WO2009096292A1 - 感光性樹脂積層体 - Google Patents
感光性樹脂積層体 Download PDFInfo
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- WO2009096292A1 WO2009096292A1 PCT/JP2009/050882 JP2009050882W WO2009096292A1 WO 2009096292 A1 WO2009096292 A1 WO 2009096292A1 JP 2009050882 W JP2009050882 W JP 2009050882W WO 2009096292 A1 WO2009096292 A1 WO 2009096292A1
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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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/161—Coating processes; Apparatus therefor using a previously coated surface, e.g. by stamping or by transfer lamination
Definitions
- the present invention relates to a photosensitive resin laminate and its use. More specifically, the present invention relates to a printed wiring board, a flexible substrate, a lead frame substrate, a COF (chip on film) substrate, a semiconductor package substrate, a liquid crystal transparent electrode, and a liquid crystal substrate.
- the present invention relates to a photosensitive resin laminate suitable for manufacturing conductor patterns such as TFT wiring and PDP (plasma display panel) electrodes, and a resist pattern forming method using the same.
- a photosensitive resin laminate formed by laminating a photosensitive resin layer on a support film and further laminating a protective layer on the photosensitive resin layer, a so-called dry resin.
- a film resist (hereinafter abbreviated as DF) is used.
- DF film resist
- an alkali developing type using a weak alkaline aqueous solution as a developing solution is generally used.
- a protective layer To produce a printed wiring board using DF, if there is a protective layer, first peel off the protective layer and then use a laminator or the like on a permanent circuit production board such as a copper-clad laminate or a flexible board. Laminate DF and expose through a wiring pattern mask film. Next, if necessary, the support film is peeled off, and the unexposed photosensitive resin layer is dissolved or dispersed and removed with a developer to form a cured resist pattern on the substrate.
- the process for forming a circuit is roughly divided into two methods.
- the first method is a method (etching method) in which after removing a copper surface such as a copper clad laminate not covered with a resist pattern by etching, the resist pattern portion is removed with an alkaline aqueous solution stronger than the developer.
- the second method is a method in which the copper surface of the above is subjected to plating treatment of copper, solder, nickel, tin, etc., and then the resist pattern portion is similarly removed, and the copper surface such as a copper-clad laminate appearing is etched ( Plating method).
- etching cupric chloride, ferric chloride, a copper ammonia complex solution, or the like is used.
- a polyester film is generally used as a support film of DF, a very small part is shielded during exposure by a trace component such as a lubricant contained in the polyester film, and as a result, a side wall (side wall) of the cured resist pattern is obtained. ) And a surface (surface) facing the substrate in the cured resist pattern may be rattled or recessed. In particular, this influence cannot be ignored for forming fine wiring of 10 ⁇ m or less.
- the photosensitive layer is 10 ⁇ m or less, the photosensitive layer does not sufficiently follow the minute irregularities and scratches of the base material when laminating, so that a laminate air void is generated, and the conductor is disconnected due to the penetration of the etching solution into that portion.
- Patent Document 2 discloses a technique in which the intermediate layer is made of an oxypropylene group-containing polyvinyl alcohol resin, and the photosensitive resin layer contains a (meth) acrylic acid partial ester of a polyhydric alcohol. Discloses a technique using polyvinyl alcohol obtained by copolymerizing an olefin in an intermediate layer, polyethylene oxide having a polymerization degree of 4,000 or more, etc., but even in these methods, high resolution and high adhesion, soot after development, The followability was unsolved.
- Patent Document 4 below describes a photosensitive transfer material in which a thermoplastic resin layer, a separation layer, and a photosensitive resin layer are provided in this order on a temporary support.
- thermoplastic resin layer has been difficult to peeling between the thermoplastic resin layer and the separation layer.
- Photosensitive resin composition having a characteristic that the resist shape after development does not cause wobbling or dents on the side wall, is excellent, and has a very small width after development, and a photosensitive resin laminate Has been demanded.
- JP 2001-159817 A Japanese Patent Laid-Open No. 04-371957 Japanese Patent Laid-Open No. 06-242611 Japanese Patent Laid-Open No. 05-072724
- the present invention has good followability at the time of laminating, expresses high resolution and high adhesion, is free from side wall rattling and surface dents in the cured resist pattern after development, and after development It is an object of the present invention to provide a photosensitive resin laminate having characteristics of extremely small sushi, and to provide a method for forming a resist pattern using the laminate and a method for producing a conductor pattern.
- this invention is invention of the following photosensitive resin laminated bodies, the resist pattern formation method, and the manufacturing method of a conductor pattern.
- a photosensitive resin obtained by sequentially laminating a first layer having a layer thickness of 10 ⁇ m to 100 ⁇ m, a second layer having a layer thickness of 0.1 ⁇ m to 10 ⁇ m, and a photosensitive resin layer on a support film.
- the first layer contains a thermoplastic resin
- the second layer contains polyvinyl alcohol: 75 to 99% by mass
- R 1 and R 2 are H or CH 3 , which may be the same or different, and n 1 is an integer from 3 to 25.
- n 1 is an integer from 3 to 25.
- thermoplastic resin has the following general formula (I): R 1 —O— (CH 2 CH 2 O) n 1 —R 2 (I) ⁇ Wherein R 1 and R 2 are H or CH 3 , which may be the same or different, and n 1 is an integer from 3 to 25. ⁇
- R 1 and R 2 are H or CH 3 , which may be the same or different, and n 1 is an integer from 3 to 25.
- n 1 is an integer from 3 to 25.
- the photosensitive resin layer comprises: (a) a binder resin having a carboxyl group content of 100 to 600 in terms of acid equivalent and a weight average molecular weight of 5,000 to 500,000: 20 to 90 mass %, (B) at least one photopolymerizable unsaturated compound: 3 to 70% by mass, and (c) a photopolymerization initiator: 0.1 to 20% by mass, a layer comprising a photosensitive resin composition
- a binder resin having a carboxyl group content of 100 to 600 in terms of acid equivalent and a weight average molecular weight of 5,000 to 500,000: 20 to 90 mass %
- B at least one photopolymerizable unsaturated compound: 3 to 70% by mass
- a photopolymerization initiator 0.1 to 20% by mass
- R 6 and R 7 are H or CH 3 , which may be the same or different, A is C 2 H 4 , and B is CH 2 CH (CH 3 N 6 + n 7 is an integer of 2 to 40, n 8 + n 9 is an integer of 0 to 40, and n 6 and n 7 are each independently an integer of 1 to 39. , N 8 and n 9 are each independently an integer of 0 to 40, and the arrangement of repeating units of — (A—O) — and — (B—O) — is a block even if random. In the case of a block, the order of — (A—O) — and — (B—O) — may be either on the bisphenyl group side. ⁇ ;
- R 8 and R 9 are H or CH 3 , which may be the same or different, D is C 2 H 4 , and E is CH 2 CH (CH 3 M 1 + m 2 is an integer of 2 to 40, m 3 + m 4 is an integer of 0 to 40, and m 1 and m 2 are each independently an integer of 1 to 39. , M 3 and m 4 are each independently an integer of 0 to 40, and the arrangement of repeating units of — (DO) — and — (EO) — is a block even if it is random. In the case of a block, any of — (D—O) — and — (E—O) — may be on the cyclohexyl group side.
- R 10 is a diisocyanate residue having 4 to 12 carbon atoms
- R 11 and R 12 are H or CH 3 , which may be the same or different
- m 5 and m 6 are integers of 1 to 15.
- R 13 is H or CH 3 , which may be the same or different
- R 14 is an alkyl group having 4 to 14 carbon atoms
- a ′ is C 2 H 4
- B ′ is CH 2 CH (CH 3 )
- m 7 is 1 to 12
- m 8 is 0 to 12
- m 9 is an integer of 0 to 3
- the arrangement of repeating units of (A′-O) — and — (B′—O) — may be random or block. In the case of a block, — (A′—O) — and — ( Any order of B′—O) — may be on the phenyl group side. ⁇ .
- the photosensitive resin laminate according to any one of (1) to (5) above is laminated on the surface of a metal plate or a metal-coated insulating plate, the first layer is peeled off together with the support film, and active light is exposed. And then removing the unexposed portions by development.
- a method for producing a conductor pattern comprising etching or plating a substrate on which a resist pattern is formed by the method described in (6).
- the followability at the time of lamination is good, high resolution and high adhesion are developed after development, and the cured resist pattern after development has sidewalls.
- a first layer having a layer thickness of 10 ⁇ m to 100 ⁇ m, a second layer having a layer thickness of 0.1 ⁇ m to 10 ⁇ m, and a photosensitive resin layer are sequentially formed on the support film.
