CN103282829B - Photosensitive polymer combination - Google Patents

Photosensitive polymer combination Download PDF

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Publication number
CN103282829B
CN103282829B CN201180062574.6A CN201180062574A CN103282829B CN 103282829 B CN103282829 B CN 103282829B CN 201180062574 A CN201180062574 A CN 201180062574A CN 103282829 B CN103282829 B CN 103282829B
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mass
polymer combination
photosensitive polymer
integer
compound
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CN103282829A (en
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国松真
国松真一
筒井大和
内藤也
内藤一也
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Asahi Kasei Corp
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Asahi Kasei Kogyo KK
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/46Polymerisation initiated by wave energy or particle radiation
    • C08F2/48Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06Polymers provided for in subclass C08G
    • C08F290/062Polyethers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031Organic compounds not covered by group G03F7/029
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/038Macromolecular compounds which are rendered insoluble or differentially wettable
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/02Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/061Etching masks
    • H05K3/064Photoresists

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Polymerisation Methods In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Graft Or Block Polymers (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)

Abstract

The present invention relates to a kind of photosensitive polymer combination, it is the photosensitive polymer combination of the compound with (C) containing (A) alkali solubility macromolecule, (B) Photoepolymerizationinitiater initiater with ethylenical unsaturated double bonds, should (B) Photoepolymerizationinitiater initiater be 2,4,5 triarylimidazoles dimer or acridine compounds, and the compound that (C) has ethylenical unsaturated double bonds comprises the compound shown in following logical formula (I), in formula, R1、R2、A、B、n1、n2And n3It is defined as in the description.The developer solution dispersion stabilization of described photosensitive polymer combination is excellent, can suppress the generation of aggregation, has the developability of appropriateness, the flexibility of solidification resist layer and good elching resistant.

Description

Photosensitive polymer combination
Technical field
The present invention relates to photosensitive polymer combination etc..
Background technology
The Precision Machining etc. of printed circuit board (PCB) or metal was manufactured by photoetching process in the past.Photoetching process is this Sample one method, i.e. be coated on substrate by photosensitive polymer combination, by pattern exposure, makes The exposed portion polymerizing curable of this photosensitive polymer combination, removes unexposed portion with developer solution, Form corrosion-resisting pattern on substrate, implement etching or plating, form conductive pattern, then, from this Peel off on substrate and remove this corrosion-resisting pattern, thus the method forming conductive pattern on substrate.
In photolithography, when being coated on substrate by photosensitive polymer combination, following can be used One method: photoresist solution is coated on substrate and is allowed to dry method, or by supporter, The layer (hereinafter referred to as photo-sensitive resin) formed by photosensitive polymer combination and guarantor as required The photosensitive-resin layered product that sheath is sequentially laminated and obtains is laminated to the method on substrate, at printing electricity The manufacture of road plate is used mostly the latter.
The method that the above-mentioned photosensitive-resin layered product of use briefly described below manufactures printed circuit board (PCB).
First, from photosensitive-resin layered product, the protective layers such as polyethylene film are peeled off.Then, use Laminating machine, on the substrates such as copper clad laminate, according to this substrate, photo-sensitive resin, supporter Sequentially, photo-sensitive resin and supporter are laminated.Then, across having the photomask of wiring pattern, This photo-sensitive resin is exposed, so that exposed portion polymerizing curable.Then, will be by poly-to benzene two The supporter that formic acid glycol ester etc. are formed is peeled off.Then, aobvious by having the weakly alkaline aqueous solution etc. Shadow liquid, dissolves the unexposed portion of photo-sensitive resin or dispersion is removed, and is formed against corrosion on substrate Pattern.The operation quilt of the photo-sensitive resin of unexposed portion is removed by this developing solution dissolution or dispersion It is referred to as developing procedure, the shortest time quilt needed for making the photo-sensitive resin of unexposed portion dissolve It is referred to as minimum developing time.
Photosensitive polymer combination not all dissolving in developer solution, be often repeated once developing procedure, The insoluble composition of developer solution bad dispersibility increases, and produces aggregation.Aggregation is attached on substrate, Become the reason of short trouble.
Then, the corrosion-resisting pattern formed, as protection mask, carries out known etch processes or pattern Plating.Finally, from substrate, peel off this corrosion-resisting pattern, manufacture have conductive pattern substrate, I.e. printed circuit board (PCB).
In an etching process, the elching resistant of corrosion-resisting pattern is important.If elching resistant is poor, erosion During quarter, etching solution is penetrated into from the gap between corrosion-resisting pattern and substrate, and the part at circuit top is eclipsed Carve.Appearance in terms of top-direction has seen the variable color because infiltration causes, oxidation, segment conductor The repeatability of the width of pattern is deteriorated, and linearity is poor and unstable.Additionally, during elching resistant difference, send out The breach of raw conductive pattern or broken string.Conductive pattern is the finest, and these defects are the most notable.With above-mentioned shape The operation that the etched pattern become carries out known etch processes as protection mask is referred to as etching work procedure. Mostly above-mentioned developing procedure is linked with etching work procedure, need not leading of part owing to needing to be completely dissolved Body, therefore the transporting velocity of substrate depends on etching work procedure.Now, in the minimum of photo-sensitive resin In the case of developing time is short, exists and be exceedingly exposed to developer solution, infringement base material and resisting of being formed The situation of the adaptation of corrosion figure case, this is especially using to improve image resolution ratio and etching efficiency Become notable in the case of the photo-sensitive resin that thickness is thin.It addition, at developing procedure and etching work procedure In, time solidification resist layer lacks flexibility, with contacting or developer solution or etching solution of conveying roller Spraying will cause part corrosion-resisting pattern defect, and breach or the broken string of conductive pattern occur sometimes.
Under the above conditions, in order to improve flexibility and the chemical-resistant of solidification resist layer, report has The method using polytetramethylene glycol two (methyl) acrylate or the method using carbamate compounds (with reference to patent document 1,2).
Prior art literature
Patent document
Patent document 1: Japanese Laid-Open Patent Publication 61-228007 publication
Patent document 2: No. 3859934 publications of Japanese Patent No.
Summary of the invention
The problem that invention is to be solved
Chemical-resistant described in patent document 1 and 2 with aqueous alkali or plating liquid as object, The patience of the not open acidic chemical to using in etching work procedure, does not the most disclose developability or poly- Collection property.Therefore, however it remains provide that developer solution dispersion stabilization is excellent, can suppress aggregation generation, There is the developability of appropriateness, the flexibility of solidification resist layer and the photoresist group of good elching resistant The necessity of compound.
In view of above-mentioned present situation, problem to be solved by this invention be to provide developer solution dispersion stabilization excellent, The generation that can suppress aggregation, the developability with appropriateness, the solidification flexibility of resist layer and the most resistance to The photosensitive polymer combination etc. of etching.
For solving the scheme of problem
The present inventor in order to solve the problems referred to above further investigation, repeatedly test, it was found that by with Lower technological means can solve the problems referred to above, this completes the present invention.
That is, the present invention is as described below.
[1] a kind of photosensitive polymer combination, it is to gather containing (A) alkali solubility macromolecule, (B) light Close the photosensitive polymer combination that initiator has the compound of ethylenical unsaturated double bonds with (C), be somebody's turn to do (B) Photoepolymerizationinitiater initiater is 2,4,5-triarylimidazoles dimer or acridine compounds, and should (C) have The compound of ethylenical unsaturated double bonds comprises the compound shown in following logical formula (I):
In formula (I), R1And R2Representing hydrogen atom or methyl independently of one another, A is C2H4Or C3H6, At-(A-O)n1-and-(A-O)n3In-,-C2H4-O-and-C3H6The arrangement of the repetitive of-O-is optionally nothing That advise or block, in the case of this is arranged as block ,-C2H4-O-and-C3H6Any one of-O-exists -B-O-group side, B is the divalent alkyl chain of carbon number 4~8, n1It is the integer of 0~10, n3It is 0~10 Integer, n1+n3It is the integer of 0~10, and n2It it is the integer of 1~20.
