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WO2014024951A1 - Stratifié de film photosensible, carte de circuit imprimé flexible et procédé de fabrication de ceux-ci - Google Patents

Stratifié de film photosensible, carte de circuit imprimé flexible et procédé de fabrication de ceux-ci Download PDF

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Publication number
WO2014024951A1
WO2014024951A1 PCT/JP2013/071447 JP2013071447W WO2014024951A1 WO 2014024951 A1 WO2014024951 A1 WO 2014024951A1 JP 2013071447 W JP2013071447 W JP 2013071447W WO 2014024951 A1 WO2014024951 A1 WO 2014024951A1
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WIPO (PCT)
Prior art keywords
photosensitive film
film
wiring
group
photosensitive
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Ceased
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PCT/JP2013/071447
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English (en)
Japanese (ja)
Inventor
有久　慎司
洋朗 佐々木
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Asahi Kasei Corp
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Asahi Kasei E Materials Corp
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Application filed by Asahi Kasei E Materials Corp filed Critical Asahi Kasei E Materials Corp
Priority to KR1020167029251A priority Critical patent/KR102130430B1/ko
Priority to KR1020157002019A priority patent/KR101684195B1/ko
Priority to CN201380041043.8A priority patent/CN104583867B/zh
Priority to JP2014529547A priority patent/JP5903164B2/ja
Publication of WO2014024951A1 publication Critical patent/WO2014024951A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

Definitions

  • the present invention relates to a photosensitive film laminate using a photosensitive film containing a photosensitive resin composition, which is useful as a surface protective film for a semiconductor element, an interlayer insulating film, a semiconductor package substrate, and a protective insulating film for a flexible printed circuit board.
  • the present invention relates to a printed wiring board and a manufacturing method thereof.
  • FPC flexible printed circuit board
  • This FPC has a structure with a coverlay made of polyimide film etc. on a processed FCCL (Flexible Copper Clad Laminate), mainly mobile phones, smartphones, tablet terminals, notebook computers. Used in devices such as digital cameras. Since FPC maintains its function even when bent, it has become an indispensable material for reducing the size and weight of equipment.
  • electronic devices represented by smartphones and tablet terminals have been reduced in size and weight, and by adopting FPC in such products, the size and weight of the electronic devices are reduced. This contributes to reducing product costs and simplifying design.
  • the FPC is provided with a cover lay which is a layer of an insulating material used for covering the conductor pattern on the outer surface of the printed board in whole or in part.
  • the most basic coverlay is a film coverlay composed of a highly reliable non-photosensitive punching material, but the automation of the bonding process is extremely difficult, and even a roll-to-roll attempt is not made. The fact is that it relies on manpower.
  • coverlay processing process the use of screen printing with coverlay ink is being considered, as is the case with solder masks on hard printed circuit boards. Compared to the above, it is inferior in mechanical properties and chemical resistance (particularly plating resistance), and has not been widely used.
  • photosensitive coverlays for performing microfabrication by lithography have been energetically developed for miniaturization of FPC and labor saving of manufacturing processes.
  • materials designed for alkaline aqueous solution development have been made for environmental considerations.
  • photosensitive coverlays using polyimide precursors have mechanical properties such as electrical insulation reliability derived from polyimide, mechanical properties such as bending resistance, and heat resistance. It is expected as an excellent cover lay from the viewpoint of safety, chemical resistance and flame retardancy.
  • the dry film type photosensitive cover lay film not only saves labor and time for application and drying compared to the method of applying a liquid photosensitive resin, but also by laminating and lithography on both sides at once. Since a roll-to-roll production system in which a large number of holes are drilled can be achieved, the FPC manufacturing process can be shortened and labor can be saved.
  • an alkali negative developing type photosensitive polyimide precursor by a method of introducing a photoreactive group into a part of the total alkali-soluble groups, or an alkali-soluble group in polyimide.
  • Negative-type photosensitive polyimides have been developed by adding a polymerizable compound and a photopolymerization initiator to an alkali-soluble polyimide into which is introduced (see, for example, Patent Documents 1 to 3).
  • the present invention has been made in view of such points, and is capable of alkali development, excellent in photosensitivity, and has excellent wiring coverage even when thinned, and an exposed portion and an unexposed portion It aims at providing the photosensitive film laminated body using the photosensitive film excellent in the visibility of this, a flexible printed wiring board, and its manufacturing method.
  • the photosensitive film laminate of the present invention is provided on a base material, the base material, (A) an alkali-soluble resin, (B) a polymerizable compound having an unsaturated double bond, and (C) photopolymerization. And a photosensitive film containing a photosensitive resin composition having a structure represented by the following general formula (1), wherein the photopolymerization initiator (C) contains: an initiator.
  • Ar 1 is a monovalent organic group containing an aromatic group
  • R 1 is an organic group having an alkyl group or an aryl group
  • R 2 is a branched alkyl group, and a straight chain.
  • It is a monovalent hydrocarbon group having 3 to 50 carbon atoms, which is either an alkyl group, an alkyl group having an alicyclic structure, or an alkyl group having an aromatic structure.
  • the flexible printed wiring board of the present invention is characterized by comprising a circuit board having wiring and the above-mentioned photosensitive film formed by baking on the circuit board.
  • the method for producing a flexible printed wiring board of the present invention is characterized in that the photosensitive film laminate is laminated on a wiring surface on a circuit board having wiring using a roll-type thermal vacuum laminator, and then fired to form a film. To do.
  • the flexible printed wiring board of the present invention is manufactured by the above manufacturing method.
  • a flexible printed wiring board includes a circuit board having wiring, and a film obtained by firing a coverlay film provided on the circuit board so as to cover the wiring. And the minimum thickness (a) of the film
  • a flexible printed wiring board includes a circuit board having wiring, and a film obtained by firing a coverlay film provided on the circuit board so as to cover the wiring.
  • the maximum value (b) of the surface step of the film obtained by baking between the wiring and the portion without the wiring is 3 ⁇ m or less.
  • the photosensitive film is capable of alkali development, has excellent photosensitivity, has excellent wiring coverage even when thinned, and has excellent visibility between exposed and unexposed areas.
  • the photosensitive film laminated body using this, a flexible printed wiring board, and its manufacturing method are realizable.
  • the photosensitive film laminated body which concerns on this Embodiment has a base material and the photosensitive film containing the photosensitive resin composition provided on this base material.
  • the photosensitive resin composition according to the present embodiment contains (A) an alkali-soluble resin, (B) a polymerizable compound having an unsaturated double bond, and (C) a photopolymerization initiator, C)
  • the photopolymerization initiator has a structure represented by the following general formula (1).
  • Ar 1 is a monovalent organic group containing an aromatic group
  • R 1 is an organic group having an alkyl group or an aryl group
  • R 2 is a branched alkyl group, and a straight chain.
  • It is a monovalent hydrocarbon group having 3 to 50 carbon atoms, which is either an alkyl group, an alkyl group having an alicyclic structure, or an alkyl group having an aromatic structure.
  • ⁇ Photosensitive resin composition> (A) Alkali-soluble resin
  • the alkali-soluble resin various polymers conventionally used in photosensitive resin compositions can be used. Examples of such polymers include (meth) acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, phenol novolac resins, and cresols.
  • a (meth) acrylic acid copolymer means both an acrylic acid copolymer and a methacrylic acid copolymer.
  • the alkali-soluble resin the above-described polymer may be used alone, or two or more kinds may be mixed and used.
  • the alkali-soluble resin those having a weight average molecular weight of 10,000 to 250,000 and an acid value of 50 to 300 mgKOH / g are preferably used.