- a laminated photosensitive resin laminate, The first layer contains a thermoplastic resin;
- the second layer comprises polyvinyl alcohol: 75 to 99% by mass, and the following general formula (I): R 1 —O— (CH 2 CH 2 O) n 1 —R 2 (I) ⁇ Wherein R 1 and R 2 are H or CH 3 , which may be the same or different, and n 1 is an integer from 3 to 25.
- the first layer needs to be peeled off from the second layer after lamination together with the support film before exposure.
- the first layer can be peeled off together with the support film.
- a thermoplastic resin used for a 1st layer the compound which has the glass transition temperature below the roll temperature at the time of lamination is preferable, and the thermoplastic resin which specifically has a glass transition temperature of 120 degrees C or less is preferable.
- the glass transition temperature is equal to or lower than the roll temperature at the time of laminating, and when the photosensitive layer is transferred onto an uneven substrate with heat and pressure (when laminating), the unevenness on the substrate surface is completely absorbed and bubbles are generated. This is because laminating can be performed in a state where there is no remaining.
- the glass transition temperature of the thermoplastic resin used in the first layer is preferably 10 ° C. or higher from the viewpoint of preventing the thermoplastic resin from protruding from the roll end face when stored in the form of a roll as the photosensitive resin laminate. More preferably, it is 20 ° C. or higher, and further preferably 30 ° C. or higher.
- thermoplastic resins having a glass transition temperature of 120 ° C. or lower examples include polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylate esters or saponified products thereof, and polyvinyl chloride.
- Vinyl chloride copolymer such as vinyl chloride and vinyl acetate or saponified product thereof, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof , Polyvinyltoluene, vinyltoluene copolymer such as vinyltoluene and (meth) acrylic acid ester or saponified product thereof, poly (meth) acrylic acid ester, (meth) acrylic acid such as butyl (meth) acrylate and vinyl acetate Ester copolymer, vinyl acetate copolymer, Nai It is preferable to select at least one thermoplastic resin such as polyamide resin such as nylon, copolymer nylon, N-alkoxymethylated nylon, and N-dimethylaminated nylon.
- Thermoplastic resins having a glass transition temperature of 120 ° C. or lower and 10 ° C. or higher as described in the Federation, edited by the All Japan Plastics Molding Industry Association, published by the Industrial Research Council, published on October 25, 1968) can be used.
- the content of the thermoplastic resin is preferably 50 to 100% by mass, particularly 65 to 100% by mass in the first layer.
- various plasticizers compatible with the thermoplastic resin can be added to lower the substantial glass transition temperature.
- additives such as various polymers and supercooled substances, adhesion within a range where the substantial glass transition temperature does not exceed 120 ° C. It is possible to add an improving agent, a surfactant or a release agent in the range of 5 to 50% by mass. More preferably, it is 35 mass% or less.
- plasticizer examples include phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, and tri-n-acetyl citrate.
- phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, and tri-n-acetyl citrate.
- phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acety
- polyalkylene glycols such as polyethylene glycol and polypropylene glycol and polyalkylene glycol methyl ethers can be added.
- polyalkylene glycols such as polyethylene glycol and polypropylene glycol and polyalkylene glycol methyl ethers
- R 1 and R 2 are H or CH 3 , which may be the same or different, and n 1 is an integer from 3 to 25.
- ⁇ Is preferably added from the viewpoint of improving followability.
- the thickness of the thermoplastic resin layer is preferably 10 ⁇ m or more. This is because, if the thickness of the thermoplastic resin layer is less than 10 ⁇ m, it is impossible to completely absorb the irregularities on the substrate surface of 1 ⁇ m or more.
- the upper limit is not particularly limited in terms of performance, but is about 100 ⁇ m or less, preferably about 50 ⁇ m or less, more preferably 30 ⁇ m or less, from the viewpoint of production suitability.
- the second layer is polyvinyl alcohol: 75 to 99% by mass, and the following general formula (I): R 1 —O— (CH 2 CH 2 O) n 1 —R 2 (I) ⁇ Wherein R 1 and R 2 are H or CH 3 , which may be the same or different, and n 1 is an integer from 3 to 25. ⁇ And the following general formula (II): ⁇ Wherein R 3 is H or an alkyl group having 1 to 6 carbon atoms, and n 2 is an integer of 9 to 10,000. ⁇ , At least one compound selected from the group consisting of compounds represented by: 1 to 25% by mass.
- the interlayer adhesion between the first layer and the second layer can be made lower than the interlayer adhesion between the support film and the first layer and the interlayer adhesion between the second layer and the photosensitive resin layer. It becomes.
- the blending ratio of polyvinyl alcohol in the second layer is preferably 75% by mass or more and 99% by mass or less from the viewpoint of developability and cost. More preferably, it is 85 mass% or more and 95 mass% or less.
- polyvinyl alcohol is produced by saponifying polyvinyl acetate with alkali.
- the weight average molecular weight of the polyvinyl alcohol used in the present invention is preferably 1,000 to 100,000. From the viewpoint of oxygen barrier properties and developability, a more preferred weight average molecular weight is 5,000 to 50,000.
- the saponification degree is preferably 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more from the viewpoint of developability.
- the weight average molecular weight of polyvinyl alcohol is determined by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (trademark) (HFIP-805, manufactured by Showa Denko KK). HFIP-803) 2 in series, moving bed solvent: hexafluoroisopropanol, polystyrene standard sample (use of calibration curve by Shodex STANDARD SM-105 manufactured by Showa Denko KK) is obtained as a weight average molecular weight (polystyrene conversion).
- GPC gel permeation chromatography
- n1 is preferably 3 or more from the viewpoint of odor, and n1 is preferably 25 or less from the viewpoint of compatibility with polyvinyl alcohol and developability. n1 is more preferably 5 or more and 20 or less, and still more preferably 7 or more and 15 or less.
- Specific examples of the compound represented by the general formula (I) include polyethylene glycol having an average molecular weight of 200 (PEG 200 manufactured by NOF Corporation), polyethylene glycol having an average molecular weight of 300 (PEG 300 manufactured by NOF Corporation, average) Polyethylene glycol having a molecular weight of 400 (PEG 400 manufactured by NOF Corporation), polyethylene glycol having an average molecular weight of 600 (PEG 600 manufactured by NOF Corporation), polyethylene glycol having an average molecular weight of 1000 (PEG 1000 manufactured by NOF Corporation), Polyethylene glycol monomethyl ether having an average molecular weight of 400 (Uniox M-400, manufactured by NOF Corporation), polyethylene glycol monomethyl ether having an average molecular weight of 550 (UNIOX M, manufactured by NOF Corporation) 550), polyethylene glycol monomethyl ether is the average molecular weight of 1000 (manufactured by NOF CORPORATION Uniox M-1000) and the like.
- n 2 in terms of peeling of the first layer and the second layer is preferably 9 or more, n 2 from the viewpoint of developability is preferably 10,000 or less. n 2 is more preferably 20 or more and 2,000 or less, and still more preferably 30 or more and 1,500 or less.
- Specific examples of the compound represented by the general formula (II) include polyvinyl pyrrolidone. Specific examples include K-15 with a weight average molecular weight of 40,000 manufactured by Nippon Shokubai Co., Ltd., K-30 with a weight average molecular weight of 100,000, K-85 with a weight average molecular weight of 900,000, and K with a weight average molecular weight of 1,000,000. -90 mag.
- the content in the second layer of at least one compound selected from the group consisting of the compound represented by the general formula (I) and the compound represented by the general formula (II) is as follows. From the viewpoint of peelability from the layer, it is 1% by mass or more, preferably 3% by mass or more, and more preferably 5% by mass or more. Further, from the viewpoint of sensitivity, it is 25% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less.
- the second layer includes other known water-soluble polymers such as polyvinyl ether-maleic anhydride water-soluble salts, carboxyalkyl starch water-soluble salts, polyacrylamide, polyamide, polyacrylic acid water-soluble salts, gelatin. Polypropylene glycol and the like can be contained.
- the layer thickness of the second layer is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and further preferably 3 ⁇ m or less from the viewpoints of resolution, adhesion, and developability. Further, from the viewpoint of oxygen barrier properties, it is 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more.
- the support film since the support film is peeled off before the ultraviolet exposure, it is not necessary to use a transparent film that transmits ultraviolet light.
- the support film in the present invention include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate having a thickness of about 10 ⁇ m to 100 ⁇ m. Usually, polyethylene terephthalate having appropriate flexibility and strength is preferably used. In order to make it difficult to generate wrinkles during lamination and to prevent the support film from being damaged, the film thickness is preferably 10 ⁇ m or more.