[2] according to the photosensitive polymer combination described in [1st] item, wherein, described (C) have olefinic The compound of unsaturated double-bond also comprises the compound shown in following logical formula (II):
In formula (II), R3And R4It is hydrogen atom or methyl independently of one another, n4And n7It is independently of one another The integer of 0~20, n4+n7It is the integer of 0~40, n5And n6It is the integer of 1~20 independently of one another, n5+n6 It is the integer of 2~40, and-(C2H4-O)-and-(C3H6-O)-the arrangement of repetitive be optionally random Or block, in the case of this is arranged as block ,-(C2H4-O)-and-(C3H6-O)-any one Bisphenol group side.
[3] according to the photosensitive polymer combination described in [2nd] item, wherein, in described logical formula (II), n4And n7It is the integer of 1~20 independently of one another, and n4+n7It it is the integer of 2~40.
[4] according to [1st]~[3] item any one described in photosensitive polymer combination, wherein, described (A) alkali solubility macromolecule selected from containing styrene and/or (methyl) benzyl acrylate as copolymer The alkali solubility macromolecule of composition.
[5] according to [1st]~[4] item any one described in photosensitive polymer combination, wherein, described In logical formula (I), n2It is the integer of 1~10, and n1+n3It is 0.
[6] according to [1st]~[5] item any one described in photosensitive polymer combination, wherein, described (C) There is the compound of ethylenical unsaturated double bonds also comprise intramolecular there is at least one amino-formate bond Compound.
[7] according to [1st]~[6] item any one described in photosensitive polymer combination, wherein, described (C) There is the compound of ethylenical unsaturated double bonds and also comprise the compound shown in following logical formula (III):
In formula (III), R5And R6It is hydrogen atom or methyl independently of one another, n8And n9It is independently of one another The integer of 3~40, and-(C2H4-O)-and-(C3H6-O)-the arrangement of repetitive be optionally random Or block.
[8] according to [1st]~[7] item any one described in photosensitive polymer combination, wherein, described (C) The compound with ethylenical unsaturated double bonds also comprises the change shown in following logical formula (IV) and/or (V) Compound:
In formula (IV), R5And R6It is hydrogen atom or methyl independently of one another, n10~n12Independently of one another It it is the integer of 1~30;
In formula (V), R5And R6It is hydrogen atom or methyl independently of one another, n10~n12It is independently of one another The integer of 1~30.
[9] according to [1st]~[8] item any one described in photosensitive polymer combination, wherein, described (C) There is the compound of ethylenical unsaturated double bonds also comprise intramolecular there is the compound of isocyanurate group.
[10] according to [1st]~[9] item any one described in photosensitive polymer combination, wherein, with sense The solid point gross mass of photosensitive resin composition is 100 mass % meters, described (A) alkali solubility macromolecule Use level be 40 mass %~80 mass %;With the solid point gross mass of photosensitive polymer combination for 100 Quality % is counted, and the use level of described (B) Photoepolymerizationinitiater initiater is 0.1 mass %~20 mass %;With sense The solid point gross mass of photosensitive resin composition is 100 mass % meters, and described (C) has olefinic insatiable hunger It is 5 mass %~50 mass % with the use level of the compound of double bond.
[11] a kind of photosensitive-resin layered product, it is to be pressed with by [1st]~[10] supporting film upper strata The photo-sensitive resin of the photo-sensitive resin that the photosensitive polymer combination described in any one of item is formed Laminate.
[12] manufacture method of a kind of substrate being formed with corrosion-resisting pattern, it is included in substrate overlaminate [11] the lamination operation of the photosensitive-resin layered product described in item;Across mask by this layered photosensitive-resin The exposure process of body exposure;And remove the developing procedure of unexposed portion.
[13] a kind of method forming circuit substrate, it is to by the method manufacture described in [12nd] item Substrate be etched or plating and form circuit substrate.
The effect of invention
By the invention it is possible to provide that developer solution dispersion stabilization is excellent, can suppress aggregation generation, There is the developability of appropriateness, flexibility and the good elching resistant of solidification resist layer, be applicable to be formed The photosensitive polymer combination of good conductive pattern and there is the photonasty tree formed by said composition The photosensitive-resin layered product etc. of lipid layer.
Detailed description of the invention
Hereinafter, the mode (hereinafter referred to as embodiment) for implementing the present invention is described in detail.Wherein, The present invention is not limited to implementation below, can carry out various deformation and implement in the range of its main idea.
<photosensitive polymer combination>
In the present embodiment, photosensitive polymer combination contains (A) alkali solubility macromolecule, (B) Photoepolymerizationinitiater initiater and (C) have the compound of ethylenical unsaturated double bonds.
<(A) alkali solubility macromolecule>
(A) alkali solubility macromolecule refers to the vinyl resin containing carboxyl, such as, is (methyl) The copolymer of acrylic acid, (methyl) acrylate, (methyl) acrylonitrile, (methyl) acrylamide etc.. (A) alkali solubility macromolecule contains carboxyl, and acid equivalent is preferably 100~600.From improve resistance to developability, From the viewpoint of improving image resolution ratio and adaptation, acid equivalent is preferably more than 100, from improving development From the viewpoint of property and fissility, preferably less than 600.Acid equivalent is more preferably 250~450.
(A) the high molecular weight average molecular weight of alkali solubility is preferably more than 5,000 and less than 500,000.From Edge-melting (edge fuse) when the proterties of development aggregation, formation photosensitive-resin layered product, chip Property etc. unexposed film proterties from the viewpoint of, the high molecular weight average molecular weight of (A) alkali solubility be preferably More than 5,000, from the viewpoint of improving developability, preferably 500, less than 000.Herein, edge-melting When property is to coil into drum as photosensitive-resin layered product, photosensitive polymer combination layer is from reel End face overflow phenomenon.The phenomenon that when chip is to be cut off by unexposed film with cutter, fragment splashes, When fragment is attached to the upper surface etc. of photosensitive-resin layered product, in post-exposure process etc., transfer On mask, constitute the reason of substandard products.(A) the high molecular weight average molecular weight of alkali solubility is more preferably 5,000 Above and 300, less than 000, more preferably 10, more than 000 and 200, less than 000.
(A) alkali solubility macromolecule such as can be by by each one or in following two class monomers Plant the above incompatible acquisition of monomer copolymerization.
First monomer is carboxylic acid or the acid anhydrides in molecule with a polymerism unsaturated group.Such as, Can list (methyl) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, Acid half ester etc..Particularly preferably (methyl) acrylic acid.Wherein, (methyl) acrylic acid refers to propylene Acid or methacrylic acid.
Second comonomer is non-acid and has the list of at least one polymerism unsaturated group in molecule Body.Such as, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) can be listed N-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) third Olefin(e) acid isobutyl ester, (methyl) tert-butyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) third Olefin(e) acid 2-hydroxypropyl acrylate, (methyl) 2-EHA, (methyl) benzyl acrylate;Vinyl alcohol Esters, such as, vinylacetate;(methyl) acrylonitrile;Styrene, styrene derivative etc..Especially Its preferred (methyl) methyl acrylate, (methyl) n-butyl acrylate, styrene, styrene derived Thing and (methyl) benzyl acrylate.