  • a polyimide precursor is particularly preferable from the viewpoint of obtaining a mechanical property such as electrical insulation reliability and bending resistance, heat resistance, chemical resistance, and flame retardant excellent. Moreover, it is preferable to use a polyimide precursor also in order to implement
  • a polyimide precursor means what becomes a polyimide by imidation, and does not mean only polyamic acid, but also includes a part of polyamic acid imidized.
  • the polyimide precursor can be obtained, for example, by reacting tetracarboxylic dianhydride and diamine.
  • tetracarboxylic dianhydride A conventionally well-known tetracarboxylic dianhydride can be used.
  • tetracarboxylic dianhydride aromatic tetracarboxylic acid or aliphatic tetracarboxylic dianhydride can be applied.
  • limiting in the diamine to be used A conventionally well-known diamine can be used.
  • tetracarboxylic dianhydride examples include biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride (hereinafter abbreviated as “BPDA”), benzophenone-3,3 ′, 4,4′- Tetracarboxylic dianhydride (hereinafter abbreviated as “BTDA”), oxydiphthalic dianhydride (hereinafter abbreviated as “ODPA”), diphenylsulfone-3,3 ′, 4,4′-tetracarboxylic acid dianhydride
  • TMEG ethylene glycol bis (trimellitic acid monoester acid anhydride)
  • TMEG ethylene glycol bis (trimellitic acid monoester acid anhydride)
  • TMEG ethylene glycol bis (trimellitic acid monoester acid anhydride)
  • TMEG p-phenylene bis (trimellitic acid monoester acid anhydride)
  • tetracarboxylic dianhydrides described above may be used alone or in combination of two or more. From the viewpoint of developability of the polyimide precursor, BPDA, ODPA, BTDA, TMEG, 5-BTA, and decandioldiol bis (trimellitic acid monoester acid anhydride) are more preferable.
  • diamine examples include 1,3-bis (4-aminophenoxy) alkane, 1,4-bis (4-aminophenoxy) alkane, 1,5-bis (4-aminophenoxy) alkane, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'- Diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 3,7-diamino-dimethyldibenzothiophene-5 5-dioxide, 4,4′-diaminobenzophenone, 3,3′-diamino
  • APB, BAPP, and TMAB are preferable from the viewpoint of lowering the glass transition point (Tg) of the polyimide precursor and improving developability.
  • These diamines can also be used as diamine components used for the synthesis of the polyimide structure part of the polyimide precursor described later.
  • a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may be the same or different, and R 11 , R 14 , R 17 , R 20 , and R 23 are carbon
  • R 25 represents a divalent organic group having 1 to 90 carbon atoms
  • R 26 represents a tetravalent organic group having 1 to 50 carbon atoms.
  • R ⁇ 9 >, R ⁇ 10 >, R ⁇ 12 >, R ⁇ 13> , R ⁇ 15> , R ⁇ 16> , R ⁇ 18> , R ⁇ 19> , R ⁇ 21> , and R ⁇ 22> are each independently a hydrogen atom or 1 carbon atom.
  • R 11 , R 14 , R 17 , R 20 , and R 23 each have 1 to 20 carbon atoms.
  • Represents a tetravalent organic group, and m, n, and p are each independently an integer of 0 or more and 30 or less, and satisfy 1 ⁇ (m + n + p) ⁇ 30.)
  • the molecular chain of the polyimide precursor has an appropriate flexibility due to the oxyalkylene skeleton introduced into the molecular chain of the polyimide precursor. Therefore, the developability of the photosensitive resin composition can be improved.
  • the oxyalkylene skeleton is introduced into the polyamic acid structure part of the polyimide precursor by the diamine represented by the general formula (7), a secondary amino group derived from the diamine is introduced into the polyamic acid structure part. Is done.
  • This secondary amino group has a high basicity and has a problem in that the depolymerization of the polyamic acid structure portion is promoted and the molecular weight of the polyimide precursor is significantly lowered as compared with the conventional polyamic acid.
  • the basicity of the secondary amino group mentioned above is introduce
  • the developability of the photosensitive resin composition can be improved while preventing the adverse effects of the composition and stabilizing the molecular weight.
  • m, n, and p are each independently an integer of 0 or more and 30 or less. From the viewpoint of insulation reliability, 1 ⁇ (m + n + p) ⁇ 30 is preferable, and 3 ⁇ (m + n + p) ⁇ 10 is more preferable. If it is within the range of 1 ⁇ (m + n + p) ⁇ 30, the skeleton having an oxyalkylene group is shortened, so that the elastic modulus of the polyimide precursor is increased and the insulation reliability is estimated to be improved.
  • the diamine represented by the general formula (7) is not limited as long as the polyimide structure represented by the general formula (5) can be obtained.
  • Examples of such diamines include polyoxyethylenediamine compounds such as 1,8-diamino-3,6-dioxyoctane, polyoxyalkylenediamine compounds such as Jeffamine EDR-148 and EDR-176 manufactured by Huntsman, and Jeffamine D. -230, D-400, D-2000, D-4000, polyoxypropylenediamine compounds such as polyetheramine D-230, D-400, D-2000 manufactured by BASF, and HK-511, ED-600 And compounds having different oxyalkylene groups such as ED-900, ED-2003, and XTJ-542.
  • the skeleton having these oxyalkylene groups can reduce the warpage of FPC after baking of the polyimide.
  • the main chain terminal of the polyimide precursor is not particularly limited as long as it does not affect the performance.
  • a terminal structure derived from an acid dianhydride or a diamine used for producing a polyimide precursor may be used, or a structure in which the terminal is sealed with another acid anhydride or an amine compound may be used.
  • the weight average molecular weight of the polyimide precursor is preferably from 1,000 to 1,000,000.
  • the weight average molecular weight refers to a molecular weight measured by gel permeation chromatography using polystyrene having a known weight average molecular weight as a standard.
  • the weight average molecular weight is preferably 1000 or more from the viewpoint of the strength of the resin layer obtained by the photosensitive resin composition, and preferably 1000000 or less from the viewpoint of the viscosity and moldability of the photosensitive resin composition. .
  • the weight average molecular weight is more preferably from 5,000 to 500,000, particularly preferably from 10,000 to 300,000, and most preferably from 15,000 to 80,000.
  • a polyimide precursor having a polyimide structure and a polyamic acid structure as repeating units, respectively, is a step of reacting acid dianhydride and diamine in a non-equal molar amount to synthesize a first-stage polyimide portion (step 1), followed by 2 It can be prepared by a step of synthesizing the polyamic acid portion at the stage (step 2).
  • step 1 A polyimide precursor having a polyimide structure and a polyamic acid structure as repeating units, respectively, is a step of reacting acid dianhydride and diamine in a non-equal molar amount to synthesize a first-stage polyimide portion (step 1), followed by 2 It can be prepared by a step of synthesizing the polyamic acid portion at the stage (step 2).
  • the process of synthesizing the first stage polyimide portion will be described.
  • the step of synthesizing the first-stage polyimide portion is not particularly limited, and a known method can be applied. More specifically, the polyimide portion can be synthesized by the following method. First, diamine is dissolved and / or dispersed in a polymerization solvent, and acid dianhydride powder is added thereto. Then, a solvent that is azeotroped with water is added, and the mixture is heated and stirred for 0.5 to 96 hours, more preferably for 0.5 to 30 hours while removing by-product water azeotropically using a mechanical stirrer. At this time, the monomer concentration is preferably 0.5% by mass or more and 95% by mass or less, and more preferably 1% by mass or more and 90% by mass or less.
  • the polyimide part can be synthesized by adding a known imidization catalyst or without a catalyst.