- the photosensitive resin laminate of the present invention there is no problem in the peelability from the first layer by taking the above-described configuration in the second layer, that is, the first layer is peeled off together with the support film before the exposure step. In this case, it is possible to obtain an adhesive having a lower interlayer adhesive force between the first layer and the second layer than an interlayer adhesive force between the support film, the first layer, and the second layer and the photosensitive layer.
- the protective layer As a characteristic of the protective layer, it is important that the interlayer adhesive force between the photosensitive resin layer and the protective layer is lower than the interlayer adhesive force between the first layer and the second layer.
- the protective layer can be easily peeled off.
- the protective layer there are synthetic resin films such as polyethylene, polypropylene, polycarbonate and polyethylene terephthalate having a thickness of about 10 to 100 ⁇ m, and a polyethylene film or a polypropylene film is preferably used.
- the film thickness of the photosensitive resin layer of the present invention varies depending on the use, the upper limit of the thickness is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, further preferably 30 ⁇ m or less, and most preferably 10 ⁇ m or less.
- the lower limit is preferably 0.5 ⁇ m or more, and more preferably 1 ⁇ m or more.
- the photosensitive resin layer in the photosensitive resin laminate of the present invention comprises: (a) a binder resin having a carboxyl group content of 100 to 600 in terms of acid equivalent and a weight average molecular weight of 5,000 to 500,000: 20 From a photosensitive resin composition containing ⁇ 90% by mass, (b) at least one photopolymerizable unsaturated compound: 3 to 70% by mass, and (c) photopolymerization initiator: 0.1 to 20% by mass. It is preferable that it is a layer.
- the photosensitive resin composition used for the photosensitive resin laminate of the present invention will be described in detail below.
- the amount of the carboxyl group contained in the binder resin is preferably 100 to 600, more preferably 250 to 450 in terms of acid equivalent.
- An acid equivalent means the mass of resin for binders which has 1 equivalent of a carboxyl group in it.
- the carboxyl group in the binder resin is necessary to give the photosensitive resin layer developability and releasability with respect to an aqueous alkali solution.
- the acid equivalent is preferably 100 or more from the viewpoint of development resistance, resolution, and adhesion, and is preferably 600 or less from the viewpoint of developability and peelability.
- the weight average molecular weight of the binder resin is preferably 5,000 to 500,000.
- the weight average molecular weight of the binder resin is preferably 500,000 or less from the viewpoint of resolution, and is preferably 5,000 or more from the viewpoint of edge fuse. In order to exhibit the effects of the present invention better, the weight average molecular weight of the binder resin is more preferably 5,000 to 200,000, and still more preferably 5,000 to 100,000.
- the degree of dispersion is about 1 to 6, and preferably 1 to 4.
- the acid equivalent is measured by a potentiometric titration method using a Hiranuma automatic titration apparatus (COM-555) manufactured by Hiranuma Sangyo Co., Ltd. and using a 0.1 mol / liter sodium hydroxide aqueous solution.
- COM-555 Hiranuma automatic titration apparatus
- the molecular weight is 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) 4 in series, moving bed solvent: tetrahydrofuran, using polystyrene standard sample (use calibration curve by Shodex STANDARD SM-105 manufactured by Showa Denko KK) as the weight average molecular weight (polystyrene conversion) It is done.
- GPC gel permeation chromatography
- the binder resin is 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, maleic acid half ester, and the like.
- 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.
- Examples of the compound include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate, (meth) acrylonitrile, benzyl (meth) acrylate, methoxybenzyl (meth) acrylate, chlorobenzyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl ( Aryl (meth) acrylates such as meth) acrylate, phenyl (meth) acrylate, cresyl (meth) acrylate, naphthyl (meth) acrylate, and vinyl compounds having a phenyl group
- the binder resin is prepared by diluting a mixture of the first monomer and the second monomer with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and adding benzoyl peroxide, azoisobutyro
- the synthesis is preferably carried out by adding an appropriate amount of a radical polymerization initiator such as nitrile 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.
- synthesis means bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.
- the ratio of the binder resin to the entire photosensitive resin composition is preferably in the range of 20 to 90% by mass, more preferably 30 to 70% by mass. 20 mass% or more and 90 mass% or less are preferable from a viewpoint that the cured resist pattern formed by exposure and image development has characteristics as a resist, for example, sufficient resistance in tenting, etching, and various plating processes.
- the at least one photopolymerizable unsaturated compound includes at least one light selected from the group consisting of compounds represented by the following general formulas (III) to (VII) from the viewpoint of high resolution.
- the use of a polymerizable unsaturated compound in the photosensitive resin composition is a preferred embodiment: ⁇ Wherein R 4 and R 5 are H or CH 3 , which may be the same or different, and n 3 , n 4 and n 5 are each independently an integer of 3 to 20 It is. ⁇ ;
- R 6 and R 7 are H or CH 3 , which may be the same or different, A is C 2 H 4 , and B is CH 2 CH (CH 3 N 6 + n 7 is an integer of 2 to 40, n 8 + n 9 is an integer of 0 to 40, and n 6 and n 7 are each independently an integer of 1 to 39. , N 8 and n 9 are each independently an integer of 0 to 40, and the arrangement of repeating units of — (A—O) — and — (B—O) — is a block even if random. In the case of a block, the order of — (A—O) — and — (B—O) — may be either on the bisphenyl group side. ⁇
- R 8 and R 9 are H or CH 3 , which may be the same or different, D is C 2 H 4 , and E is CH 2 CH (CH 3 M 1 + m 2 is an integer of 2 to 40, m 3 + m 4 is an integer of 0 to 40, and m 1 and m 2 are each independently an integer of 1 to 39. , M 3 and m 4 are each independently an integer of 0 to 40, and the arrangement of repeating units of — (DO) — and — (EO) — is a block even if it is random. In the case of a block, any of — (D—O) — and — (E—O) — may be on the cyclohexyl group side. ⁇ ;
- R 10 is a diisocyanate residue having 4 to 12 carbon atoms, and R 11 and R 12 are H or CH 3 , which may be the same or different, m 5 and m 6 are integers of 1 to 15. ⁇ ;
- R 13 is H or CH 3 , which may be the same or different
- R 14 is an alkyl group having 4 to 14 carbon atoms
- a ′ is C 2 H 4
- B ′ is CH 2 CH (CH 3 )
- m 7 is an integer from 1 to 12
- m 8 is an integer from 0 to 12
- m 9 is from 0 to 3.
- the arrangement of repeating units of-(A'-O)-and-(B'-O)- may be random or block, and in the case of a block,-(A'-O ) — And — (B′—O) — may be in any order on the phenyl group side.
- n 3 , n 4 and n 5 are preferably 3 or more from the viewpoints of boiling point and odor. From the viewpoint of sensitivity due to the concentration of the photoactive site per unit mass, n 3 , n 4 and n 5 are preferably 20 or less.
- Specific examples of the compound represented by the above general formula (III) used in the present invention include, for example, a glyco-glycol in which ethylene oxide is further added to both ends at an average of 3 mol on polypropylene glycol to which an average of 12 mol of propylene oxide is added.
- the preferred dimethacrylate is bismuth dimethacrylate.
- n 6 + n 7 and n 8 + n 9 need to be 40 or less, and exceeding 40 is not preferable from the viewpoint of sensitivity. Preferably it is 30 or less.
- Specific examples of the compound represented by the above general formula (IV) used in the present invention include polyalkylene glycol dimethacrylate in which an average of 2 mol of propylene oxide and an average of 6 mol of ethylene oxide are added to both ends of bisphenol A, respectively.
- m 1 + m 2 and m 3 + m 4 need to be 40 or less, and exceeding 40 is not preferable from the viewpoint of sensitivity. Preferably it is 30 or less.
- Specific examples of the compound represented by the general formula (V) include polyethylene glycol dimethacrylate in which an average of 5 mol of ethylene oxide is added to both ends of hydrogenated bisphenol A. In the compound represented by the general formula (VI), when m 5 and m 6 exceed 15, sufficient sensitivity cannot be obtained.
- the compound represented by the general formula (VI) include, for example, a diisocyanate compound such as hexamethylene diisocyanate, tolylene diisocyanate, or 2,2,4-trimethylhexamethylene diisocyanate, and one molecule.
- urethane compounds of compounds having a hydroxyl group and a (meth) acryl group such as 2-hydroxypropyl acrylate and oligopropylene glycol monomethacrylate.
- hexamethylene diisocyanate and oligopropylene glycol monomethacrylate Nippon Yushi Co., Ltd., Blenmer PP1000.
- the compound represented by the general formula (VII) when m 7 and m 8 exceed 12, sufficient sensitivity cannot be obtained. m 9 is not sufficient sensitivity can be obtained even beyond 3.
