WO2012131912A1 - 感光性樹脂組成物及びその積層体 - Google Patents
感光性樹脂組成物及びその積層体 Download PDFInfo
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- WO2012131912A1 WO2012131912A1 PCT/JP2011/057853 JP2011057853W WO2012131912A1 WO 2012131912 A1 WO2012131912 A1 WO 2012131912A1 JP 2011057853 W JP2011057853 W JP 2011057853W WO 2012131912 A1 WO2012131912 A1 WO 2012131912A1
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- photosensitive resin
- resin composition
- resist pattern
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
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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
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
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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
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
Definitions
- the present invention relates to a photosensitive resin composition that can be developed with an alkaline aqueous solution, a photosensitive resin composition laminate in which the photosensitive resin composition is laminated on a support, and a substrate using the photosensitive resin composition laminate.
- the present invention relates to a method for forming a resist pattern and a use of the resist pattern.
- lead frames manufacture of printed wiring boards, the manufacture of flexible printed wiring boards, the manufacture of lead frames for IC chip mounting (hereinafter referred to as lead frames), metal foil precision processing such as metal mask manufacturing, BGA (ball grid array) Manufacture of semiconductor packages such as CSP (chip size package), manufacture of tape substrates represented by TAB (Tape Automated Bonding) and COF (Chip On Film: a semiconductor IC mounted on a film-like fine wiring board), semiconductor Photosensitive resin that provides a resist pattern suitable for the production of bumps, suitable for the production of materials such as ITO electrodes, address electrodes, and electromagnetic wave shields in the field of flat panel displays, or as a protective mask member when processing a substrate by sandblasting Relates to the composition.
- the photolithographic method is a method in which a photosensitive resin composition is applied onto a substrate, pattern exposure is performed to polymerize and cure the exposed portion of the photosensitive resin composition, and an unexposed portion is removed with a developer to form a resist on the substrate.
- a method of forming a conductor pattern on a substrate by forming a pattern, forming a conductor pattern by etching or plating, and then peeling and removing the resist pattern from the substrate.
- a method for producing a printed wiring board using the dry film resist will be described below.
- the dry film resist has a protective layer such as a polyethylene film
- it is peeled off from the photosensitive resin layer.
- the photosensitive resin layer and the support are laminated on a substrate such as a copper-clad laminate using a laminator so that the substrate, the photosensitive resin layer, and the support are in this order.
- the exposed portion is polymerized and cured by exposing the photosensitive resin layer to ultraviolet rays containing i-line (365 nm) emitted from an ultra-high pressure mercury lamp through a photomask having a wiring pattern.
- the support made of polyethylene terephthalate or the like is peeled off.
- a non-exposed portion of the photosensitive resin layer is dissolved or dispersed and removed by a developing solution such as an aqueous solution having weak alkalinity to form a resist pattern on the substrate.
- a developing solution such as an aqueous solution having weak alkalinity
- a known etching process or pattern plating process is performed using the formed resist pattern as a protective mask.
- the resist pattern is peeled from the substrate to produce a substrate having a conductor pattern, that is, a printed wiring board.
- a semi-additive construction method is used to create a high-density wiring with a uniform conductor shape.
- the semi-additive method first, a resist pattern is formed on the seed copper thin film by the method described above. Next, plating is performed between the resist patterns to form a plated copper wiring, the resist is peeled off, and the plated copper wiring and the seed copper thin film are simultaneously etched by a technique called flash etching. Unlike the pattern plating method, the semi-additive method has a thin seed copper thin film. For this reason, there is almost no influence by etching, and a rectangular and high-density wiring can be created.
- Patent Document 1 discloses the resolution of a photosensitive resin composition containing a quaternary copolymer of methacrylic acid / methyl methacrylate / butyl acrylate / 2-ethylhexyl acrylate and tricyclodecane dimethanol dimethacrylate.
- a photosensitive resin composition containing a quaternary copolymer of methacrylic acid / methyl methacrylate / butyl acrylate / 2-ethylhexyl acrylate and tricyclodecane dimethanol dimethacrylate.
- An object of the present invention is to provide a photosensitive resin composition having particularly high resolution and adhesiveness as a resist material such as an etching resist or a plating resist, and a photosensitive resin laminate using the same.
- the present inventor has achieved high resolution by controlling the water contact angle and Young's modulus of the cured product obtained by exposing and developing the photosensitive resin composition to predetermined values. Unexpectedly, it has been discovered that high performance and excellent adhesion can be achieved, and the present invention has been completed. That is, the present invention is as follows:
- the (A) binder polymer includes a first monomer that is a carboxylic acid or carboxylic anhydride having one polymerizable unsaturated group in the molecule and a polymerizable unsaturated group in the molecule.
- a copolymer having a weight average molecular weight of 5,000 to 100,000 obtained by copolymerizing at least a second monomer that is non-acidic and has a weight average molecular weight of 5,000 to 100,000.
- the polymerizable compound is an addition polymerizable monomer having at least one terminal ethylenically unsaturated group in the molecule, and is exposed to the photosensitive resin composition with an exposure amount of 5 steps of a 21-step Stouffer step tablet. And then 1% charcoal
- the water contact angle of the photosensitive resin layer obtained after development for 2 times the minimum development time using an aqueous sodium solution (30 ° C.) exceeds 60 °, and the Young modulus is 1.5 GPa or more and 4 GPa
- the photosensitive resin composition characterized by being less than.
- a photosensitive resin laminate obtained by laminating the photosensitive resin composition according to any one of [1] to [5] on a support.
- a resist comprising a laminating step, an exposing step, and a developing step for forming a layer of the photosensitive resin composition according to any one of [1] to [5] on a substrate. Pattern formation method.
- a method for manufacturing a printed wiring board including a step of etching or plating a substrate on which a resist pattern is formed by the method for forming a resist pattern according to [7] or [8].
- a method for producing a substrate having a concavo-convex pattern comprising a step of processing a substrate on which a resist pattern has been formed by the resist pattern forming method according to [7] or [8] by sandblasting.
- a method for manufacturing a semiconductor package or bump comprising a step of etching or plating a substrate on which a resist pattern is formed by the method for forming a resist pattern according to [7] or [8].
- a method for manufacturing a lead frame comprising a step of etching or plating a substrate on which a resist pattern is formed by the method for forming a resist pattern according to [7] or [8].
- the photosensitive resin composition, the photosensitive resin laminate of the present invention, and the resist pattern obtained by the method of forming a resist pattern using these have a water contact angle of more than 60 ° and a Young modulus of 1.5 GPa or more and less than 4 GPa. Due to having predetermined characteristics, it has particularly high resolution and adhesion.