  • the imidation catalyst is not particularly limited, but may be an acid anhydride such as acetic anhydride, ⁇ -valerolactone, ⁇ -butyrolactone, ⁇ -tetronic acid, ⁇ -phthalide, ⁇ -coumarin, and ⁇ -phthalido acid. Lactone compounds, and tertiary amines such as pyridine, quinoline, N-methylmorpholine, and triethylamine. Moreover, you may use 1 type, or 2 or more types of these mixtures as needed. Among these, a mixed system of ⁇ -valerolactone and pyridine and non-catalyst are particularly preferable from the viewpoint of high reactivity and reducing the influence on the next reaction.
  • the amount of the imidization catalyst added is preferably 50 parts by mass or less and more preferably 30 parts by mass or less with respect to 100 parts by mass of the polyamic acid.
  • the reaction solvent used in the synthesis of the polyimide part includes 2 or more carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether.
  • Particularly preferable solvents include ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 12 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and 2 carbon atoms. Examples thereof include nitrogen-containing compounds having 10 or less carbon atoms. These can be arbitrarily selected in consideration of industrial productivity and influence on the next reaction.
  • the reaction temperature is preferably 15 ° C. or higher and 250 ° C. or lower. If the reaction temperature is 15 ° C. or higher, the reaction starts, and if it is 250 ° C. or lower, there is no deactivation of the catalyst.
  • the reaction temperature is preferably 20 ° C. or higher and 220 ° C. or lower, and more preferably 20 ° C. or higher and 200 ° C. or lower.
  • the time required for the reaction varies depending on the purpose and reaction conditions, but is usually within 96 hours, particularly preferably in the range of 30 minutes to 30 hours.
  • the synthesis of the polyamic acid moiety at the second stage can be carried out by using the polyimide moiety obtained in Step 1 as a starting material and adding diamine and / or acid dianhydride for polymerization.
  • the polymerization temperature in the synthesis of the second stage polyamic acid moiety is preferably 0 ° C. or higher and 250 ° C. or lower, more preferably 0 ° C. or higher and 100 ° C. or lower, and particularly preferably 0 ° C. or higher and 80 ° C. or lower.
  • the time required for the reaction in the synthesis of the polyamic acid varies depending on the purpose or reaction conditions, it is usually within 96 hours, particularly preferably in the range of 30 minutes to 30 hours.
  • the reaction solvent the same solvent as used for the synthesis of the polyimide part in Step 1 can be used.
  • the polyamic acid moiety can be synthesized using the reaction solution of Step 1 as it is.
  • the produced polyimide precursor may be used while dissolved in a reaction solvent, and may be recovered and purified by the following method.
  • the polyimide precursor after the production can be recovered by distilling off the solvent in the reaction solution under reduced pressure.
  • Examples of the method for purifying the polyimide precursor include a method of removing insoluble acid dianhydride and diamine in the reaction solution by vacuum filtration, pressure filtration, or the like. Moreover, you may implement the purification method by what is called reprecipitation which adds a reaction solution to a poor solvent and precipitates. Furthermore, when a highly pure polyimide precursor is required, a purification method by extraction using supercritical carbon dioxide is also possible.
  • the photosensitive resin composition in this Embodiment contains the polymeric compound which has an unsaturated double bond.
  • the polymerizable compound having an unsaturated double bond in the present embodiment includes a polymerizable unsaturated functional group such as a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group. Those having a vinyl group, acryloyl group, and methacryloyl group of the mold are preferred in view of polymerizability.
  • the number of polymerizable unsaturated functional groups in the polymerizable compound is preferably 2 or more from the viewpoint of polymerizability. In this case, the polymerizable unsaturated functional group may not necessarily be the same functional group.
  • the molecular weight of the polymerizable compound is preferably 100 to 5000. In particular, when the molecular weight is in the range of 60 to 2500, the compatibility with the alkali-soluble resin is good and the storage stability is excellent.
  • the compound having an unsaturated double bond according to the present embodiment contributes to the property that the solubility of the photosensitive resin composition in an alkaline developer changes due to the structure change caused by light irradiation.
  • the photosensitive resin composition according to the present embodiment since a crosslinked product is formed by light irradiation by including a compound having an unsaturated double bond and a photopolymerization initiator, the developer resistance and blocking In addition, the sticking property to the transport metal in the solder reflow furnace is improved.
  • Examples of the compound having an unsaturated double bond include tricyclodecane dimethylol diacrylate, ethylene oxide (EO) modified bisphenol A dimethacrylate, EO modified hydrogenated bisphenol A diacrylate, 1,6-hexanediol (meth) acrylate, 1 , 4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, tris (2-acryloxyethyl) Isocyanurate, ⁇ -caprolactone modified tris (acryloxyethyl) isocyanurate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypro Lutrimethylolpropane tri (meth) acrylate, polyoxyethyltrimethylolpropane tri (meth
  • EO-modified bisphenol A dimethacrylate EO-modified hydrogenated bisphenol A diacrylate, and pentaerythritol tri / tetra (meth) acrylate are preferable from the viewpoint of developability and warpage after firing. These may be used alone or in combination of two or more.
  • the compound having an unsaturated double bond it is preferable to contain a (di) pentaerythritol (meth) acrylate ester compound from the viewpoint of blocking and sticking property to a carrier metal in a solder reflow furnace.
  • the (di) pentaerythritol (meth) acrylate ester compound means a dipentaerythritol methacrylate ester compound, a dipentaerythritol acrylate ester compound, a pentaerythritol methacrylate ester compound, and a pentaerythritol acrylate ester compound.
  • pentaerythritol (meth) acrylate ester compounds include pentaerythritol tri / tetraacrylate (trade name: Aronix (registered trademark) M-303, 305, 306, 450, 452 manufactured by Toagosei Co., Ltd.), pentaerythritol tetraacrylate (Trade name: A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethoxylated pentaerythritol tetraacrylate (trade name: SARTOMER SR-494, manufactured by Sartomer), dipentaerythritol penta / hexaacrylate (trade name: Aronix M- 400, 402, 403, 404, 405, 406, manufactured by Toagosei Co., Ltd.).
  • the amount of the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds is from 5 parts by weight to 100 parts by weight from the viewpoint of developability when the amount of the polyimide precursor is 100 parts by weight. Is preferably 10 parts by mass or more and 80 parts by mass or less.
  • (C) Photopolymerization initiator The photopolymerization initiator according to the present embodiment is represented by the following general formula (1).
  • Ar 1 is a monovalent organic group containing an aromatic group
  • R 1 is an organic group having an alkyl group or an aryl group
  • R 2 is a branched alkyl group, and a straight chain.
  • It is a monovalent hydrocarbon group having 3 to 50 carbon atoms, which is either an alkyl group, an alkyl group having an alicyclic structure, or an alkyl group having an aromatic structure.
  • the photopolymerization initiator in the present embodiment is a property in which the solubility of the photosensitive resin composition in an alkaline developer is changed by generating a radical by light irradiation and polymerizing a compound having an unsaturated double bond. Contribute to.
  • R 2 when R 2 is a long-chain alkyl group, a branched-chain alkyl group, an alkyl group having an aromatic structure, or an alkyl group having an alicyclic structure, it has a hydrophobic or bulky skeleton.
  • the compatibility with the compound having a heavy bond is improved, and the polymerization reactivity is improved.
  • the photosensitive resin composition is highly sensitive and highly effective when combined with a compound having an unsaturated double bond having a quaternary carbon, such as a (di) pentaerythritol (meth) acrylate ester compound. Even when the film is thinned, it exhibits excellent wiring coverage.