As the copolymer composition in (A) alkali solubility macromolecule, optimization styrene or styrene derivative, Its combined polymerization ratio is preferably 20 mass %~60 mass %.From having sufficient aggregation and elching resistant From the viewpoint of Deng, this combined polymerization ratio is preferably more than 20 mass %, from the developability with appropriateness From the viewpoint of cured film flexibility, below preferably 60 mass %.This combined polymerization ratio is more preferably It is 20 mass %~50 mass %, more preferably 20 mass %~30 mass %.Additionally, as copolymerization Thing composition, preferably by styrene or styrene derivative, (methyl) methyl acrylate and (methyl) third Olefin(e) acid copolymerization and the copolymer that obtains.It addition, in addition to the foregoing, divide to obtain the image of excellence The combined polymerization ratio of resolution, styrene or styrene derivative is preferably 40 mass %~60 mass %, this Outward, as copolymer composition, preferably by styrene or styrene derivative, (methyl) methyl acrylate (methyl) acrylic acid copolymer and the copolymer that obtains.
It is 100 mass % timing with the solid point gross mass of photosensitive polymer combination, photoresist group The high molecular use level of (A) alkali solubility in compound is preferably 40 mass %~the scope of 80 mass %, More preferably 50 mass %~70 mass %.From the viewpoint of edge-melting, this use level is preferably 40 matter Amount more than %, from the viewpoint of developing time, below preferably 80 mass %.
<(B) Photoepolymerizationinitiater initiater>
Above-mentioned photosensitive polymer combination contains 2,4,5-triarylimidazoles dimer or acridine compounds is made Required composition for (B) Photoepolymerizationinitiater initiater.As their object lesson, such as, can list 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dimer, 2-(Chloro-O-Phenyl)-4,5-two (methoxyphenyl) imidazoles Dimer, 2-(adjacent fluorophenyl)-4,5-diphenyl-imidazole dimer, 2-(o-methoxyphenyl)-4,5-hexichol The 2,4,5-triarylimidazoles such as base imidazoles dimer, 2-(p-methoxyphenyl)-4,5-diphenyl-imidazole dimer Dimer, 9-phenylacridine, 1, the acridine derivatives etc. such as double (9,9-acridinyl) heptane of 7-.
Except 2, beyond 4,5-triarylimidazoles dimers or acridine compounds, as photosensitive resin composition The Photoepolymerizationinitiater initiater that can contain further in thing, such as, can list benzophenone, N, N '-tetramethyl Base-4,4 '-dimethylamino benzopheone (Michler's keton), N, N '-tetraethyl-4,4 '-diaminobenzophenone, 4-methoxyl group-4 '-dimethylamino benzopheone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-1-fourth The aromatic ketones such as ketone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl-1-acetone;2-EAQ, Phenanthrenequione, 2-tert-butyl group anthraquinone, prestox anthraquinone, 1,2 benzae thracene quinone, 2,3-benzo anthraquinone, 2-phenyl Anthraquinone, 2,3-diphenyl anthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinones, 9,10-phenanthrenequione, 2- The quinones such as methyl-1,4-naphthaquinone, 2,3-dimethyl anthraquinone;Benzoin methylether, benzoin ethyl ether, benzoin The benzoin ether compounds such as phenylate;The benzil derivatives such as benzil methyl ketal;N-phenylglycine Derivative;Coumarin series compounds;4,4 '-bis-(lignocaine) benzophenone etc..These photopolymerization cause Agent can be used alone, it is also possible to is used in combination of two or more.
It is 100 mass % timing with the solid point gross mass of photosensitive polymer combination, photoresist group The use level of (B) Photoepolymerizationinitiater initiater in compound is preferably 0.1 mass~20 mass %.Fill from obtaining From the viewpoint of the speed divided, this use level is preferably more than 0.1 mass %, from making the abundant transmission of light To resist layer bottom surface, obtain good high image resolution from the viewpoint of, preferably 20 mass % with Under.The preferred scope of this use level is 0.5 mass %~10 mass %.
The compound of ethylenical unsaturated double bonds<(C) have>
(C) compound with ethylenical unsaturated double bonds refers to have unsaturated pair of olefinic as described in literal The compound of key.There is as (C) compound of ethylenical unsaturated double bonds, such as, two can be listed (methyl) esters of acrylic acid.Wherein, (methyl) acrylate refers to acrylate or methacrylic acid Ester.
Photosensitive polymer combination contains the compound shown in following logical formula (I) and has alkene as (C) Belong to the compound of unsaturated double-bond.
In formula (I), R1And R2Representing hydrogen atom or methyl independently of one another, A is C2H4Or C3H6, At-(A-O)n1-and-(A-O)n3In-,-C2H4-O-and-C3H6The arrangement of the repetitive of-O-is optionally nothing That advise or block, in the case of this is arranged as block ,-C2H4-O-and-C3H6Any one of-O-exists -B-O-group side, B is the divalent alkyl chain of carbon number 4~8, n1It is the integer of 0~10, n3It is 0~10 Integer, n1+n3It is the integer of 0~10, and n2It it is the integer of 1~20.
Wherein, by two (methyl) acrylate shown in above-mentioned logical formula (I) and other technical scheme group When being combined into photosensitive polymer combination, it is possible to provide developer solution dispersion stabilization is excellent, can suppress aggregation Generation, there is the developability of appropriateness, the solidification flexibility of resist layer and the sense of good elching resistant Photosensitive resin composition, although the detail of its mechanism is the most indefinite, but is speculated as following effect.
I.e. being speculated as, logical two (methyl) acrylate shown in formula (I) has the group shown in-B-O-, Compared with normally used oxy ethylene or oxypropylene, strand is longer and does not has side chain, because of The free degree of this main chain is high, the flexibility of chemical constitution (being sometimes referred to as protuberance property (tenting)) is excellent.
Ftracture it addition, ehter bond typically has because acid causes the carbon adjacent with oxygen to stand nucleophilic substitution Tendency, logical two (methyl) acrylate shown in formula (I) had-group of (B-O)-shown In, the ratio at the cleacvage reaction position that acid produces is less than oxy ethylene or oxypropylene, it is believed that resistance to Acid (being sometimes referred to as elching resistant) is excellent.
Additionally it is believed that logical two (methyl) acrylate shown in formula (I) had-(B-O)-shown Group there is high lipophile, easily form the dispersion stabilization containing phenyl initiator of development aggregation Excellent (generation of aggregation can be suppressed).
Wherein, about the developability of appropriateness, thus it is speculated that be derived from two (methyl) propylene shown in logical formula (I) The lipophile of the appropriateness that acid esters is had.
In the compound shown in above-mentioned logical formula (I), n1And n3The integer of preferably 0.That is, n1+n3 The integer of preferably 0.More specifically, consider from the viewpoint such as edge-melting, ease of manufacturing, above-mentioned logical The polytetramethylene glycol two (methyl) shown in the most following logical formula (VI) of compound preference shown in formula (I) Acrylate.
In formula (VI), R1And R2Represent hydrogen atom or methyl, and n independently of one another2Preferably 1~20 Integer, the integer of more preferably 1~15, the integer of particularly preferably 1~10.
More specifically, such as, butanediol two (methyl) acrylate, dibutylene glycol can be listed Two (methyl) acrylate, three butanediol two (methyl) acrylate, four butanediols two (methyl) Acrylate, five butanediol two (methyl) acrylate, six butanediol two (methyl) acrylate, Seven butanediol two (methyl) acrylate, eight butanediol two (methyl) acrylate, nine butanediols Two (methyl) acrylate, ten butanediol two (methyl) acrylate, 11 butanediol two (first Base) acrylate, ten dibutylene glycol two (methyl) acrylate, thirteen kinds of furuncles glycol two (methyl) Acrylate, 14 butanediol two (methyl) acrylate, 15 butanediol two (methyl) propylene Acid esters etc..
