CN104583867A - Photosensitive film laminate, flexible printed wiring board, and method for manufacturing same - Google Patents

Photosensitive film laminate, flexible printed wiring board, and method for manufacturing same Download PDF

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Publication number
CN104583867A
CN104583867A CN201380041043.8A CN201380041043A CN104583867A CN 104583867 A CN104583867 A CN 104583867A CN 201380041043 A CN201380041043 A CN 201380041043A CN 104583867 A CN104583867 A CN 104583867A
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China
Prior art keywords
general formula
photosensitive film
wiring
film
photosensitive
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Granted
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CN201380041043.8A
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CN104583867B (en
Inventor
有久慎司
佐佐木洋朗
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Asahi Kasei Corp
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Asahi Chemical Co Ltd
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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

Abstract

A photosensitive film laminate is provided with a substrate and a photosensitive film provided on the substrate. The photosensitive film contains a photosensitive resin composition containing (A) an alkali-soluble resin, (B) a polymerizable compound having an unsaturated double bond, and (C) a photopolymerization initiator, the (C) photopolymerization initiator having the structure expressed by general formula (1) (Ar<1> represents a monovalent organic group including an aromatic, R<1> represents an organic group having an alkyl or aryl group, and R<2> represents a C3-50 monovalent hydrocarbon group that is any of a branched alkyl group, a straight alkyl group, an alkyl group having an alicyclic structure, or an alkyl group having an aromatic structure). It is possible to provide an exceptionally photosensitive film that can be developed in alkali, has exceptional wiring coverage even when formed into a thin film, and allows excellent visibility of an exposure part and a non-exposure part. It is also possible to provide a flexible printed wiring board using the photosensitive film.

Description

Photosensitive film lamination body, flexible printing wiring board and manufacture method thereof
Technical field
The present invention relates to the photosensitive film lamination body, flexible printing wiring board and the manufacture method thereof that employ photosensitive film; described photosensitive film contains photosensitive polymer combination, is useful as the surface protection film of semiconductor element, interlayer dielectric, conductor package substrate, flexible printed board protection dielectric film.
Background technology
In recent years, the membranaceous printed base plate being called as flexible printed board (hereinafter also referred to as " FPC ") obtains positive development.This FPC has the FCCL (flexible copper clad laminate after wiring processing, Flexible Copper CladLaminate) on possess the tectal structure be made up of polyimide film etc., it is mainly used in the instruments such as mobile phone, smart mobile phone, panel type terminal, subnotebook PC, digital camera.Even if FPC bending also can maintain function, because of but the indispensable material of equipment oriented miniaturization, lightweight.Particularly in recent years along with miniaturization, the light-weighted development of the electronic equipment being representative with smart mobile phone and panel type terminal, by adopting FPC in such goods, size and weight minimizing, the reduction of goods cost and the simplification etc. of design of this electronic equipment can be contributed to.
FPC executes the overlayer as insulation material layer of the conductive pattern for all or part of covering printed panel outer surface.The most basic overlayer is the film coating be made up of the die-cut material of the non-photosensitive that reliability is high, but is very difficult to the robotization carrying out its bonding process, does not even carry out the trial of roll-to-rollization, in fact also depends on craft.As the solution of the actuality in overlayer treatment process, think the serigraphy that can adopt overlayer ink in the same manner as the solder mask of hard printed base plate, but compared with film coating, the mechanical property, chemical proofing (particularly resistance to plating) etc. of material commercially available are at present all poor, are not yet used by general widely.
Towards the Labor-saving of the miniaturization of FPC, manufacturing process, in order to utilize photoetching to carry out microfabrication, concentrate one's energy to have carried out the exploitation of photosensitive cover lay.In recent years, for the consideration to environment, carry out the design of material corresponding to aqueous alkali development, wherein, from the viewpoint of being derived from the electric insulation reliability of polyimide, mechanical properties such as bending patience etc., thermotolerance, chemical proofing, anti-flammability, expect to employ the overlayer of photosensitive cover lay as excellence of polyimide precursor.Particularly compared with the method for the liquid photoresist of coating, the photosensitive cover lay film of dry-film type not only can save time and the time of coating and drying, but also can adopt and carry out the disposable roll-to-roll mode of production of carrying out multiple perforation processing by two sides lamination film forming together and photoetching, thus can reach shortening and the Labor-saving of the manufacturing process of FPC.
In order to obtain the photosensitive polyimide that can carry out the development of these aqueous alkalis, have developed the type photosensitive polyimide based on following method, in the method, the alkaline negative development type sensitive polyimide precursor obtained in the method by a part of lead-in light reactive group at whole alkali solubility group or be imported with in the alkaline soluble polyimide of alkali solubility group in polyimide, add polymerizable compound and Photoepolymerizationinitiater initiater (such as, see patent documentation 1 ~ patent documentation 3).
But these photosensitive polyimides do not obtain sufficient luminous sensitivity.On the other hand, further developed the photosensitive polymer combination (such as, see patent documentation 4 and patent documentation 5) using specific oxime compound as the Photoepolymerizationinitiater initiater that luminous sensitivity is high.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 3-220558 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2002-182378 publication
Patent documentation 3: International Publication No. 2004/109403 pamphlet
Patent documentation 4: Japanese Unexamined Patent Application Publication 2004-534797 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2007-133377 publication
Summary of the invention
Invent problem to be solved
But when the demand of the filming corresponding to program circuit substrate also carries out the filming of photosensitive cover lay, if use the such photosensitive polymer combination described in patent documentation 5, then the coating reliability in wiring may be deteriorated.Further, in order to avoid two re-exposure of production scene, exposure portion and unexposed portion may can not get sufficient observability.
The present invention carries out in view of above-mentioned aspect, its object is to provide the photosensitive film lamination body, flexible printing wiring board and the manufacture method thereof that employ photosensitive film, this photosensitive film can carry out alkali development, luminous sensitivity is excellent, and even if also there is when filming excellent being coated to property of wiring, the observability in the portion of exposure simultaneously and unexposed portion is excellent.
Solve the means of problem
The feature of photosensitive film lamination body of the present invention is, it possesses base material and is arranged on the photosensitive film containing photosensitive polymer combination on above-mentioned base material, this photosensitive polymer combination contains (A) alkali soluble resins, (B) has the polymerizable compound of unsaturated double-bond and (C) Photoepolymerizationinitiater initiater, the structure of above-mentioned (C) Photoepolymerizationinitiater initiater represented by following general formula (1).
[changing 1]
General formula (1)
(in general formula (1), Ar 1for the 1 valency organic group containing aromatic series, R 1for there is the organic group of alkyl or aryl, R 2for the 1 valency alkyl that carbon number is 3 ~ 50, be branched alkyl, straight chained alkyl, the alkyl with alicyclic structure or have in the alkyl of aromatic structure any one.)
The feature of flexible printing wiring board of the present invention is, it possesses: have the circuit substrate of wiring and on foregoing circuit substrate, carry out being fired into the above-mentioned photosensitive film of film.
The feature of the manufacture method of flexible printing wiring board of the present invention is, use roll-type thermovacuum laminator, lamination above-mentioned photosensitive film lamination body on the wiring side on the circuit substrate with wiring, carries out firing film forming afterwards.
The feature of flexible printing wiring board of the present invention is, it is manufactured by above-mentioned manufacture method.
Flexible printing wiring board of the present invention is possess the circuit substrate with wiring and the flexible printing wiring board covering layer film arranged in the mode covering above-mentioned wiring being fired the film obtained on foregoing circuit substrate, it is characterized in that, above-mentioned the firing in above-mentioned wiring and the minimum thickness (a) of the film obtained are more than 0.1 μm and are less than 10 μm.
Flexible printing wiring board of the present invention is possess the circuit substrate with wiring and the flexible printing wiring board covering layer film arranged in the mode covering above-mentioned wiring being fired the film obtained on foregoing circuit substrate, it is characterized in that, in above-mentioned wiring with without the part that connects up, the above-mentioned maximal value (b) firing the surperficial difference of height (section is poor) of the film obtained is less than 3 μm.
The effect of invention
According to the present invention, can realize employing the photosensitive film lamination body of following photosensitive film, flexible printing wiring board and manufacture method thereof, this photosensitive film can carry out alkali development, luminous sensitivity is excellent, and even if also there is when filming excellent being coated to property of wiring, the observability in the portion of exposure simultaneously and unexposed portion is excellent.
Accompanying drawing explanation
Fig. 1 is the minimum thickness of the flexible printing wiring board that present embodiment is shown and the key diagram of surperficial difference of height.
Embodiment
Below this embodiment (hereinafter referred to as embodiment) is described in detail.It should be noted that, the present invention is not limited to following embodiment, can carry out being out of shape implementing in the scope of its main points.
The photosensitive film lamination body of present embodiment has base material and arranges the photosensitive film containing photosensitive polymer combination on the substrate.The photosensitive polymer combination of present embodiment contains (A) alkali soluble resins, (B) has polymerizable compound and (C) Photoepolymerizationinitiater initiater of unsaturated double-bond, the structure of (C) Photoepolymerizationinitiater initiater represented by following general formula (1).
[changing 2]
General formula (1)
(in general formula (1), Ar 1for 1 valency organic group, R containing aromatic series 1for there is the organic group of alkyl or aryl, R 2for the 1 valency alkyl that carbon number is 3 ~ 50, be branched alkyl, straight chained alkyl, there is the alkyl of alicyclic structure or there is any one of alkyl of aromatic structure.)
Utilize this photosensitive film, due to containing (A) alkali soluble resins, thus can carry out alkali development; Meanwhile, owing to having the Photoepolymerizationinitiater initiater of the structure represented by above-mentioned general formula (1) containing (C), thus luminous sensitivity improves.Further, in this (C) Photoepolymerizationinitiater initiater, due at R 2imported hydrophobicity, bulky skeleton, thus (C) Photoepolymerizationinitiater initiater improves with the compatibility of (B) polymerizable compound.Thus, (C) Photoepolymerizationinitiater initiater improves with the polymerisation reactivity of (B) polymerizable compound, thus moderately defines three-dimensional network by the crosslinked combination between strand.Its result, obtains and easily can be dissolved in alkaline-based developer before exposure, be insoluble to the photosensitive film of the luminous sensitivity excellence in alkaline-based developer after exposure.Further, even if this photosensitive film also has excellent being coated to property of wiring when filming, the observability in exposure portion and unexposed portion is excellent.Below each constitutive requirements are described.
< photosensitive polymer combination >
(A) alkali soluble resins
First the alkali soluble resins in the photosensitive polymer combination of present embodiment is described.As alkali soluble resins, the various polymkeric substance all the time used in photosensitive polymer combination can be used.As such polymkeric substance, such as, can enumerate following organic high molecular polymer solvable in alkaline-based developer: (methyl) acrylic copolymer, itaconic acid copolymer, crotonic acid copolymers, maleic acid, partial esterification maleic acid, linear phenol-aldehyde resin, cresol novolaks, polyimide precursor and side chain have the polyimide resin etc. of carboxyl and/or hydroxyl.It should be noted that, (methyl) acrylic copolymer refers to both acrylic copolymer and methacrylic acid copolymer.
As alkali soluble resins, can be used alone above-mentioned polymkeric substance, also two or more above-mentioned polymer mixed can be used.As alkali soluble resins, weight-average molecular weight is preferably used to be 10000 to 250000 and the acid number alkali soluble resins that is 50mgKOH/g to 300mgKOH/g.
As alkali soluble resins, from the viewpoint of can obtain electric insulation reliability, mechanical properties such as bending patience etc., thermotolerance, chemical proofing, excellent in flame retardance tectal, particularly preferably polyimide precursor.In addition, under the condition of exposure lower than suitable etching condition, cross under development conditions and more filming condition under, in order to realize the coating property of high wiring, preferably use polyimide precursor.It should be noted that, polyimide precursor refers to the material becoming polyimide by imidizate, and it not only refers to polyamic acid, also comprises the material of a part of imidizate of polyamic acid.
Polyimide precursor such as obtains by the reaction of tetracarboxylic dianhydride and diamines.Used tetracarboxylic dianhydride is not limited, existing known tetracarboxylic dianhydride can be used.As tetracarboxylic dianhydride, aromatic tetracarboxylic acid or aliphatics tetracarboxylic dianhydride etc. can be applied.Further, used diamines is not limited, existing known diamines can be used.