- Specific examples of the compound represented by the general formula (VII) include, for example, an acrylate of a compound obtained by adding polypropylene glycol added with an average of 2 mol of propylene oxide and polyethylene glycol added with an average of 7 mol of ethylene oxide to nonylphenol. 4-normalnonylphenoxyheptaethylene glycol dipropylene glycol acrylate.
- 4-normal nonyl phenoxy octaethylene glycol acrylate (manufactured by Toagosei Co., Ltd., M-114), which is an acrylate of a compound obtained by adding polyethylene glycol with an average of 8 moles of ethylene oxide added to nonylphenol.
- the ratio of the entire at least one photopolymerizable unsaturated compound to the entire photosensitive resin composition is preferably 3% by mass or more from the viewpoint of sensitivity, and preferably 70% by mass or less from the viewpoint of edge fuse. More preferably, it is 10 to 60% by mass, and further preferably 15 to 55% by mass.
- the ratio of at least one photopolymerizable unsaturated compound selected from the group consisting of the compounds represented by the general formulas (III) to (VII) to the entire photosensitive resin composition is 3 to 70% by mass. Range. From the viewpoint of resolution, it is 3% by mass or more, and from the viewpoint of flexibility of the resist pattern, it is 70% by mass or less. More preferably, it is 3 to 30% by mass or less.
- the photopolymerization initiator may be any compound that is activated by various actinic rays, such as ultraviolet rays, and initiates polymerization, and is represented by the following general formula (VIII): ⁇ Wherein X, Y, and Z each independently represent hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or a halogen group; and p, q, and r each independently represent 1 is an integer of 1 to 5. ⁇ And the following general formula (IX):
- X, Y, and Z each independently represent hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or a halogen group; and p, q, and r each independently represent 1 is an integer of 1 to 5.
- ⁇ At least one 2,4,5-triarylimidazole dimer selected from the group consisting of compounds represented by the formula: is a preferred embodiment from the viewpoint of high resolution.
- Examples of the 2,4,5-triarylimidazole dimer 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 photopolymerization initiator (c) used in the present invention is at least one 2,4 selected from the group consisting of the compound represented by the general formula (VIII) and the compound represented by the general formula (IX).
- 5-triallylimidazole dimer and p-aminophenyl ketones are preferred.
- p-aminophenyl ketones include p-aminobenzophenone, p-butylaminoacetophenone, p-dimethylaminoacetophenone, p-dimethylaminobenzophenone, p, p′-bis (ethylamino) benzophenone, p, p ′.
- photopolymerization initiators other than the above-described compounds include, for example, quinones such as 2-ethylanthraquinone and 2-tert-butylanthraquinone, aromatic ketones such as benzophenone, benzoin, benzoin methyl ether, and benzoin ethyl ether.
- Benzoin ethers, acridine compounds such as 9-phenylacridine, benzyldimethyl ketal, benzyldiethyl ketal, pyrazolines such as 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert- Butyl-phenyl) -pyrazoline.
- thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and tertiary amine compounds such as dimethylaminobenzoic acid alkyl ester compounds.
- the photosensitive resin composition in the photosensitive resin laminate of the present invention preferably contains (c) a photopolymerization initiator in an amount of 0.1 to 20% by mass based on the entire photosensitive resin composition. From the viewpoint of obtaining sufficient sensitivity, it is preferably 0.1% by mass or more and 20% by mass or less from the viewpoint of preventing halation of light passing through a photomask during exposure.
- a basic dye can be used for the photosensitive resin composition.
- Specific examples of basic dyes include fuchsin, phthalocyanine green, auramine base, chalcoxide green S, paramadienta, crystal violet, methyl orange, nile blue 2B, malachite green (Eizen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.) ), Basic Blue 20, Diamond Green (Eizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.), Victoria Blue (Eisen (registered trademark) VICTORIA PURE BLUE manufactured by Hodogaya Chemical Co., Ltd.), and the like.
- the photosensitive resin composition may contain a coloring dye that develops color when irradiated with light.
- Examples of the coloring dye used include a combination of a leuco dye or a fluorane dye and a halogen compound.
- Examples of the leuco dye include tris (4-dimethylamino-2-methylphenyl) methane [leucocrystal violet], tris (4-dimethylamino-2-methylphenyl) methane [leucomalachite green], and the like.
- Halogen compounds 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 and the like.
- halogenated triazine compound examples include 2,4,6-tris (trichloromethyl) -s-triazine and 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine.
- the photosensitive resin composition contains a radical polymerization inhibitor.
- 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-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), diphenylnitrosamine and the like.
- the photosensitive resin composition may contain a plasticizer as necessary.
- plasticizers include, for example, phthalates such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl citrate tri -N-propyl, tri-n-butyl acetylcitrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, phthalates.
- Phthalate esters include dibutyl phthalate.
- thermoplastic resin for example, a methyl ethyl ketone solution of polymethyl methacrylate obtained by solution polymerization (weight average molecular weight 60,000, solid content concentration 40% by mass, glass transition temperature 105 ° C.) is coated on a support film with a bar coater or roll. Apply using a coater and dry. Thereby, a 1st layer can be laminated
- the viscosity of the methyl ethyl ketone solution of polymethyl methacrylate is preferably adjusted to 10 to 2000 mPa ⁇ s.
- polyvinyl alcohol for example, polyvinyl alcohol PVA-205 resin manufactured by Kuraray Co., Ltd.
- one or more compounds selected from the group of compounds represented by the above general formula (I) or (II), for example, polyethylene Glycol, polyoxyethylene monomethyl ether and polyvinyl pyrrolidone are gradually added to water heated to 85 ° C. so that the solid content ratio is about 10% by mass and stirred for about 1 hour to uniformly dissolve.
- the aqueous solution containing polyvinyl alcohol is applied onto the first layer obtained by laminating the first layer on the support film, as described above, and dried using a bar coater or a roll coater.
- the viscosity of the aqueous solution containing polyvinyl alcohol is preferably adjusted to 10 to 500 mPa ⁇ s.
- a photosensitive resin layer composed of a photosensitive resin composition is applied to a bar coater or a roll coater in the same manner as the application of the second layer. Apply and dry.
- a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.
- a printed wiring board is manufactured through the following steps.
- Step A of dissolving or dispersing and removing the unexposed portions of the second layer and the photosensitive resin layer using an alkali developer to form a cured resist pattern on the substrate.
- Examples of the active light source used in the (2) exposure step include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet fluorescent lamp, a carbon arc lamp, and a xenon lamp. In order to obtain a finer resist pattern, it is more preferable to use a parallel light source. When it is desired to reduce the influence of dust or foreign matter as much as possible, exposure (proximity exposure) may be performed with the photomask floating above the second layer by several tens to several hundreds of ⁇ m.
- Examples of the alkali developer used in the above (3) development step include aqueous solutions of sodium carbonate and potassium carbonate. These alkaline aqueous solutions are selected in accordance with the characteristics of the photosensitive resin layer, but generally an aqueous sodium carbonate solution of 0.5% by mass to 3% by mass is used.
- Said (4) etching process is performed by the method suitable for DF to be used, such as acidic etching and alkali etching.
- the alkali stripping solution used in the above (5) stripping step an alkaline aqueous solution that is generally stronger than the alkaline aqueous solution used in the development, for example, 1% by weight to 5% by weight of sodium hydroxide, potassium hydroxide An aqueous solution may be mentioned.
- a plating process such as a semi-additive method is provided, the copper surface that appears under the resist pattern may be etched after the resist pattern is removed.
- Examples 1 to 15, Comparative Examples 1 to 4 The photosensitive resin laminates in Examples and Comparative Examples were produced as follows. ⁇ Preparation of photosensitive resin laminate> The methyl ethyl ketone solution of the first layer shown in Table 1 was uniformly applied to the surface of a 16 ⁇ m thick polyethylene terephthalate film (Toray 16QS48 level 3) using a bar coater, and dried for 2 minutes in a 95 ° C. drier. A uniform first layer was formed on the film. The thickness of the first layer was 20 ⁇ m.
- the aqueous solution of the composition of the second layer shown in Table 1 is thoroughly stirred and mixed, and uniformly applied to the surface of the first layer of the support film on which the first layer has been laminated, using a bar coater, 100 ° C. In the dryer for 3 minutes to form a uniform second layer on the first layer.
- the thickness of the second layer was 2 ⁇ m.
- the photosensitive resin composition shown in Table 1 was uniformly applied on the second layer laminated on the support film using a bar coater, and dried for 3 minutes in a dryer at 95 ° C. to obtain uniform photosensitivity.
- a resin layer was formed.
- the thickness of the photosensitive resin layer was 2 ⁇ m.