In the compound shown in above-mentioned logical formula (I) and (VI), n2The integer of preferably 1~20, more The integer of preferably 1~15, the integer of particularly preferably 1~10.From the viewpoint of cured film flexibility, n2It is preferably more than 1, on the other hand, from the viewpoint of elching resistant, n2It is preferably less than 20.More Preferably, n2It it is the integer of 5~10.
It is 100 mass % timing with the solid point gross mass of photosensitive polymer combination, photoresist group Above-mentioned logical formula (I) or the use level of the compound shown in (VI) in compound are preferably 1 mass %~15 Quality %.From the viewpoint of obtaining cured film flexibility, this use level is preferably more than 1 mass %, From the viewpoint of elching resistant, below preferably 15 mass %.The preferred scope of this use level Being 1 mass %~10 mass %, further preferred range is 3 mass %~10 mass %.
It addition, from the viewpoint of improving flexibility further, it is preferred that photosensitive resin composition Thing has the change of ethylenical unsaturated double bonds possibly together with the compound shown in following logical formula (II) as (C) Compound.
In formula (II), R3And R4It is hydrogen atom or methyl independently of one another, n4And n7It is independently of one another The integer of 0~20, n4+n7It is the integer of 0~40, n5And n6It is the integer of 1~20 independently of one another, n5+n6 It is the integer of 2~40, and-(C2H4-O)-and-(C3H6-O)-the arrangement of repetitive be optionally random Or block, in the case of this is arranged as block ,-(C2H4-O)-and-(C3H6-O)-any one Bisphenol group side.
Wherein, by shown in the compound shown in above-mentioned logical formula (I) or (VI) and above-mentioned logical formula (II) Compound when being applied in combination, it is achieved the photosensitive polymer combination that flexibility improves further, although The detail of its mechanism is the most indefinite, but is speculated as the effect of the following stated.
That is, by shown in the compound shown in above-mentioned logical formula (I) or (VI) and above-mentioned logical formula (II) When compound is applied in combination, thus it is speculated that improve the reactivity of photopolymerization.And, thus speculate, exposure After cured film become more tough, be demonstrated by good toughness.
In above-mentioned logical formula (II), n4And n7It is the integer of 0~20 independently of one another, n4+n7Be 0~40 whole Number, n5And n6It is the integer of 1~20 independently of one another, n5+n6It it is the integer of 2~40.It addition, n4+n5+n6+n7 Lower limit be preferably more than 2, on the other hand, its upper limit is preferably less than 40.From the flexibility of cured film From the viewpoint of, n4+n5+n6+n7It is preferably more than 2, on the other hand, examines from the viewpoint of image resolution ratio Consider, preferably less than 40.It addition, from the viewpoint of elching resistant, n4+n5+n6+n7More preferably The lower limit of scope be more than 4, the upper limit be less than 20, the lower limit of further preferred range is more than 6, The upper limit is less than 12.It addition, from the viewpoint of protuberance property, n4+n5+n6+n7Preferred scope Lower limit be more than 16, the upper limit be less than 40, the lower limit of further preferred range is more than 30, on It is limited to less than 40.Additionally, n4And n7It is the integer of 1~10 the most independently of one another, n4+n7More preferably The integer of 1~20, on the other hand, n5+n6The integer of more preferably 2~20.
As the object lesson of the compound shown in above-mentioned logical formula (II), can list at the two of bisphenol-A Hold the dimethylacrylate of the ethylene glycol of the oxirane of average 2 moles of addition respectively or at bisphenol-A Average 5 moles of two ends respectively addition oxirane ethylene glycol dimethylacrylate, double The oxirane of average 6 moles of addition and the Asia of the expoxy propane of average 2 moles are distinguished in the two ends of phenol A The dimethylacrylate of alkyl diol, at the two ends addition addition ring of average 15 moles of bisphenol-A The alkylidene of the dimethylacrylate of the aklylene glycol of the expoxy propane of oxidative ethane and average 2 moles The dimethylacrylate etc. of glycol.
It is 100 mass % timing with the solid point gross mass of photosensitive polymer combination, photoresist group The use level of the compound shown in above-mentioned logical formula (II) in compound is preferably 5 mass %~20 mass %. From the viewpoint of obtaining elching resistant, this use level is preferably more than 5 mass %, soft from cured film From the viewpoint of property, below preferably 20 mass %.The preferred scope of this use level is 5 matter Amount %~15 mass %, further preferred range is 7 mass %~15 mass %.
From the viewpoint of improving cured film flexibility, photosensitive polymer combination is preferably possibly together with following Logical compound shown in formula (III) has the compound of ethylenical unsaturated double bonds as (C).
In formula (III), R5And R6It is hydrogen atom or methyl independently of one another, n8And n9It is independently of one another The integer of 3~40, and-(C2H4-O)-and-(C3H6-O)-the arrangement of repetitive be optionally random Or block.
In the compound shown in above-mentioned logical formula (III), from the viewpoint of improving cured film flexibility, n8And n9It is the integer of more than 3 the most independently of one another, the integer of more preferably more than 5.
As the object lesson of the compound shown in above-mentioned logical formula (III), such as, can list and add Become average 9 moles expoxy propane polypropylene glycol on further average 1 moles of ethylene oxide of addition The dimethylacrylate etc. of PAG.
It is 100 mass % timing with the solid point gross mass of photosensitive polymer combination, photoresist group The use level of the compound shown in above-mentioned logical formula (III) in compound is preferably 1 mass %~20 mass %. From the viewpoint of obtaining cured film flexibility, this use level is preferably more than 1 mass %, from etch resistant From the viewpoint of property, below preferably 20 mass %.The preferred scope of this use level is 3 matter Amount %~15 mass %, further preferred range is 5 mass %~10 mass %.
From the viewpoint of improving cured film flexibility, photosensitive polymer combination is preferably possibly together with following Compound shown in logical formula (IV) and/or (V) has the chemical combination of ethylenical unsaturated double bonds as (C) Thing.
In formula, R5And R6It is hydrogen atom or methyl independently of one another, n10~n12It is 1~30 independently of one another Integer;
In formula, R5And R6It is hydrogen atom or methyl independently of one another, n10~n12It is 1~30 independently of one another Integer.
In the compound shown in above-mentioned logical formula (IV) or (V), from improving cured film flexibility Viewpoint considers, n10~n12Preferably it is each independently the integer of more than 1, the integer of more preferably more than 3.
As the object lesson of the compound shown in above-mentioned logical formula (IV) or (V), such as, can arrange The addition respectively at two ends further on the polypropylene glycol of the expoxy propane having enumerated in addition average 18 moles The dimethylacrylate of the PAG of each average 7 moles of ethylene oxide, in addition average 18 Mole expoxy propane polypropylene glycol on respectively each average 3 moles of epoxy second of addition at two ends further The dimethylacrylate of the PAG of alkane, in addition the expoxy propane of average 12 moles Further at the PAG of two ends difference each average 3 moles of ethylene oxide of addition on polypropylene glycol Dimethylacrylate, exist further on the polyethylene glycol of the oxirane of average 6 moles in addition The dimethylacrylate etc. of the two ends PAG of each average 6 mol propylenoxy of addition respectively.
It is 100 mass % timing with the solid point gross mass of photosensitive polymer combination, photoresist group Above-mentioned logical formula (IV) or the use level of the compound shown in (V) in compound are preferably 1 mass %~30 Quality %.From the viewpoint of obtaining elching resistant, this use level is preferably more than 1 mass %, from solid From the viewpoint of changing film flexibility, below preferably 30 mass %.The preferred scope of this use level Being 5 mass %~25 mass %, further preferred range is 5 mass %~23 mass %.
