor package can be manufactured by using a wafer on which an LSI circuit has been formed as a substrate and performing the following steps following the resist pattern forming method described above.
- columnar plating with, for example, copper or solder is applied to the opening exposed by development in the resist pattern forming method 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.
- the present invention can also be suitably applied to a method for producing a substrate having an uneven pattern.
- a glass substrate coated with a glass rib paste is used as the substrate, and the same method as described above is used on the substrate.
- the photosensitive resin laminate is laminated by the method, and exposure and development are performed.
- the substrate is subjected to a sand blasting process in which a blasting material is sprayed from the formed resist pattern and cut to a desired depth, and a resin part remaining on the substrate is removed from the substrate with an alkaline stripping solution.
- a fine concavo-convex pattern can be processed on top.
- a known material is used as the blasting material used in the sand blasting process.
- the material is made of SiO, SiO 2 , Al 2 O 3 , CaCO 3 , ZrO, glass, or stainless steel and has a particle size of about 2 to 100 ⁇ m. Fine particles are used.
- ⁇ Preparation of photosensitive resin laminate Prepare the compounds shown in Table 1, thoroughly stir and mix the photosensitive resin compositions in the composition ratios shown in Tables 2 and 3, and uniformly use a bar coater on the surface of a 19 ⁇ m-thick polyethylene terephthalate film as a support. This was applied and dried in a dryer at 95 ° C. for 3 minutes to form a photosensitive resin layer. The thickness of the photosensitive resin layer was 30 ⁇ m. Next, a 23 ⁇ m thick polyethylene film was laminated as a protective layer on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated to obtain a photosensitive resin laminate.
- P corresponds to (a) an alkali-soluble polymer
- M-1 and M-2 are (b) photopolymerizable monomers in an ethylenically unsaturated addition polymerizable monomer
- M-3 corresponds to a compound having an acrylic group in (b) an ethylenically unsaturated addition polymerizable monomer
- I-1 corresponds to (c) an acridine derivative in a photopolymerization initiator.
- I-2 corresponds to (c) the N-aryl- ⁇ -amino acid compound in the photopolymerization initiator
- I-3 corresponds to (e)
- I-4 corresponds to (e)
- D-1 corresponds to (d) leuco dye.
- the mass part of P in Tables 2 and 3 is a value including methyl ethyl ketone.
- ⁇ Laminate> While peeling the polyethylene film of the photosensitive resin laminate, a copper-clad laminate as a substrate preheated to 60 ° C. is coated with a hot roll laminator (AL-70, manufactured by Asahi Kasei Co., Ltd.) at a roll temperature of 105 ° C. The laminate was laminated. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.
- a hot roll laminator AL-70, manufactured by Asahi Kasei Co., Ltd.
- a photosensitive resin laminate laminated on a copper-clad laminate is 20 mJ / with a direct drawing type exposure apparatus (manufactured by Hitachi Via Mechanics Co., Ltd., DI exposure machine DE-1AH, light source: GaN blue-violet diode, main wavelength 407 ⁇ 3 nm). It exposed with the exposure amount of cm ⁇ 2 >.
- Evaluation results Tables 2 and 3 show the evaluation results of Examples and Comparative Examples.
- the present invention includes, for example, production of printed wiring boards, production of lead frames for mounting IC chips, precision metal foil processing represented by metal mask production, production of packages represented by BGA and CSP, and representative of COF and TAB. It can be suitably used for the production of tape substrates, semiconductor bumps, flat panel display partitions represented by ITO electrodes, address electrodes and electromagnetic wave shields, and the production of substrates having uneven patterns by sandblasting. .