- a 25 ⁇ m thick polyethylene film was laminated as a protective layer on the surface of the photosensitive resin layer to obtain a photosensitive resin laminate.
- ⁇ Laminate> While peeling off the protective layer of the photosensitive resin laminate of the present invention, the laminate was laminated at a roll temperature of 105 ° C. with a hot roll laminator (Asahi Kasei Engineering Co., Ltd., AL-70). The air pressure was 0.35 MPa, and the laminating speed was 1.0 m / min. In the lamination air void evaluation (followability evaluation), the air pressure was 0.2 MPa, and the lamination speed was 2.0 m / min.
- Evaluation method (1) After laminating under the above conditions, exposure was performed at 100 mJ, a range of 10 cm ⁇ 10 cm was observed with an optical microscope, the number of laminate air voids was counted, and the following ranking was performed: A: No occurrence of laminated air voids; ⁇ : About several laminate air voids are observed; ⁇ : Occurrence of several tens of laminate air voids is observed; X: Generation
- Adhesion evaluation The substrate which had passed 15 minutes after lamination was exposed and developed as described above using a line pattern mask of the exposed portion alone as a mask film at the time of exposure.
- the minimum mask width over which the cured resist pattern was normally formed was taken as the adhesion value, and the adhesion was ranked as follows: A: Adhesion value is 5 ⁇ m or less; ⁇ : Adhesion value exceeds 5 ⁇ m and 10 ⁇ m or less; (Triangle
- P-1 Methyl ethyl ketone solution of binary copolymer of benzyl methacrylate 80 mass% and methacrylic acid 20 mass% (solid content concentration 50 mass%, weight average molecular weight 25,000, acid equivalent 430, dispersity 2.7)
- P-2 Methyl ethyl ketone solution of a terpolymer of methyl methacrylate 50% by mass, methacrylic acid 25% by mass and styrene 25% by mass (solid content concentration 35% by mass, weight average molecular weight 50,000, acid equivalent 344, dispersity 3.1)
- M-1 Polymethacrylate glycol dimethacrylate obtained by adding an average of 3 moles of ethylene oxide to both ends of polypropylene glycol with an average of 12 moles of propylene oxide added
- M-2 Propylene oxide of an average of 2 moles on both ends of bisphenol A
- M-3 Polyethylene glycol dimethacrylate with an average of 2 moles of ethylene oxide added to both ends of bisphenol A (Shin Nakamura Chemical Co., Ltd., NK SL BPE-200)
- M-4 dimethacrylate of polyethylene glycol in which 5 mol of ethylene oxide is added to both ends of bisphenol A on the both ends (NK SL BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.)
- M-5 2,2-bis ⁇ 4- (methacryloxypentaethoxy) cyclohexyl ⁇ propane
- M-6 Reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (Nippon Yushi Co., Ltd., Blenmer PP1000)
- a certain urethane polypropylene glycol dimethacrylate A certain urethane polypropylene glycol dimethacrylate
- M-7 Trimethylolpropane trimethacrylate
- M-8 Trioxyethyltrimethylolpropane triacrylate (NK ester A-TMPT-3EO manufactured by Shin-Nakamura Chemical Co., Ltd.)
- M-9 Nonaethylene glycol diacrylate
- G-1 4,4′-bis (diethylamino) benzophenone
- G-2 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer
- J-1 Diamond green (Eizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.)
- J-2 Leuco Crystal Violet
- L-1 1: 1 mixture of 1- (2-di-n-butylaminomethyl) -5-carboxylbenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxylbenzotriazole
- L- 2 3,5-di-t-butyl-4-hydroxyphenylpropionic acid tetraester of pentaerythritol (IRGANOX 245 manufactured by Ciba Specialty Chemicals)
- Q-1 polyoxyethylene monomethyl ether (Yuox M-550 manufactured by NOF Corporation, weight average molecular weight 550)
- Q-2 Methyl ethyl ketone solution of polymethyl methacrylate (solid concentration 40% by mass, weight average molecular weight 60,000)
- Q-3 Methyl ethyl ketone solution of binary copolymer of 80% by mass of methyl methacrylate and 20% by mass of methyl acrylate (solid content concentration 40% by mass, weight average molecular weight 60,000)
- Q-4 Methyl ethyl ketone solution of binary copolymer of 80% by mass of methyl methacrylate and 20% by mass of styrene (solid content concentration 40% by mass, weight average molecular weight 50,000)
- Q-5 Dibutyl phthalate
- Q-6 Polyvinyl alcohol (PVA-205, manufactured by Kuraray Co., Ltd.)
- Q-7 Polyethylene glycol (weight average molecular weight 400)
- Q-8 Polyvinylpyrrolidone (weight average molecular weight 40,000) (manufactured by Nippon Shokubai Co., Ltd., K-15 (product number))
- a printed wiring board a flexible wiring board, a COF (chip on film) substrate, a lead frame, a semiconductor package substrate, a liquid crystal transparent electrode, a liquid crystal TFT wiring, and a PDP (plasma display panel) electrode