Photosensitive polymer combination preferably has the change of at least one amino-formate bond possibly together with intramolecular Compound has the compound of ethylenical unsaturated double bonds as (C).Specifically, six methylenes can be listed Group diisocyanate, toluene di-isocyanate(TDI), 2,2,4-trimethyl hexamethylene diisocyanates etc. two are different Cyanate esters and (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid oligoethylene glycol ester, Hydroxyl (methyl) acrylate compounds such as (methyl) oligomeric propylene glycol ester of acrylic acid react and obtain Carbamate compounds.From the viewpoint of elching resistant, it is preferred that intramolecular have to Few the compound e.g. hexamethylene diisocyanate of an amino-formate bond, toluene diisocynate The diisocyanate cpds such as ester, 2,2,4-trimethyl hexamethylene diisocyanate and (methyl) propylene The carbamate compounds that acid oligomeric propylene glycol ester reaction obtains.
It is 100 mass % timing with the solid point gross mass of photosensitive polymer combination, photoresist group Above-mentioned intramolecular in compound has the use level of the compound of at least one amino-formate bond and is preferably 5 mass %~20 mass %.From the viewpoint of obtaining elching resistant, this use level is preferably 5 mass % Above, from the viewpoint of aggregation, below preferably 20 mass %.This use level preferred Scope is 8 mass %~20 mass %, and further preferred range is 8 mass %~17 mass %.
Photosensitive polymer combination preferably has the compound conduct of isocyanurate group possibly together with intramolecular (C) there is the compound of ethylenical unsaturated double bonds.Specifically, as intramolecular, there is isocyanuric acid The compound of ester group, such as, can list ethoxylation isocyanuric acid triacrylate, 6-caprolactone Modified single (2-acryloyl-oxyethyl) isocyanuric acid ester, 6-caprolactone modified double (2-acryloyl-oxyethyl) Isocyanuric acid ester, 6-caprolactone modification three (2-acryloyl-oxyethyl) isocyanuric acid ester, isocyanuric acid ring The ethylene-oxide-modified diacrylate of oxidative ethane modification acrylate, isocyanuric acid, isocyanuric acid epoxy Oxide-modified triacrylate, isocyanuric acid epoxy pronane modification acrylate, isocyanuric acid epoxy third Alkane modified diacrylate, isocyanuric acid epoxy pronane modification triacrylate etc..
It is 100 mass % timing with the solid point gross mass of photosensitive polymer combination, photoresist group The use level of the compound that the intramolecular in compound has isocyanurate group is preferably 1 mass %~20 matter Amount %.From the viewpoint of obtaining elching resistant, this use level is preferably more than 1 mass %, from solidification From the viewpoint of film flexibility, below preferably 20 mass %.This use level more preferably in the range of 1 Quality %~15 mass %, further preferred range is 2 mass %~10 mass %.
Have the compound of ethylenical unsaturated double bonds as (C), photosensitive polymer combination is except containing Compound shown in choosing freely above-mentioned logical formula (I)~(VI), intramolecular have at least one amino first The compound of acid esters key, intramolecular have isocyanuric acid base compound composition group in compound with Outward, also can be containing the alefinically unsaturated compounds of following shown photopolymerization.
Specifically, as the alefinically unsaturated compounds of photopolymerization, polypropylene glycol two can be listed (methyl) acrylate, polyethylene glycol (methyl) acrylate, 2-bis-(p-hydroxybenzene) propane (first Base) acrylate, glycerine three (methyl) acrylate, trihydroxy methyl three (methyl) acrylate, Polyoxyethyl propyl trimethylolpropane tris (methyl) acrylate, polyoxyethanyl trimethylolpropane tris (first Base) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) third Olefin(e) acid ester, trimethyl propane triglycidyl ether three (methyl) acrylate, phenoxy group polyethylene glycol (methyl) acrylate, Nonylphenoxy polyethylene glycol (methyl) acrylate etc..These are permissible It is used alone, it is also possible to be used in combination of two or more.
It is 100 mass % timing with the solid point gross mass of photosensitive polymer combination, photoresist group The use level of the compound that (C) in compound has ethylenical unsaturated double bonds is preferably 5 mass %~50 Quality %.From the viewpoint of speed, image resolution ratio, adaptation, this use level is preferably 5 matter Amount more than %, from the viewpoint of the stripping of suppression cold flow and solidification resist layer postpones, preferably 50 matter Amount below %.This use level is more preferably 25 mass %~45 mass %.
<leuco dye, fluoran dyes, coloring material>
Photosensitive polymer combination can also contain leuco dye, fluoran dyes or coloring material.Pass through Containing these dyestuffs, exposed portion develops the color, is therefore preferred from the viewpoint of visuality, it addition, Inspection equipment etc. read when the alignment mark of exposure, exposed portion and the contrast of unexposed portion If great, then easily identify but favourable.
As leuco dye, three (4-dimethylamino phenyl) methane [leuco crystal violet], double (4-can be listed Dimethylamino phenyl) phenylmethane [leucogentian violet].Especially, from the viewpoint of contrast is good, As leuco dye, leuco crystal violet is preferably used.
As fluoran dyes, 2-(dibenzyl amino) fluorane, 2-anilino--3-methyl-6-diethyl can be listed Amino fluorane, 2-anilino--3-methyl-6-dibutylamino fluorane, 2-anilino--3-methyl-6-N-ethyl-N- C fluorane, 2-anilino--3-methyl-6-N-methyl-N-cyclohexyl amino fluorane, 2-anilino- -3-chloro-6-lignocaine fluorane, 2-anilino--3-methyl-6-N-ethyl-N-isobutylamino fluorane, 2- Anilino--6-dibutylamino fluorane, 2-anilino--3-methyl-6-N-ethyl-N-tetrahydrofurfuryl amino fluorane, 2-anilino--3-methyl-6-piperidyl amino fluorane, 2-(o-chloraniline base)-6-lignocaine fluorane, 2-(3,4-dichloroanilino)-6-lignocaine fluorane etc..
It is 100 mass % timing with the solid point gross mass of photosensitive polymer combination, photoresist group Leuco dye or the content of fluoran dyes in compound are preferably 0.1 mass %~10 mass %.From exposure portion Point with the contrast of unexposed portion from the viewpoint of, this content is preferably more than 0.1 mass %, from dimension From the viewpoint of holding storage stability, below preferably 10 mass %.
As coloring material, such as, magenta, phthalocyanine green, alkali Chinese scholartree Huang, paramagenta (para can be listed Magenta), crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (soil conservation paddy Chemistry (strain) Aizen(processed registration mark), MALACHITE GREEN), alkali blue 20, alkali Property green (hodogaya chemical (strain) Aizen(processed registration mark) DIAMOND GREEN GH). It is 100 mass % timing with the solid point gross mass of photosensitive polymer combination, photosensitive polymer combination In the content of coloring material be preferably 0.001 mass %~1 mass %.Examine from the viewpoint improving treatability Considering, this content is preferably more than 0.001 mass %, and from the viewpoint of maintaining storage stability, this contains Amount is preferably below 1 mass %.
<halogen compounds>
In embodiments of the present invention, from the viewpoint of adaptation and contrast, it is preferred that Leuco dye is applied in combination by photosensitive polymer combination with following halogen compounds.
As halogen compounds, such as, can list amyl bromide, isoamyl bromide, brominated isobutylene, Ethylene bromide, diphenylmethyl bromide, benzyl bromide a-bromotoluene, methylene bromide, trisbromomethyl phenyl sulfone, tetrabormated Carbon, three (2,3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-tri- Chloro-2,2-double (rubigan) ethane, chlorination triaizine compounds etc., particularly preferred trisbromomethyl phenyl Sulfone.It is 100 mass % timing with the solid point gross mass of photosensitive polymer combination, photoresist group The content of the halogen compounds in compound is preferably 0.01 mass %~3 mass %, from obtaining adaptation and right From the viewpoint of degree, this use level is preferably more than 0.01%, from the viewpoint of storage stability, It is preferably below 3 mass %.