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Abstract
Description
(2)前記(b)アクリル基を有する化合物を少なくとも1種含有するエチレン性不飽和付加重合性モノマー中の、アクリル基を有する化合物が、下記一般式(II):
(3)上記(e)メルカプトチアジアゾール化合物が、5-メチルチオ-2-メルカプト-1,3,4-チアジアゾール、2-アミノ-5-メルカプト-1,3,4-チアジアゾール、5-メチルアミノ-2-メルカプト-1,3,4-チアジアゾール及び2,5-ジメルカプト-1,3,4-チアジアゾールからなる群より選ばれる少なくとも1種の化合物である、上記(1)又は(2)に記載の感光性樹脂組成物。
(4)上記(c)光重合開始剤が含有する上記N-アリール-α-アミノ酸化合物がN-フェニルグリシンである、上記(1)~(3)のいずれかに記載の感光性樹脂組成物。
(5)上記(b)アクリル基を有する化合物を少なくとも1種含有するエチレン性不飽和付加重合性モノマーが、下記一般式(III):
(6)基材フィルムからなる支持体上に、上記(1)~(5)のいずれかに記載の感光性樹脂組成物からなる感光性樹脂層を積層してなる、感光性樹脂積層体。
(7)上記(6)に記載の感光性樹脂積層体を基板上に積層する積層工程、
感光性樹脂積層体における感光性樹脂層を露光する露光工程、及び
感光性樹脂層の未露光部を現像除去する現像工程
を含む、レジストパターン形成方法。
(8)上記露光工程を、描画パターンの直接描画により行う、上記(7)に記載のレジストパターン形成方法。
本発明は、(a)カルボン酸を含有し、酸当量が100~600であり、重量平均分子量が5,000~500,000であるアルカリ可溶性高分子(本明細書において、(a)アルカリ可溶性高分子ともいう。):20~80質量%、(b)アクリル基を有する化合物を少なくとも1種含有するエチレン性不飽和付加重合性モノマー(本明細書において、(b)エチレン性不飽和付加重合性モノマーともいう。):5~60質量%、(c)N-アリール-α-アミノ酸化合物を含有する光重合開始剤(本明細書において、(c)光重合開始剤ともいう。):0.1~20質量%、(d)ロイコ染料:0.1~10質量%、及び(e)下記一般式(I):
本発明の感光性樹脂組成物における(a)アルカリ可溶性高分子は、カルボン酸を含有し、酸当量が100~600であり、重量平均分子量が5,000~500,000のアルカリ可溶性高分子である。
示差屈折率計:RI-1530
ポンプ:PU-1580
デガッサー:DG-9-80-50
カラムオーブン:CO-1560
カラム:順にKF-802.5、KF-806M×2、KF-807
溶離液:THF
本発明の感光性樹脂組成物における(b)アクリル基を有する化合物を少なくとも1種含有するエチレン性不飽和付加重合性モノマーは、エチレン性不飽和結合を1つ以上有するモノマーである。アクリル基を有する化合物を少なくとも1種含有することにより、露光直後のコントラスト向上効果が付与される。アクリル基を有する化合物としては、1,6-ヘキサンジオ-ルジアクリレート、1,4-シクロヘキサンジオ-ルジアクリレート、ポリプロピレングリコ-ルジアクリレート、ポリエチレングリコ-ルジアクリレート、2-ジ(p-ヒドロキシフェニル)プロパンジアクリレート、グリセロ-ルトリアクリレート、トリメチロ-ルプロパントリアクリレート、ポリオキシプロピルトリメチロ-ルプロパントリアクリレート、ポリオキシエチルトリメチロ-ルプロパントリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリト-ルペンタアクリレート、トリメチロールプロパントリグリシジルエーテルトリアクリレート、ビスフェノールAジグリシジルエーテルジアクリレート、β-ヒドロキシプロピル-β’-(アクリロイルキシ)プロピルフタレート、フェノキシポリエチレングリコールアクリレート、ノニルフェノキシポリエチレングリコールアクリレート、ノニルフェノキシポリアルキレングリコールアクリレート、ポリプロピレングリコールモノアクリレート、ビスフェノールAのアルキレンオキサイド付加物(例えば、両端に平均5モルずつのエチレンオキサイドを付加してなる付加物、両端に平均2モルずつのプロピレンオキサイド及び両端に平均15モルずつのエチレンオキサイドを付加してなる付加物)のジアクリレート、トリエチレングリコールドデカプロピレングリコール、プロピレンオキサイドを付加したポリプロピレングリコールにエチレンオキサイドをさらに両端付加した(平均12モルのプロピレンオキサイドを付加したポリプロピレングリコ-ルの両端にエチレンオキサイドをそれぞれ平均3モルずつ付加)ポリアルキレングリコールのジアクリレートが挙げられる。中でも、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ビスフェノールAジグリシジルエーテルジアクリレート、ビスフェノールAのアルキレンオキサイド付加物のジアクリレートが好ましい。
本発明の感光性樹脂組成物における(c)光重合開始剤は、N-アリール-α-アミノ酸化合物を必須成分として含む。N-アリール-α-アミノ酸化合物が含まれることによって良好な感度が確保される。中でも、N-アリール-α-アミノ酸化合物がN-フェニルグリシンであることが感度の点から特に好ましい。
本発明の感光性樹脂組成物における(d)ロイコ染料としては、ロイコクリスタルバイオレット、フルオラン染料等が挙げられる。中でも、ロイコクリスタルバイオレットを用いた場合、露光直後のコントラストが良好であり好ましい。フルオラン染料としては、例えば、3-ジエチルアミノ-6-メチル-7-アニリノフルオラン、3-ジブチルアミノ-6-メチル-7-アニリノフルオラン、2-(2-クロロアニリノ)-6-ジブチルアミノフルオラン、2-ブロモ-3-メチル-6-ジブチルアミノフルオラン、2-N,N-ジベンジルアミノ-6-ジエチルアミノフルオラン、3-ジエチルアミノ-7-クロロアミノフルオラン、3,6-ジメトキシフルオラン、3-ジエチルアミノ-6-メトキシ-7-アミノフルオラン等が挙げられる。
本発明の感光性樹脂組成物における(e)メルカプトチアジアゾール化合物は、下記一般式(I):
本発明は、基材フィルムからなる支持体上に、上述した本発明の感光性樹脂組成物からなる感光性樹脂層を積層してなる、感光性樹脂積層体も提供する。本発明の感光性樹脂積層体は、感光性樹脂層と、該感光性樹脂層を支持する基材フィルムからなる支持体とを有し、必要により感光性樹脂層の支持体と反対側の表面に保護層を有してもよい。
上述した本発明に係る感光性樹脂組成物及び感光性樹脂積層体は、ネガ型レジストパターンの形成のために使用できる。本発明は、上述した本発明の感光性樹脂積層体を基板上に積層する積層工程、感光性樹脂積層体における感光性樹脂層を露光する露光工程、及び感光性樹脂層の未露光部を現像除去する現像工程を含む、レジストパターン形成方法も提供する。具体的な方法の一例を以下に示す。
積層工程においては、例えばラミネーター等を用いて感光性樹脂積層体を基板上に積層する。感光性樹脂積層体が保護層を有する場合には保護層を剥離した後、ラミネーターで感光性樹脂層を基板表面に加熱圧着し積層する。この場合、感光性樹脂層は基板表面の片面だけに積層しても良いし、両面に積層しても良い。この時の加熱温度は一般的に40~160℃である。また該加熱圧着は2回以上行うことにより密着性及び耐薬品性が向上する。この時、圧着には二連のロールを備えた二段式ラミネーターを使用しても良いし、感光性樹脂積層体と基板とを何回か繰り返してロールに通し圧着しても良い。
次に、露光工程では、露光機を用いて、感光性樹脂積層体における感光性樹脂層を露光する。必要ならば露光前に支持体を剥離し、フォトマスクを通して活性光により露光する。露光量は、光源照度及び露光時間により決定され、光量計を用いて測定しても良い。また露光工程は、描画パターンの直接描画により行ってもよい。直接描画露光方法は、フォトマスクを使用せず、基板上に直接描画して露光する方法である。光源としては例えば、波長350~410nmの半導体レーザー又は超高圧水銀灯が用いられる。描画パターンはコンピューターによって制御され、この場合の露光量は光源照度及び基板の移動速度によって決定される。