- the water contact angle of the cured product obtained by exposing and developing the photosensitive resin composition of the present invention is more than 60 °, and its Young modulus is 1.5 GPa or more and less than 4 Gpa, preferably 2 GPa or more and 4 Gpa.
- the water contact angle exceeds 60 °, the cured portion after exposure does not swell, the washout property during development is excellent, the resolution is good, and the Young's modulus is 1.5 GPa or more and 4 Gpa. If it is less than 2, the resist pattern at the time of development is excellent in standing property, and the standing property is better at 2 GPa or more and less than 4 GPa, and the standing property is further improved at 3 GPa or more and less than 4 GPa.
- the water contact angle of the cured product obtained by exposing and developing the photosensitive resin composition of the present invention must exceed 60 °.
- the upper limit is preferably 95 ° or less, more preferably 80 ° or less, still more preferably 70 ° or less, and most preferably 65 ° or less from the viewpoint of developability.
- the lower limit is preferably 62 ° or more, more preferably 63 ° or more, from the viewpoint of preventing swelling during development and improving resolution.
- the concept of controlling the water contact angle to a predetermined value does not exist in the prior art from the viewpoint of preventing swelling of the cured portion after exposure, improving washout performance during development, and improving resolution. It was.
- the Young's modulus of the cured product obtained by exposing and developing the photosensitive resin composition of the present invention must be 1.5 GPa or more and less than 4 GPa.
- the Young's modulus is 1.5 Gpa or more, the resist pattern is excellent in standing property, and when it is less than 4 Gpa, the resist pattern has excellent adhesion.
- the present invention is a discovery that the resolution and adhesion of a cured product obtained by exposing and developing a photosensitive resin composition are remarkably improved by controlling both the water contact angle and Young's modulus to predetermined values. Based on this, the effect was confirmed.
- the “water contact angle” is specifically 1.5 ⁇ l from the needle tip using an optical mirror (automatic) contact angle meter DropMaster DM500 manufactured by Kyowa Interface Science Co., Ltd. according to JIS R3257.
- the measurement target resin composition is laminated on a substrate, exposed to light, contacted with the surface of the photosensitive resin composition on the developed substrate, and measured 60 seconds after the contact of the water droplet.
- “Young Modulus” can be measured by a nanoindentation method using a nanoindenter DCM manufactured by Toyo Technica Co., Ltd.
- “Young Modulus” is a method of laminating a resin composition to be measured on a substrate, exposing and developing the surface of the photosensitive resin composition on the substrate using Nanoindenter DCM manufactured by Toyo Technica Co., Ltd. taking measurement. Measurement methods include DCM Basic Hardness, Modulus, Tip Cal, Load Control.
- the Young's modulus was the value of “Modulas At Max Load”.
- the resin for (A) binder polymer used in the present invention can be obtained by copolymerizing one or more monomers from the following two types of monomers.
- the first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. Examples include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester.
- the second monomer is a non-acidic compound having one polymerizable unsaturated group in the molecule.
- the compound is selected so as to maintain various properties such as developability of the photosensitive resin layer, resistance in etching and plating processes, and flexibility of the cured film.
- the resin for the binder polymer (A) used in the present invention includes, for example, styrene and styrene derivatives such as ⁇ -methylstyrene, p-hydroxystyrene, p-methylstyrene, p-methoxystyrene, p-chlorostyrene, benzyl (Meth) acrylate, 4-hydroxybenzyl (meth) acrylate, 4-methoxybenzyl (meth) acrylate, 4-methylbenzyl (meth) acrylate, 4-chlorobenzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meta ) Acrylate, n-propyl (meth) acrylate, cyclohexyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acryl
- the resin for the binder polymer (A) used in the present invention is prepared by mixing the first monomer and the second monomer and diluting with a solvent such as acetone, methyl ethyl ketone, or isopropanol. It is preferable to carry out the synthesis by adding a suitable amount of a polymerization initiator, for example, benzoyl peroxide or azoisobutyronitrile, and stirring with heating. In some cases, the synthesis is performed while a part of the mixture is dropped into the reaction solution. After completion of the reaction, a solvent may be further added to adjust to a desired concentration. As synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.
- a solvent such as acetone, methyl ethyl ketone, or isopropanol. It is preferable to carry out the synthesis by adding a suitable amount of a polymerization initiator, for example, benzoyl per
- the amount of carboxyl groups contained in the resin for binder polymer (A) of the present invention is preferably 100 or more and 600 or less, more preferably 250 or more and 450 or less in terms of acid equivalent.
- An acid equivalent means the mass of resin for binders which has 1 equivalent of carboxyl groups in it.
- the carboxyl group in the binder resin is necessary to give the photopolymerizable resin layer developability and releasability with respect to an aqueous alkali solution.
- the acid equivalent of the carboxyl group in the binder resin is 100 or more from the viewpoint of improving development resistance and improving resolution and adhesion, and is 600 or less from the viewpoint of improving developability and peelability.
- the acid equivalent is measured by a potentiometric titration method using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd., using 0.1 mol / L sodium hydroxide.
- the weight average molecular weight of the resin for the (A) binder polymer used in the present invention is 5,000 to 500,000.
- This weight average molecular weight is 500,000 or less from the viewpoint of improving developability and resolution, and a phenomenon in which the photosensitive resin composition oozes out from the end face of the roll when the photosensitive resin laminate is rolled up. That is, it is 5,000 or more from the viewpoint of suppressing edge fuse.
- the weight average molecular weight of the binder resin is 5,000 to 100,000, preferably 5,000 to 60,000.
- the weight average molecular weight was determined by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK (KF-807, KF-806M). , KF-806M, KF-802.5) in series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (use of calibration curve by Shodex STANDARD SM-105 manufactured by Showa Denko KK) as polystyrene conversion.
- GPC gel permeation chromatography
- the ratio of the resin for the binder polymer (A) used in the present invention to the total sum of the photosensitive resin composition (solid content, hereinafter the same) is in the range of 20 to 90% by mass, preferably 30 to 70% by mass. It is.
- the resist pattern formed by exposure and development is 20% by mass or more and 90% by mass or less from the viewpoint that resist characteristics, for example, sufficient resistance in tenting, etching, and various plating processes are provided.
- the monomer constituting the resin for the (A) binder polymer used in the present invention can be selected from a phenyl group-containing monomer or a cyclohexyl group-containing monomer. Preferred is a phenyl group-containing monomer. In order to make the water contact angle of the photosensitive resin layer after curing the photosensitive resin composition exceed 60 °, it is effective to use a phenyl group-containing monomer or a cyclohexyl group-containing monomer-containing binder polymer. Means.