As tetracarboxylic dianhydride, biphenyl-3,3 ' can be enumerated, 4,4 '-tetracarboxylic dianhydride (hereinafter referred to as " BPDA "), BP-3,3 ', 4,4 '-tetracarboxylic dianhydride (hereinafter referred to as " BTDA "), the two phthalic anhydride (hereinafter referred to as " ODPA ") of oxygen, diphenylsulphone-3,3 ', 4,4 '-tetracarboxylic dianhydride, ethylene glycol bis (trimellitic acid monoester anhydride) (hereinafter referred to as " TMEG "), TOPOT 2,2′ p phenylenebis (trimellitic acid monoester anhydride), to biphenylene two (trimellitic acid monoester anhydride), metaphenylene two (trimellitic acid monoester anhydride), adjacent phenylene two (trimellitic acid monoester anhydride), two (trimellitic acid monoester anhydride) (hereinafter referred to as " 5-BTA ") of pentanediol, decanediol two (trimellitic acid monoester anhydride), pyromellitic acid dianhydride, two (3,4-dicarboxyphenyi) ether dicarboxylic anhydride, 4,4 '-(2,2-hexafluoroisopropylidenyl) two phthalic anhydride, meta-terphenyl-3,3 ', 4,4 '-tetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, dicyclo [2,2,2] pungent-7-alkene-2,3,5,6-tetracarboxylic dianhydride, cyclo-butane-1,2,3,4-tetracarboxylic dianhydride, 1-ethyloic-2,3,5-ring penta tricarboxylic acids-2,6:3,5-dicarboxylic anhydride, 4-(2,5-dioxotetrahydro furans-3-base)-1,2,3,4-naphthane-1,2-dicarboxylic anhydrides, and 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride etc.Above-mentioned tetracarboxylic dianhydride can be used alone, also can be used in combination by two or more.It should be noted that, from the aspect of the developability of polyimide precursor, more preferably BPDA, ODPA, BTDA, TMEG, 5-BTA and decanediol two (trimellitic acid monoester anhydride).
As diamines, two (4-amino-benzene oxygen) alkane of 1,3-can be enumerated, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) alkane, two (4-amino-benzene oxygen) alkane of 1,5-, Isosorbide-5-Nitrae-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, 3,7-diamido-dimethyl Dibenzothiophene-5,5-dioxide, 4,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, 4,4 '-bis-(4-aminophenyl) thioether, 4,4 '-diaminobenzene formailide, two (4-amino-benzene oxygen)-2, the 2-dimethylpropanes of 1,3-, two [2-(4-amino-benzene oxygen) ethoxy] ethane of 1,2-, two (4-aminophenyl) fluorenes of 9,9-, 5-amino-1-(4-amino methyl)-1,3,3-trimethyl dihydroindene, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, two (3-amino-benzene oxygen) benzene (hereinafter referred to as " APB ") of 1,3-, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, 4,4 '-bis-(3-amino-benzene oxygen) biphenyl, two (4-aminophenoxy phenyl) propane (hereinafter referred to as " BAPP ") of 2,2-, trimethylene-bis-(PABA ester) (hereinafter referred to as " TMAB "), 4-aminophenyl-PABA ester, 2-methyl-4-aminophenyl-PABA ester, two [4-(4-amino-benzene oxygen) phenyl] sulfone, two [4-(3-amino-benzene oxygen) phenyl] sulfone, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, 1-amino-3-amino methyl-3,5,5-trimethyl-cyclohexane, 3,3 '-dicarboxyl-4,4 '-diaminodiphenyl-methane, 3,5-diaminobenzoic acid, 3,3 '-dihydroxy-4,4 '-benzidine, and 1,3-two (4-amino-benzene oxygen benzene) etc.Wherein, from the viewpoint of reduce polyimide precursor glass transition point (Tg), improve developability, preferred APB, BAPP and TMAB.These diamines also can be used as the diamine component used in the synthesis in the polyimide structures portion of aftermentioned polyimide precursor.
In the photosensitive polymer combination of present embodiment, as polyimide precursor, from the aspect of developability and molecular weight stability, particularly preferably there is the polyimide structures represented by following general formula (5) and the polyamic acid structure represented by following general formula (6) respectively as constitutional repeating unit.
[changing 3]
General formula (5)
General formula (6)
(in general formula (5) and formula (6), R 9, R 10, R 12, R 13, R 15, R 16, R 18, R 19, R 21and R 22represent that hydrogen atom or carbon number are the 1 valency organic group of 1 ~ 20 independently of one another, they can be the same or different.R 11, R 14, R 17, R 20and R 23represent that carbon number is the 4 valency organic groups of 1 ~ 20, m, n and p represent the integer of less than more than 0 100 independently of one another.R 24represent 4 valency organic groups, R 25represent that carbon number is the divalent organic group of 1 ~ 90, R 26represent that carbon number is the 4 valency organic groups of 1 ~ 50.)
In addition, as polyimide precursor, preferably containing the diamine component of the diamines represented by following general formula (7) as the polyimide structures formed represented by above-mentioned general formula (5).
[changing 4]
General formula (7)
(in general formula (7), R 9, R 10, R 12, R 13, R 15, R 16, R 18, R 19, R 21and R 22represent that hydrogen atom or carbon number are the 1 valency organic group of 1 ~ 20 independently of one another, they can be the same or different.R 11, R 14, R 17, R 20and R 23represent that carbon number is the 4 valency organic groups of 1 ~ 20, m, n and p are the integer of less than more than 0 30 independently of one another, meet 1≤(m+n+p)≤30.)
In the polyimide precursor represented by above-mentioned general formula (5) and above-mentioned general formula (6), by importing to the oxyalkylene skeleton in the strand of polyimide precursor, the strand of polyimide precursor is given to the flexibility of appropriateness, thus can improve the developability of photosensitive polymer combination.Herein, utilize the diamines represented by above-mentioned general formula (7) when the polyamic acid structure portion of polyimide precursor imports oxyalkylene skeleton, the secondary amino group derived by this diamines is directed to polyamic acid structure portion.The alkalescence of this secondary amino group is high, compared with existing polyamic acid, have promote the depolymerization in polyamic acid structure portion, the molecular weight of polyimide precursor reduces and becomes significant problem.Therefore, in the present embodiment, oxyalkylene skeleton is imported in the polyimide structures portion of polyimide precursor by utilizing the diamines represented by above-mentioned general formula (7), the harmful effect of the alkalescence of above-mentioned secondary amino group can be prevented, make molecular weight stabilizers, the developability of photosensitive polymer combination can be improved simultaneously.
M, n and p in above-mentioned general formula (5) are the integer of less than more than 0 30 independently of one another.From the aspect of insulating reliability, preferably 1≤(m+n+p)≤30, more preferably 3≤(m+n+p)≤10.If in the scope of 1≤(m+n+p)≤30, then the skeleton with oxyalkylene alkyl can shorten, and thus the elastic modulus of polyimide precursor increases, and infers that insulating reliability improves.
As the diamines represented by above-mentioned general formula (7), as long as the polyimide structures that can obtain represented by above-mentioned general formula (5) does not just limit.As such diamines, the polyethylene oxide diamine compounds such as 1,8-diamido-3,6-dioxy base octane can be enumerated; Huntsman society manufactures the polyoxyalkylene diamines compounds such as Jeffamine EDR-148, EDR-176; The polypropyleneoxide diamine compounds such as polyetheramine D-230, D-400, D-2000 that Jeffamine D-230, D-400, D-2000, D-4000, BASF society manufactures; And HK-511, ED-600, ED-900, ED-2003, XTJ-542 etc. have the compound etc. of different oxyalkylene alkyl.Be there is by these skeleton of oxyalkylene alkyl, the warpage of the FPC after the firing of polyimide can be reduced.
As long as the main chain terminal of polyimide precursor is the structure of impact will be brought just to be not particularly limited on performance.Can for when manufacturing polyimide precursor the dicarboxylic anhydride that uses or diamines the end structure that derive, also can be by the structure by end-capped such as other acid anhydrides or amines etc.
As the weight-average molecular weight of polyimide precursor, be preferably less than more than 1,000 1000000.Herein, weight-average molecular weight refers to the polystyrene of known heavy average molecular weight for standard, the molecular weight recorded by gel permeation chromatography.From the aspect of the intensity of the resin bed obtained by photosensitive polymer combination, weight-average molecular weight is preferably more than 1000; From the viscosity of photosensitive polymer combination and the aspect of mouldability, weight-average molecular weight is preferably less than 1000000.Weight-average molecular weight is more preferably less than more than 5,000 500000, is particularly preferably less than more than 10,000 300000, most preferably is less than more than 15,000 80000.
There is polyimide structures and polyamic acid structure respectively make by following operation as the polyimide precursor of repetitive: the operation (operation 1) at the synthesis of polyimides position in the 1st stage that dicarboxylic anhydride and diamines are reacted with non-equimolar amounts; Then, the operation (operation 2) at the synthesizing polyamides acid position in the 2nd stage.Below each operation is described.
(operation 1)
The operation at the synthesis of polyimides position in the 1st stage is described.Operation as the synthesis of polyimides position in the 1st stage is not particularly limited, and can use known method.More particularly, by following method synthesis of polyimides position.First by two amine solvents and/or be dispersed in polymer solvent, dicarboxylic anhydride powder is added wherein.Then add the solvent with water azeotropic, use the water of the secondary generation of mechanical stirrer azeotropic removing while add thermal agitation 0.5 hour ~ 96 hours, be more preferably 0.5 hour ~ 30 hours.Now, monomer concentration is preferably below more than 0.5 quality % 95 quality %, is more preferably below more than 1 quality % 90 quality %.
In the synthesis at polyimide position, by adding known imidization catalyst to synthesize this polyimide position, also can synthesize this polyimide position when catalyst-free.Be not particularly limited as imidization catalyst, the acid anhydrides of acetic anhydride and so on can be enumerated; The lactone compound of gamma-valerolactone, gamma-butyrolacton, γ-tetronic acid, γ-phthalide, γ-cumarin, γ-phthalide acid (γ-Off タ リ De acid) and so on; And the tertiary amine etc. of pyridine, quinoline, N-methylmorpholine, triethylamine and so on.Further, a kind or use their potpourri of more than two kinds can be used as required.Among them, from the viewpoint of reactive height with reduce the impact of subsequent reactions, the particularly preferably mixed stocker of gamma-valerolactone and pyridine and catalyst-free.
The addition of imidization catalyst is preferably below 50 mass parts relative to polyamic acid 100 mass parts, is more preferably below 30 mass parts.
As the reaction dissolvent used when the synthesis at polyimide position, can enumerate dimethyl ether, diethyl ether, ethyl methyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether, diethylene glycol dimethyl ether and TRIGLYME and so on carbon number be less than more than 29 ether compound; The carbon number of acetone and methyl ethyl ketone and so on is the ketonic compound of less than more than 26; The carbon number of n-pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane and decahydronaphthalenes and so on is the saturated hydrocarbon compound of less than more than 5 10; The carbon number of benzene,toluene,xylene, trimethylbenzene and tetralin and so on is the aromatic hydrocarbon compound of less than more than 6 10; The carbon number of methyl acetate, ethyl acetate, gamma-butyrolacton and methyl benzoate and so on is the ester compounds of less than more than 3 12; The carbon number of methenyl choloride, methylene chloride and 1,2-ethylene dichloride and so on is the halide-containing of less than more than 1 10; The carbon number of acetonitrile, DMF, DMA and METHYLPYRROLIDONE and so on is the nitrogen-containing compound of less than more than 2 10; The sulfocompound of dimethyl sulfoxide (DMSO) and so on.These dissolvings can be used alone as required, also can use with the form of mixed solvent of more than two kinds.As particularly preferred solvent, can enumerate carbon number be less than more than 29 ether compound, carbon number be less than more than 3 12 ester compounds, carbon number be less than more than 6 10 aromatic hydrocarbon compound and carbon number be less than more than 2 10 nitrogen-containing compound.These solvents can consider that industrial productivity and the impact etc. on subsequent reactions are selected arbitrarily.
In the synthesis at polyimide position, preferable reaction temperature is more than 15 DEG C less than 250 DEG C.When temperature of reaction is more than 15 DEG C, can initiation reaction; In addition, when temperature of reaction is below 250 DEG C, the inactivation of catalyzer can not be there is.Temperature of reaction is preferably more than 20 DEG C less than 220 DEG C, is more preferably more than 20 DEG C less than 200 DEG C.