現像工程においては、現像装置を用いて感光性樹脂層の未露光部を現像除去する。露光後、感光性樹脂層上に支持体がある場合には、必要に応じてこれを除き、続いてアルカリ水溶液の現像液を用いて未露光部を現像除去し、レジストパターンを得る。アルカリ水溶液としては、例えばNa2CO3又はK2CO3の水溶液を用いる。これらは感光性樹脂層の特性に合わせて選択されるが、0.2~2質量%の濃度、20~40℃のNa2CO3水溶液が一般的である。該アルカリ水溶液中には、表面活性剤、消泡剤、現像を促進させるための少量の有機溶剤等を混入させてもよい。
本発明は導体パターンの製造方法及びプリント配線板の製造方法に好適に適用できる。例えば、基板として銅張積層板又はフレキシブル基板を用い、上述のレジストパターン形成方法に続いて以下の工程を経ることで、導体パターン及びプリント配線板を製造できる。
本発明はリードフレームの製造方法にも好適に適用できる。具体的には、基板として金属板、例えば、銅、銅合金又は鉄系合金の板を用い、上述のレジストパターン形成方法に続いて、以下の工程を経ることでリードフレームを製造できる。
本発明は半導体パッケージの製造方法にも好適に適用できる。具体的には、基板として、LSIとしての回路形成が終了したウェハを用い、上述のレジストパターン形成方法に続いて、以下の工程を経ることで半導体パッケージを製造できる。
本発明は凹凸パターンを有する基材の製造方法にも好適に適用できる。本発明の感光性樹脂積層体をドライフィルムレジストとして用いてサンドブラスト工法により基板に加工を施す場合には、基板としてガラスリブペーストを塗布したガラス基板を用い、基板上に、前記した方法と同様な方法で感光性樹脂積層体をラミネートし、露光及び現像を施す。
更に、形成されたレジストパターン上からブラスト材を吹き付けて目的の深さに切削するサンドブラスト処理工程、基材上に残存した樹脂部分をアルカリ剥離液で基材から除去する剥離工程を経て、基材上に微細な凹凸パターンを加工することができる。前記サンドブラスト処理工程に用いるブラスト材としては公知のものが用いられ、例えば、SiO,SiO2、Al2O3、CaCO3、ZrO、ガラス、又はステンレスを材質とした、粒径2~100μm程度の微粒子が用いられる。
実施例及び比較例における感光性樹脂積層体は次の様にして作製した。
表1に示す化合物を用意し、表2及び3に示す組成割合の感光性樹脂組成物をよく攪拌、混合し、支持体としての19μm厚のポリエチレンテレフタレートフィルムの表面にバーコーターを用いて均一に塗布し、95℃の乾燥機中で3分間乾燥して感光性樹脂層を形成した。感光性樹脂層の厚みは30μmであった。次いで、感光性樹脂層のポリエチレンテレフタレートフィルムを積層していない表面上に、保護層として23μm厚のポリエチレンフィルムを張り合わせて感光性樹脂積層体を得た。なお、表1中、「P」は(a)アルカリ可溶性高分子に対応し、「M-1」及び「M-2」は(b)エチレン性不飽和付加重合性モノマーにおける光重合可能な不飽和化合物に対応し、「M-3」は(b)エチレン性不飽和付加重合性モノマーにおけるアクリル基を有する化合物に対応し、「I-1」は(c)光重合開始剤におけるアクリジン誘導体に対応し、「I-2」は(c)光重合開始剤におけるN-アリール-α-アミノ酸化合物に対応し、「I-3」、「I-4」及び「I-5」は(e)メルカプトチアジアゾール化合物に対応し、「D-1」は(d)ロイコ染料に対応する。また、表2及び3におけるPの質量部は、メチルエチルケトンを含んだ値である。
35μm圧延銅箔を積層した0.4mm厚の銅張積層板を用い、表面をジェットスクラブ(株式会社石井表記製)で研磨した。
感光性樹脂積層体のポリエチレンフィルムを剥がしながら、60℃に予熱した基板としての銅張積層板に、ホットロールラミネーター(旭化成(株)社製、AL-70)によりロール温度105℃で感光性樹脂積層体をラミネートした。エアー圧力は0.35MPaとし、ラミネート速度は1.5m/minとした。