- a conductor pattern such as, it is suitable as an etching resist or a plating resist.
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Abstract
Description
ここで用いられる感光性樹脂層としては、現在、現像液として弱アルカリ水溶液を用いるアルカリ現像型のものが一般的である。
DFを用いてプリント配線板等を作製するには、保護層が有る場合には、まず保護層を剥離した後、銅張積層板やフレキシブル基板等の永久回路作製用基板上にラミネーター等を用いDFをラミネートし、配線パターンマスクフィルム等を通し露光を行う。次に必要に応じて支持フィルムを剥離し、現像液により未露光部分の感光性樹脂層を溶解、もしくは分散除去し、基板上に硬化レジストパターンを形成させる。
第一の方法は、レジストパターンによって覆われていない銅張積層板等の銅面をエッチング除去した後、レジストパターン部分を現像液よりも強いアルカリ水溶液で除去する方法(エッチング法)である。第二の方法は同上の銅面に銅、半田、ニッケルおよび錫等のめっき処理を行った後、同様にレジストパターン部分の除去、さらに現れた銅張積層板等の銅面をエッチングする方法(めっき法)である。エッチングには塩化第二銅、塩化第二鉄、銅アンモニア錯体溶液等が用いられる。
また、感光層が10μm以下の薄膜では基材の微小な凹凸やキズにラミネート時に感光層が充分に追従しないことにより、ラミネートエアーボイドを生じ、その部分にエッチング液の染み込みにより導体が断線するという問題点が発生することがある。
ラミネートエアーボイドなく高追従性とするには感光層の粘度を低くする方法があるが、ロール端面からの感光層のしみだし、いわゆるエッジフューズが発生という問題がある。
また、感光層が10μm以下と薄くなると感光層の絶対量が不足し、基材の凹凸やキズに対して感光層の粘度を下げても、追従性が充分ではないことがある。
高解像度とするには、支持フィルムと感光性樹脂層の間にポリビニルアルコールからなる中間層を設けて露光工程前に支持フィルムを剥離して中間層上から露光することにより高解像度とし、且つ支持フィルムの滑剤等によるレジスト形状に対する影響を排除する、という手法があるが、追従性を同時に解決する手法ではない。
以下の特許文献4には、仮支持体上に、熱可塑性樹脂層、分離層、感光性樹脂層をこの順に設けた感光性転写材料についての記載がある。しかしながら、熱可塑性樹脂層と分離層間の剥離には難があった。
プリント配線板の微細化や薄膜で高解像性が必要なCOF用基板作製、半導体パッケージ用基板作製等にはラミネート時の追従性が良好であり、高解像、高密着性を発現し、現像後のレジスト形状において、サイドウオールにガタツキや表面に凹みを生じることがなく、良好であり、かつ現像後のスソが極めて小である特性を有する感光性樹脂組成物、及び感光性樹脂積層体が求められてきた。
(1)支持フィルム上に、層厚が10μm以上100μm以下の第一層と、層厚が0.1μm以上10μm以下の第二層と、感光性樹脂層とを順次積層してなる感光性樹脂積層体であって、該第一層が、熱可塑性樹脂を含有し、そして該第二層が、ポリビニルアルコール:75~99質量%と、下記一般式(I):
R1-O-(CH2CH2O)n1-R2 (I)
{式中、R1及びR2は、H又はCH3であり、これらは同一であっても相違してもよく、そしてn1は、3~25の整数である。}で表される化合物、及び下記一般式(II):
R1-O-(CH2CH2O)n1-R2 (I)
{式中、R1及びR2は、H又はCH3であり、これらは同一であっても相違してもよく、そしてn1は、3~25の整数である。}で表される化合物を含有する、前記(1)に記載の感光性樹脂積層体。
(3)前記感光性樹脂層上に保護層を更に積層してなる、前記(1)又は(2)に記載の感光性樹脂積層体。
(4)前記感光性樹脂層が、(a)カルボキシル基含有量が酸当量で100~600であり、かつ、重量平均分子量が5,000~500,000であるバインダー用樹脂:20~90質量%、(b)少なくとも一種の光重合可能な不飽和化合物:3~70質量%、及び(c)光重合開始剤:0.1~20質量%、を含有する感光性樹脂組成物からなる層である、前記(1)~(3)のいずれかに記載の感光性樹脂積層体。
(7)前記(6)に記載の方法によって、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ことを特徴とする導体パターンの製造方法。
本発明の感光性樹脂積層体は、支持フィルム上に、層厚が10μm以上100μm以下の第一層と、層厚が0.1μm以上10μm以下の第二層と、感光性樹脂層とを順次積層してなる感光性樹脂積層体であって、
該第一層が、熱可塑性樹脂を含有し、
該第二層が、ポリビニルアルコール:75~99質量%と、下記一般式(I):
R1-O-(CH2CH2O)n1-R2 (I)
{式中、R1及びR2は、H又はCH3であり、これらは同一であっても相違してもよく、そしてn1は、3~25の整数である。}で表される化合物、及び下記一般式(II):
また、第一層に用いられる熱可塑性樹脂のガラス転移温度は、感光性樹脂積層体としてロール状で保管したときに、ロール端面から熱可塑性樹脂がはみ出すことを防ぐ観点から、10℃以上が好ましく、より好ましくは20℃以上、更に好ましくは、30℃以上である。
第一層には、上述の熱可塑性樹脂に加えて、該熱可塑性樹脂と相溶性のある各種の可塑剤を添加して、実質的なガラス転移温度を下げることも可能である。また、これらの第一層中に第二層との接着力を調節するために、実質的なガラス転移温度が120℃を超えない範囲で添加剤、例えば、各種のポリマーや過冷却物質、密着改良剤あるいは界面活性剤や離型剤を、5~50質量%の範囲で加えることが可能である。より好ましくは、35質量%以下である。
他に、ポリエチレングリコールやポリプロピレングリコールなどのポリアルキレングリコールやポリアルキレングリコールメチルエーテルを加えることも可能である。中でも下記一般式(I):
R1-O-(CH2CH2O)n1-R2 (I)
{式中、R1及びR2は、H又はCH3であり、これらは同一であっても相違してもよく、そしてn1は、3~25の整数である。}で表される化合物を加えることが、追従性が向上する観点から好ましい。
また、第二層が、ポリビニルアルコール:75~99質量%と、下記一般式(I):
R1-O-(CH2CH2O)n1-R2 (I)
{式中、R1及びR2は、H又はCH3であり、これらは同一であっても相違してもよく、そしてn1は、3~25の整数である。}で表される化合物、及び下記一般式(II):
第二層におけるポリビニルアルコール配合比率としては、現像性及びコストの観点から75質量%以上99質量%以下であることが好ましい。より好ましくは85質量%以上95質量%以下である。
ポリビニルアルコールの重量平均分子量は、日本分光(株)製ゲルパーミエーションクロマトグラフィー(GPC)(ポンプ:Gulliver、PU-1580型、カラム:昭和電工(株)製Shodex(登録商標)(HFIP-805、HFIP-803)2本直列、移動層溶媒:ヘキサフルオロイソプロパノール、ポリスチレン標準サンプル(昭和電工(株)製Shodex STANDARD SM-105)による検量線使用)により重量平均分子量(ポリスチレン換算)として求められる。
上記一般式(I)で表される化合物及び上記一般式(II)で表される化合物からなる群より選ばれる少なくとも1種の化合物の、第二層における含有量は、第二層と第一層との剥離性の観点から、1質量%以上であり、好ましくは3質量%以上であり、更に好ましくは5質量%以上である。また、感度の観点から、25質量%以下であり、より好ましくは20質量%以下であり、更に好ましくは15質量%以下である。
第二層の層厚は、解像度、密着性、現像性の観点から10μm以下が好ましく、より好ましくは、5μm以下、さらに好ましくは3μm以下である。また、酸素遮断性の観点から、0.1μm以上、好ましくは0.5μm以上、より好ましくは1μm以上である。
また、本発明の感光性樹脂積層体としては、支持フィルム上に、第一層、第二層及び感光性樹脂層とを順次積層した上に、さらに保護層を積層してもよい。
保護層としては10~100μm厚程度のポリエチレン、ポリプロピレン、ポリカーボネート、ポリエチレンテレフタレートなどの合成樹脂フィルムがあるが、ポリエチレンフィルム又はポリプロピレンフィルムが好ましく用いられる。
本発明の感光性樹脂積層体における感光性樹脂層は、(a)カルボキシル基含有量が酸当量で100~600であり、重量平均分子量が5,000~500,000であるバインダー用樹脂:20~90質量%、(b)少なくとも一種の光重合可能な不飽和化合物:3~70質量%、(c)光重合開始剤:0.1~20質量%、を含有する感光性樹脂組成物からなる層であることが好ましい。本発明の感光性樹脂積層体に用いられる感光性樹脂組成物を以下、詳細に説明する。
バインダー用樹脂中のカルボキシル基は、感光性樹脂層にアルカリ水溶液に対する現像性や剥離性を与えるために必要である。酸当量は、現像耐性、解像性および密着性の観点から100以上が好ましく、現像性および剥離性の観点から600以下が好ましい。
(分散度)=(重量平均分子量)/(数平均分子量)
分子量は、日本分光(株)製ゲルパーミエーションクロマトグラフィー(GPC)(ポンプ:Gulliver、PU-1580型、カラム:昭和電工(株)製Shodex(登録商標)(KF-807、KF-806M、KF-806M、KF-802.5)4本直列、移動層溶媒:テトラヒドロフラン、ポリスチレン標準サンプル(昭和電工(株)製Shodex STANDARD SM-105)による検量線使用)により重量平均分子量(ポリスチレン換算)として求められる。
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等が挙げられる。
第二の単量体は、非酸性で、分子中に重合性不飽和基を一個有する化合物である。該化合物は、感光性樹脂層の現像性、エッチング及びめっき工程での耐性、硬化膜の可とう性等の種々の特性を保持するように選ばれる。該化合物としては、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート等のアルキル(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、(メタ)アクリロニトリル、ベンジル(メタ)アクリレート、メトキシベンジル(メタ)アクリレート、クロロベンジル(メタ)アクリレート、フルフリル(メタ)アクリレート、テトラヒドロフルフリル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、フェニル(メタ)アクリレート、クレジル(メタ)アクリレート、ナフチル(メタ)アクリレートなどのアリール(メタ)アクリレート、フェニル基を有するビニル化合物(例えば、スチレン)等を用いることができる。特に、解像性、現像液凝集性の観点から、ベンジル(メタ)アクリレートが好ましい。