Time required for reaction is different from the difference of object or reaction conditions, within being generally 96 hours, is suitably the scope of 30 minutes to 30 hours especially.
(operation 2)
Then the operation at the synthesizing polyamides acid position in the 2nd stage is described.In the synthesis at the polyamic acid position in the 2nd stage, the polyimide position obtained in operation 1 can be used as initiation material, additional diamines and/or dicarboxylic anhydride are polymerized, thus can implement this synthesis.As the 2nd stage synthesizing polyamides acid position time polymerization temperature, be preferably more than 0 DEG C less than 250 DEG C, more preferably more than 0 DEG C less than 100 DEG C, be particularly preferably more than 0 DEG C less than 80 DEG C.
The time required for reaction during polyamic acid synthesis is different according to the difference of object or reaction conditions, within being generally 96 hours, is suitable for especially implementing to react in the scope of 30 minutes to 30 hours.
As reaction dissolvent, the reaction dissolvent identical with the reaction dissolvent used when synthesis of polyimides position in operation 1 can be used.In this case, can directly use the reaction solution of operation 1 to carry out the synthesis at polyamic acid position.In addition, the solvent different from reaction dissolvent used during synthesis of polyimides position can also be used.
Manufactured polyimide precursor directly can use with the state be dissolved in reaction dissolvent, and following method also can be utilized to carry out reclaiming and refining.The recovery manufacturing the polyimide precursor after stopping can be undertaken by carrying out decompression distillation removing to the solvent in reaction solution.
As the process for purification of polyimide precursor, the method by the undissolved dicarboxylic anhydride in the removal such as filtration under diminished pressure, pressure filtration reaction solution and diamines can be enumerated.Further, also can implement based on the reppd process for purification of what is called, that is, reaction solution to be added in poor solvent the method making it separate out.And then ， Te Do is when the highly purified polyimide precursor of needs, the process for purification based on the extraction using supercritical carbon dioxide can also be adopted.
(B) polymerizable compound
Photosensitive polymer combination in present embodiment comprises the polymerizable compound with unsaturated double-bond.The polymerizable compound with unsaturated double-bond in present embodiment refers to the compound containing polymerism unsaturated functional groups such as vinyl, allyl, acryloyl group and methacryls; among them; from the viewpoint of polymerism, preferably there is the compound of the vinyl of conjugated type, acryloyl group and methacryl.In addition, as the number of the polymerism unsaturated functional group in polymerizable compound, from the aspect of polymerism, be preferably more than 2.In this case, polymerism unsaturated functional group also can differ and is decided to be identical functional group.In addition, as the molecular weight of polymerizable compound, 100 ~ 5000 are preferably.When particularly molecular weight is the scope of 60 ~ 2500, good with the compatibility of alkali soluble resins, excellent storage stability.
The compound with unsaturated double-bond of present embodiment plays a role in following character, and this character is penetrated by illumination structure to be changed thus the character that changes of the dissolubility of photosensitive polymer combination in alkaline-based developer.In the photosensitive polymer combination of present embodiment, by containing compound and the Photoepolymerizationinitiater initiater with unsaturated double-bond, penetrate through illumination and form crosslinked, thus developer solution patience and adhesion (Block ロ ッ キ Application グ) can be improved and in scolding tin reflow oven with the adhesiveness (Zhang り pay I) transmitting metal species.
As the compound with unsaturated double-bond, tristane dihydroxymethyl diacrylate can be enumerated, ethylene oxide (EO) modified bisphenol A dimethylacrylate, the modified hydrogenated bisphenol a diacrylate of EO, 1,6-hexanediol (methyl) acrylate, Isosorbide-5-Nitrae-cyclohexanediol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, polyglycol two (methyl) acrylate, 2-bis-(p-hydroxybenzene) propane two (methyl) acrylate, three (2-acryloyl-oxyethyl) isocyanuric acid ester, 6-caprolactone modification three (acryloyl-oxyethyl) isocyanuric acid ester, glycerine three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, polyoxyethyl propyl trimethylolpropane tris (methyl) acrylate, polyoxyethanyl trimethylolpropane tris (methyl) acrylate, dipentaerythritol five (methyl) acrylate, trihydroxymethylpropanyltri diglycidyl ether (methyl) acrylate, bisphenol A diglycidyl ether two (methyl) acrylate, β-hydroxy propyl-Beta '-(acryloyl-oxy)-propyl group phthalic ester, phenoxy group polyglycol (methyl) acrylate, Nonylphenoxy polyglycol (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, ethoxylation pentaerythrite four (methyl) acrylate, dipentaerythritol five/six (methyl) acrylate etc.Wherein, from developability, fire after the aspect of warpage, preferred EO modified bisphenol A dimethylacrylate, the modified hydrogenated bisphenol a diacrylate of EO, pentaerythrite three/tetra-(methyl) acrylate.They can be used alone, also can be used in combination of two or more.
About as the particularly preferred form of compound with unsaturated double-bond, from adhesion and in scolding tin reflow oven with transmit the adhering aspect of metal species, preferably comprise (two) pentaerythrite (methyl) acrylate compounds.It should be noted that, (two) pentaerythrite (methyl) acrylate compounds refers to dipentaerythritol methacrylate compound, dipentaerythritol acrylate compounds, pentaerythrite methacrylate compound and pentaerythritol acrylate compound.
As (two) pentaerythrite (methyl) acrylate compounds, pentaerythrite three/tetraacrylate (trade name: Aronix (registered trademark) M-303 can be enumerated, 305, 306, 450, 452 East Asia synthesis societies manufacture), tetramethylol methane tetraacrylate (trade name: A-TMMT, chemical industry society of Xin Zhong village manufactures), ethoxylation tetramethylol methane tetraacrylate (trade name: SARTOMER SR-494, Sartomer society manufactures), dipentaerythritol five/six acrylate (trade name: Aronix M-400, 402, 403, 404, 405, 406, East Asia synthesis society manufactures) etc.
When setting the amount of polyimide precursor as 100 mass parts, from the aspect of developability, the amount with (methyl) acrylate compounds of the unsaturated double-bond of the photopolymerization of more than 2 is preferably below more than 5 mass parts 100 mass parts, is more preferably below more than 10 mass parts 80 mass parts.
(C) Photoepolymerizationinitiater initiater
The Photoepolymerizationinitiater initiater of present embodiment is represented by following general formula (1).
[changing 5]
General formula (1)
(in general formula (1), Ar 1for the 1 valency organic group containing aromatic series, R 1for there is the organic group of alkyl or aryl, R 2for the 1 valency alkyl that carbon number is 3 ~ 50, be branched alkyl, straight chained alkyl, the alkyl with alicyclic structure or have in the alkyl of aromatic structure any one.)
Photoepolymerizationinitiater initiater in present embodiment plays a role in following character, this character is penetrated the compound polymerization reaction take place producing free radical, make to have unsaturated double-bond by illumination, thus makes the character that the dissolubility of photosensitive polymer combination in alkaline-based developer changes.
Particularly by making R 2for chain alkyl, branched alkyl, there is the alkyl of aromatic structure or there is the alkyl of alicyclic structure, this Photoepolymerizationinitiater initiater has hydrophobicity, bulky skeleton, thus, polymerisation reactivity good with the compatibility of the compound with unsaturated double-bond improves.Particularly by the compound combination with unsaturated double-bond with quaternary carbon such with (two) pentaerythrite (methyl) acrylate compounds, significant effect, highly sensitive can be demonstrated, even if when excellent being coated to property of wiring also will be shown when photosensitive polymer combination filming.From the aspect of polymerisation reactivity, R 2preferably there is the alkyl of alicyclic structure, be more preferably and there is the alkyl that carbon number is the alicyclic structure of 5 ~ 7.
By there is 1 valency organic group containing aromatic series as Ar 1, this Photoepolymerizationinitiater initiater demonstrates higher luminous sensitivity at the i line (365nm) as the industrial widely used exposure wavelength in photoetching technique to g line (436nm).Now, by selecting chain alkyl, branched alkyl, have the alkyl of aromatic structure or there is alicyclic structure alkyl as R 2, exposure portion observability can be improved.
In addition, in the Photoepolymerizationinitiater initiater of present embodiment, the R in preferred above-mentioned general formula (1) 2there is the structure represented by following general formula (2).
[changing 6]
General formula (2)
(in general formula (2), R 3, R 4, R 5, R 6and R 7for hydrogen or carbon number are the alkyl of 1 ~ 20, each other can be identical or different.N is the integer of 0 ~ 20, and m is the integer of 0 ~ 20.)
In this case, by making R 2be made up of, at R the alkyl with ester ring type structure 2middle importing has hydrophobic bulky skeleton, thus above-mentioned effect improves further.It should be noted that, in above-mentioned general formula (2), also comprise multiple R 6and R 7in several be the structure of the alkyl of 1 to 20 independently for carbon number, a such as R 6for methyl, other R 6and R 7for the structure of hydrogen.
And then, in the photosensitive polymer combination of present embodiment, the Ar of preferred formula (1) 1for replace or without replace following general formula (3) or replace or without replace following general formula (4) represented by structure.In this case, the structure that the hydrogen during the structure of general formula (3) and general formula (4) comprises in general formula (3) and general formula (4) aromatic series base is replaced by other substituting group and unsubstituted both structures.
[changing 7]
General formula (3)
General formula (4)
(in general formula (3), X is monovalent organic group, R 8for replacement or without the furyl replaced, thienyl or phenyl.)
From the aspect of luminous sensitivity and photolithographic characteristics, relative to polyimide precursor 100 mass parts, the amount of Photoepolymerizationinitiater initiater is preferably below more than 0.01 mass parts 40 mass parts, is more preferably below more than 0.1 mass parts 20 mass parts.
The Photoepolymerizationinitiater initiater of present embodiment also can combinationally use with other known Photoepolymerizationinitiater initiater.As other known Photoepolymerizationinitiater initiater, the benzoin dimethylether class of 2,2-dimethoxy-1,2-diphenylethane-1-ketone and so on can be enumerated; Benzyl dipropyl ketal class, benzyldiphenyl ketal class, benzoin methylether class, benzoin ethyl ether; Thioxanthones, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, ITX, ITX, 2, ITX, 2-fluorine thioxanthones, 4-fluorine thioxanthones, CTX, CTX, the chloro-4-propoxythioxanthone of 1-, benzophenone, 4,4 '-bis-(dimethylamino) benzophenone [michler's ketone], 4, the aromatic ketone compounds such as 4 '-bis-(diethylamino) benzophenone, 2,2-dimethoxy-2-phenyl acetophenone; The triarylimidazoles dipolymers such as lophine dipolymer; The acridine compounds such as 9-phenylacridine; α, the oxime ester compounds such as alpha, alpha-dimethyl oxygen base-α-morpholino-methylthio phenyl benzoylformaldoxime, TMDPO, N-aryl-a-amino acid; P-(dimethylamino)-benzoic acid, p-(dimethylamino)-benzoic acid, to diethyl amino yl benzoic acid, to diisopropylaminoethyl benzoic acid, parabenzoic acid ester, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone, 2-hydroxyl-1-{4-[(2-hydroxy-2-methyl propiono)-benzyl] phenyl the Alpha-hydroxy alkyl benzene ketone such as-2-methylpropane-1-ketone; 2-methyl isophthalic acid-alpha-aminoalkyl benzophenone class such as (4-methyl mercapto phenyl)-2-morpholinyl-1-acetone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone; The acylphosphine oxide classes such as TMDPO, two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide; Sulfonium salt system light cationic polymerization initiators and salt compounded of iodine system light cationic polymerization initiators etc.They can be used alone, and also can be used in combination of two or more.
In order to improve thermal stability, the storage stability of the photosensitive composite of present embodiment, also polymerization inhibitor can be contained.As such polymerization inhibitor, such as can enumerate p methoxy phenol, quinhydrones, 1,2,3,-thrihydroxy-benzene, naphthylamines, tert-butyl catechol, stannous chloride, 2,6-BHT, 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol) and 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol) etc.
(D) nitroso compound and/or nitro compound
In the photosensitive composite of present embodiment, as the polymerization inhibitor used in thermal stability, particularly preferably contain at least one of nitroso compound and/or nitro compound.Nitroso compound and/or nitro compound refer to the compound containing nitroso-and/or nitro in structural formula.