  • R 2 is preferably an alkyl group having an alicyclic structure, and more preferably an alkyl group having an alicyclic structure having 5 to 7 carbon atoms.
  • the general formula R 2 is in the (1) preferably has a structure represented by the following general formula (2).
  • R 3 , R 4 , R 5 , R 6 , and R 7 are hydrogen or an alkyl group having 1 to 20 carbon atoms, which may be the same or different.
  • N is an integer from 0 to 20, and m is an integer from 0 to 20.
  • R 2 is composed of an alkyl group having an alicyclic structure, a bulky skeleton having hydrophobicity is introduced into R 2, and thus the above-described effects are further improved.
  • some of the plurality of R 6 and R 7 are each independently an alkyl group having 1 to 20 carbon atoms, for example, one R 6 is a methyl group
  • other structures in which R 6 and R 7 are hydrogen are also included.
  • Ar 1 in the general formula (1) is substituted or unsubstituted, the following general formula (3), or substituted or unsubstituted, the following general formula (4). It is preferable that it is a structure represented by these. In this case, the structures of the general formula (3) and the general formula (4) are replaced with those in which the hydrogen in the aromatic group in the general formula (3) and the general formula (4) is replaced by another substituent. It includes both of those that are not.
  • X is a monovalent organic group
  • R 8 is a substituted or unsubstituted furyl group, thienyl group, or phenyl group.
  • the amount of the photopolymerization initiator is preferably 0.01 parts by weight or more and 40 parts by weight or less, and 0.1 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the polyimide precursor from the viewpoint of photosensitivity and lithography characteristics. It is more preferable that the amount is not more than parts.
  • the photopolymerization initiator according to the present embodiment can be used in combination with other known photopolymerization initiators.
  • Other known photopolymerization initiators include benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one, benzyl dipropyl ketals, benzyl diphenyl ketals, and benzoin methyl ethers.
  • a polymerization inhibitor can also be contained.
  • a polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert. -Butyl catechol, cuprous chloride, 2,6-di-tert. -Butyl-p-cresol, 2,2'-methylenebis (4-ethyl-6-tert.butylphenol), 2,2'-methylenebis (4-methyl-6-tert.butylphenol) and the like.
  • at least one nitroso compound and / or nitro compound is contained as a polymerization inhibitor used for thermal stability.
  • a nitroso compound and / or a nitro compound contains a nitroso group and / or a nitro group in the structural formula.
  • nitroso compounds include nitroso aromatic hydrocarbons such as nitrosobenzene, nitrosotoluene, p-nitrosophenol, nitrosolesorcinol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, and N-nitrosodiphenylamine N-nitroso such as N-nitroso-N-methylaniline, N-nitroso-N-phenylaniline, N-nitrosophenylhydroxylamine, N-nitrosophenylhydroxylamine salts (metal salts, ammonium salts, etc.) .
  • nitroso aromatic hydrocarbons such as nitrosobenzene, nitrosotoluene, p-nitrosophenol, nitrosolesorcinol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, and N-nitrosodiphenylamine N-nitroso such as N-
  • nitro compound examples include o-dinitrobenzene, m-dinitrobenzene, p-dinitrobenzene, 2,4-dinitrochlorobenzene, 1,5-dinitronaphthalene, 2,4-dinitro-1-naphthol, 2, Such as 4-dinitrophenol, 2,5-dinitrophenol, 2,4-dinitro-6-secondary-butyl-phenol, 4,6-dinitro-o-cresol, and 1,3,5-trinitrobenzene A nitro aromatic compound is mentioned.
  • N-nitrosophenylhydroxylamine ammonium salt N-nitrosophenylhydroxylamine aluminum salt, and 2,4-dinitrophenol are preferred in consideration of the ability to inhibit polymerization and availability.
  • the addition amount of the polymerization inhibitor is preferably 1 ppm to 100,000 ppm, more preferably 100 ppm to 10,000 ppm with respect to the mass of the alkali-soluble resin. Further, the addition amount is preferably 1 ppm or more from the viewpoint of sufficiently exhibiting the polymerization inhibition effect, and preferably 100000 ppm or less from the viewpoint of maintaining photosensitivity.
  • a polymerization inhibitor composed of a nitroso compound and / or a nitro compound may coexist with another polymerization inhibitor as long as the photosensitivity is not significantly impaired.
  • examples of such other polymerization inhibitors include p-tertiary-butylcatechol, hydroquinone, and p-methoxyphenol.
  • Block isocyanate In the resin composition in this Embodiment, it is preferable that block isocyanate is included from a viewpoint of prevention of sticking to the metal conveyance system of a high-temperature furnace and a metal jig in the solder reflow process at the time of component mounting. .
  • the blocked isocyanate is a compound obtained by reacting a blocking agent with an isocyanate having two or more isocyanate groups in the molecule.
  • isocyanate examples include 1,6-hexane diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate.
  • the blocking agent examples include alcohols, phenols, ⁇ -caprolactam, oximes, active methylenes, mercaptans, amines, imides, acid amides, imidazoles, ureas, and carbamine.
  • examples include acid salts, imines, and sulfites.
  • blocked isocyanate examples include trade names Duranate SBN-70D, TPA-B80E, TPA-B80X, 17B-60PX, MF-B60X, E402-B80T, ME20-B80S, MF-K60X, manufactured by Asahi Kasei Chemicals Corporation, and Hexamethylene diisocyanate (hereinafter also referred to as “HDI”) block isocyanate such as K6000, trade name Takenate B-882N of Mitsui Chemicals Polyurethanes product, trade name Takenate B-830, 4, which is a tolylene diisocyanate block isocyanate Trade name Takenate B-815N, which is 4'-diphenylmethane diisocyanate block isocyanate, and Takene, which is 1,3-bis (isocyanatomethyl) cyclohexane block isocyanate B-846N, trade names Coronate AP-M, 2503, 2515, 2507, 2513 and
  • (F) Phosphorus compound In the resin composition in this Embodiment, it is preferable that a phosphorus compound is included from a viewpoint of the flame retardance of a resin composition improving.
  • a phosphorus compound it is especially preferable that a phosphazene compound is included. Thereby, especially the flame retardance of a resin composition improves.
  • the phosphazene compound is a compound having a phosphazene structure in the molecule.
  • the phosphorus compound one type of phosphorus compound may be used, or two or more types of phosphorus compounds may be used in combination.
  • Examples of the phosphazene compound include compounds having a structure represented by the following general formula (8) and the following general formula (9).
  • R 27 , R 28 , R 29 and R 30 in the general formula (8) and the general formula (9) are not limited as long as they are organic groups having 1 to 20 carbon atoms.
  • a carbon number of 1 or more is preferable because flame retardancy tends to be exhibited.
  • a carbon number of 20 or less is preferred because it tends to be compatible with the alkali-soluble resin.
  • a functional group derived from an aromatic compound having 6 to 18 carbon atoms is particularly preferable from the viewpoint of flame retardancy.
  • functional groups include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2 -Functional groups having a phenyl group such as cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group, functional groups having a naphthyl group such as 1-naphthyl group, 2-naphthyl group, and pyridine, imidazole, triazole And functional groups derived from nitrogen-containing heterocyclic compounds such as tetrazole.
  • These compounds having a functional group may be used singly or in combination of two or more as necessary.
  • compounds having a phenyl group, a 3-methylphenyl group, a 4-hydroxyphenyl group, and a 4-cyanophenyl group are preferable because of their availability.
  • V in the phosphazene compound represented by the general formula (8) is not limited as long as it is 3 or more and 25 or less. When V is 3 or more, flame retardancy is exhibited, and when it is 25 or less, solubility in organic solvents is improved. Among these, V is preferably 3 or more and 10 or less because of availability.