(a)バインダー用樹脂の感光性樹脂組成物全体に対する割合は、20~90質量%の範囲が好ましく、より好ましくは30~70質量%である。露光、現像によって形成される硬化レジストパターンが、レジストとしての特性、例えば、テンティング、エッチング及び各種めっき工程において十分な耐性等を有するという観点から20質量%以上90質量%以下が好ましい。
上記一般式(IV)で表される化合物において、n6+n7及びn8+n9は、40以下である必要があり、40を超えると感度の観点から好ましくない。好ましくは30以下である。
上記一般式(VI)で表される化合物は、m5及びm6が、15を超えると充分な感度が得られない。上記一般式(VI)で表される化合物の具体例としては、例えば、ヘキサメチレンジイソシアネート、トリレンジイソシアネート、又は2,2,4-トリメチルヘキサメチレンジイソシアネート等のジイソシアネ-ト化合物と、一分子中にヒドロキシル基と(メタ)アクリル基を有する化合物(2-ヒドロキシプロピルアクリレート、オリゴプロピレングリコールモノメタクリレート等)とのウレタン化合物等が挙げられる。具体的には、ヘキサメチレンジイソシアネートとオリゴプロピレングリコールモノメタクリレート(日本油脂(株)製、ブレンマーPP1000)との反応物がある。
上記一般式(VII)で表される化合物の具体例としては、例えば、平均2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ールと平均7モルのエチレンオキサイドを付加したポリエチレングリコールをノニルフェノールに付加した化合物のアクリレートである4-ノルマルノニルフェノキシヘプタエチレングリコールジプロピレングリコールアクリレートが挙げられる。平均8モルのエチレンオキサイドを付加したポリエチレングリコールをノニルフェノールに付加した化合物のアクリレートである4-ノルマルノニルフェノキシオクタエチレングリコールアクリレート(東亞合成(株)製、M-114)が挙げられる。
また、上記一般式(III)~(VII)で表される化合物からなる群から選ばれた少なくとも一種の光重合可能な不飽和化合物の感光性樹脂組成物全体に対する割合は、3~70質量%の範囲である。解像度の観点から3質量%以上であり、レジストパターンの可とう性の観点から70質量%以下である。より好ましくは3~30質量%以下である。
本発明に用いられる(c)光重合開始剤としては、上記一般式(VIII)で表される化合物及び上記一般式(IX)で表される化合物からなる群より選ばれる少なくとも一種の2,4,5-トリアリ-ルイミダゾール二量体とp-アミノフェニルケトン類を併用する系が好ましい。p-アミノフェニルケトン類としては、例えば、p-アミノベンゾフェノン、p-ブチルアミノアセトフェノン、p-ジメチルアミノアセトフェノン、p-ジメチルアミノベンゾフェノン、p,p’-ビス(エチルアミノ)ベンゾフェノン、p,p’-ビス(ジメチルアミノ)ベンゾフェノン[ミヒラーズケトン]、p,p’-ビス(ジエチルアミノ)ベンゾフェノン、p,p’-ビス(ジブチルアミノ)ベンゾフェノンが挙げられる。
本発明の感光性樹脂積層体における感光性樹脂組成物は、(c)光重合開始剤を、感光性樹脂組成物全体に対して0.1~20質量%含有することが好ましい。十分な感度を得る観点から、0.1質量%以上、露光時にフォトマスクを通した光のハレーション防止の観点から20質量%以下が好ましい。
感光性樹脂組成物には、光照射により発色する発色系染料を含有させることもできる。
ハロゲン化合物としては、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フォン、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等が挙げられる。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。
本発明における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を含有させることは好ましいことである。このようなラジカル重合禁止剤としては、例えば、p-メトキシフェノール、ハイドロキノン、ピロガロール、ナフチルアミン、tert-ブチルカテコール、塩化第一銅、2,6-ジ-tert-ブチル-p-クレゾール、2,2’-メチレンビス(4-エチル-6-tert-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-tert-ブチルフェノール)、ジフェニルニトロソアミン等が挙げられる。
まず、熱可塑性樹脂、例えば、溶液重合で得られたポリメタクリル酸メチルのメチルエチルケトン溶液(重量平均分子量6万、固形分濃度40質量%、ガラス転移温度105℃)を支持フィルム上にバーコーターやロールコーターを用いて塗布して乾燥する。これにより、支持フィルム上に第一層を積層することができる。ポリメタクリル酸メチルのメチルエチルケトン溶液の粘度は、10~2000mPa・sに調整するのが好ましい。
プリント配線板は、以下の各工程を経て製造される。
(1)ラミネート工程
感光性樹脂積層体に保護層がある場合には、保護層を剥がしながら該感光性樹脂積層体を銅張積層板やフレキシブル基板等の基板上にホットロールラミネーターを用いて密着させる工程。
(2)露光工程
感光性樹脂積層体から、第一層と第二層との間で剥離しながら第一層が支持フィルムとともに接着したままで剥離し、所望の配線パターンを有するマスクフィルムを第二層上に密着させ活性光線源を用いて露光を施す工程。
アルカリ現像液を用いて第二層及び感光性樹脂層の未露光部分を溶解又は分散除去し、硬化レジストパタ-ンを基板上に形成する工程。
(4)エッチング工程又はめっき工程
形成されたレジストパターン上からエッチング液を吹き付けレジストパターンによって覆われていない銅面をエッチングする工程、又はレジストパターンによって覆われていない銅面に銅、半田、ニッケル、錫等のめっき処理を行う工程。
(5)剥離工程
アルカリ剥離液を用いて基板からレジストパターンを除去する工程。
また、上記(3)現像工程で用いられるアルカリ現像液としては、炭酸ナトリウム、炭酸カリウム等の水溶液が挙げられる。これらのアルカリ水溶液は感光性樹脂層の特性に合わせて選択されるが、一般的に0.5質量%以上3質量%以下の炭酸ナトリウム水溶液が用いられる。
上記(5)剥離工程で用いられるアルカリ剥離液としては、一般的に現像で用いたアルカリ水溶液よりも更に強いアルカリ性の水溶液、例えば1質量%以上5質量%以下の水酸化ナトリウム、水酸化カリウムの水溶液が挙げられる。
また、セミアディティブ工法等めっき工程を設けた場合には、レジストパターンを剥離後に、レジストパターンの下に現れた銅面をエッチングする場合もある。
以下、実施例により本発明の実施形態の例をさらに詳しく説明する。
〔実施例1~15、比較例1~4〕
1.評価用サンプルの作製
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。
<感光性樹脂積層体の作製>
表1に示す第一層のメチルエチルケトン溶液を16μm厚のポリエチレンテレフタレートフィルム(東レ製16QS48水準3)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分間乾燥して支持フィルム上に均一な第一層を形成した。第一層の厚みは20μmであった。次に表1に示す第二層の組成物の水溶液をよく撹拌、混合し、前記第一層を積層された支持フィルムの第一層の表面にバーコーターを用いて均一に塗布し、100℃の乾燥機中で3分間乾燥して第一層上に均一な第二層を形成した。第二層の厚みは2μmであった。さらに、支持フィルムに積層された第二層上に、表1に示す感光性樹脂組成物をバーコーターを用いて均一に塗布し、95℃の乾燥機中で3分間乾燥して均一な感光性樹脂層を形成した。感光性樹脂層の厚みは2μmであった。
次いで、感光性樹脂層上の表面上に、保護層として25μm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、密着性、現像後のスソ、硬化レジストパターンのサイドウオールのガタツキ及び表面状態は、絶縁樹脂に8μm銅箔を積層した住友金属(株)製エスパーフレックスを用いて評価した。また、ラミネート後のラミネートエアーボイドの評価に関してはRa=0.2程度のフレキシブル基材を用いて評価した。
<ラミネート>
本発明の感光性樹脂積層体の保護層を剥がしながらホットロールラミネーター(旭化成エンジニアリング(株)社製、AL-70)により、ロ-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1.0m/minとした。ラミネートエアーボイド評価(追従性評価)においてはエアー圧力は0.2MPa、ラミネート速度は2.0m/minとした。
ポリエチレンテレフタレートフィルムに第一層が積層された支持フィルムを剥離した後、感光性樹脂層の評価に必要なマスクフィルムを第二層上に置き、超高圧水銀ランプ(オーク製作所製、HMW-801)により140mJ/cm2の露光量で露光した。
<現像>
30℃の0.5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する最も少ない時間を最小現像時間とした。実際の現像時間は最小現像時間の2倍で現像し、硬化レジストパターンを得た。
(1)追従性評価
前記条件でラミネート後、100mJで露光し、光学顕微鏡で10cm×10cmの範囲を観察し、ラミネートエアーボイドの数をカウントし、下記ランク付けをした:
◎:全くラミネートエアーボイドの発生無し;
○:数個程度ラミネートエアーボイドの発生が認められる;
△:数十個程度のラミネートエアーボイドの発生が認められる;
×:無数のラミネートエアーボイドの発生が認められる。
露光前にポリエチレンテレフタレートフィルムに第一層が積層された支持フィルムを剥離する時、剥離性について下記ランク付けをした:
○:第一層と第二層間で問題なく剥離された;
×:第一層と第二層間で剥離されず、支持フィルムであるポリエチレンテレフタレートと第一層間または第二層と感光性樹脂層間で剥離された。
ラミネート後15分経過した感度、解像度評価用基板を、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た。露光後、最小現像時間の2倍の現像時間で現像し、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4である露光量により、次の様にランク分けした:
○:露光量が140mJ/cm2以下;
△:露光量が140mJ/cm2を超え、150mJ/cm2以下;
×:露光量が150mJ/cm2を超える。