As nitroso compound, such as, can enumerate the N-nitrous base class such as the nitroso-aromatic hydrocarbons such as nitrosobenzene, nitrosotoluene, p-Nitrosophenol, nitroso-resorcin, 1-Nitroso-2-naphthol, 2-nitroso--1-naphthols and N-nitrosodiphenylamine int he, N-nitroso--methylphenylamine, N-nitroso--N-phenylaniline, N-nitrosophenylhydroxylamine, N-nitrosophenylhydroxylamine salt (slaine, ammonium salt etc.).
In addition, as nitro compound, such as, can enumerate o-dinitrobenzene, meta-dinitro-benzent, paradinitrobenzene, DNFB, 1,5-dinitronaphthalene, 2,4-dinitro-1-naphthols, 2,4-DNP, 2,5-dinitrophenol, 2,4-dinitro-6-sec-butyl-phenol, 4, the nitro-aromatic compounds such as 6-dinitro-o-cresol and 1,3,5-trinitrobenzen.
Among them, if consider the easiness of polymerization inhibiting capacity and acquisition, then preferred N-nitrosophenylhydroxylamine ammonium salt, N-nitrosophenylhydroxylamine aluminium salt, 2,4-DNP.
As the addition of polymerization inhibitor, elect 1ppm ~ 100000ppm as relative to the Functionality, quality and appealing design of alkali soluble resins, be more preferably 100ppm ~ 10000ppm.In addition, from the viewpoint of giving full play of polymerization inhibition effect, addition is preferably more than 1ppm; From the viewpoint of maintaining luminous sensitivity, addition is preferably below 100000ppm.
In the present embodiment, in order to improve polymerization inhibition effect further, the polymerization inhibitor that is made up of nitroso compound and/or nitro compound and other polymerization inhibitor can be made in the scope significantly can not damaging luminous sensitivity to coexist.As other such polymerization inhibitor, such as, can enumerate p-tert-butyl catechol, quinhydrones, p methoxy phenol.
(E) blocked isocyanate
In the resin combination of present embodiment, from the scolding tin back welding process when parts are installed, prevent from transmitting with the metal of high temperature furnace the aspect that system or metal fixture adhere to, preferably containing blocked isocyanate.This blocked isocyanate is the compound of instigating the isocyanates in molecule with more than 2 isocyanate groups and end-capping reagent to react and obtain.
As isocyanates, such as can enumerate 1, hexamethylene-diisocyanate, 4, 4 '-methyl diphenylene diisocyanate, 2, 4-toluenediisocyanate, 2, 6-toluenediisocyanate, eylylene diisocyanate, 4, 4 '-dicyclohexyl methyl hydride diisocyanate, 4, 4 '-hydroxide diisocyanate, isophorone diisocyanate, 1, 5-naphthalene diisocyanate, 4, 4-diphenyl diisocyanate, 1, two (isocyanatomethyl) cyclohexane of 3-, phenylene 1, 4-diisocyanate, phenylene 2, 6-diisocyanate, 1, 3, 6-hexa-methylene triisocyanate and hexamethylene diisocyanate.
As end-capping reagent, such as, can enumerate alcohols, phenols, epsilon-caprolactams, oximes, active methylene group class, thio-alcohol, amine, acid imide, amide-type, imidazoles, ureas, Carbamates, imines class and sulfites.
As the concrete example of blocked isocyanate, can enumerate: the trade name DURANATESBN-70D that chemistry society of Asahi Chemical Industry manufactures, the hexamethylene diisocyanate (hereinafter referred to as " HDI ") of TPA-B80E, TPA-B80X, 17B-60PX, MF-B60X, E402-B80T, ME20-B80S, MF-K60X and K6000 etc. are blocked isocyanate; The trade name Takenate B-882N of Mitsui Chemicals polyurethane society manufacture, as the trade name Takenate B-830 of toluene diisocyanate system blocked isocyanate, as 4, the trade name Takenate B-815N of 4 '-methyl diphenylene diisocyanate system blocked isocyanate and the Takenate B-846N as two (isocyanatomethyl) hexamethylene methane series blocked isocyanate of 1,3-; The trade name CORONET AP-M that Japanese polyurethane industry society manufactures, 2503,2515,2507,2513 and Millionate MS-50 etc.; As the article number 7950,7951,7990 etc. that the Baxenden society of isophorone diisocyanate system blocked isocyanate manufactures.These blocked isocyanates can be used alone, and also can be used in combination of two or more.
It should be noted that, in the present embodiment, example for the blocked isocyanate being used as polyfunctional isocyanate is illustrated, but in the scope of effect can having given play to present embodiment, also can use the polyfunctional isocyanate with more than 2 isocyanate groups.
(F) phosphorus compound
In the resin combination of present embodiment, from the viewpoint of the anti-flammability improving resin combination, preferably contain phosphorus compound.As phosphorus compound, particularly preferably containing phosphazene compound.The anti-flammability of resin combination can be improved thus especially.It should be noted that, phosphazene compound refers to the compound in molecule with phosphine nitrile structure.In addition, as phosphorus compound, a kind of phosphorus compound can be used, also can combinationally use two or more phosphorus compounds.
As phosphazene compound, the compound etc. with following general formula (8), structure represented by following general formula (9) can be enumerated.
[changing 8]
General formula (8)
General formula (9)
R in above-mentioned general formula (8) and above-mentioned general formula (9) 27, R 28, R 29, R 30as long as the organic group being less than more than 1 20 for carbon number does not just limit.When carbon number is more than 1, often show anti-flammability, thus preferably.When carbon number is less than 20, there is the tendency compatible with alkali soluble resins, thus preferably.
As R 27, R 28, R 29, R 30, from the aspect showing anti-flammability, be particularly preferably the functional group of the phenolic compound of less than more than 6 18 derived from carbon number.As such functional group, such as, can enumerate the functional group that phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 2-hydroxy phenyl, 3-hydroxy phenyl, 4-hydroxy phenyl, 2-cyano-phenyl, 3-cyano-phenyl, 4-cyano-phenyl etc. have phenyl; 1-naphthyl, 2-naphthyl etc. have the functional group of naphthyl; And derived from the functional group etc. of the nitrogen-containing heterocycle compounds such as pyridine, imidazoles, triazole, tetrazole ring.The compound with these functional groups can be used alone as required, also can be used in combination of two or more.Among them, from the viewpoint of the easiness obtained, preferably there is the compound of phenyl, 3-aminomethyl phenyl, 4-hydroxy phenyl and 4-cyano-phenyl.
V in phosphazene compound represented by above-mentioned general formula (8) is not limited, as long as be less than more than 3 25.When V is more than 3, anti-flammability can be shown; When V is less than 25, dissolubility in organic solvent improves.Wherein, from the viewpoint of the easiness obtained, particularly preferably V is less than more than 3 10.
W in phosphazene compound represented by above-mentioned general formula (9) is not limited, as long as be less than more than 3 10000.When W is more than 3, anti-flammability can be shown; When W is less than 10000, dissolubility is in organic solvent high.Wherein, from the viewpoint of the easiness obtained, particularly preferably W is less than more than 3 100.
G and J in phosphazene compound represented by above-mentioned general formula (9) is not limited, if for carbon number be the organic group of less than more than 3 30.Wherein, G is preferably-N=P (OC 6h 5) 3,-N=P (OC 6h 5) 2(OC 6h 4oH) ,-N=P (OC 6h 5) (OC 6h 4oH) 2,-N=P (OC 6h 4oH) 3,-N=P (O) (OC 6h 5) ,-N=P (O) (OC 6h 4oH) etc.J is preferably-P (OC 6h 5) 4,-P (OC 6h 5) 3(OC 6h 4oH) ,-P (OC 6h 5) 2(OC 6h 4oH) 2,-P (OC 6h 5) (OC 6h 4oH) 3,-P (OC 6h 4oH) 4,-P (O) (OC 6h 5) 2,-P (O) (OC 6h 4oH) 2,-P (O) (OC 6h 5) (OC 6h 4oH) etc.
From the aspect of developability etc., relative to alkali soluble resins 100 mass parts, the addition of phosphorus compound is preferably below 50 mass parts; From the aspect of the anti-flammability of the solidfied material of photosensitive polymer combination, the addition of phosphorus compound is more preferably below 45 mass parts.In addition, when addition is more than 5 mass parts, anti-flammability improves.
(G) other compound
In the resin combination of present embodiment, can not causing in dysgenic scope containing other compound its performance.As other compound, specifically, the thermoset resin of the toughness for improving the film after firing, solvent resistance, thermotolerance (thermal stability) can be enumerated; With alkali soluble resinss such as polyimide precursors, there is reactive compound; For improving the heterogeneous ring compound of adaptation; And the coloring material such as pigment, dyestuff of the painted middle use of the film to obtain at use sense photosensitive resin composition.
As thermoset resin, epoxy resin, cyanate ester resin, unsaturated polyester resin, benzoxazine colophony, benzoxazole quinoline, phenol resin, melamine resin and maleimide compound etc. can be enumerated.
As with alkali soluble resins, there is reactive compound, can enumerate and react with the carboxyl in polymkeric substance and the amino or end had derived from the structure of acid anhydrides and form the compound etc. of three-dimensional crosslinking structure.Among them, preferred so-called hot generated base alkaline agent, is the compound producing the amino as alkali by heating.As hot generated base alkaline agent, such as, can enumerate and form salt structure thus the compound carrying out protecting with the form of two carbonate products, chloride compounds and obtain between the acid such as amino and sulfonic acid of the alkali cpds such as amine.Therefore, hot generated base alkaline agent can not show alkalescence in room temperature, be stable, can produce alkali by heating deprotection.
As heterogeneous ring compound, as long as containing heteroatomic ring type compound, and indefinite.As heteroatoms, oxygen, sulphur, nitrogen and phosphorus can be enumerated.As heterogeneous ring compound, such as can enumerate the imidazolium compoundss such as siliceous imidazoles such as imidazoles, imidizole silane containing the cyano-containing such as imidazoles, 1-cyano ethyl-glyoxal ethyline, 1-cyano ethyl-2-ethyl-4-methylimidazole, 1-cyano ethyl-2-undecyl imidazole, 1-cyano ethyl-2-phenylimidazole of aromatic group such as the N-alkyl substituted imidazoles such as the imidazoles of glyoxal ethyline, 2-undecyl imidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and so on, 1,2-methylimidazole, 1 benzyl 2 methyl imidazole, 1-benzyl-2-phenylimidazole; The triazole compounds such as 5-methylbenzotrazole, 1-(1 ', 2 '-dicarboxyethyl benzotriazole), 1-(2-ethylhexylamino methylbenzotrazole); And 2-methyl-5-Ben base benzoxazole oxazole compounds.
As coloring material, such as, can enumerate the phthalocyanine based compounds such as phthalocyanine green, magenta, auramine alkali, the green S of alkoxide, paramagenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green, alkali blue 20 and diamond green.
In addition, as coloring material, can also use and be penetrated by illumination and the color appearance system dyestuff developed the color.As such color appearance system dyestuff, there are leuco dye or fluoran dyes and halid combination.As such combination, such as, can enumerate three (4-dimethylamino-2-aminomethyl phenyl) methane [leuco crystal violet], three (4-dimethylamino-2-aminomethyl phenyl) methane [leucogentian violet].As halogenide, such as can enumerate amyl bromide, isoamyl bromide, brominated isobutylene, ethylene bromide, diphenyl methyl bromine, dibromomethylbenzene, methylene bromide, trisbromomethyl phenyl sulfone, carbon tetrabromide, three (2,3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-tri-chloro-2,2-two (rubigan) ethane, carbon trichloride and triaizine compounds.As triaizine compounds, such as, can enumerate 2,4,6-tri-(trichloromethyl)-s-triazine and two (the trichloromethyl)-s-triazine of 2-(4-methoxyphenyl)-4,6-.
The addition of other compound is not limited, as long as be below more than 0.01 mass parts 30 mass parts relative to alkali soluble resins 100 mass parts.When addition is more than 0.01 mass parts, the effect of interpolation can be given full play of; When addition is below 30 mass parts, harmful effect can not be caused to luminous sensitivity etc.