  • W in the phosphazene compound represented by the general formula (9) is not limited as long as it is 3 or more and 10,000 or less. When it is 3 or more, flame retardancy is exhibited, and when it is 10,000 or less, the solubility in organic solvents is high. Among these, 3 or more and 100 or less are preferable in view of availability.
  • G and J in the phosphazene compound represented by the general formula (9) are not limited as long as they are organic groups having 3 to 30 carbon atoms.
  • G represents —N ⁇ P (OC 6 H 5 ) 3 , —N ⁇ P (OC 6 H 5 ) 2 (OC 6 H 4 OH), —N ⁇ P (OC 6 H 5 ) (OC 6 H 4 OH) 2 , —N ⁇ P (OC 6 H 4 OH) 3 , —N ⁇ P (O) (OC 6 H 5 ), —N ⁇ P (O) (OC 6 H 4 OH), etc.
  • G represents —N ⁇ P (OC 6 H 5 ) 3 , —N ⁇ P (OC 6 H 5 ) 2 (OC 6 H 4 OH), —N ⁇ P (OC 6 H 5 ) (OC 6 H 4 OH) 2 , —N ⁇ P (OC 6 H 4 OH) 3 , —N ⁇ P (O) (OC 6 H 5 ), —N ⁇ P (O) (OC
  • J represents —P (OC 6 H 5 ) 4 , —P (OC 6 H 5 ) 3 (OC 6 H 4 OH), —P (OC 6 H 5 ) 2 (OC 6 H 4 OH) 2 , —P (OC 6 H 5 ) (OC 6 H 4 OH) 3 , —P (OC 6 H 4 OH) 4 , —P (O) (OC 6 H 5 ) 2 , —P (O) (OC 6 H 4 OH ) 2 , —P (O) (OC 6 H 5 ) (OC 6 H 4 OH) or the like.
  • the addition amount of the phosphorus compound is preferably 50 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin from the viewpoint of developability and the like, and 45 from the viewpoint of flame retardancy of the cured product of the photosensitive resin composition. It is more preferable that the amount is not more than part by mass. Moreover, if the addition amount is 5 parts by mass or more, flame retardancy is improved.
  • thermosetting resins examples include epoxy resins, cyanate ester resins, unsaturated polyester resins, benzoxazine resins, benzoxazolines, phenol resins, melamine resins, and maleimide compounds.
  • Examples of the compound having reactivity with the alkali-soluble resin include a compound that reacts with a carboxyl group and an amino group in the polymer and a terminal having a structure derived from an acid anhydride to form a three-dimensional crosslinked structure.
  • a so-called thermal base generator which is a compound that generates an amino group as a base by heating, is preferable.
  • Examples of the thermal base generator include compounds obtained by forming a salt structure between an amino group of a base compound such as amine and an acid such as sulfonic acid and protecting it as a dicarbonate compound or an acid chloride compound. . For this reason, the thermal base generator does not exhibit basicity at room temperature and is stable, and can be deprotected by heating to generate a base.
  • the heterocyclic compound is not limited as long as it is a cyclic compound containing a hetero atom.
  • Heteroatoms include oxygen, sulfur, nitrogen, and phosphorus.
  • Examples of heterocyclic compounds include N-alkyl group substitution such as 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, imidazole such as 2-phenylimidazole, and 1,2-dimethylimidazole.
  • Aromatic group-containing imidazole such as imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1 Cyano group-containing imidazoles such as cyanoethyl-2-undecylimidazole and 1-cyanoethyl-2-phenylimidazole, imidazole compounds such as silicon-containing imidazoles such as imidazolesilane, 5-methylbenzotriazole, 1- (1 ′ 2'-di-carboxyethyl benzotriazole), 1- (2-ethyl-F carboxymethyl aminomethyl benzotriazole) triazole compounds such as, and, oxazole compounds such as 2-methyl-5-phenyl-benzoxazole and the like.
  • coloring substance examples include phthalocyanine-based compounds such as phthalocyanine green, fuchsin, auramine base, chalcoxide green S, paramagenta, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, Malachite Green, Basic Blue 20, and Diamond green is an example.
  • phthalocyanine-based compounds such as phthalocyanine green, fuchsin, auramine base, chalcoxide green S, paramagenta, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, Malachite Green, Basic Blue 20, and Diamond green is an example.
  • coloring substance a coloring dye that develops color by light irradiation can also be used.
  • coloring dyes include a combination of a leuco dye or a fluorane dye and a halogen compound. Examples of such combinations include tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet] and tris (4-dimethylamino-2-methylphenyl) methane [leucomalachichi green]. .
  • halogen compound examples include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2 , 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, and triazine compounds.
  • triazine compound examples include 2,4,6-tris (trichloromethyl) -s-triazine and 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine. .
  • the addition amount of other compounds is not limited as long as it is 0.01 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin. If the addition amount is 0.01 parts by mass or more, the added effect tends to be sufficiently exerted, and if it is 30 parts by mass or less, there is no adverse effect on photosensitivity.
  • the photosensitive resin composition in the present embodiment may further contain an organic solvent.
  • the organic solvent is not limited as long as it can uniformly dissolve and / or disperse the alkali-soluble resin.
  • organic solvents include dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and ether compounds having 2 to 9 carbon atoms such as triethylene glycol dimethyl ether; acetone And ketone compounds having 2 to 6 carbon atoms such as methyl ethyl ketone; saturated carbonization having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane, and decalin Hydrogen compounds; aromatic hydrocarbon compounds having 6 to 10 carbon atoms, such as benzene, toluene, xylene, mesitylene,
  • organic solvents include ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 9 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and carbon numbers.
  • a nitrogen-containing compound having 2 or more and 10 or less carbon atoms and a mixed solvent of two or more kinds thereof can be mentioned. From the viewpoint of solubility of the alkali-soluble resin, triethylene glycol dimethyl ether, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylformamide, and N, N-dimethylacetamide are preferable.
  • the concentration of the alkali-soluble resin is not particularly limited as long as it is a concentration capable of forming a resin molding.
  • the concentration of the alkali-soluble resin is preferably 1% by mass or more from the viewpoint of the film thickness of the resin molded body to be produced, and the concentration of the alkali-soluble resin is 90% by mass or less from the uniformity of the film thickness of the resin molded body. Is preferable, and 2 mass% or more and 80 mass% or less are more preferable.
  • the photosensitive resin composition according to the present embodiment can be suitably used for forming a photosensitive film.
  • a solvent drying and volatilization process at the printed wiring board production site is not required, and the working environment is improved as compared with the liquid product form.
  • both sides can be processed simultaneously, it contributes to productivity improvement.
  • there is an advantage that a product excellent in surface smoothness of the cover material on the wiring can be easily produced.
  • the photosensitive film laminated body which concerns on this Embodiment has a base material and the photosensitive film containing the photosensitive resin composition provided on this base material.
  • the photosensitive film laminated body which concerns on this Embodiment, it formed on the photosensitive resin containing the base material, the said photosensitive resin composition provided on this base material, and this photosensitive resin.
  • a photosensitive film laminate comprising an antifouling or protective cover film is preferred.
  • the substrate is not limited as long as it is a substrate that does not damage the photosensitive film when forming the photosensitive film laminate.
  • a substrate examples include a silicon wafer, glass, ceramic, heat resistant resin, and carrier film.
  • a carrier film is preferable from the viewpoint of compatibility in a roll-to-roll production method and ease of handling.
  • the carrier film is preferably a transparent film that transmits ultraviolet light.