<radical polymerization inhibitor, benzotriazole, carboxyl benzotriazole class>
It addition, in order to improve the heat endurance of photosensitive polymer combination, storage stability, photonasty Resin combination can contain the free radical polymerization inhibitor of choosing, benzotriazole and carboxyl further At least one above compound in the group of benzotriazole composition.
As radical polymerization inhibitor, such as, p methoxy phenol, quinhydrones, adjacent benzene can be listed Triphenol, naphthylamines, tert-butyl catechol, stannous chloride, 2,6-di-t-butyl-paracresol, 2,2 '-methylene Base double (4-methyl-6-tert-butylphenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), nitroso Phenylhydroxylamine aluminium salt, diphenyl nitroso-amines etc..
As benzotriazole, such as, 1,2,3-BTAs, chloro-1,2, the 3-benzos three of 1-can be listed Azoles, double (N-2-ethylhexyl) aminomethylene-l, 2,3 triazole, double (N-2-ethylhexyl) amino Methylene-1,2,3-tolytriazole, double (N-2-ethoxy) aminomethylene-l, 2,3 triazole etc..
As carboxyl benzotriazole class, such as, 4-carboxyl-1,2,3-BTAs, 5-carboxyl can be listed -l, 2,3 triazole, N-(N, N-bis--2-ethylhexyl) aminomethylene carboxyl benzotriazole, N-(N, N- Two-2-ethoxys) aminomethylene carboxyl benzotriazole, N-(N, N-bis--2-ethylhexyl) aminoethylene Carboxyl benzotriazole etc..
The total content of radical polymerization inhibitor, BTA and carboxyl benzotriazole class is relative to whole Individual photosensitive polymer combination is preferably 0.01 mass %~3 mass %, more preferably 0.05 mass %~1 matter Amount %.From the viewpoint of imparting photosensitive polymer combination is with storage stability, this content is preferably More than 0.01 mass %, from maintain speed, suppress dye decolored from the viewpoint of, preferably 3 mass % Below.
<plasticizer>
Photosensitive polymer combination can also contain plasticizer as required.As this plasticizer, example As, the Phthalates such as diethyl phthalate can be listed;Orthotoluene sulfonamide, to toluene Sulfonamide, ATBC, triethyl citrate, CitroflexA-2, acetyl group lemon Lemon acid three n-propyls, acetyl tributyl citrate, polyethylene glycol, polypropylene glycol, polyethylene glycol Alkyl ether, polypropylene glycol alkyl ether etc..
It is 100 mass % timing with the solid point gross mass of photosensitive polymer combination, photoresist group The content of the plasticizer in compound is preferably 1 mass %~50 mass %, more preferably 1~30 mass %.From From the viewpoint of suppression developing time delay, imparting cured film are with flexibility, this content is preferably 1 matter Amount more than %, from the viewpoint of suppression solidifies insufficient or cold flow, below preferably 50 mass %.
<solvent>
As the solvent for dissolving photosensitive polymer combination, can list with MEK (MEK) For the ketone represented, the alcohols etc. with methyl alcohol, ethanol or isopropanol as representative.This solvent preferably adds In photosensitive polymer combination so that for being applied to the photosensitive polymer combination on support film The viscosity of solution be 500mPa s~4000mPa s at 25 DEG C.
<photosensitive-resin layered product>
In the present embodiment, photosensitive-resin layered product includes being formed by photosensitive polymer combination Photo-sensitive resin and support film.It addition, photo-sensitive resin preferably layer is pressed on support film. As required, the surface with support film side opposite side of photo-sensitive resin can have guarantor Sheath.
As supporting film, it is generally desirable to, through the transparent support film of the light launched from exposure light source. As this support film, such as, ethylene glycol terephthalate film, polyvinyl alcohol can be listed Film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, inclined two chloroethenes Alkene copolymer film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile Film, styrol copolymer film, polyamide film, cellulose derivative film etc..These films Stretched film, the preferably film of mist degree less than 5 can be used as required.The thickness of film is thin at figure As the aspect of formative and economy is favourable, but in order to maintain intensity, 10 μm are preferably used ~30 films of μm.
The key property of the protective layer used in photosensitive-resin layered product is itself and photo-sensitive resin Closing force is sufficiently smaller than the closing force supporting film with photo-sensitive resin, can be easily peeled off.Example As, polyethylene film, polypropylene film etc. use preferably as protective layer.Furthermore it is also possible to use The film that fissility shown in Japanese Laid-Open Patent Publication 59-202457 publication is excellent.The thickness of protective layer is excellent Elect 10 μm~100 μm, more preferably 10 μm~50 μm as.Photonasty in photosensitive-resin layered product The thickness of resin bed is different according to purposes, preferably 5 μm~100 μm, more preferably 7 μm~60 μm, The thinnest image resolution ratio is the highest, and more thick film intensity is the highest.Additionally, in the erosion that need not high protuberance property Carving in purposes, the thickness of the photo-sensitive resin in photosensitive-resin layered product is preferably 10 μm ~20 μm.From the viewpoint of elching resistant, the thickness of photo-sensitive resin is more than 10 μm, from figure As, from the viewpoint of resolution ratio, this thickness is below 20 μm.
<preparation method of photosensitive-resin layered product>
It is sequentially laminated as by supporting film, photo-sensitive resin and protective layer as required and makes The method of photosensitive-resin layered product, can use known method.Such as, photonasty tree will be used for The photosensitive polymer combination of lipid layer and dissolve its solvent mixing, forms homogeneous solution, first, Use bar coater or roll coater coating on film supporting, be then dried, such that it is able to supporting film The photo-sensitive resin that overlaminate is formed by photosensitive polymer combination.Then, as required photosensitive Property resin bed overlaminate protective layer, such that it is able to make photosensitive-resin layered product.
<there is the manufacture method of the substrate of corrosion-resisting pattern>
Following description uses the method that photosensitive-resin layered product manufactures the substrate being formed with corrosion-resisting pattern An example.As required, by the substrate etch that will so manufacture or plating, can manufacture Circuit substrate or printed circuit board (PCB).
Use photosensitive-resin layered product to manufacture be formed with the substrate of corrosion-resisting pattern and employ this base The circuit substrate of plate or the method for printed circuit board (PCB) include following operation.Wherein, operation (4) and (4 ') Either of which person can be used, or both of which can be utilized.
(1) lamination operation
The protective layer of photosensitive-resin layered product is peeled off on limit, and limit uses hot roll laminator to make photoresist The closely sealed operation on the substrate such as copper clad laminate, flexible base board of layered product.
(2) exposure process
Make the mask film with required wiring pattern closely sealed on supporter (such as supporting film etc.), Utilize activity light source to be exposed, or implement the work of exposure by directly drawing required wiring pattern Sequence.
(3) developing procedure
After exposure, the supporter on photo-sensitive resin is peeled off, is then used by the development of aqueous alkali Liquid, development is removed unexposed portion, is formed the operation of corrosion-resisting pattern on substrate.
As aqueous alkali, it is, for example possible to use Na2CO3Or K2CO3The aqueous solution.Aqueous alkali Characteristic according to photo-sensitive resin suitably selects, it is common that concentration be about 0.2 mass %~2 mass %, About 20 DEG C~the Na of 40 DEG C2CO3The aqueous solution.
Through above-mentioned each operation, it is possible to obtain corrosion-resisting pattern, according to circumstances can also carry out about further 100 DEG C~the heating process of 300 DEG C.By implementing this heating process, chemicals-resistant can be improved further Property.Heating can be to use hot blast, infrared ray, the heating furnace of far infrared mode.
(4) etching work procedure
Etching solution, the copper face that will do not covered by corrosion-resisting pattern is sprayed above the corrosion-resisting pattern formed The operation of etching.