- the content ratio of the phenyl group-containing monomer or cyclohexyl group-containing monomer in the binder polymer in the photosensitive resin composition is preferably 5 to 95% by mass, more preferably 10 to 85% by mass.
- the resin for the binder polymer (A) used in the present invention include ⁇ -methylstyrene, p-hydroxystyrene, p-methylstyrene, p-methoxystyrene, p-chlorostyrene, benzyl (meth) acrylate, 4 -Hydroxybenzyl (meth) acrylate, 4-methoxybenzyl (meth) acrylate, 4-methylbenzyl (meth) acrylate, 4-chlorobenzyl (meth) acrylate, and cyclohexyl (meth) acrylate are preferred.
- the photopolymerizable compound used in the present invention is an addition polymerizable monomer having at least one terminal ethylenically unsaturated group.
- the addition polymerizable monomer (B) that is a photopolymerizable compound used in the photosensitive resin composition of the present invention include 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxy Hexaethylene glycol acrylate, reaction product of a half ester compound of phthalic anhydride and 2-hydroxypropyl acrylate and propylene oxide (manufactured by Nippon Shokubai Chemical Co., Ltd., trade name OE-A 200), 4-normal octylphenoxypentapropylene glycol acrylate, 2,2-bis [ ⁇ 4- (meth) acryloxypolyethoxy ⁇ phenyl] propane, 2,2-bis ⁇ (4-acryloxypolyethoxy) cyclohe
- the amount of the (B) addition polymerizable monomer contained in the photosensitive resin composition of the present invention is in the range of 5 to 75% by mass with respect to the entire photosensitive resin composition, and more preferably in the range of 15 to 70. % By mass. This amount is 5% by mass or more from the viewpoint of suppressing poor curing and a delay in development time, and is 75% by mass or less from the viewpoint of suppressing cold flow and delayed peeling of the cured resist.
- the photopolymerizable compound (B) used in the present invention has an ethylenically unsaturated bond concentration of the photosensitive resin composition of 0.01 mol / 100 g to 0.1 mol in order to make the Young modulus 2 GPa or more and less than 4 GPa. / 100g is preferable.
- a photopolymerizable compound having 3 or more double bonds or a photopolymerizable compound having a molecular weight of 600 or less is combined with a binder polymer and a polymerizable compound. It is an effective means to make it 20 mass% or less of the total mass part.
- a 7: 3 mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Mitsubishi M-306, manufactured by Toagosei Co., Ltd.), triacrylate with an average of 3 moles of ethylene oxide added to trimethylolpropane (Shin Nakamura Chemical) A-TMPT-3EO (product name), urethanized product of hexamethylene diisocyanate and polypropylene glycol monomethacrylate, tricyclodecane dimethanol dimethacrylate (NK ester DCP, product name, Shin-Nakamura Chemical Co., Ltd.), bisphenol- Polyethylene glycol dimethacrylate (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd., product name) having an average of 2 moles of ethylene oxide added to both ends of A.
- the photopolymerizable compound (B) used in the present invention in order to make the water contact angle of the photosensitive resin layer after curing the photosensitive resin composition exceed 60 °, the number of double bonds is one. It is an effective means to make the content of the photopolymerizable compound 10% by mass or less of the total mass part of the binder polymer and the polymerizable compound.
- the photopolymerizable compound is represented by the following general formula (II):
- R 1 and R 2 are each independently a hydrogen atom or a methyl group, and A and B represent an alkylene group having 2 to 6 carbon atoms, which may be the same or different.
- the repeating unit of-(AO)-and-(BO)- may be a block structure or a random structure, and m1, m2, m3 and m4 are 0 or a positive integer. The total of these is 2 to 40.
- R 3 and R 4 each independently represents a hydrogen atom or a methyl group
- a and B represent an alkylene group having 2 to 6 carbon atoms, which may be the same or different. If they are different, the repeating unit of-(AO)-and-(BO)-may be a block structure or a random structure, and m5, m6, m7 and m8 are 0 or a positive integer. And the sum of these is 0 to 40
- R 5 is a halogen atom or an alkyl group having 1 to 3 carbon atoms, and n is 0 to 14.
- the content of the photopolymerizable compound (B) represented by the general formula (II) or (III) is preferably 10% by mass or more, and more preferably 20% by mass or more, based on the total mass part of the binder polymer and the polymerizable compound.
- X, Y and Z each independently represent a group selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms and an alkoxy group, and a halogen group, and p, q and r Are each independently an integer of 1 to 5.
- ⁇ Is a preferred embodiment from the viewpoint of high resolution.
- the covalent bond connecting two lophine groups is 1,1′-, 1,2′-, 1,4′-, 2,2′-, although it is in the 2,4′- or 4,4′-position, a compound in the 1,2′-position is preferred.
- 2,4,5-triarylimidazole dimer examples include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis- ( m-methoxyphenyl) imidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, etc., and in particular, 2- (o-chlorophenyl) -4,5-diphenylimidazole Dimers are preferred.
- the ratio is 0.1-20. Mass% is preferred. From the viewpoint of resolution and adhesiveness, it is 0.1% by mass or more, and from the viewpoint of development aggregation, it is 20% by mass or less. A more preferable range is 0.5 to 15% by mass, and a further preferable range is 1 to 10% by mass.
- photopolymerization initiator (C) used in the present invention a system in which 2,4,5-triarylimidazole dimer represented by the general formula (I) and p-aminophenyl ketone are used in combination is used. preferable.
- p-aminophenyl ketone examples include p-aminobenzophenone, p-butylaminoacetophenone, p-dimethylaminoacetophenone, p-dimethylaminobenzophenone, p, p'-bis (ethylamino) benzophenone, p, p'- Bis (dimethylamino) benzophenone [Michler's ketone], p, p′-bis (diethylamino) benzophenone, and p, p′-bis (dibutylamino) benzophenone.
- a combination with a pyrazoline compound such as 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline is also a preferred embodiment.
- a pyrazoline compound such as 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline is also a preferred embodiment.
- other photopolymerization initiators can be used in combination.
- the photopolymerization initiator is a compound that is activated by various actinic rays such as ultraviolet rays and starts polymerization.
- photopolymerization initiators include quinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, aromatic ketones such as benzophenone, benzoin and benzoin ethers such as benzoin methyl ether and benzoin ethyl ether. , Acridine compounds such as 9-phenylacridine, benzyldimethyl ketal, benzyldiethyl ketal.
- thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and tertiary amine compounds such as dimethylaminobenzoic acid alkyl ester compounds.
- oxime esters such as 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime.
- N-aryl- ⁇ -amino acid compounds can also be used, and among these, N-phenylglycine is particularly preferred.