In the photosensitive polymer combination of present embodiment, also can contain organic solvent further.Do not limit as organic solvent, as long as can dissolve equably and/or disperse alkali soluble resins.As such organic solvent, can enumerate dimethyl ether, diethyl ether, ethyl methyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether, diethylene glycol dimethyl ether and TRIGLYME and so on carbon number be less than more than 29 ether compound; The carbon number of acetone and methyl ethyl ketone and so on is the ketonic compound of less than more than 26; The carbon number of n-pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane and decahydronaphthalenes and so on is the saturated hydrocarbon compound of less than more than 5 10; The carbon number of benzene,toluene,xylene, trimethylbenzene and tetralin and so on is the aromatic hydrocarbon compound of less than more than 6 10; The carbon number of methyl acetate, ethyl acetate, gamma-butyrolacton and methyl benzoate and so on is the ester compounds of less than more than 39; The carbon number of methenyl choloride, methylene chloride and 1,2-ethylene dichloride and so on is the halide-containing of less than more than 1 10; The carbon number of acetonitrile, DMF, DMA and METHYLPYRROLIDONE and so on is the nitrogen-containing compound of less than more than 2 10; The sulfocompound of dimethyl sulfoxide (DMSO) and so on.
These organic solvents can be used alone as required, also can use with the form of mixed solvent of more than two kinds.As particularly preferred organic solvent, can enumerate carbon number be less than more than 29 ether compound, carbon number be less than more than 39 ester compounds, carbon number be less than more than 6 10 aromatic hydrocarbon compound and carbon number be nitrogen-containing compound and their mixed solvent of more than two kinds of below more than 2 10 carbon numbers.In addition, from the deliquescent aspect of alkali soluble resins, preferred TRIGLYME, METHYLPYRROLIDONE, gamma-butyrolacton, DMF, DMA.
In the resin combination formed by alkali soluble resins and organic solvent, the concentration as alkali soluble resins is not particularly limited, as long as the concentration for forming resin-formed body.From the aspect of the thickness of made resin-formed body, the concentration of preferred bases soluble resin is more than 1 quality %; From the aspect of the homogeneity of the thickness of resin-formed body, the concentration of preferred bases soluble resin is below 90 quality %, and this concentration is more preferably below more than 2 quality % 80 quality %.
< photosensitive film lamination body >
The photosensitive polymer combination of present embodiment can suitably for the formation of photosensitive film.By making the goods form of photosensitive film, compared with the goods form of liquid state, do not need the drying and volatilizing operation of solvent in printed wiring board production scene, operating environment improves.Can process on two sides in addition simultaneously, thus contribute to the raising of throughput rate.And there is the advantage of the goods of the surface smoothness excellence of the cover material can easily produced in wiring.The photosensitive film lamination body of present embodiment has base material and arranges the photosensitive film containing photosensitive polymer combination on the substrate.In addition; in the photosensitive film lamination body of present embodiment, preferably make the photosensitive film lamination body possessing base material, the cover film containing the photosensitive film of above-mentioned photosensitive polymer combination and the antifouling use formed on this photoresist or protection is on the substrate set.
Do not limit as base material, as long as the base material for can not damage photosensitive film when forming photosensitive film lamination body.As such base material, such as, can enumerate silicon wafer, glass, pottery, heat-resistant resin, carrier film.Among them, from the aspect of the easiness of the adaptability in the roll-to-roll mode of production and process, preferred vector film.
As carrier film, preferably can pass through the transparent carrier film of UV active light.As the carrier film that can pass through UV active light, such as, can enumerate polyethylene terephthalate (PET) film, polyvinyl alcohol film, polychloroethylene film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer membrane, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrol copolymer film, polyamide membrane, cellulose derivative film.Among them, from the aspect of the fissility after circuit substrate crimping, exposure, preferred PET film.As these films, use after also can stretching as required.During the thinner thickness of these films, be favourable from the viewpoint of imaging, economy, but maintain intensity etc. due to needs, thus thickness is generally 10 μm ~ 30 μm.
As cover film, as long as be the film that the photosensitive film that can obtain photosensitive polymer combinations such as using Low Density Polyethylene is protected, just do not limit.
Next, the manufacture method of photosensitive film lamination body is described.When use sense photosensitive resin composition manufactures photosensitive film lamination body, any means is utilized to be coated on arbitrary base material by the solution of photosensitive polymer combination.Then dry film is carried out in photosensitive polymer combination drying, such as make the photosensitive film lamination body with carrier film and photosensitive film afterwards.The coating processes such as rod painting, roller coat, mould painting, scraper plate coating, dip coated, scraper, spraying, flow coat, rotary coating, slot coated and brushing such as can be used during photosensitive resin coating composition on base material.After coating, can heating plate etc. be utilized as required to carry out being called as the heating of prebake.
< flexible printing wiring board >
The photosensitive film of present embodiment can suitably for the manufacture of flexible printing wiring board.The flexible printing wiring board of present embodiment possess the circuit substrate with wiring and carry out arranging in the mode covering the wiring on this circuit substrate fire the above-mentioned photosensitive film that film forming obtains.Wiring is such as thin copper film, is not particularly limited.This flexible printing wiring board, by crimping photosensitive film on the circuit substrate with wiring, carrying out alkali development, carries out firing to obtain afterwards.Now, from the aspect of method of volume production of effectively carrying out flexible printing wiring board, preferably carry out firing film forming after the above-mentioned photosensitive film of wiring side lamination using roll-type thermovacuum laminator on the circuit substrate with wiring.
Fig. 1 is the minimum thickness of the flexible printing wiring board that present embodiment is shown and the key diagram of surperficial difference of height.In Fig. 1, symbol 11 indication circuit substrate, symbol 12 represents the photosensitive film fired film forming and obtain, and symbol 13 represents wiring.In the flexible printing wiring board 10 of present embodiment, the minimum thickness (a) that above-mentioned wiring 13 is fired the photosensitive film 12 that film forming obtains is preferably more than 0.1 μm less than 10 μm, is more preferably more than 1 μm less than 8 μm, more preferably more than 2 μm less than 5 μm.Anti-oxidant or insulating reliability from the viewpoint of wiring 13, preferably (a) is more than 0.1 μm; Occur from the viewpoint of the crackle prevented when bending (は ぜ rolls over り), preferably (a) is less than 10 μm.
It should be noted that, the minimum thickness (a) firing the photosensitive film 12 that film forming obtains in wiring 13 carries out observation to try to achieve for flexible printing wiring board 10 through-thickness is ground the face obtained by utilizing optical microscope.Specifically, ratio for the interval (L/S) of thin copper film pattern and thin copper film pattern interval is below 1:5, more than 5 wirings 13 arranged in parallel, vertically grind with them, mean value for the minimum thickness of the photosensitive film 12 in the wiring 13 arranged in parallel of more than 3 of the central authorities of removing thin copper film pattern ends measures, this mensuration carries out more than 5 places, and the mean value of measured value is defined as (a).
In addition, wiring 13 is connected up with nothing 13 parts, and the maximal value (b) of the surperficial difference of height of photosensitive film 12 is preferably less than 10 μm, is more preferably less than 6 μm, more preferably less than 3 μm.
It should be noted that, what the maximal value (b) of above-mentioned surperficial difference of height represented is, when measuring distance from the surface of circuit substrate 11 to the surface of photosensitive film 12, the distance (b1) in wiring 13 with without connect up 13 the difference of distance (b2) of part.The maximal value (b) of surface difference of height carries out observation to try to achieve for flexible printing wiring board 10 through-thickness is ground the face obtained by utilizing optical microscope.
Specifically, the ratio for the interval (L/S) of thin copper film pattern and thin copper film pattern interval is below 1:5, vertical lapping is carried out in more than 5 wirings arranged 13.Then the distance (b1) from circuit substrate 11 surface of the photosensitive film 12 on thin copper film 13 apart from the part of circuit substrate 11 most portionafrom theasurface is measured.And the distance (b2) from circuit substrate 11 surface measured without the photosensitive film 12 of the part of thin copper film 13 part nearest with circuit substrate 11 surface.Obtain (b1)-the difference of (b2).Measure the difference at more than 5 places, its mean value is defined as (b).
As the circuit substrate with wiring in flexible printing wiring board, the hard substrate of epoxy glass substrate, maleimide glass substrate etc. and so on can be enumerated; And the flexible base, board etc. such as copper clad laminate.Wherein, from can the aspect of bending, preferred flexible substrate.
The manufacture method of flexible printing wiring board is not particularly limited, as long as photosensitive film is arranged on circuit substrate in the mode covering wiring.As such manufacture method, under the state contacted with the photosensitive film lamination body of present embodiment in the wiring side of the circuit substrate with wiring can be enumerated, carry out the method etc. of hot pressing, heat lamination, vacuum hotpressing, Vacuum Heat lamination etc.Wherein, from by the aspect between photosensitive film buried wiring, preferred vacuum hot-pressing, vacuum hot platen press.
Heating-up temperature when amassing body to lamination photosensitive film layer on the circuit substrate with wiring does not limit, if for photosensitive film can be closely sealed with circuit substrate temperature.From the viewpoint closely sealed with circuit substrate or from the decomposition of photosensitive film or the aspect of subsidiary reaction, this heating-up temperature is preferably more than 30 DEG C less than 400 DEG C.Be more preferably more than 50 DEG C less than 150 DEG C.
Whole process of the circuit substrate with wiring is not particularly limited, HCl treatment, sulfuric acid treatment and sodium persulfate aqueous solution process etc. can be enumerated.
For photosensitive film lamination body, arbitrary photomask selective light illuminated portion can be utilized, illumination penetrate after by the part beyond alkali developer dissolves illumination part position, thus carry out the photoetching of minus.In this case, after circuit substrate is room temperature, preferably carry out illumination to penetrate.In addition, make the free radical inactivation produced by (C) Photoepolymerizationinitiater initiater, the stability improving luminous sensitivity from the viewpoint of the impact prevented because oxygen suppresses, after illumination is penetrated, preferably peel off carrier film, carry out alkali development treatment.Hit the light source of use as illumination, high-pressure sodium lamp, ultrahigh pressure mercury lamp, low pressure mercury lamp, metal halide lamp, xenon lamp, fluorescent light, tungsten lamp, argon laser and helium cadmium laser etc. can be enumerated.Wherein preferred high-pressure sodium lamp, ultrahigh pressure mercury lamp.
Do not limit, as long as can by the partly soluble solution beyond illumination part position as aqueous alkali used in development.As such solution, such as, can enumerate aqueous sodium carbonate, wet chemical, sodium hydrate aqueous solution, potassium hydroxide aqueous solution, tetramethylammonium hydroxide aqueous solution.From the aspect of developability, preferred aqueous sodium carbonate and sodium hydrate aqueous solution.As developing method, spray development, immersion development and puddle developing etc. can be enumerated.Also washing process or dry process can be implemented as required.
Next, flexible printing wiring board is obtained by firing the printed wiring board being crimped with photosensitive film.Consider from the aspect of removal of solvents or the aspect such as subsidiary reaction or decomposition, fire the preferably temperature enforcement of less than 400 DEG C more than 30 DEG C, more preferably less than 300 DEG C enforcements more than 100 DEG C.
About the reaction atmosphere in firing, fire and can implement in air atmosphere, also can implement under inert gas atmosphere.In the manufacture of printed wiring board, it is different according to the difference of reaction conditions to fire the required time, but is usually suitable for implementing in the 1 little scope up to 8 hours within 24 hours, especially.
The photosensitive film lamination body warpage aspect after curing employing the photosensitive film of present embodiment is good, and developability is also good, chemical proofing is demonstrated when making firming body, thus can be used for being formed in the purposes of film on electronic components, thus for the printed wiring board that uses in the guidance panel etc. of electronic equipment various in electronic applications or the formation of protective seam of circuit substrate, the formation of the insulation course of laminated substrate; The silicon wafer used in semiconductor devices, semi-conductor chip, semiconductor device circumferential component, substrate for mounting semiconductor, heat liberation board, the protection of drawing pin, semiconductor self etc., insulation and bonding.
In addition; the photosensitive film lamination body employing the photosensitive film of present embodiment also can automatically combine (TAB) in flexible printed wiring circuit (FPC) substrate, winding and be used with in the electrical insulation film in substrate, various electron device and LCDs substrate, organic electroluminescent (EL) display screen substrate, Electronic Paper substrate, substrate used for solar batteries; especially suitably can be used as overlayer, this overlayer is the diaphragm protected silicon wafer, copper clad laminate, flexible printed wiring circuit use etc.