Etching work procedure uses acid etching, alkali etching etc. to be suitable for photosensitive-resin layered product used Method carry out.
(4 ') plating process
Use copper facing, plating weldering (solder plating) etc., the substrate being formed with corrosion-resisting pattern is plated The operation covered.
As the method for plating, can list and carry out electric plating method etc. using substrate as electrode.
(5) peel off
The aqueous solution using alkalescence to be better than developer solution afterwards peels off corrosion-resisting pattern from substrate.Use peeling off Aqueous alkali be not particularly limited, generally use concentration about 2 mass %~5 mass %, temperature about 40 DEG C ~the aqueous solution of NaOH, KOH etc. of 70 DEG C.Stripper can also add a small amount of water-soluble solvent.
As it has been described above, present embodiment relates to the photosensitive resin composition that can be developed by alkaline aqueous solution Thing, the photosensitive-resin layered product that this photosensitive polymer combination is formed at supporter overlaminate, This photosensitive-resin layered product is used to form the method for corrosion-resisting pattern and this corrosion-resisting pattern on substrate Purposes etc..These photosensitive polymer combinations etc. can provide the corrosion-resisting pattern being suitable for following manufacture: The manufacture of printed circuit board (PCB), the manufacture of flexible printed circuit board, IC chip are installed with lead frame (following Be referred to as lead frame) manufacture, metal forming Precision Machining, the BGA(BGA such as metal mask manufacture) Or CSP(chip size packages) etc. semiconductor packages manufacture, with TAB(Tape Automated Bonding, tape-automated bonding) or COF(Chip On Film: at the fine wiring plate of film-form Upper installation semiconducter IC) it is the manufacture of tape winding substrate (tape substrate) of representative, semiconductor projection Manufacture, ITO electrode in field of flat panel displays, addressing electrode, the parts such as electromagnetic wave shield Manufacture.
Embodiment
By the following examples 1~14 and comparative example 1 and 2 specifically describe further.
First, the preparation method of the sample for evaluation of embodiment and comparative example is described, then shows institute Obtain evaluation method and the evaluation result thereof of sample.
(1) preparation method of sample for evaluation
The sample for evaluation of embodiment and comparative example makes as follows.
<making of photosensitive layer laminate>
By the composition shown in table 1 below, (numeral of the most each composition represents the use level in terms of solid is divided (mass parts)) photosensitive polymer combination and solvent be sufficiently stirred for, mix, formed photoresist Composition blending liquid, uses bar coater to be coated on the poly-to benzene two of 16 μ m-thick as supporter equably The surface of formic acid glycol ester film (Mitsubishi Polyester Film GmbH system, R130-16), The drying machine of 95 DEG C is dried 1.5 minutes, forms photosensitive resin composition layer.Photosensitive resin composition The thickness of layer is 15 μm.
Then, pet film it is not laminated at photosensitive resin composition layer On surface, polyethylene film (TAMAPOLY CO., the LTD. of 19 μ m-thick fitted as protective layer System, GF-818), it is thus achieved that photosensitive-resin layered product.Table 2 below shows in table 1 and use shorthand notation The title of the material composition in the photosensitive polymer combination blending liquid represented.
<substrate leveling>
As developability, the evaluation substrate of elching resistant, use the 1.6mm being laminated 35 μm rolled copper foils Thick copper clad laminate.Substrate surface is carried out wet type polishing roll grinding (3M company system, Scotch Brite(registration mark) HD#600, by 2 times).
<lamination>
The polyethylene film of photosensitive-resin layered product is peeled off on limit, and limit uses hot roll laminator (Asahi Chemical Industry (strain) makes, AL-700) it is pressed onto leveling in 105 DEG C of lower floors of roll temperature and is preheated to the copper clad layers pressure of 60 DEG C On plate.Air pressure is set as, and 0.35MPa, laminate speed are set as 2.0m/ minute.
<exposure>
The necessary mask film of evaluating of photosensitive resin composition layer is placed on gathering as supporter On ethylene glycol terephthalate film, at embodiment 1~6, embodiment 9~14 and comparative example 1 and 2 In, use ultrahigh pressure mercury lamp (ORC MANUFACTURING CO., LTD. system, HMW-801) with 70mJ/cm2Light exposure be exposed.In embodiment 7 and 8, use and directly paint Standard exposure device (Hitachi Via Mechanics, Ltd. system, DI exposure machine DE-1DH, light Source: GaN royal purple diode, dominant wavelength 405 ± 5nm) with 15mJ/cm2Light exposure be exposed.
For the evaluation sample of cured film flexibility, at photosensitive-resin layered product fabricated as described above The pet film as supporter on place that to evaluate necessary mask thin Film, in embodiment 1~6, embodiment 9~14 and comparative example 1 and 2, uses ultrahigh pressure mercury lamp (ORC MANUFACTURING CO., LTD. system, HMW-801) with 70mJ/cm2Light exposure It is exposed.In embodiment 7 and 8, use and directly draw formula exposure device (Hitachi Via Mechanics, Ltd. system, DI exposure machine DE-1DH, light source: GaN royal purple diode, dominant wavelength 405 ± 5nm) with 15mJ/cm2Light exposure be exposed.
<development>
About the evaluation substrate of developability and elching resistant, pet film is shelled From afterwards, use alkali developing machine (FUJI KIKO., Co.Ltd. system, dry film developing machine), spraying 1 mass %Na of 30 DEG C of stipulated time2CO3The aqueous solution, dissolves and removes the unexposed of photo-sensitive resin Part.Now, with the time development of 2 times of minimum developing time, solidification corrosion-resisting pattern is made.Wherein, Minimum developing time refers to needed for the photo-sensitive resin for dissolving unexposed portion the most as mentioned above Short time.
About the evaluation sample of cured film flexibility, after polyethylene film is peeled off, develop by minimum Develop under 2 times of times, the same terms of time, it is thus achieved that solidification resist layer.
<etching>
On the evaluation substrate being defined corrosion-resisting pattern by development, use mantoquita Etaching device (Tokyo Chemical industry machine (strain) is made, mantoquita Etaching device), spray stipulated time copper chloride concentration 250g/L, hydrochloric acid 50 DEG C of copper chloride etching solutions of concentration 3mol/L, dissolve remove on copper clad laminate not by resist pattern The Copper Foil of the part that case covers.
<stripping>
On evaluation substrate after the etching, spraying is heated to the 3 mass % sodium hydrate aqueous solutions of 50 DEG C, The resist layer of solidification is peeled off.
(2) evaluation method of sample
Then, the evaluation method of sample is described.
(i) developability
According to the preparation method of above-mentioned (1) sample for evaluation, make substrate, lamination, development, it is thus achieved that Corrosion-resisting pattern.According to minimum developing time, classification as described below:
A: minimum developing time is more than 14 seconds.
B: minimum developing time be 10 seconds less than 14 seconds.
C: minimum developing time was less than 10 seconds.
(ii) elching resistant
According to the preparation method of above-mentioned (1) sample for evaluation, by exposed portion and unexposed portion Width ratio is the line style pattern mask of 1:1, through the elching resistant evaluation substrate of 15 minutes after being laminated Exposure.Further, by 2 times of time developments of minimum developing time, needed for Copper Foil being removed by etching Time be set to minimum etching period, be etched with 1.4 times of times of minimum etching period.Use hydrogen-oxygen Change sodium water solution and peel off solidification resist layer, use observation by light microscope conductive pattern, according to relevant sight Examine result, proceed as described below classification:
A: conductive pattern is formed as linearity, does not see the infiltration of etching solution.
B: conductive pattern is formed as linearity, but sees the infiltration of etching solution.
C: conductive pattern is formed without as linearity, it is seen that concavo-convex.