- the proportion of the (C) photopolymerization initiator contained in the photosensitive resin composition of the present invention is 0.01 to 30% by mass. If this ratio is less than 0.01% by mass, sufficient sensitivity cannot be obtained. On the other hand, if this ratio exceeds 30% by mass, fogging 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 0.1 to 15% by mass, and further preferably 0.1 to 10% by mass.
- a leuco dye can be contained in order to express the contrast after exposure (discrimination between an exposed part and an unexposed part).
- the content is preferably 0.1 to 10% by mass.
- leuco dyes include tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet], tris (4-dimethylamino-2-methylphenyl) methane [leucomalachite green], and fluorane dye. It is done. Among these, when leuco crystal violet is used, the contrast is good and preferable.
- the leuco dye and the halogen compound are used in combination in the photosensitive resin composition.
- the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2 , 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, and halogenated triazine compounds.
- halogenated triazine compound examples include 2,4,6-tris (trichloromethyl) -s-triazine and 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine.
- the content of the halogen compound in the photosensitive resin composition is preferably 0.01 to 10% by mass.
- coloring substances examples include fuchsin, phthalocyanine green, auramine base, paramadienta, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, Malachite Green (Eisen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), Basic Blue 20 and Diamond Green (Eizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.) can be used.
- the addition amount is preferably 0.001 to 1% by mass in the photosensitive resin composition.
- a content of 0.001% by mass or more has an effect of improving handleability, and a content of 1% by mass or less has an effect of maintaining storage stability.
- a combination of tribromomethylphenylsulfone and a leuco dye or a combination of a triazine compound and a leuco dye is useful.
- the photosensitive resin composition is selected from the group consisting of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles. It is preferable to contain at least one compound.
- radical polymerization inhibitors examples include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2 Examples include '-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine.
- benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, and bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzo.
- examples include triazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole.
- carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl). Examples include aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole.
- the total amount of radical polymerization inhibitors, benzotriazoles, or carboxybenzotriazoles is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass in the photosensitive resin composition. is there. This amount is preferably 0.01% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin composition, and more preferably 3% by mass or less from the viewpoint of maintaining sensitivity.
- the photosensitive resin composition of the present invention may contain a plasticizer as necessary.
- plasticizers include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, and polyoxyethylene monoethyl.
- Glycol esters such as ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, citric acid Tributyl, triethyl citrate, acetyl triethyl citrate, acetyl tri-n-propyl citrate, tri-n-acetyl citrate Chill, and the like.
- the amount when the plasticizer is contained is preferably 5 to 50% by mass, more preferably 5 to 30% by mass in the photosensitive resin composition. 5 mass% or more is preferable from the viewpoint of suppressing delay in development time and imparting flexibility to the cured film, and 50 mass% or less is preferable from the viewpoint of suppressing insufficient curing and cold flow.
- the photosensitive resin composition of the present invention may be a photosensitive resin composition preparation liquid to which a solvent is added.
- Suitable solvents include ketones represented by methyl ethyl ketone (MEK), or alcohols such as methanol, ethanol, isopropyl alcohol. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of the photosensitive resin composition preparation liquid is 500 to 4,000 mPa ⁇ sec at 25 ° C.
- the photosensitive resin laminate of the present invention comprises a photosensitive resin layer and a support that supports the layer. If necessary, the photosensitive resin laminate may have a protective layer on the surface opposite to the support of the photosensitive resin layer. Good.
- the support used here is preferably a transparent one that transmits light emitted from the exposure light source. Examples of such a support include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film.
- haze is preferably 5 or less.
- a thinner film is more advantageous in terms of image formation and economy, but a film having a thickness of 10 to 30 ⁇ m is preferably used because of the need to maintain the strength.
- an important characteristic of the protective layer used in the photosensitive resin laminate is that the protective layer is sufficiently smaller than the support and can be easily peeled with respect to the adhesion with the photosensitive resin layer.
- a polyethylene film or a polypropylene film can be preferably used as the protective layer.
- a film having excellent peelability described 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 is preferably 5 to 100 ⁇ m, more preferably 5 to 50 ⁇ m. As the thickness is thinner, the resolution is improved, and as the thickness is increased, the film strength is improved. Therefore, the thickness can be appropriately selected according to the application.
- a conventionally known method can be adopted as a method for preparing the photosensitive resin laminate of the present invention by sequentially laminating a support, a photosensitive resin layer, and if necessary, a protective layer.
- the photosensitive resin composition used for the photosensitive resin layer is made into the above-mentioned photosensitive resin composition preparation liquid, first applied onto a support using a bar coater or a roll coater, and dried, and then on the support.
- a photosensitive resin layer made of the photosensitive resin composition is laminated on the substrate. Then, if necessary, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.
- a resist pattern using the photosensitive resin laminate of the present invention can be formed by a process including a laminating process, an exposing process, and a developing process.
- An example of a specific method is shown.
- a laminating process is performed using a laminator.
- 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 on only one surface of the substrate surface, or may be laminated on both surfaces as necessary.
- the heating temperature at this time is generally 40 to 160 ° C.
- substrate of the obtained resist pattern improves by performing this thermocompression bonding twice or more.
- a two-stage laminator provided with two rolls may be used for pressure bonding, or it may be repeatedly pressed through the roll several times.
- an exposure process is performed using an exposure machine. If necessary, the support is peeled off and exposed to active light through a photomask.
- the exposure amount is determined from the light source illuminance and the exposure time. You may measure using a photometer.
- a maskless exposure method may be used.
- maskless exposure exposure is performed directly on a substrate by a drawing apparatus without using a photomask.
- the light source a semiconductor laser having a wavelength of 350 to 410 nm, an ultrahigh pressure mercury lamp, or the like is used.
- the drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the illuminance of the exposure light source and the moving speed of the substrate.
- a developing process is performed using a developing device. After exposure, if there is a support on the photosensitive resin layer, it is removed. Subsequently, the unexposed portion is developed and removed using a developer composed of an alkaline aqueous solution to obtain a resist image.
- an aqueous solution of Na 2 CO 3 or K 2 CO 3 is preferable. These are selected according to the characteristics of the photosensitive resin layer, but an aqueous Na 2 CO 3 solution having a concentration of 0.2 to 2% by mass is generally used.
- a surface active agent, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution.
- the temperature of the developer in the development step is preferably maintained at a constant temperature in the range of 20 to 40 ° C.
- a heating step at 100 to 300 ° C. can be further performed in some cases.
- chemical resistance can be further improved.
- a heating furnace of a hot air, infrared ray, far infrared ray, or the like can be used.