ラミネート後15分経過した基板を、露光時のマスクフィルムとして、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を用いて、上記のように、露光し、現像した。硬化レジストパターンが正常に形成されている最小マスク幅を解像度の値とし、解像性を下記のようにランク分けした:
◎:解像度の値が5μm以下;
○:解像度の値が5μmを超え、10μm以下;
△:解像度の値が10μmを超え、15μm以下;
×:解像度の値が15μmを超える。
ラミネート後15分経過した基板を、露光時のマスクフィルムとして、露光部単独のラインパターンマスクを用いて、上記のように、露光し、現像した。硬化レジストパターンが正常に形成されている最小マスク幅を密着性の値とし、密着性を下記のようにランク分けした:
◎:密着性の値が5μm以下;
○:密着性の値が5μmを超え、10μm以下;
△:密着性の値が10μmを超え、15μm以下;
×:密着性の値が15μmを超える。
露光時のマスクフィルムとしてクロムガラスフォトマスクを用いて、上記のように、露光し、現像した。得られた硬化パターンの10μmラインの形状を下記によりランク付けした:
◎:硬化レジストのフット部の切れは良好でスソ引きが無い;
○:硬化レジストのフット部の切れは良好でスソ引きが極小である;
△:硬化レジストのフット部に3μm以下のスソ引きが認められる;
×:硬化レジストのフット部に3μmを超えるスソ引きが認められる。
基板にラミネートされた積層体に、クロムガラスフォトマスクを用いて、上記のように、露光し、現像した。得られた硬化パターンの10μmラインのレジストサイドウォール形状を下記によりランク付けした:
○:形成されたレジストサイドウォールにガタツキはほとんど無い;
△:形成されたレジストサイドウォールにごく僅かにガタツキが存在する;
×:形成されたレジストサイドウォールのところどころにガタツキが存在する。
基板にラミネートされた積層体に、クロムガラスフォトマスクを用いて、上記のように、露光し、現像した。得られた硬化パターンの10μmラインのレジスト表面状態を下記によりランク付けした:
○:形成されたレジスト表面には凹みがほとんど無い;
△:形成されたレジスト表面にごく僅かに凹みが存在する;
×:形成されたレジスト表面にところどころに凹みが存在する。
実施例及び比較例の評価結果を、以下の表1に示す。表1におけるP-1~P-2、Q-2~Q-4の質量部は、メチルエチルケトン溶液としての量である。表1中、比較例1は第一層が無く、比較例2は第二層が無く、比較例3は第二層において上記一般式(I)又は一般式(II)で表される化合物を欠いている。比較例4は、上記一般式(I)又はい一般式(II)で表される化合物の含有量が本願構成を欠いている。
P-1:ベンジルメタクリレート80質量%、メタクリル酸20質量%の2元共重合体のメチルエチルケトン溶液(固形分濃度50質量%、重量平均分子量2.5万、酸当量430、分散度2.7)
P-2:メタクリル酸メチル50質量%、メタクリル酸25質量%、スチレン25質量%の三元共重合体のメチルエチルケトン溶液(固形分濃度35質量%、重量平均分子量5万、酸当量344、分散度3.1)
M-2:ビスフェノールAの両端にそれぞれ平均2モルのプロピレンオキサイドと平均6モルのエチレンオキサイドを付加したポリアルキレングリコールのジメタクリレート
M-3:ビスフェノールAの両端にそれぞれ平均2モルのエチレンオキサイドを付加したポリエチレングリコールのジメタクリレート(新中村化学工業(株)製NKエスエルBPE-200)
M-5:2,2-ビス{4-(メタクリロキシペンタエトキシ)シクロヘキシル}プロパン
M-6:ヘキサメチレンジイソシアネートとオリゴプロピレングリコールモノメタクリレート(日本油脂(株)製、ブレンマーPP1000)との反応物であるウレタンポリプロピレングリコールジメタクリレート
M-8:トリオキシエチルトリメチロールプロパントリアクリレート(新中村化学工業(株)製 NKエステルA-TMPT-3EO)
M-9:ノナエチレングリコールジアクリレート
G-1:4,4’-ビス(ジエチルアミノ)ベンゾフェノン
G-2:2-(o-クロロフェニル)-4、5-ジフェニルイミダゾール二量体
J-1: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)
J-2:ロイコクリスタルバイオレット
L-2:ペンタエリスリトールの3,5-ジ-t-ブチル-4-ヒドロキシフェニルプロピオン酸テトラエステル(チバスペシャリティケミカルズ(株)製IRGANOX245)
Q-1:ポリオキシエチレンモノメチルエーテル(日本油脂(株)製ユオックスM-550、重量平均分子量550)
Q-2:ポリメタクリル酸メチルのメチルエチルケトン溶液(固形分濃度40質量%、重量平均分子量6万)
Q-4:メタクリル酸メチル80質量%、スチレン20質量%の2元共重合体のメチルエチルケトン溶液(固形分濃度40質量%、重量平均分子量5万)
Q-5:フタル酸ジブチル
Q-6:ポリビニルアルコール((株)クラレ製 PVA-205)
Q-7:ポリエチレングリコール(重量平均分子量400)
Q-8:ポリビニルピロリドン(重量平均分子量4万)((株)日本触媒製、K-15(品番))
Claims (7)
- 支持フィルム上に、層厚が10μm以上100μm以下の第一層と、層厚が0.1μm以上10μm以下の第二層と、感光性樹脂層とを順次積層してなる感光性樹脂積層体であって、該第一層が、熱可塑性樹脂を含有し、そして該第二層が、ポリビニルアルコール:75~99質量%と、下記一般式(I):
R1-O-(CH2CH2O)n1-R2 (I)
{式中、R1及びR2は、H又はCH3であり、これらは同一であっても相違してもよく、そしてn1は、3~25の整数である。}で表される化合物、及び下記一般式(II):
- 前記熱可塑性樹脂が、下記一般式(I):
R1-O-(CH2CH2O)n1-R2 (I)
{式中、R1及びR2は、H又はCH3であり、これらは同一であっても相違してもよく、そしてn1は、3~25の整数である。}で表される化合物を含有する、請求項1に記載の感光性樹脂積層体。 - 前記感光性樹脂層上に保護層を更に積層してなる、請求項1又は2に記載の感光性樹脂積層体。
- 前記感光性樹脂層が、(a)カルボキシル基含有量が酸当量で100~600であり、かつ、重量平均分子量が5,000~500,000であるバインダー用樹脂:20~90質量%、(b)少なくとも一種の光重合可能な不飽和化合物:3~70質量%、及び(c)光重合開始剤:0.1~20質量%、を含有する感光性樹脂組成物からなる層である、請求項1又は2に記載の感光性樹脂積層体。
- 前記(b)少なくとも一種の光重合可能な不飽和化合物が、下記一般式(III)~(VII)で表される化合物からなる群から選ばれる少なくとも一種の光重合可能な不飽和化合物である、請求項4に記載の感光性樹脂積層体:
- 請求項1又は2に記載の感光性樹脂積層体を金属板又は金属被覆絶縁板の表面にラミネートし、支持フィルムとともに第一層を剥離し、活性光を露光した後、現像により未露光部を除去することを特徴とするレジストパターンの形成方法。
- 請求項6に記載の方法によって、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ことを特徴とする導体パターンの製造方法。
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CN200980102705.1A CN101925861B (zh) | 2008-01-29 | 2009-01-21 | 感光性树脂层压体 |
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JP2012215676A (ja) * | 2011-03-31 | 2012-11-08 | Asahi Kasei E-Materials Corp | 感光性樹脂組成物及びそれを用いた積層体 |
US20150241772A1 (en) * | 2012-08-27 | 2015-08-27 | Zhuhai Dynamic Technology Optical Industry Co., Ltd. | Double coated negative-working dry-film photoresist |
US20150293443A1 (en) * | 2012-11-20 | 2015-10-15 | Hitachi Chemical Company, Ltd. | Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board |
JP2018517168A (ja) * | 2015-04-21 | 2018-06-28 | フジフイルム エレクトロニック マテリアルズ ユー.エス.エー., インコーポレイテッド | 感光性ポリイミド組成物 |
JP2019191518A (ja) * | 2018-04-27 | 2019-10-31 | 富士フイルム株式会社 | 感光性転写材料、レジストパターンの製造方法、回路配線の製造方法 |
WO2020054075A1 (ja) * | 2018-09-14 | 2020-03-19 | 日立化成株式会社 | 転写型感光性フィルム、樹脂硬化膜の形成方法及び樹脂硬化膜付センサ基板の製造方法 |
WO2020261523A1 (ja) * | 2019-06-27 | 2020-12-30 | 昭和電工マテリアルズ株式会社 | 転写型感光性フィルム、樹脂硬化膜の形成方法及び樹脂硬化膜付基板の製造方法 |
WO2020261512A1 (ja) * | 2019-06-27 | 2020-12-30 | 昭和電工マテリアルズ株式会社 | 被覆膜付き基体及びその製造方法、並びに、検査センサ |
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WO2019124307A1 (ja) * | 2017-12-20 | 2019-06-27 | 住友電気工業株式会社 | プリント配線板の製造方法及び積層体 |
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TWI388933B (zh) | 2013-03-11 |
CN101925861B (zh) | 2013-07-03 |
TW200947135A (en) | 2009-11-16 |
CN103091989B (zh) | 2016-03-09 |
CN101925861A (zh) | 2010-12-22 |
CN103091989A (zh) | 2013-05-08 |
JPWO2009096292A1 (ja) | 2011-05-26 |
JP4778588B2 (ja) | 2011-09-21 |
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