  • carrier films that transmit ultraviolet light are, for example, polyethylene terephthalate (PET) film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, and polymethacrylic acid.
  • PET polyethylene terephthalate
  • Examples include a methyl copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film.
  • a PET film is preferable from the viewpoint of circuit board pressure bonding and peelability after exposure.
  • those stretched as necessary can also be used. The thinner these films are, the more advantageous in terms of image forming properties and economic efficiency, but those having a thickness of 10 to 30 ⁇ m are generally used because of the need to maintain the strength.
  • the cover film is not limited as long as it is a film that protects a photosensitive film obtained by using a photosensitive resin composition such as low-density polyethylene.
  • a method for producing a photosensitive film laminate When manufacturing a photosensitive film laminated body using a photosensitive resin composition, the solution of the photosensitive resin composition is apply
  • Application of the photosensitive resin composition onto the base material is, for example, bar coating, roller coating, die coating, blade coating, dip coating, doctor knife, spray coating, flow coating, spin coating, slit coating, and brush coating.
  • a coating method such as can be used. After the coating, if necessary, a heat treatment called pre-baking may be performed with a hot plate or the like.
  • the photosensitive film which concerns on this Embodiment can be used suitably for manufacture of a flexible printed wiring board.
  • the flexible printed wiring board according to the present embodiment includes a circuit board having wiring, and the above-described photosensitive film that is provided so as to cover the wiring on the circuit board and is formed by baking.
  • the wiring is, for example, a copper wiring, but is not particularly limited.
  • This flexible printed wiring board can be obtained by press-bonding a photosensitive film on a circuit board having wiring, developing it with an alkali, and performing baking. At this time, from the viewpoint of efficiently mass-producing flexible printed wiring boards, laminating the photosensitive film on the wiring surface on the circuit board having wiring using a roll-type thermal vacuum laminator and then firing the film preferable.
  • FIG. 1 is an explanatory view showing a minimum thickness and a surface step of the flexible printed wiring board according to the present embodiment.
  • reference numeral 11 denotes a circuit board
  • reference numeral 12 denotes a baked photosensitive film
  • reference numeral 13 denotes a wiring.
  • the minimum thickness (a) of the photosensitive film 12 formed by baking on the wiring 13 is preferably 0.1 ⁇ m or more and 10 ⁇ m or less, and preferably 1 ⁇ m or more and 8 ⁇ m. More preferably, it is more preferably 2 ⁇ m or more and 5 ⁇ m or less. It is preferable that (a) is 0.1 ⁇ m or more from the viewpoint of preventing oxidation of the wiring 13 and insulation reliability, and it is preferable that it is 10 ⁇ m or less from the viewpoint of preventing generation of cracks at the time of folding.
  • the minimum thickness (a) of the photosensitive film 12 formed by baking on the wiring 13 can be obtained by observing the surface of the flexible printed wiring board 10 polished in the thickness direction with an optical microscope. Specifically, the ratio of the distance (L / S) between the copper wiring pattern and the copper wiring pattern gap is 1: 5 or less, and five or more wirings 13 arranged in parallel are polished perpendicularly to the copper wiring pattern. The average value of the minimum thicknesses of the photosensitive film 12 on the three or more parallel wirings 13 in the center excluding both ends is measured, and the average value of the measured values measured at five or more locations is defined as (a). .
  • the maximum value (b) of the surface step of the photosensitive film 12 is preferably 10 ⁇ m or less, more preferably 6 ⁇ m or less, and more preferably 3 ⁇ m or less on the wiring 13 and the portion without the wiring 13. More preferably.
  • the maximum value (b) of the surface step is the distance (b1) on the wiring 13 and the distance between the portions without the wiring 13 when the distance from the surface of the circuit board 11 to the surface of the photosensitive film 12 is measured. The difference of (b2) is shown.
  • the maximum value (b) of the surface step can be obtained by observing the surface of the flexible printed wiring board 10 polished in the thickness direction with an optical microscope.
  • the ratio of the distance (L / S) between the copper-resistant wiring pattern and the copper wiring pattern gap is 1: 5 or less, and five or more wirings 13 aligned are polished vertically.
  • the distance (b1) from the surface of the circuit board 11 of the portion of the photosensitive film 12 farthest from the surface of the circuit board 11 on the copper wiring 13 is measured.
  • the distance (b2) from the circuit board 11 surface of the part nearest to the circuit board 11 surface of the photosensitive film 12 of the part without the copper wiring 13 is measured.
  • the difference between (b1) and (b2) is obtained.
  • the difference is measured at five or more locations, and the average value is defined as (b).
  • circuit boards having wiring in flexible printed wiring boards include hard boards such as glass epoxy boards and glass maleimide boards, and flexible boards such as copper-clad laminates. Among these, a flexible substrate is preferable from the viewpoint of bendability.
  • the manufacturing method of the flexible printed wiring board is not particularly limited as long as the photosensitive film is provided on the circuit board so as to cover the wiring.
  • a manufacturing method in a state where the wiring side of the circuit board having wiring and the photosensitive film laminate according to the present embodiment are in contact, hot pressing, thermal laminating, thermal vacuum pressing, thermal vacuum laminating, etc.
  • the method of performing etc. is mentioned.
  • the thermal vacuum pressing method and the thermal vacuum laminating method are preferable.
  • the heating temperature when laminating the photosensitive film laminate on the circuit board having wiring is not limited as long as the photosensitive film can be in close contact with the circuit board. From the viewpoint of adhesion to the circuit board and from the viewpoint of decomposition of the photosensitive film and side reactions, 30 ° C. or higher and 400 ° C. or lower is preferable. More preferably, it is 50 degreeC or more and 150 degrees C or less.
  • the surface treatment of the circuit board having wiring is not particularly limited, and examples thereof include hydrochloric acid treatment, sulfuric acid treatment, and sodium persulfate aqueous solution treatment.
  • the photosensitive film laminate can be subjected to negative photolithography by selecting a light-irradiated portion with an arbitrary photomask and dissolving the portion other than the light-irradiated portion by alkali development after light irradiation. In this case, it is preferable to irradiate light after the circuit board reaches room temperature.
  • the carrier film is peeled off after the light irradiation and the alkali development treatment is performed to prevent the radical generated by the photopolymerization initiator (C) from being deactivated due to the influence of oxygen inhibition, and the stability of the photosensitivity. From the viewpoint of improving the ratio.
  • Examples of the light source used for the light irradiation include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a xenon lamp, a fluorescent lamp, a tungsten lamp, an argon laser, and a helium cadmium laser.
  • a high pressure mercury lamp and an ultrahigh pressure mercury lamp are preferable.
  • the aqueous alkali solution used for development is not limited as long as it is a solution capable of dissolving other than the light irradiation site.
  • aqueous sodium carbonate solution an aqueous potassium carbonate solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, and an aqueous tetramethylammonium hydroxide solution.
  • an aqueous sodium carbonate solution and an aqueous sodium hydroxide solution are preferred.
  • the development method include spray development, immersion development, and paddle development. If necessary, a water washing treatment or a drying treatment can be performed.
  • a flexible printed wiring board is obtained by firing the printed wiring board to which the photosensitive film is pressure bonded. Firing is preferably performed at a temperature of 30 ° C. or higher and 400 ° C. or lower, more preferably 100 ° C. or higher and 300 ° C. or lower, from the viewpoint of solvent removal, side reactions, decomposition, or the like.
  • the reaction atmosphere in the firing can be performed in an air atmosphere or an inert gas atmosphere.
  • the time required for firing varies depending on the reaction conditions, but is usually within 24 hours, and particularly preferably in the range of 1 to 8 hours.