- the method for producing a printed wiring board of the present invention is performed by performing the following steps after forming a resist pattern on a copper-clad laminate or flexible substrate as a substrate by the above-described resist pattern forming method. First, a step of forming a conductor pattern on the copper surface of the substrate exposed by development using a known method such as an etching method or a plating method is performed. Thereafter, the resist pattern is peeled off from the substrate with an aqueous solution having alkalinity stronger than that of the developer to obtain a desired printed wiring board.
- stripping solution an aqueous solution of NaOH or KOH having a concentration of 2 to 5% by mass is generally used. It is possible to add a small amount of a water-soluble solvent to the stripping solution.
- the temperature of the stripping solution in the stripping step is preferably in the range of 40 to 70 ° C.
- the lead frame manufacturing method of the present invention is performed by performing the following steps after forming a resist pattern on a metal plate such as copper, copper alloy, iron-based alloy or the like as a substrate by the above-described resist pattern forming method. First, a step of etching the substrate exposed by development to form a conductor pattern is performed. Then, the peeling process which peels a resist pattern with the method similar to the manufacturing method of the above-mentioned printed wiring board is performed, and a desired lead frame is obtained.
- a semiconductor package is manufactured by mounting a chip on which circuit formation as an LSI has been completed by the following steps. First, copper sulfate plating is performed on the exposed portion of the base metal in the resist pattern-attached base material obtained by development to form a conductor pattern. Thereafter, a peeling process for peeling the resist pattern by the same method as the printed wiring board manufacturing method described above is performed, and further, etching is performed to remove a thin metal layer for portions other than the columnar plating, and the chip is formed. A desired semiconductor package is obtained by mounting.
- the bump manufacturing method of the present invention is performed for mounting a chip on which circuit formation as an LSI has been completed, and bumps are manufactured by the following steps. First, copper sulfate plating is performed on the exposed portion of the base metal in the resist pattern-attached base material obtained by development to form a conductor pattern. Then, a desired bump is formed by performing a peeling process for peeling the resist pattern by the same method as the above-described printed wiring board manufacturing method, and further removing a thin metal layer by etching other than the plating. Get.
- the resist pattern can be used as a protective mask member when the substrate is processed by the sandblasting method.
- the substrate include glass, silicon wafer, amorphous silicon, polycrystalline silicon, ceramic, sapphire, and metal material.
- a resist pattern is formed on the substrate such as glass by the same method as the resist pattern forming method described above. After that, a blasting material is sprayed from the formed resist pattern to be cut to a desired depth, and a resist pattern portion remaining on the substrate is removed from the substrate with an alkaline stripping solution or the like, and then the substrate is processed.
- the substrate can have a fine concavo-convex pattern.
- blasting material used in the sandblasting process known materials are used. For example, fine particles of about 2 to 100 ⁇ m such as SiC, SiO 2 , Al 2 O 3 , CaCO 3 , ZrO, glass, stainless steel and the like are used.
- the above-described method for producing a substrate having a concavo-convex pattern by the sandblasting method can be used for the production of flat panel display partition walls, organic EL glass cap processing, silicon wafer drilling processing, ceramic pinning processing, and the like. Further, it can be used for the production of a ferroelectric film and a metal material layer electrode selected from the group consisting of noble metals, noble metal alloys, refractory metals, and refractory metal compounds.
- Examples 1 to 4, Comparative Examples 1 to 5 First, a method for producing samples for evaluation of Examples and Comparative Examples will be described, and then an evaluation method and evaluation results for the obtained samples will be shown.
- Evaluation samples in Examples and Comparative Examples were produced as follows.
- ⁇ Preparation of photosensitive resin laminate> A photosensitive resin composition mixed solution obtained by thoroughly stirring and mixing a photosensitive resin composition and a solvent having the composition shown in the following Table 1 (however, the numbers of each component indicate the blending amount (part by mass) as a solid content).
- a 16 ⁇ m thick polyethylene terephthalate film as a support was uniformly coated using a bar coater and dried in a dryer at 95 ° C. for 2.5 minutes to form a photosensitive resin layer.
- the thickness of the photosensitive resin layer was 25 ⁇ m.
- a 21 ⁇ 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.
- Table 2 shows the names of the material components B-1 to D-2 in the photosensitive resin composition preparation liquid represented by abbreviations in Table 1.
- ⁇ Board surface preparation> As a substrate for resolution evaluation, a substrate for contact angle evaluation, and a substrate for elastic modulus evaluation, the surface of a 0.4 mm thick copper clad laminate on which 35 ⁇ m rolled copper foil is laminated is (A) jet scrub polished at a spray pressure of 0.20 MPa. (Nippon Carlit Co., Ltd., Sac Random R (registered trademark) # 220) was prepared.
- the substrate for resolution evaluation was exposed with a super high pressure mercury lamp super high pressure mercury lamp (OMW Seisakusho, HMW-201KB) using a chromium glass photomask.
- the contact angle evaluation substrate and the elastic modulus evaluation substrate were exposed without using a mask.
- Each evaluation method is as follows. (1) Resolution The substrate for resolution evaluation that had passed 15 minutes after the lamination was exposed through a line pattern mask (chrome glass photomask) in which the width of the exposed area and the unexposed area was 1: 1. Development was performed with a development time twice as long as the minimum development time, and the minimum mask line width in which a cured resist line was normally formed was ranked as a resolution value as follows: A: Resolution value is 8 ⁇ m or less; ⁇ : Resolution value exceeds 8 ⁇ m and 10 ⁇ m or less; X: The value of resolution exceeds 10 ⁇ m.
- Adhesiveness The substrate for resolution evaluation that had passed 15 minutes after lamination was exposed through a pattern mask (chrome glass photomask) composed of independent lines of various widths. Development was performed with a development time twice as long as the minimum development time, and the minimum mask line width in which a cured resist line was normally formed was ranked as an adhesion value as follows: ⁇ : Adhesion value is 10 ⁇ m or less; ⁇ : Adhesion value exceeds 10 ⁇ m
- the present invention relates to the manufacture of printed wiring boards, the manufacture of lead frames for mounting IC chips, the precision processing of metal foil such as the manufacture of metal masks, the manufacture of packages such as BGA and CSP, the manufacture of tape substrates such as COF and TAB, the manufacture of semiconductor bumps
- metal foil such as the manufacture of metal masks
- packages such as BGA and CSP
- tape substrates such as COF and TAB
- semiconductor bumps In addition, it can be used for manufacturing a partition of a flat panel display such as an ITO electrode, an address electrode, and an electromagnetic wave shield, and a method for manufacturing a substrate having a concavo-convex pattern by a sandblasting method.