Embodiment
Under regard to the embodiment implemented in order to effect clearly of the present invention and be described, but the present invention is by any restriction of these embodiments.It should be noted that, the various physical property in embodiment and the determination method of characteristic, be defined as follows described in.
< reagent >
In embodiment and comparative example, the reagent used is as follows.It should be noted that, in following embodiment 1 to embodiment 10 and comparative example 1 to comparative example 7, suitably indicate the abbreviation of following reagent.
(A) alkali soluble resins composition
BPDA (manufacture of Mitsui Chemicals society)
APB (trade name: APB-N, Mitsui Chemicals society manufacture)
Diamines represented by general formula (5): polyetheramine (trade name: polyetheramine D-400 (being only designated as below " D-400 "), BASF society manufacture, m+n+p=6.1)
Jeffamine (trade name: Jeffamine D-230 (being only designated as below " D-230 "), Huntsman society manufacture, m+n+p=2.5)
Methacrylic acid (Wako Pure Chemical Industries, Ltd.'s manufacture)
Methyl methacrylate (monomer, Wako Pure Chemical Industries, Ltd. manufacture)
Styrene (monomer, Wako Pure Chemical Industries, Ltd. manufacture)
2,2 '-azoisobutyronitrile (AIBN, Wako Pure Chemical Industries, Ltd. manufacture)
(B) there is the compound of unsaturated double-bond
EO modified bisphenol A dimethylacrylate (trade name: chemical industry society of BPE-500, Xin Zhong village manufactures)
Ethoxylation tetramethylol methane tetraacrylate (trade name: SARTOMER SR-494 (being only designated as below " SR-494 "), Sartomer society manufacture)
Trimethylolpropane PO modified triacrylate (trade name: Aronix M-310 (being only designated as below " M-310 "), East Asia synthesis society manufacture)
(C) Photoepolymerizationinitiater initiater
1,2-pentanedione-3-cyclopentyl-1-[4-(thiophenyl) phenyl]-2-(O benzoyl oximes) (trade name: PBG-305, Changzhou electronic strong society manufacture)
3-cyclopentyl acetone-1-(6-2-formylthien-9-ethyl carbazole-3-base)-1-oxime acetic acid esters (trade name: PBG-314, Changzhou electronic strong society manufacture)
3-cyclopentyl acetone-1-(6-formylfuran-9-ethyl carbazole-3-base)-1-oxime acetic acid esters (trade name: PBG-314F, Changzhou brute force synthesis society manufacture)
3-cyclopentyl-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base] acetone-1-(O-acetyl group oxime) (trade name: PBG-304, Changzhou electronic strong society manufacture)
Ethyl ketone 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O-acetyl group oxime) (trade (brand) name: IRGACURE OXE-02 (being only designated as below " OXE-02 "), Ciba Japan society manufacture)
(D) polymerization inhibitor
N-nitrosophenylhydroxylamine aluminium (trade name: Q-1301, Wako Pure Chemical Industries, Ltd. manufacture)
N-nitrosophenylhydroxylamine ammonium salt (trade name: Q-1300, Wako Pure Chemical Industries, Ltd. manufacture)
P methoxy phenol (Wako Pure Chemical Industries, Ltd.'s manufacture)
(E) blocked isocyanate
Blocked isocyanate (trade name: DURANATESBN-70D (being only designated as below " SBN-70D "), chemistry society of Asahi Chemical Industry manufacture)
(F) phosphorus compound
Phosphazene compound (trade name: FP-300, volt are shown in that society of pharmacy institute manufactures)
(G) other compound
Solvent blue 70 (manufacture of trade name: OIL BLUE650, Orient chemical industry society)
Toluene (Wako Pure Chemical Industries, Ltd. manufactures, and organic synthesis is used)
Gamma-butyrolacton (Wako Pure Chemical Industries, Ltd.'s manufacture)
Methyl ethyl ketone (MEK, Wako Pure Chemical Industries, Ltd. manufacture)
Sodium carbonate (Wako Pure Chemical Industries, Ltd.'s manufacture)
< Weight-average molecular quantitative determination >
The determination method of weight-average molecular weight uses gel permeation chromatography (GPC), is measured by following condition.N is used as solvent, (Wako Pure Chemical Industries, Ltd. manufactures dinethylformamide, high performance liquid chromatography is used), use lithium bromide monohydrate (the Wako Pure Chemical Industries, Ltd.'s manufacture adding before the assay and have 24.8mmol/L, purity 99.5%) and the solvent of phosphoric acid (Wako Pure Chemical Industries, Ltd. manufacture, high performance liquid chromatography with) of 63.2mmol/L.In addition, the calibration curve for calculating weight-average molecular weight uses polystyrene standard (Dong Caoshe manufacture) to make.
Post: Shodex KD-806M (manufacture of Showa electrician society)
Flow velocity: 1.0mL/ minute
Column temperature: 40 DEG C
Pump: PU-2080Plus (manufacture of JASCO society)
Detecting device: RI-2031Plus (RI: differential refractometer, JASCO society manufacture)
UV-2075Plus (UV-VIS: UV, visible light absorptiometer, JASCO society manufacture)
The manufacture method > of < photosensitive film lamination body
The coating process of photosensitive polymer combination be by use FILM COATER (TESTER SANGYO society manufactures, PI1210) scrape the skill in using a kitchen knife in cookery to carry out.In PET film, (Di Ren DuPont Film society manufactures, G2, thickness=16 μm) on drip photosensitive polymer combination, be 15 μm according to dried thickness to be coated with, use dryer (manufacture of SPHH-10l, ESPEC society) 95 DEG C of dryings 12 minutes afterwards, thus obtain photosensitive film lamination body.Thickness uses film thickness gauge (manufacture of ID-C112B, Mitutoyo society) to measure.
The photoengraving pattern method for making > of < photosensitive film
Form resistance to migration test wiring (conductor is wide/conductor gap is 50/50 μm, pattern numbers is 10) according to JPCA-2006-DG2 annex 2 and solid copper foil portion is divided (5cm × 5cm) flexible base, board (Espanex:MC12-20-00CEM, chemistry society of Nippon Steel manufacture) is upper, substrate is tested in making.
Then, use vacuum press (manufactures of SA-501, TESTER SANGYO society), molding temperature is set to 80 DEG C, drum pressure is set to 0.5MPa, clamp time is set to 30 seconds, test the thin copper film laminated photosensitive film lamination body of substrate.
Then, the mode of carrying out shading according to the electrode part connected up to resistance to migration test configures photomask, at the stage metraster of solid copper paper tinsel partial configuration (step tablet) (Stouffer21).Further, after vacuum both inciting somebody to action are closely sealed, ultrahigh pressure mercury lamp (HMW-201KB, OAK make society of institute and manufacture) is utilized to carry out 200mJ/cm 2exposure.Thereafter, peel off PET film by obtained laminate, utilize 1.0 quality % aqueous sodium carbonates to carry out spray development process in 22 seconds at 30 DEG C and after utilizing water to carry out rinsing, carry out drying, making the photoengraving pattern of photosensitive film.
The practical evaluating characteristics > of <
By visual or microscope, practical characteristic is observed in the photoengraving pattern manufacturing process of photosensitive film, carry out the practical evaluating characteristics of photosensitive film lamination body according to its quality.In evaluating at following 5, ◎ or zero is qualified.
(luminous sensitivity evaluation)
Observed by the exponent number of photoengraving pattern for the stage metraster not carrying out the part that development is removed, copper face does not expose completely.
More than ◎: 9 rank
Zero: 7 ~ 8 rank
×: below 6 rank
(evaluation of exposure portion observability)
After photomask exposure, immediately under gold-tinted room environmental by the tone difference in visualization exposure portion and unexposed portion.
◎: clearly can pick out exposure portion and unexposed portion
Zero: exposure portion and unexposed portion can be picked out
×: exposure portion and unexposed portion can not be picked out
(evaluation of development residue)
Utilizing the copper face of the stage metraster that photoengraving pattern is removed for having carried out developing, copper face exposes completely to carry out visualization, carrying out tone with the copper face of untreated test substrate and comparing.
Zero: the tone indifference on copper surface
×: carry out developing the copper face generation variable color of removing
(adhesion evaluation)
Rubber rollers is utilized to fit according to the mode contacted with the photoengraving pattern face after development treatment low density polyethylene films (GF-858, thickness=35um, Tamapoly society manufactures).By its 23 DEG C, preserve 24 hours under the environment of 50%RH, under the condition of peeling rate 0.1m/min, peel angle 90 °, carry out disbonded test.Determinator uses cupping machine (ORIENTEC society manufactures, Tensilon RTM-500: the specified 1Kgf of force cell).Disbonded test distance is 60mm, divides average load by cumulative mean loading (Plot when mapping to loading relative to length growth rate) evaluate the laminated paper release (He Paper From shape property after developing).
◎: cumulative mean loading is less than 0.01N/25mm
Zero: cumulative mean loading is 0.01N/25mm ~ be less than 0.1N/25mm
×: cumulative mean loading is more than 0.1N/25mm
(evaluation of the coating property of wiring)
Optical microscope (50 times) is utilized to observe for the state of the photosensitive film in the resistance to migration test wiring of photoengraving pattern.
Zero: do not observe the expansion of the photosensitive film in wiring, stripping
×: the photosensitive film in wiring expands, surface configuration is viewed as corrugated; Or the photosensitive film in wiring is peeled off, thin copper film exposes
(with the adhering evaluation of metal fixture)
SUS plate (150mm × 75mm, thickness=0.5mm, SUS304 manufactures) is utilized to be clipped in the middle from both sides by obtained photoengraving pattern, use baking furnace (NRY-325-5Z, large and make manufactured), SUS plate surface temperature 260 DEG C, maintain 30 seconds condition under fire in air atmosphere.After naturally cooling to room temperature, peeled off from SUS plate by photoengraving pattern, visualization is to the transfer state of SUS plate transfer printing.
◎: photosensitive film layer is not to the transfer printing of SUS plate
Zero: a part of melting of photosensitive film layer is transferred to SUS plate
×: photosensitive film layer and the complete welding of SUS plate, fail to peel
< synthesis example >
(alkali soluble resins (A1))
In a nitrogen atmosphere, gamma-butyrolacton (255g), toluene (51.0g), polyetheramine D-400 (86.8g (201.9mmol)), BPDA (120g (407.9mmol)) is added in the removable flask possessing Dean-Stark device and return channel, be warming up to 180 DEG C, add thermal agitation 1 hour at 180 DEG C.Removing, as after the toluene of azeotropic solvent, is cooled to 40 DEG C, then adds APB-N (48.4g (165.7mmol)), stirs 4 hours, obtain the solution of polyimide precursor (A1) at 40 DEG C.The weight-average molecular weight of the polyimide precursor (A1) obtained is 23000.
(alkali soluble resins (A2))
In a nitrogen atmosphere, gamma-butyrolacton (80.0g), toluene (16.0g), polyetheramine D-230 (16.8g (73.04mmol)), BPDA (30.0g (102.0mmol)) is added in the removable flask possessing Dean-Stark device and return channel, be warming up to 180 DEG C, add thermal agitation 1 hour at 180 DEG C.Removing, as after the toluene of azeotropic solvent, is cooled to 40 DEG C, and (5.60g (19.16mmol) stirs 4 hours at 40 DEG C, obtains the solution of polyimide precursor (A2) then to add APB-N.The weight-average molecular weight of the polyimide precursor (A2) obtained is 21000.
(alkali soluble resins (A3))
In a nitrogen atmosphere, in the removable flask possessing Dean-Stark device and return channel, add MEK 300g and methacrylic acid (100g), methyl methacrylate (200g), styrene (100g), under agitation the temperature of hot bath is elevated to 70 DEG C.Next, AIBN 2g is dissolved in the MEK of 30g, adds in flask, be polymerized 6 hours.Be dissolved in the MEK of 30g by AIBN 3g further, the interval 1 little time-division adds for 2 times, afterwards the temperature in flask is increased to the boiling point of solvent, is polymerized 2 hours at such a temperature.After polymerization stops, add MEK240g, polymerization reactant is taken out from flask, obtains the solution of acrylic resin (A3).The weight-average molecular weight of the alkali-soluble acrylic's resin (A3) obtained is 55000.