  • the photosensitive film laminate using the photosensitive film according to the present embodiment has good warpage after curing and good developability, and exhibits chemical resistance when used as a cured product
  • Printed wiring boards used for operation panels of various electronic devices in the electronics field formation of protective layers on circuit boards, formation of insulating layers on laminated boards, silicon wafers used in semiconductor devices, semiconductor chips, and components around semiconductor devices It is used for film formation on electronic components for use in protection, insulation and adhesion of semiconductor mounting substrates, heat sinks, lead pins, semiconductors, etc.
  • the photosensitive film laminated body using the photosensitive film which concerns on this Embodiment is a board
  • FPC flexible printed wiring circuits
  • TAB tape automation bonding
  • EL organic electroluminescence
  • Alkali-soluble resin component BPDA Mitsubishi Chemicals
  • APB trade name: APB-N, manufactured by Mitsui Chemicals
  • B Compound having unsaturated double bond EO-modified bisphenol A dimethacrylate (trade name: BPE-500, manufactured by Shin-N
  • Etanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (trade name: IRGACURE OXE-02 (hereinafter simply referred to as “OXE-02”) ”, Manufactured by Ciba Japan)
  • OXE-02 Polymerization inhibitor N-nitrosophenylhydroxylamine aluminum (trade name: Q-1301, manufactured by Wako Pure Chemical Industries, Ltd.) N-nitrosophenylhydroxylamine ammonium salt (trade name: Q-1300, manufactured by Wako Pure Chemical Industries, Ltd.) p-Methoxyphenol (Wako Pure Chemical Industries, Ltd.)
  • E) Blocked isocyanate Blocked isocyanate (trade name: Duranate SBN-70D (hereinafter simply referred to as “SBN-70D”), manufactured by Asahi Kasei Chemicals)
  • Phosphorus compound Phosphazene compound (
  • GPC Gel permeation chromatography
  • a calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation). Column: Shodex KD-806M (made by Showa Denko) Flow rate: 1.0 mL / min Column temperature: 40 ° C Pump: PU-2080 Plus (manufactured by JASCO) Detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO) UV-2075 Plus (UV-VIS: UV-Visible Absorber, manufactured by JASCO)
  • the coating method of the photosensitive resin composition was performed by a doctor blade method using FILM COATER (manufactured by TESTER SANGYO, PI1210).
  • the product was dried at 95 ° C. for 12 minutes to obtain a photosensitive film laminate.
  • the film thickness was measured using a film thickness meter (ID-C112B, manufactured by Mitutoyo).
  • the press temperature is set to 80 ° C.
  • the cylinder pressure is set to 0.5 MPa
  • the press time is set to 30 seconds. Laminated the body.
  • a photomask was disposed so as to shield the electrode portion of the migration resistance test wiring, and a step tablet (Stuffer 21) was disposed on the solid copper foil portion. Then, after both were brought into vacuum contact, they were exposed to 200 mJ / cm 2 with an ultrahigh pressure mercury lamp (HMW-201KB, manufactured by Oak Manufacturing Co., Ltd.). Thereafter, the PET film is peeled off from the obtained laminate, spray development treatment and water rinsing are performed at 30 ° C. and a 1.0 mass% sodium carbonate aqueous solution for 22 seconds, and then the photolithography pattern of the photosensitive film is dried. Was made.
  • HMW-201KB ultrahigh pressure mercury lamp
  • Exposed part visibility evaluation Immediately after exposure through a photomask, the difference in color between the exposed and unexposed areas was visually observed in a yellow room environment. ⁇ : Exposed part and unexposed part can be clearly distinguished ⁇ : Exposed part and unexposed part can be distinguished ⁇ : Exposed part and unexposed part cannot be distinguished
  • a tensile tester Orientec, Tensilon RTM-500: load cell rating 1 Kgf
  • the peel test distance was 60 mm, and the interleaf separation property after development was evaluated from the integrated average weight when the weight was plotted against the elongation.
  • O Integral average weight is less than 0.01 to 0.1 N / 25 mm.
  • X Integral average weight is 0.1 N / 25 mm or more.
  • O A part of the photosensitive film layer is melt-transferred to the SUS plate.
  • X The photosensitive film layer is completely welded to the SUS plate and cannot be peeled off.
  • Alkali-soluble resin (A2) In a nitrogen atmosphere, in a separable flask equipped with a Dean Stark apparatus and a refluxer, ⁇ -butyrolactone (80.0 g), toluene (16.0 g), polyetheramine D-230 (16.8 g (73.04 mmol)) BPDA (30.0 g (102.0 mmol)) was added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the solution was cooled to 40 ° C., APB-N (5.60 g (19.16 mmol)) was added, and the mixture was stirred at 40 ° C. for 4 hours to obtain a polyimide precursor (A2) solution.
  • the resulting polyimide precursor (A2) had a weight average molecular weight of 21,000.
  • Alkali-soluble resin (A3)) Under a nitrogen atmosphere, MEK 300 g, methacrylic acid (100 g), methyl methacrylate (200 g), and styrene (100 g) were placed in a separable flask equipped with a Dean-Stark apparatus and a refluxer. I raised it. Next, 2 g of AIBN was dissolved in 30 g of MEK and added, and polymerized for 6 hours. Further, 3 g of AIBN was dissolved in 30 g of MEK and added in two portions every other hour, and then the temperature in the flask was raised to the boiling point of the solvent and polymerization was carried out at that temperature for 2 hours.
  • AIBN Alkali-soluble resin
  • the obtained alkali-soluble acrylic resin (A3) had a weight average molecular weight of 55,000.
  • BPE-500 (15 parts by mass), SR-494 (10 parts by mass), PBG-305 (0.5 parts by mass), Q-1301 (0.1 parts by mass) with respect to 50 parts by mass of the alkali-soluble resin (A1) Part), SBN-70D (10 parts by mass), FP-300 (15 parts by mass) and OIL BLUE650 (0.15 parts by mass) were mixed to prepare a photosensitive resin composition.
  • a photosensitive film having a thickness of 15 ⁇ m was obtained from the obtained photosensitive resin composition by the above-described method.
  • the photosensitive film was evaluated for the photosensitivity, the exposed portion visibility, the development residue, the blocking, the wiring coverage, and the sticking property by the above-described methods.
  • the composition of the photosensitive resin composition is shown in Table 1 below, and the evaluation results are shown in Table 2 below.
  • Example 2 A photosensitive film having a thickness of 15 ⁇ m was obtained in the same manner as in Example 1 except that the compounds shown in Table 1 were used as the alkali-soluble resin and the photopolymerization initiator.
  • the photosensitive film was evaluated for the photosensitivity, the exposed portion visibility, the development residue, the blocking, the wiring coverage, and the sticking property by the above-described methods.
  • the composition of the photosensitive resin composition is shown in Table 1 below, and the evaluation results are shown in Table 2 below.
  • Example 4 to Example 6 A photosensitive film having a thickness of 15 ⁇ m was obtained in the same manner as in Example 1 except that the compounds shown in Table 1 were used as the photopolymerization initiator.
  • the photosensitive film was evaluated for the photosensitivity, the exposed portion visibility, the development residue, the blocking, the wiring coverage, and the sticking property by the above-described methods.
  • the composition of the photosensitive resin composition is shown in Table 1 below, and the evaluation results are shown in Table 2 below.
  • Example 7, Example 8, Comparative Example 4, and Comparative Example 5 A photosensitive film having a thickness of 15 ⁇ m was obtained in the same manner as in Example 1 except that the compounds shown in Table 1 were used as the photopolymerization initiator and the polymerization inhibitor. The photosensitive film was evaluated for the photosensitivity, the exposed portion visibility, the development residue, the blocking, the wiring coverage, and the sticking property by the above-described methods.