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Abstract
Description
さらに詳しくは、プリント配線板の製造、フレキシブルプリント配線板の製造、ICチップ搭載用リードフレーム(以下、リードフレームという)の製造、メタルマスク製造などの金属箔精密加工、BGA(ボールグリッドアレイ)やCSP(チップサイズパッケージ)等の半導体パッケージ製造、TAB(Tape Automated Bonding)やCOF(Chip On Film:半導体ICをフィルム状の微細配線板上に搭載したもの)に代表されるテープ基板の製造、半導体バンプの製造、フラットパネルディスプレイ分野におけるITO電極、アドレス電極、電磁波シールドなどの部材の製造に好適な、又はサンドブラスト工法によって基材を加工する際の保護マスク部材として好適なレジストパターンを与える感光性樹脂組成物に関する。
まず、ドライフィルムレジストがポリエチレンフィルム等の保護層を有する場合には、感光性樹脂層からこれを剥離する。次いで、ラミネーターを用いて銅張り積層板等の基板上に、該基板、感光性樹脂層、支持体の順序になるよう、感光性樹脂層及び支持体を積層する。次いで、配線パターンを有するフォトマスクを介して、該感光性樹脂層を超高圧水銀灯が発するi線(365nm)を含む紫外線で露光することによって、露光部分を重合硬化させる。次いでポリエチレンテレフタレート等から成る支持体を剥離する。次いで、弱アルカリ性を有する水溶液等の現像液により感光性樹脂層の未露光部分を溶解又は分散除去して、基板上にレジストパターンを形成させる。次いで、形成されたレジストパターンを保護マスクとして公知のエッチング処理又はパターンめっき処理を行う。最後に、該レジストパターンを基板から剥離して導体パターンを有する基板、すなわちプリント配線板を製造する。
以下の特許文献1には、メタクリル酸/メチルメタクリレート/ブチルアクリレート/2-エチルヘキシルアクリレートの四元共重合体とトリシクロデカンジメタノールジメタクリレートを含有する感光性樹脂組成物の解像度について開示されているが、解像度と密着に関しては現状に十分対応しているものとは言えなかった。
本発明の感光性樹脂組成物を露光・現像して得られた硬化物の水接触角が60°超過であり、かつ、そのヤングモジュラスが1.5GPa以上、4Gpa未満、好ましくは2GPa以上、4Gpa未満、より好ましくは3GPa以上、4Gpa未満であることが、高解像度と優れた密着性を有するレジストパターンを取得するために必要である。
第一の単量体は、分子中に重合性不飽和基を一個有するカルボン酸又は酸無水物である。例えば、(メタ)アクリル酸、フマル酸、ケイ皮酸、クロトン酸、イタコン酸、マレイン酸無水物、マレイン酸半エステルが挙げられる。
本発明に用いられる(A)バインダーポリマー用の樹脂は、例えばスチレン、及びスチレン誘導体、例えば、α-メチルスチレン、p-ヒドロキシスチレン、p-メチルスチレン、p-メトキシスチレン、p-クロロスチレン、ベンジル(メタ)アクリレート、4-ヒドロキシベンジル(メタ)アクリレート、4-メトキシベンジル(メタ)アクリレート、4-メチルベンジル(メタ)アクリレート、4-クロロベンジル(メタ)アクリレート、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、n-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、ポリエチレングリコールモノ(メタ)アクリレート、ポリプロピレングリコールモノ(メタ)アクリレート、(メタ)アクリルアミド、N-メチロールアクリルアミド、N-ブトキシメチルアクリルアミド、(メタ)アクリロニトリル、(メタ)アクリル酸グリシジル等が挙げられ、それぞれ単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
本発明に用いられる(A)バインダーポリマー用の樹脂としては、例えば、α-メチルスチレン、p-ヒドロキシスチレン、p-メチルスチレン、p-メトキシスチレン、p-クロロスチレン、ベンジル(メタ)アクリレート、4-ヒドロキシベンジル(メタ)アクリレート、4-メトキシベンジル(メタ)アクリレート、4-メチルベンジル(メタ)アクリレート、4-クロロベンジル(メタ)アクリレート、シクロヘキシル(メタ)アクリレートが好ましい。
D=(E1×F1×100)/(Mw1×G)+(E2×F2×100)/(Mw2×G)+・・・・+(En×Fn×100)/(Mwn×G)
D:感光性樹脂組成物100gに対するエチレン不飽和基の濃度(mol/100g)
E1・・・En:配合量
F1・・・Fn:重合末端数
Mw1・・・Mwn:光重合性化合物の重量平均分子量
n:配合する光重合性化合物の数
G:感光性樹脂組成物の総重量
また感光性樹脂組成物の硬化後の感光性樹脂層の水接触角を60°超過にするために(B)光重合性化合物は、下記一般式(II):
本発明に用いられる(C)光重合開始剤として、下記一般式(I):
また、上記で示された化合物以外に、他の光重合開始剤との併用も可能である。ここでの光重合開始剤とは、各種の活性光線、例えば紫外線等により活性化され、重合を開始する化合物である。
また、オキシムエステル類、例えば、1-フェニル-1,2-プロパンジオン-2-O-ベンゾイルオキシム、1-フェニル-1,2-プロパンジオン-2-(O-エトキシカルボニル)オキシムがある。また、N-アリール-α-アミノ酸化合物も用いることも可能であり、これらの中では、N-フェニルグリシンが特に好ましい。
本発明の感光性樹脂組成物中には、露光後のコントラスト(露光部と未露光部の識別)を発現させる目的で、ロイコ染料を含有することができる。ロイコ染料を含有する場合の含有量は、0.1~10質量%が好ましい。このようなロイコ染料としては、トリス(4-ジメチルアミノ-2-メチルフェニル)メタン[ロイコクリスタルバイオレット]、トリス(4-ジメチルアミノ-2-メチルフェニル)メタン[ロイコマラカイトグリーン]、フルオラン染料が挙げられる。中でも、ロイコクリスタルバイオレットを用いた場合、コントラストが良好であり好ましい。
ハロゲン化合物としては、例えば、臭化アミル、臭化イソアミル、臭化イソブチレン、臭化エチレン、臭化ジフェニルメチル、臭化ベンザル、臭化メチレン、トリブロモメチルフェニルスルホン、四臭化炭素、トリス(2,3-ジブロモプロピル)ホスフェート、トリクロロアセトアミド、ヨウ化アミル、ヨウ化イソブチル、1,1,1-トリクロロ-2,2-ビス(p-クロロフェニル)エタン、ヘキサクロロエタン、ハロゲン化トリアジン化合物が挙げられる。該ハロゲン化トリアジン化合物としては、2,4,6-トリス(トリクロロメチル)-s-トリアジン、2-(4-メトキシフェニル)-4,6-ビス(トリクロロメチル)-s-トリアジンが挙げられる。