[embodiment 1]
Relative to alkali soluble resins (A1) 50 mass parts, mixing BPE-500 (15 mass parts), SR-494 (10 mass parts), PBG-305 (0.5 mass parts), Q-1301 (0.1 mass parts), SBN-70D (10 mass parts), FP-300 (15 mass parts), OIL BLUE650 (0.15 mass parts), prepare photosensitive polymer combination.The photosensitive film of 15 μm of thickness is obtained as stated above by obtained photosensitive polymer combination.As stated above luminous sensitivity, exposure portion observability, development residue, adhesion, being coated to property of wiring, adhering evaluation are carried out to this photosensitive film.The composition of photosensitive polymer combination is listed in the table below 1, evaluation result is listed in the table below 2.
[embodiment 2, embodiment 3 and comparative example 1 to comparative example 3]
Use the compound described in table 1 as alkali soluble resins and Photoepolymerizationinitiater initiater, in addition, obtain the photosensitive film of 15 μm of thickness similarly to Example 1.As stated above luminous sensitivity, exposure portion observability, development residue, adhesion, being coated to property of wiring, adhering evaluation are carried out to this photosensitive film.The composition of photosensitive polymer combination is listed in the table below 1, evaluation result is listed in the table below 2.
[embodiment 4 to embodiment 6]
Use the compound described in table 1 as Photoepolymerizationinitiater initiater, in addition, obtain the photosensitive film of 15 μm of thickness similarly to Example 1.As stated above luminous sensitivity, exposure portion observability, development residue, adhesion, being coated to property of wiring, adhering evaluation are carried out to this photosensitive film.The composition of photosensitive polymer combination is listed in the table below 1, evaluation result is listed in the table below 2.
[embodiment 7, embodiment 8, comparative example 4 and comparative example 5]
Use the compound described in table 1 as Photoepolymerizationinitiater initiater and polymerization inhibitor, in addition, obtain the photosensitive film of 15 μm of thickness similarly to Example 1.As stated above luminous sensitivity, exposure portion observability, development residue, adhesion, being coated to property of wiring, adhering evaluation are carried out to this photosensitive film.The composition of photosensitive polymer combination is listed in the table below 1, evaluation result is listed in the table below 2.
[embodiment 9 and comparative example 6]
As Photoepolymerizationinitiater initiater and there is unsaturated double-bond polymerizable compound use table 1 described in compound, in addition, obtain the photosensitive film of 15 μm of thickness similarly to Example 1.As stated above luminous sensitivity, exposure portion observability, development residue, adhesion, being coated to property of wiring, adhering evaluation are carried out to this photosensitive film.The composition of photosensitive polymer combination is listed in the table below 1, evaluation result is listed in the table below 2.
[embodiment 10 and comparative example 7]
Remove blocked isocyanate compounds, use the compound described in table 1 in addition, obtain the photosensitive film of 15 μm of thickness in addition similarly to Example 1.As stated above luminous sensitivity, exposure portion observability, development residue, adhesion, being coated to property of wiring, adhering evaluation are carried out to this photosensitive film.The composition of photosensitive polymer combination is listed in the table below 1, evaluation result is listed in the table below 2.
Shorthand notation in following table 1 is as follows.It should be noted that, in following table 1, combined amount represents with quality solid composition ratio.
(A) composition: alkali soluble resins
A1: alkali soluble resins (A1)
A2: alkali soluble resins (A2)
A3: alkali soluble resins (A3)
(B) composition: the compound with unsaturated double-bond
B1:EO modified bisphenol A dimethylacrylate
B2: ethoxylation tetramethylol methane tetraacrylate
B3: trimethylolpropane PO modified triacrylate
(C) composition: Photoepolymerizationinitiater initiater
C1:1,2-pentanedione-3-cyclopentyl-1-[4-(thiophenyl) phenyl]-2-(O benzoyl oximes)
C2:3-cyclopentyl acetone-1-(6-2-formylthien-9-ethyl carbazole-3-base)-1-oxime acetic acid esters
C3:3-cyclopentyl acetone-1-(6-formylfuran-9-ethyl carbazole-3-base)-1-oxime acetic acid esters
C4:3-cyclopentyl-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base] acetone-1-(O-acetyl group oxime)
C5: ethyl ketone 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O-acetyl group oxime)
(D) composition: polymerization inhibitor
D1:N-nitrosophenylhydroxylamine aluminium
D2:N-nitrosophenylhydroxylamine ammonium salt
D3: p methoxy phenol
(E) composition: blocked isocyanate
E1: blocked isocyanate
(F) composition: phosphorus compound
F1: phosphazene compound
(G) composition: other compound
G1: solvent blue 70
With employ comparative example 1 to comparative example 7 photosensitive film wiring protective film compared with, the being coated to property of wiring employing the wiring protective film of the photosensitive film obtained in embodiment 1 to embodiment 10 is good, and showing excellent practical characteristic, is the article of high-quality.In addition, in the wiring protective film employing the photosensitive film obtained in embodiment 1 to embodiment 10, the observability in exposure portion and unexposed portion is good, easily avoids two re-exposure of production scene.Employing in the photosensitive film of the compound containing nitroso compound and/or nitro compound in embodiment 1 and embodiment 7, compared with the photosensitive film of embodiment 8, luminous sensitivity is excellent.For the photosensitive film of embodiment 1, with embodiment 9 with 10 photosensitive film compare, the viscosity of the photosensitive film layer after development and/or after firing is little, being suitable for especially for adhesion or with the raising of the process windows (process margin) such as the adhesiveness of metal fixture as having (two) pentaerythrite (methyl) acrylate compounds of compound of unsaturated double-bond and blocked isocyanate compounds, confirming it can contribute to compatibility, throughput rate raising in the roll-to-roll mode of production.
On the other hand, in the wiring protective film employing the photosensitive film obtained in comparative example 1 to comparative example 7, it is bad that exposure portion observability and wiring are coated to property.It is believed that this is because, Photoepolymerizationinitiater initiater does not have the substituting group of large volume, thus not form crosslinked fully combination between the polymerizable compound of unsaturated double-bond and Photoepolymerizationinitiater initiater having.
[embodiment 11]
The manufacture > of < photosensitive film roller
Use unfilled corner wheel coating machine (manufacture of the Hirano Tecseed society) photosensitive polymer combination described in coating Examples 1.Be applied to PET film (Di Ren Du Pont membrane society manufactures, G2, thickness=16 μm), make dried thickness be respectively 8 μm and 12 μm.Then by dry section 95 DEG C of dryings 6 minutes, fit afterwards as the polyethylene film (Tamapoly society manufacture, GF-818, thickness=19 μm) of protective seam, obtain photosensitive film roller.Thickness uses film thickness gauge (manufacture of ID-C112B, Mitutoyo society) to measure.
The manufacture > of < flexible printing wiring board
After the copper thickness half-etching of flexible base, board roller (Espanex:MC12-20-00CEM, chemistry society of Nippon Steel manufacture) is become 6 μm, this copper face forms resistance to migration test wiring (conductor is wide/conductor gap is 50/50 μm, pattern numbers is 10) according to JPCA-2006-DG2 annex 2 and solid copper foil portion is divided (5cm × 5cm), make and test roller substrate.
Then, (MCK society manufactures to use roll-type thermovacuum laminator, MVR-250), roll temperature is set to 80 DEG C, drum pressure is set to 0.4MPa, vacuum tightness=100Pa, speed is set to 1m/ minute, in lamination photosensitive film (thickness=8 μm respectively, thin copper film face of test roller substrate, 12 μm) after, cut out resistance to migration test wiring (conductor is wide/conductor gap is 50/50 μm, pattern numbers is 10) and solid copper foil portion is divided (5cm × 5cm), making test film substrate.
Then, the mode of carrying out shading according to the electrode part connected up to resistance to migration test configures photomask, at the stage metraster of solid copper paper tinsel partial configuration (Stouffer21).Further, after vacuum both inciting somebody to action are closely sealed, ultrahigh pressure mercury lamp (HMW-201KB, OAK make society of institute and manufacture) is utilized to carry out 100mJ/cm 2exposure.Thereafter, peel off PET film by obtained laminate, utilize 1.0 quality % aqueous sodium carbonates to carry out spray development process in 60 seconds at 30 DEG C and after utilizing water to carry out rinsing, carry out drying, making the photoengraving pattern of photosensitive polymer combination.
Then, use dryer (manufacture of SPHH-10l, ESPEC society) to fire 1 hour at 180 DEG C, thus obtain the flexible printing wiring board possessing covering layer film in thin copper film face.
The practical evaluating characteristics > of <
By visual or microscope, the practical characteristic of the flexible printing wiring board through said method manufacture is observed, carry out the practical evaluating characteristics of photosensitive film according to its quality.In following evaluation, ◎ or zero is qualified.Evaluation result is listed in the table below 3.
(100mJ/cm 2the evaluation of exposure and the being coated to property of wiring after developing for 60 seconds)
Optical microscope (50 times) is utilized to observe for the state of the photosensitive film in the resistance to migration test wiring of photoengraving pattern.Metewand is as follows.
◎: do not observe the expansion of the photosensitive film in wiring, stripping
Zero: the expansion observing the photosensitive film on wire ends, but unstripped, thin copper film does not expose
△ a: part for the photosensitive film in wiring is peeled off, thin copper film exposes
×: the major part of the photosensitive film in wiring is peeled off, thin copper film exposes completely
(cross-section of flexible printing wiring board)
Flexible printing wiring board through said method manufacture is utilized epoxy resin embedding, use lapping device (manufacture of this Struers of ball society), after the wiring plate embedded and wiring are vertically ground, utilize and there is the optical microscope surveying long function observe, on the mean value of the minimum thickness (a) of the covering layer film on central authorities' 8 thin copper film at copper removal wiring pattern two ends and above-mentioned wiring with without wiring portion, the value of the maximal value (b) of carrying out the surperficial difference of height firing the film obtained measures.It should be noted that, about evaluation, 10 places are observed, calculate the mean value of (a) and (b).
(folding resistance test)
Using the flexible printing wiring board that produces through said method as sample, vertically carry out 180 ° with thin copper film and bend (being bent to 180 degree) and test.When bending, taking covering layer film as the mode of inner side, by sample holder in the glass plate of 10cm × 10cm, keeping 10 seconds under the counterweight of 750g afterwards.Thereafter optical microscope (50 times) is utilized to be observed by covering layer film side.Metewand is as follows.
◎: the flawless generation of covering layer film in wiring
Zero: the covering layer film in wiring observed the generation of meticulous small crackle, but exposing without thin copper film
×: the covering layer film in wiring observed the generation of meticulous small crackle and/or very large crackle, has thin copper film to expose
[embodiment 12 ~ 20, comparative example 8 ~ 14]
Except using the photosensitive film described in embodiment 2 ~ 10, comparative example 1 ~ 7, carry out the manufacture of photosensitive film roller, the manufacture of flexible printing wiring board, practical evaluating characteristics similarly to Example 11.Evaluation result is listed in the table below 3.
[table 3]
[comparative example 15 ~ 17]
Except the mode being respectively 25 μm according to dried thickness is coated with except the photosensitive polymer combination described in comparative example 1 ~ 3, carry out the manufacture of photosensitive film roller, the manufacture of flexible printing wiring board, practical evaluating characteristics similarly to Example 11.Evaluation result is listed in the table below 4.
[table 4]
With employ comparative example 8 ~ comparative example 14 photosensitive film wiring protective film compared with; even if even if the thickness (a) of the wiring protective film employing the photosensitive film roller obtained in embodiment 11 ~ embodiment 20 in wiring less region is being crossed under development conditions in the low exposure lower than suitable etching condition, the coating property of wiring is also good.And, the covering layer film employing the photosensitive film obtained in embodiment 11 ~ embodiment 20 has the thickness region that the thickness (a) on thin copper film and (b) of presentation surface flatness all demonstrate smaller value, its result, stress equilibrium dispersion during bending, there is not crackle in covering layer film surface, thin copper film does not expose.Its results verification arrives, and the photosensitive film described in embodiment 11 ~ 20 has very excellent being coated to property of wiring and higher flexibility.