  • the composition of the photosensitive resin composition is shown in Table 1 below, and the evaluation results are shown in Table 2 below.
  • Example 9 and Comparative Example 6 A photosensitive film having a thickness of 15 ⁇ m was obtained in the same manner as in Example 1 except that the compounds shown in Table 1 were used as the polymerizable compound having a photopolymerization initiator and an unsaturated double bond.
  • the photosensitive film was evaluated for the photosensitivity, the exposed portion visibility, the development residue, the blocking, the wiring coverage, and the sticking property by the above-described methods.
  • the composition of the photosensitive resin composition is shown in Table 1 below, and the evaluation results are shown in Table 2 below.
  • Example 10 and Comparative Example 7 A photosensitive film having a thickness of 15 ⁇ m was obtained in the same manner as in Example 1 except that the compounds shown in Table 1 were used except for the blocked isocyanate compound.
  • the photosensitive film was evaluated for the photosensitivity, the exposed portion visibility, the development residue, the blocking, the wiring coverage, and the sticking property by the above-described methods.
  • the composition of the photosensitive resin composition is shown in Table 1 below, and the evaluation results are shown in Table 2 below.
  • the wiring protective film using the photosensitive film obtained in Example 1 to Example 10 has better wiring coverage than the wiring protective film using the photosensitive film of Comparative Example 1 to Comparative Example 7. And high quality with excellent practical properties. Moreover, the wiring protective film using the photosensitive film obtained in Example 1 to Example 10 has good visibility of the exposed part and the unexposed part, and it is easy to avoid double exposure at the production site. there were.
  • the photosensitive film using the nitroso compound of Example 1 and Example 7 and / or the compound comprising the nitro compound was superior in photosensitivity as compared to the photosensitive film of Example 8.
  • the photosensitive film of Example 1 is less in tackiness of the photosensitive film layer after development and / or after baking than the photosensitive film of Examples 9 and 10, and is used as a compound having an unsaturated double bond.
  • (Di) pentaerythritol (meth) acrylate ester compounds and blocked isocyanate compounds are particularly suitable for improving process margins such as blocking and sticking to metal jigs, and are suitable for roll-to-roll production systems. It was confirmed that it can contribute to improvement.
  • the wiring protective film using the photosensitive film obtained in Comparative Examples 1 to 7 had poor exposed portion visibility and wiring coverage. This is probably because the photopolymerization initiator did not have a bulky substituent, and therefore a sufficient crosslink was not formed between the polymerizable compound having an unsaturated double bond and the photopolymerization initiator. It is done.
  • Example 11 ⁇ Production of photosensitive film roll>
  • the photosensitive resin composition described in Example 1 was applied using a comma coater (manufactured by Hirano Tech Seed). It apply
  • coated to PET film (Teijin DuPont Films company make, G2, film thickness 16micrometer) so that the film thickness after drying might be 8 micrometers and 12 micrometers, respectively.
  • the film thickness was measured using a film thickness meter (ID-C112B, manufactured by Mitutoyo).
  • the roll temperature was set to 80 ° C.
  • the cylinder pressure was 0.4 MPa
  • the degree of vacuum was 100 Pa
  • the speed was 1 m / min.
  • migration resistance test wiring conductor width / conductor spacing is 50/50 ⁇ m, number of patterns is 10
  • solid copper foil A portion (5 cm ⁇ 5 cm) was cut out to prepare a test sheet substrate.
  • a photomask was disposed so as to shield the electrode portion of the migration resistance test wiring, and a step tablet (Stuffer 21) was disposed on the solid copper foil portion. Then, both were brought into vacuum contact, and then exposed to 100 mJ / cm 2 with an ultra-high pressure mercury lamp (HMW-201KB, manufactured by Oak Seisakusho). Thereafter, the PET film is peeled off from the obtained laminate, and spray development treatment and water rinsing are performed at 30 ° C. and a 1.0 mass% sodium carbonate aqueous solution for 60 seconds, followed by drying to obtain a photo of the photosensitive resin composition. A lithography pattern was prepared.
  • a flexible printed wiring board provided with a coverlay film on the copper wiring surface was obtained by baking at 180 ° C. for 1 hour using a dryer (SPHH-10l, manufactured by ESPEC).
  • the flexible printed wiring board manufactured by the above method is embedded with epoxy resin, and the embedded wiring board is polished perpendicularly to the wiring using a polishing device (manufactured by Marumoto Stratos), then the length measurement function Observed with an attached optical microscope, the average value of the minimum thickness (a) of the coverlay film on the central eight copper wirings excluding both ends of the copper wiring pattern, and firing on the wiring and the part without wiring The maximum value (b) of the surface level difference of the obtained film was measured. In addition, 10 places were observed regarding evaluation, and the average value of (a) and (b) was computed.
  • Example 12 to 20 Comparative Examples 8 to 14
  • production of a photosensitive film roll production of a flexible printed wiring board, and evaluation of practical characteristics were performed in the same manner as in Example 11.
  • the evaluation results are shown in Table 3 below.
  • the wiring protective film using the photosensitive film rolls obtained in Examples 11 to 20 was compared with the wiring protective film using the photosensitive films of Comparative Examples 8 to 14, compared with the thickness on the wiring ( Even in a region where a) was small, the wiring coverage was good even under a low exposure amount and over-development conditions as compared with appropriate photolithography conditions. Further, the coverlay film using the photosensitive film obtained in Examples 11 to 20 has a film thickness region where the film thickness (a) on the copper wiring and the surface smoothness (b) both have small values. As a result, since the stress at the time of bending is uniformly dispersed, it is considered that no crack is generated on the surface of the coverlay film and the copper wiring is not exposed. As a result, it was confirmed that the photosensitive films described in Examples 11 to 20 had very excellent wiring coverage and high flexibility.
  • the photosensitive films described in Comparative Examples 8 to 10 cannot satisfy the wiring coverage when the thickness (a) on the wiring is thin. Although the wiring coverage is improved by increasing the thickness (a) on the wiring as in Comparative Examples 15 to 17, the folding resistance cannot be satisfied. This is presumed to be caused by not having a film thickness region that simultaneously satisfies the values (a) and (b).
  • the photosensitive film of the present embodiment is a wiring protective film suitable for a flexible printed wiring board that contributes to improvement in compatibility and productivity in the roll-to-roll production method.
  • the present invention has an effect of obtaining a photosensitive film that is excellent in photosensitivity and from which a highly reliable wiring protective layer can be obtained.
  • the surface protective film of semiconductor elements, interlayer insulating films, semiconductor package substrates, flexible prints It can be suitably used in the field of protective insulating films for substrates.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerisation Methods In General (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
PCT/JP2013/071447 2012-08-08 2013-08-08 Stratifié de film photosensible, carte de circuit imprimé flexible et procédé de fabrication de ceux-ci Ceased WO2014024951A1 (fr)

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KR1020157002019A KR101684195B1 (ko) 2012-08-08 2013-08-08 감광성 필름 적층체, 플렉시블 프린트 배선판 및 그 제조 방법
CN201380041043.8A CN104583867B (zh) 2012-08-08 2013-08-08 感光性膜层积体、柔性印刷布线板及其制造方法
JP2014529547A JP5903164B2 (ja) 2012-08-08 2013-08-08 感光性フィルム積層体、及び、フレキシブルプリント配線の製造方法

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CN104583867A (zh) 2015-04-29
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TW201418883A (zh) 2014-05-16
TWI553412B (zh) 2016-10-11
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