感光性樹脂組成物の取扱い性を向上させるために、前述のロイコ染料以外に下記着色物質を入れることも可能である。このような着色物質としては、例えばフクシン、フタロシアニングリーン、オーラミン塩基、パラマジエンタ、クリスタルバイオレット、メチルオレンジ、ナイルブルー2B、ビクトリアブルー、マラカイトグリーン(保土ヶ谷化学(株)製 アイゼン(登録商標) MALACHITE GREEN)、ベイシックブルー20、ダイアモンドグリーン(保土ヶ谷化学(株)製 アイゼン(登録商標) DIAMOND GREEN GH)が挙げられる。
中でも、トリブロモメチルフェニルスルフォンとロイコ染料との組み合わせ又はトリアジン化合物とロイコ染料との組み合わせが有用である。
さらに、本発明の感光性樹脂組成物の熱安定性、保存安定性を向上させるために、感光性樹脂組成物にラジカル重合禁止剤、ベンゾトリアゾール類、及びカルボキシベンゾトリアゾール類から成る群から選ばれる少なくとも1種以上の化合物を含有させることが好ましい。
本発明の感光性樹脂組成物は、溶媒を添加した感光性樹脂組成物調合液としてもよい。好適な溶媒としては、メチルエチルケトン(MEK)に代表されるケトン類、又はメタノール、エタノール、イソプロピルアルコールなどのアルコール類が挙げられる。感光性樹脂組成物調合液の粘度が25℃で500~4,000mPa・secとなるように、溶媒を感光性樹脂組成物に添加することが好ましい。
本発明の感光性樹脂積層体は、感光性樹脂層とその層を支持する支持体から成るが、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いてもよい。
ここで用いられる支持体としては、露光光源から放射される光を透過する透明なものが望ましい。このような支持体としては、ポリエチレンテレフタレートフィルム、ポリビニルアルコールフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリ塩化ビニリデンフィルム、塩化ビニリデン共重合フィルム、ポリメタクリル酸メチル共重合体フィルム、ポリスチレンフィルム、ポリアクリロニトリルフィルム、スチレン共重合体フィルム、ポリアミドフィルム、セルロース誘導体フィルムなどが挙げられる。これらのフィルムは、必要に応じ延伸されたものも使用可能である。ヘーズ(曇り度)は5以下のものが好ましい。フィルムの厚みは、薄い方が画像形成性及び経済性の面で有利であるが、強度を維持する必要等から、10~30μmのものが好ましく用いられる。
また、特開昭59-202457号公報に示された剥離性の優れたフィルムを用いることができる。保護層の膜厚は10~100μmが好ましく、10~50μmがより好ましい。
本発明の感光性樹脂積層体を用いたレジストパターンは、ラミネート工程、露光工程、及び現像工程を含む工程によって形成することができる。具体的な方法の一例を示す。
まず、ラミネーターを用いてラミネート工程を行う。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ラミネートする。この場合、感光性樹脂層は基板表面の片面だけにラミネートしてもよいし、必要に応じて両面にラミネートしてもよい。この時の加熱温度は一般的に40~160℃である。また、該加熱圧着を二回以上行うことにより、得られるレジストパターンの基板に対する密着性が向上する。この時、圧着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よいし、何回か繰り返してロールに通し圧着してもよい。
露光工程においては、マスクレス露光方法を用いてもよい。マスクレス露光はフォトマスクを使用せず基板上に直接描画装置によって露光する。光源としては波長350~410nmの半導体レーザーや超高圧水銀灯などが用いられる。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、露光光源の照度および基板の移動速度によって決定される。
上述の工程によってレジストパターンが得られるが、場合によっては、さらに100~300℃の加熱工程を行うこともできる。この加熱工程を実施することにより、更なる耐薬品性向上が可能となる。加熱には、熱風、赤外線、遠赤外線等の方式の加熱炉を用いることができる。
本発明のプリント配線板の製造方法は、基板として銅張り積層板又はフレキシブル基板に上述のレジストパターン形成方法によってレジストパターンを形成した後に、以下の工程を経ることで行われる。
まず、現像により露出した基板の銅面にエッチング法又はめっき法等の既知の方法を用いて導体パターンを形成する工程を行う。
その後、レジストパターンを、現像液よりも強いアルカリ性を有する水溶液により基板から剥離する剥離工程を行って所望のプリント配線板を得る。剥離用のアルカリ水溶液(以下、「剥離液」ともいう。)についても特に制限はないが、2~5質量%の濃度のNaOH又はKOHの水溶液が一般的に用いられる。剥離液にも、少量の水溶性溶媒を加えることは可能である。なお、剥離工程における該剥離液の温度は、40~70℃の範囲であることが好ましい。
本発明のリードフレームの製造方法は、基板として銅、銅合金、鉄系合金等の金属板に前述のレジストパターン形成方法によってレジストパターンを形成した後に、以下の工程を経ることで行われる。
まず、現像により露出した基板をエッチングして導体パターンを形成する工程を行う。その後、レジストパターンを上述のプリント配線板の製造方法と同様の方法で剥離する剥離工程を行って、所望のリードフレームを得る。
本発明の半導体パッケージの製造方法においては、LSIとしての回路形成が終了したチップを以下の工程により実装することにより半導体パッケージを製造する。
まず、現像により得られるレジストパターン付着基材における基材の金属が露出した部分に硫酸銅めっきを施して、導体パターンを形成する。その後、レジストパターンを上述のプリント配線板の製造方法と同様の方法で剥離する剥離工程を行って、更に、柱状めっき以外の部分については薄い金属層を除去するためにエッチングを行い、上記チップを実装し、所望の半導体パッケージを得る。
本発明のバンプの製造方法は、LSIとしての回路形成が終了したチップを実装するために行われ、下記工程によりバンプが製造される。
まず、現像により得られるレジストパターン付着基材における基材の金属が露出した部分に硫酸銅めっきを施して、導体パターンを形成する。その後、レジストパターンを上述のプリント配線板の製造方法と同様の方法で剥離する剥離工程を行って、更に、めっき以外の部分の薄い金属層をエッチングにより除去する工程を行うことにより、所望のバンプを得る。
前述のレジストパターン形成方法によって、レジストパターンをサンドブラスト工法により基板に加工を施す時の保護マスク部材として使用することができる。
基板としては、ガラス、シリコンウエハー、アモルファスシリコン、多結晶シリコン、セラミック、サファイア、金属材料などが挙げられる。これらガラス等の基板上に、前述のレジストパターン形成方法と同様の方法によって、レジストパターンを形成する。その後、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、基板上に残存したレジストパターン部分をアルカリ剥離液等で基板から除去する剥離工程を経て、基板上に微細な凹凸パターンを有する基材とすることができる。前記サンドブラスト処理工程に用いるブラスト材は公知のものが用いられ、例えばSiC、SiO2、Al2O3、CaCO3、ZrO、ガラス、ステンレス等の2~100μm程度の微粒子が用いられる。