On the other hand, for the photosensitive film recorded in comparative example 8 ~ 10, when the thickness (a) on connecting up is thinner, the coating property of wiring cannot be met.Though the coating property of wiring can be improved by the thickness (a) increased as comparative example 15 ~ 17 in wiring, folding resistance cannot be met.By inference, this is caused by the thickness region owing to not having satisfied (a) value and (b) value simultaneously.
Confirmed by foregoing, the photosensitive film of present embodiment is the wiring protective film being suitable for following flexible printing wiring board, and this flexible printing wiring board contributes to the raising of compatibility in the roll-to-roll mode of production and throughput rate.
Industrial applicibility
The present invention has the effect that can obtain following photosensitive film, and the luminous sensitivity of this photosensitive film is excellent, can obtain the high wiring protective seam of reliability; It can in the field especially suitably for the surface protection film of semiconductor element, interlayer dielectric, conductor package substrate, flexible printed board protection dielectric film.
The Japanese Patent Application 2012-175936 that the application submitted to based on August 8th, 2012.Its content all comprises in this application.

Claims (17)

1. a photosensitive film lamination body, is characterized in that,
This photosensitive film lamination body possesses base material and arranges the photosensitive film containing photosensitive polymer combination on the substrate,
This photosensitive polymer combination contains (A) alkali soluble resins, (B) has the polymerizable compound of unsaturated double-bond and (C) Photoepolymerizationinitiater initiater, the structure of described (C) Photoepolymerizationinitiater initiater represented by following general formula (1)
[changing 1]
General formula (1)
In general formula (1), Ar 1for the 1 valency organic group containing aromatic series, R 1for there is the organic group of alkyl or aryl, R 2for the 1 valency alkyl that carbon number is 3 ~ 50, be branched alkyl, straight chained alkyl, the alkyl with alicyclic structure or have in the alkyl of aromatic structure any one.
2. photosensitive film lamination body as claimed in claim 1, it is characterized in that, described base material is carrier film.
3., as photosensitive film lamination body according to claim 1 or claim 2, it is characterized in that, described R 2for the structure represented by following general formula (2),
[changing 2]
General formula (2)
In general formula (2), R 3, R 4, R 5, R 6and R 7for hydrogen or carbon number are the alkyl of 1 ~ 20, be same to each other or different to each other; N is the integer of 0 ~ 20, and m is the integer of 0 ~ 20.
4. photosensitive film lamination body as claimed in claim 3, it is characterized in that, described m is the integer of 2 ~ 4.
5. the photosensitive film lamination body as described in any one of Claims 1 to 4, is characterized in that, described Ar 1for replace or without replace following general formula (3) or replace or without replace following general formula (4),
[changing 3]
General formula (3)
General formula (4)
In general formula (3), X is monovalent organic group, R 8for replacement or without the furyl replaced, thienyl or phenyl.
6. the photosensitive film lamination body as described in any one of Claims 1 to 5, it is characterized in that, described (A) alkali soluble resins has the polyimide structures represented by following general formula (5) and the polyamic acid structure represented by following general formula (6) respectively as constitutional repeating unit
[changing 4]
General formula (5)
General formula (6)
In general formula (5) and general formula (6), R 9, R 10, R 12, R 13, R 15, R 16, R 18, R 19, R 21and R 22represent that hydrogen atom or carbon number are the 1 valency organic group of 1 ~ 20 independently of one another, they are identical or different; R 11, R 14, R 17, R 20and R 23represent that carbon number is the 4 valency organic groups of 1 ~ 20, m, n and p represent the integer of less than more than 0 100 independently of one another; R 24represent 4 valency organic groups, R 25represent that carbon number is the divalent organic group of 1 ~ 90, R 26represent that carbon number is the 4 valency organic groups of 1 ~ 50.
7. photosensitive film lamination body as claimed in claim 6, is characterized in that, it contains the diamine component of the diamines represented by following general formula (7) as the polyimide structures formed represented by described general formula (5),
[changing 5]
General formula (7)
In general formula (7), R 9, R 10, R 12, R 13, R 15, R 16, R 18, R 19, R 21and R 22represent that hydrogen atom or carbon number are the 1 valency organic group of 1 ~ 20 independently of one another, they are identical or different; R 11, R 14, R 17, R 20and R 23represent that carbon number is the 4 valency organic groups of 1 ~ 20, m, n and p are the integer of less than more than 0 30 independently of one another, meet 1≤(m+n+p)≤30.
8. the photosensitive film lamination body as described in any one of claim 1 ~ 7, is characterized in that, it contains the polymerization inhibitor of at least one (D) containing nitroso compound and/or nitro compound.
9. the photosensitive film lamination body as described in any one of claim 1 ~ 8, it is characterized in that, the polymerizable compound of it contains (two) pentaerythrite (methyl) acrylate compounds has as described (B) unsaturated double-bond.
10. the photosensitive film lamination body as described in any one of claim 1 ~ 9, is characterized in that, it contains at least one (E) blocked isocyanate compounds.
11. photosensitive film lamination bodies as described in any one of claim 1 ~ 10, it is characterized in that, it contains at least one (F) phosphorus compound.
12. 1 kinds of flexible printing wiring boards, it is characterized in that, it possesses:
Have wiring circuit substrate and
Described circuit substrate carries out the photosensitive film be fired into described in any one of the claim 1 ~ 11 of film.
The manufacture method of 13. 1 kinds of flexible printing wiring boards, is characterized in that, uses roll-type thermovacuum laminator, on the wiring side on the circuit substrate with wiring lamination claim 1 ~ 11 the photosensitive film lamination body described in any one after carry out being fired into film.
14. 1 kinds of flexible printing wiring boards, is characterized in that, it is by the manufacture method manufacture of claim 13.
15. 1 kinds of flexible printing wiring boards, it possesses:
Have wiring circuit substrate and
The covering layer film arranged in the mode covering described wiring is fired by described circuit substrate and the film obtained,
It is characterized in that,
To fire described in described wiring and the minimum thickness (a) of the film obtained is more than 0.1 μm and is less than 10 μm.
16. 1 kinds of flexible printing wiring boards, it possesses:
Have wiring circuit substrate and
The covering layer film arranged in the mode covering described wiring is fired by described circuit substrate and the film obtained,
It is characterized in that,
In described wiring with without the part that connects up, described in fire the surperficial difference of height of the film obtained maximal value (b) be less than 3 μm.
17. flexible printing wiring boards as claimed in claim 16, is characterized in that, fire and the minimum thickness (a) of the film obtained is more than 0.1 μm and is less than 10 μm described in described wiring.
CN201380041043.8A 2012-08-08 2013-08-08 Photosensitive film laminate, flexible printed wiring board, and method for producing same Expired - Fee Related CN104583867B (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6362433B1 (en) * 1998-06-05 2002-03-26 Sony Chemicals Corporation Flexible printed circuit board
WO2004092838A1 (en) * 2003-04-15 2004-10-28 Kaneka Corporation Photosensitive resin composition capable of being developed with aqueous developer and photosensitive dry film resist, and use thereof
JP2009009107A (en) * 2007-05-25 2009-01-15 Toray Ind Inc Photosensitive resin composition
CN100484363C (en) * 2003-12-22 2009-04-29 日东电工株式会社 Wiring circuit board and production method thereof
JP2010135514A (en) * 2008-12-03 2010-06-17 Nitto Denko Corp Wired circuit board
CN102375337A (en) * 2010-08-10 2012-03-14 住友化学株式会社 Photosensitive resin composition
CN102597061A (en) * 2009-11-16 2012-07-18 旭化成电子材料株式会社 Polyimide precursor and photosensitive resin composition containing the polyimide precursor

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2025681A1 (en) 1989-09-22 1991-03-23 Allan E. Nader Photoreactive resin compositions developable in a semi-aqueous solution
JP2002182378A (en) 2000-12-18 2002-06-26 Hitachi Chemical Dupont Microsystems Ltd Alkali negative development type photosensitive resin composition, method for producing pattern and electronic parts
JP4799740B2 (en) 2001-01-17 2011-10-26 日東電工株式会社 Resin composition for printed circuit board, substrate for wired circuit board, and wired circuit board
DE60234095D1 (en) 2001-06-11 2009-12-03 Basf Se OXIM ESTER PHOTOINITIATORS WITH COMBINED STRUCTURE
JP2004109403A (en) 2002-09-18 2004-04-08 Hitachi Ltd Liquid crystal display element
JP2004325980A (en) * 2003-04-28 2004-11-18 Kanegafuchi Chem Ind Co Ltd Photosensitive resin composition and photosensitive dry film resist having favorable storage stability, and its use
JP4826415B2 (en) 2005-10-12 2011-11-30 東レ株式会社 Photosensitive resin composition
JP2008158421A (en) * 2006-12-26 2008-07-10 Asahi Kasei Corp Photosensitive resin composition and photosensitive dry film using the same
JP2009276526A (en) * 2008-05-14 2009-11-26 Asahi Kasei E-Materials Corp Photosensitive resin composition and flexible printed wiring board using the same
JP5368153B2 (en) * 2009-04-15 2013-12-18 旭化成イーマテリアルズ株式会社 Photosensitive resin composition and circuit board using the same
JP5673111B2 (en) * 2011-01-12 2015-02-18 東洋インキＳｃホールディングス株式会社 Photosensitive coloring composition and color filter
CN102020727B (en) * 2010-11-23 2013-01-23 常州强力先端电子材料有限公司 Pyrazole oxime ester photoinitiator with high photosensibility, preparation method and application thereof
JP5121912B2 (en) * 2010-11-24 2013-01-16 富士フイルム株式会社 Colored photosensitive resin composition, pattern forming method, color filter manufacturing method, color filter, and display device including the same
JP5981159B2 (en) * 2011-02-22 2016-08-31 東京応化工業株式会社 Photosensitive resin composition, and color filter and display device using the same
JP6009774B2 (en) * 2011-02-22 2016-10-19 東京応化工業株式会社 Photosensitive resin composition, and color filter and display device using the same
JP5793924B2 (en) * 2011-04-11 2015-10-14 日立化成株式会社 Photosensitive resin composition, photosensitive element, method for producing resist pattern, and method for producing printed wiring board
JP2013117614A (en) * 2011-12-02 2013-06-13 Hitachi Chemical Dupont Microsystems Ltd Photosensitive resin composition
JP5990965B2 (en) * 2012-03-23 2016-09-14 東レ株式会社 Photosensitive resin composition and film laminate comprising the same

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6362433B1 (en) * 1998-06-05 2002-03-26 Sony Chemicals Corporation Flexible printed circuit board
WO2004092838A1 (en) * 2003-04-15 2004-10-28 Kaneka Corporation Photosensitive resin composition capable of being developed with aqueous developer and photosensitive dry film resist, and use thereof
US20060199920A1 (en) * 2003-04-15 2006-09-07 Koji Okada Photosensitive resin composition capable of being developed with aqueous developer and photosensitive dry film resist, and use thereof
CN100484363C (en) * 2003-12-22 2009-04-29 日东电工株式会社 Wiring circuit board and production method thereof
JP2009009107A (en) * 2007-05-25 2009-01-15 Toray Ind Inc Photosensitive resin composition
JP2010135514A (en) * 2008-12-03 2010-06-17 Nitto Denko Corp Wired circuit board
CN102597061A (en) * 2009-11-16 2012-07-18 旭化成电子材料株式会社 Polyimide precursor and photosensitive resin composition containing the polyimide precursor
CN102375337A (en) * 2010-08-10 2012-03-14 住友化学株式会社 Photosensitive resin composition

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107436535A (en) * 2016-05-26 2017-12-05 太阳油墨制造株式会社 Photosensitive polymer combination, dry film, solidfied material and printed circuit board (PCB)
CN107436535B (en) * 2016-05-26 2022-06-10 太阳油墨制造株式会社 Photosensitive resin composition, dry film, cured product and printed wiring board
TWI772286B (en) * 2016-05-26 2022-08-01 日商太陽油墨製造股份有限公司 Photosensitive resin composition, dry film, cured product, and printed wiring board
CN109270792A (en) * 2018-10-30 2019-01-25 浙江福斯特新材料研究院有限公司 A kind of high tenacity, high heat resistance, can weak base water development polyimides/photosensitive epoxy acrylic resin composition
CN115315450A (en) * 2020-03-31 2022-11-08 太阳油墨制造株式会社 Curable composition and cured product thereof
CN115315450B (en) * 2020-03-31 2024-03-15 太阳控股株式会社 Curable composition and cured product thereof

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