銅張積層板にラミネートした感光性樹脂積層体を、直接描画式露光装置(日立ビアメカニクス(株)製、DI露光機DE-1AH、光源:GaN青紫ダイオード、主波長407±3nm)により20mJ/cm2の露光量で露光した。
ポリエチレンテレフタレートフィルムを剥離した後、アルカリ現像機(フジ機工製、ドライフィルム用現像機)を用いて30℃の1質量%Na2CO3水溶液を所定時間スプレーし、感光性樹脂層の未露光部分を最小現像時間の2倍の時間で溶解除去した。この際、未露光部分の感光性樹脂層が完全に溶解するのに要する最も少ない時間を最小現像時間とした。
(1)露光直後のコントラスト評価法
感光性樹脂層を露光してから30秒後及び1分後のそれぞれにおいて、未露光部と露光部との感光性樹脂層について、測色色差計(日本電色株式会社製Σ80)により色差ΔEを測定した。露光してから30秒後及び1分後でのコントラストは、それぞれ以下のようにランク分けした。
AAA :△Eが2.5以上
AA :ΔEが1以上2.5未満
B :ΔEが1未満
露光部と未露光部との幅が1:1の比率のラインパターンを直接露光により描画し、現像した。硬化レジストラインが欠けたり剥がれたりせずに正常に形成されている最小幅を解像度の値とした。解像度は次の様にランク分けした。
AA :35μm以下
A :35μmを超える
透明から黒色に21段階に明度が変化しているストーファー製21段ステップタブレットを用いて露光し、現像した。現像後レジスト膜が完全に残存しているステップタブレット段数により次のようにランク分けした。
AA :レジスト膜が完全に残存しているステップタブレット段数が5段以上
A :レジスト膜が完全に残存しているステップタブレット段数が5段未満
感光性樹脂積層体にポリエチレンテレフタレートフィルム側から露光し、露光後の感光性樹脂積層体から、ポリエチレンテレフタレートフィルムおよびポリエチレンフィルムを剥がし、硬化膜の質量を測定したのち、50℃の3質量%NaOH溶液中で3時間攪拌した。次いでNaOH溶液をろ過し、ろ紙上に残存した硬化膜を乾燥し質量を測定した。攪拌前の硬化膜の質量に対する、残存した硬化膜の質量の割合を残膜率とした。
AA :残膜率が25%以上
A :残膜率が25%未満
実施例及び比較例の評価結果を表2及び3に示す。
Claims (8)
- (a)カルボン酸を含有し、酸当量が100~600であり、重量平均分子量が5,000~500,000であるアルカリ可溶性高分子:20~80質量%、(b)アクリル基を有する化合物を少なくとも1種含有するエチレン性不飽和付加重合性モノマー:5~60質量%、(c)N-アリール-α-アミノ酸化合物を含有する光重合開始剤:0.1~20質量%、(d)ロイコ染料:0.1~10質量%、及び(e)下記一般式(I):
- 前記(e)メルカプトチアジアゾール化合物が、5-メチルチオ-2-メルカプト-1,3,4-チアジアゾール、2-アミノ-5-メルカプト-1,3,4-チアジアゾール、5-メチルアミノ-2-メルカプト-1,3,4-チアジアゾール及び2,5-ジメルカプト-1,3,4-チアジアゾールからなる群より選ばれる少なくとも1種の化合物である、請求項1又は2に記載の感光性樹脂組成物。
- 前記(c)光重合開始剤が含有する前記N-アリール-α-アミノ酸化合物がN-フェニルグリシンである、請求項1又は2に記載の感光性樹脂組成物。
- 基材フィルムからなる支持体上に、請求項1又は2に記載の感光性樹脂組成物からなる感光性樹脂層を積層してなる、感光性樹脂積層体。
- 請求項6に記載の感光性樹脂積層体を基板上に積層する積層工程、
感光性樹脂積層体における感光性樹脂層を露光する露光工程、及び
感光性樹脂層の未露光部を現像除去する現像工程
を含む、レジストパターン形成方法。 - 前記露光工程を、描画パターンの直接描画により行う、請求項7に記載のレジストパターン形成方法。
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