(実施例1~4、比較例1~5)
最初に実施例及び比較例の評価用サンプルの作製方法を説明し、次いで、得られたサンプルについての評価方法およびその評価結果を示す。
実施例及び比較例における評価用サンプルは次の様にして作製した。
<感光性樹脂積層体の作製>
下記表1に示す組成(但し、各成分の数字は固形分としての配合量(質量部)を示す。)の感光性樹脂組成物及び溶媒をよく攪拌、混合して感光性樹脂組成物調合液とし、支持体として16μm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2.5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25μm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21μm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。
解像度評価用基板、接触角評価用基板、及び弾性率評価用基板としては、35μm圧延銅箔を積層した0.4mm厚の銅張積層板表面を(A)スプレー圧0.20MPaでジェットスクラブ研磨(日本カーリット(株)製、サクランダムR(登録商標)#220)したものを用意した。
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、整面して60℃に予熱した銅張積層板に該感光性樹脂積層体をホットロールラミネーター(旭化成エレクトロニクス(株)製、AL-70)を用いてロール温度105℃でラミネートした。エアー圧力は0.35MPaとし、ラミネート速度は1.5m/min.とした。
解像度評価用基板はクロムガラスフォトマスクを用いて、超高圧水銀ランプ超高圧水銀ランプ(オーク製作所製、HMW-201KB)により露光した。接触角評価用基板、及び弾性率評価用基板は、マスクを使用せず露光した。
ポリエチレンテレフタレートフィルムを剥離した後、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した最も少ない時間を最小現像時間とした。
各評価手法は、以下の通りである。
(1)解像度
ラミネート後15分経過した解像度評価用基板を、露光部と未露光部の幅が1:1の比率のラインパターンマスク(クロムガラスフォトマスク)を通して露光した。最小現像時間の2倍の現像時間で現像し、硬化レジストラインが正常に形成されている最小マスクライン幅を解像度の値として以下のようにランク分けした:
◎:解像度の値が8μm以下;
○:解像度の値が8μmを超え、10μm以下;
×:解像度の値が10μmを超える。
ラミネート後15分経過した解像度評価用基板を、各種の幅の独立したラインから成るパターンマスク(クロムガラスフォトマスク)を通して露光した。最小現像時間の2倍の現像時間で現像し、硬化レジストラインが正常に形成されている最小マスクライン幅を密着性の値として以下のようにランク分けした:
○:密着性の値が10μm以下;
×:密着性の値が10μmを超える
ラミネート後15分経過した解像度評価用基板を、マスクなしで露光した。露光は解像度評価時の最小解像度の露光量で行った。最小現像時間の2倍の現像時間で現像し、接触角測定用の基板を得、接触角を測定した。
ラミネート後15分経過した解像度評価用基板を、マスクなしで露光した。露光は解像度評価時の最小解像度の露光量で行った。最小現像時間の2倍の現像時間で現像しヤングモジュラス測定用の基板を得、ヤングモジュラス(弾性率)を測定した。
実施例1~4、及び比較例1~5の評価結果を以下の表1に示す。
比較例1~5においては、バインダーポリマー用樹脂、及び光重合性化合物の選択並びにそれらの配合比率の変化に依存して、水接触角、及びヤングモジュラスが本願発明の範囲外になった結果、解像度または密着性が優れてないことが分かる。
Claims (14)
- (A)バインダーポリマー:20~90重量%、(B)光重合性化合物:5~75重量%、及び(C)光重合開始剤:0.01~30重量%を含有する感光性樹脂組成物であって、前記(A)バインダーポリマーは、分子中に重合性不飽和基を1個有するカルボン酸又はカルボン酸無水物である第一単量体と分子中に重合性不飽和基を1個有し、かつ非酸性である第二単量体とを少なくとも共重合することにより得られた重量平均分子量5,000~100,000である共重合体であり、前記(B)光重合性化合物は、分子中に少なくとも一つの末端エチレン性不飽和基を有する付加重合性モノマーであり、かつ、前記感光性樹脂組成物に、21段ストウファーステップタブレットの5段の露光量で露光を行い、次いで1質量%炭酸ナトリウム水溶液(30℃)を用いて最小現像時間の2倍の時間に亘り現像を行った後に得られた感光性樹脂層の水接触角が60°超過、かつ、ヤングモジュラスが1.5GPa以上4GPa未満であることを特徴とする感光性樹脂組成物。
- 前記(A)バインダーポリマーが、フェニル基含有共重合体又はシクロヘキシル基含有共重合体である、請求項1に記載の感光性樹脂組成物。
- 前記感光性樹脂層のヤングモジュラスが2Gpa以上4GPa未満である、請求項1に記載の感光性樹脂組成物。
- 前記感光性樹脂層のヤングモジュラスが3Gpa以上4GPa未満である、請求項3に記載の感光性樹脂組成物。
- 前記(C)光重合性開始剤が、2,4,5-トリアリールイミダゾール二量体を含有する、請求項1に記載の感光性樹脂組成物。
- 請求項1~5のいずれか1項に記載の感光性樹脂組成物を支持体上に積層して成る、感光性樹脂積層体。
- 請求項1~5のいずれか1項に記載の感光性樹脂組成物の層を基板上に形成するラミネート工程、露光工程、及び現像工程を含むことを特徴とする、レジストパターンの形成方法。
- 前記露光工程において、感光性樹脂組成物を用いて感光性樹脂層を直接描画して露光する、請求項7に記載の方法。
- 請求項7に記載のレジストパターンの形成方法によってレジストパターンを形成した基板を、エッチング又はめっきする工程を含む、プリント配線板の製造方法。
- 請求項7に記載のレジストパターンの形成方法によってレジストパターンを形成した基板を、サンドブラストによって加工する工程を含む、凹凸パターンを有する基材の製造方法。
- 請求項7に記載のレジストパターンの形成方法によってレジストパターンを形成した基板を、エッチング又はめっきする工程を含む、半導体パッケージ又はバンプの製造方法。
- 請求項7に記載のレジストパターンの形成方法によってレジストパターンを形成した基板を、エッチング又はめっきする工程を含む、リードフレームの製造方法。
- 請求項1~5のいずれか1項に記載の感光性樹脂組成物を硬化させて成る樹脂硬化物。
- 請求項13に記載の樹脂硬化物を支持体上に有する樹脂硬化物積層体。
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