(iii) flexibility of cured film
According to the preparation method of above-mentioned (1) sample for evaluation, rectangular by 5mm × 40mm Mask is by made photosensitive-resin layered product exposure.Further, with 2 times of minimum developing time time Between develop, it is thus achieved that solidification resist layer.With cupping machine (ORIENTEC Co., LTD. system, RTM-500) with the speed of 100mm/ minute, the solidification resist layer of made 5mm × 40mm is drawn Stretch, according to the elongation of solidification resist layer now, proceed as described below classification:
A+: the elongation of solidification resist layer is more than 45mm.
A: the elongation of solidification resist layer is that 40mm is less than 45mm.
B: the elongation of solidification resist layer is that 15mm is less than 40mm.
C: the elongation of solidification resist layer is less than 15mm.
(iv) aggregation
Make thickness 15 μm in photosensitive-resin layered product, area 2.0m2Photosensitive layer be dissolved in 200ml 1 mass %Na2CO3In the aqueous solution, use circulating sprayer unit, enter under atomisation pressure 0.1MPa Row spraying 3 hours continuously.Hereafter, developer solution is stood 1 hour, it was observed that the generation of aggregation.Produce During raw a large amount of aggregation, on the bottom surface and side of sprayer unit, it was observed that the aggregation of powdery or oil The aggregation of shape.The combination that developer solution aggregation is good does not the most produce these aggregations.According to gathering The generation state of thing, as described below carries out classification to aggregation:
A: the most do not produce aggregation.
B: see aggregation in the bottom of sprayer unit or a part for side.
C: see aggregation in whole sprayer unit.
The high molecular acid equivalent of (v) alkali solubility
Acid equivalent refers to the high molecular quality of alkali solubility wherein with the carboxyl of 1 equivalent.The survey of acid equivalent Surely use flat natural pond industry (strain) to make flat natural pond automatic titration device (COM-555), use 0.1mol/L's NaOH, carried out by potential difference titration.
(vi) weight average molecular weight
Weight average molecular weight use Japan's light splitting (strain) gel permeation chromatograph processed (GPC) (pump: Gulliver, PU-1580 type;Post: Showa electrician (strain) Shodex(processed registration mark) (KF-807, KF-806M, KF-806M, KF-802.5) 4 pieces series connection;Fluidized bed solvent: oxolane;Use polystyrene mark The calibration curve that quasi-sample (Showa electrician (strain) Shodex processed STANDARD SM-105) obtains), Obtain according to polystyrene conversion.
(3) evaluation result
Table 1 shows the evaluation result of embodiment and comparative example.
[table 1]
[table 2]
Industrial applicability
Above-mentioned photosensitive polymer combination and layered product can be suitable for printed circuit board (PCB), flexible printing The metal forming Precision Machining such as circuit board, the manufacture of lead frame or metal mask manufacture, BGA or CSP etc. Semiconductor packages manufactures, the manufacture of the tape winding substrates such as TAB or COF, the manufacture of semiconductor projection, ITO Electrode or the manufacture of addressing electrode, electromagnetic wave shield etc..

Claims (13)

1. a photosensitive polymer combination, it is containing (A) alkali solubility macromolecule, (B) photopolymerization Initiator and (C) have the photosensitive polymer combination of the compound of ethylenical unsaturated double bonds, are somebody's turn to do (B) Photoepolymerizationinitiater initiater is 2,4,5-triarylimidazoles dimer or acridine compounds, and (C) should have alkene The compound belonging to unsaturated double-bond comprises the compound shown in following logical formula (I):
In formula (I), R1And R2Representing hydrogen atom or methyl independently of one another, A is C2H4Or C3H6, -(A-O)n1-and-(A-O)n3In-,-C2H4-O-and-C3H6The arrangement of the repetitive of-O-is optionally random Or block, in the case of this is arranged as block ,-C2H4-O-and-C3H6Any one of-O-is at-B-O-base Group side, B is the divalent alkyl chain of carbon number 4~8, n1It is the integer of 0~10, n3It is the integer of 0~10, n1+n3It is the integer of 0~10, and n2It it is the integer of 5~20.
Photosensitive polymer combination the most according to claim 1, wherein, described (C) has alkene The compound belonging to unsaturated double-bond also comprises the compound shown in following logical formula (II):
In formula (II), R3And R4It is hydrogen atom or methyl independently of one another, n4And n7It is 0~20 independently of one another Integer, n4+n7It is the integer of 0~40, n5And n6It is the integer of 1~20 independently of one another, n5+n6It is 2~40 Integer, and-(C2H4-O)-and-(C3H6-O)-the arrangement of repetitive be optionally random or block , in the case of this is arranged as block ,-(C2H4-O)-and-(C3H6-O)-any one in bisphenol group side.
Photosensitive polymer combination the most according to claim 2, wherein, in described logical formula (II) In, n4And n7It is the integer of 1~20 independently of one another, and n4+n7It it is the integer of 2~40.
4. according to the photosensitive polymer combination described in any one of claims 1 to 3, wherein, described (A) Alkali solubility macromolecule selected from containing styrene and/or (methyl) benzyl acrylate as the alkali of copolymer composition Soluble macromolecular.
5. according to the photosensitive polymer combination described in any one of claims 1 to 3, wherein, described In logical formula (I), n2It is the integer of 5~10, and n1+n3It is 0.
6. according to the photosensitive polymer combination described in any one of claims 1 to 3, wherein, described (C) There is the compound of ethylenical unsaturated double bonds be also included in intramolecular there is at least one amino-formate bond Compound.
7. according to the photosensitive polymer combination described in any one of claims 1 to 3, wherein, as institute State (C) there is the compound of ethylenical unsaturated double bonds also to comprise the compound shown in following logical formula (III):
In formula (III), R5And R6It is hydrogen atom or methyl independently of one another, n8And n9It is independently of one another The integer of 3~40, and-(C2H4-O)-and-(C3H6-O)-the arrangement of repetitive be optionally random or Block.
8. according to the photosensitive polymer combination described in any one of claims 1 to 3, wherein, described (C) The compound with ethylenical unsaturated double bonds also comprises the chemical combination shown in following logical formula (IV) and/or (V) Thing:
In formula (IV), R5And R6It is hydrogen atom or methyl independently of one another, n10~n12It is independently of one another The integer of 1~30;
In formula (V), R5And R6It is hydrogen atom or methyl independently of one another, n10~n12It is independently of one another The integer of 1~30.
9. according to the photosensitive polymer combination described in any one of claims 1 to 3, wherein, described (C) There is the compound of ethylenical unsaturated double bonds also comprise intramolecular there is the compound of isocyanurate group.
10. according to the photosensitive polymer combination described in any one of claims 1 to 3, wherein, with photosensitive Property resin combination solid point gross mass be 100 mass % meter, described (A) alkali solubility is high molecular joins Resultant is 40 mass %~80 mass %,
It is in terms of 100 mass % by the solid point gross mass of photosensitive polymer combination, described (B) photopolymerization The use level of initiator is 0.1 mass %~20 mass %,
Being in terms of 100 mass % by the solid point gross mass of photosensitive polymer combination, described (C) has alkene The use level of the compound belonging to unsaturated double-bond is 5 mass %~50 mass %.
11. 1 kinds of photosensitive-resin layered products, it is pressed with by claim 1~10 on support film upper strata The photo-sensitive resin that photosensitive polymer combination described in any one is formed.
The manufacture method of 12. 1 kinds of substrates being formed with corrosion-resisting pattern, comprising: weigh at substrate overlaminate Profit requires the lamination operation of the photosensitive-resin layered product described in 11;Across mask by this photo-sensitive resin The exposure process of laminate exposure;And remove the developing procedure of unexposed portion.
13. 1 kinds of methods forming circuit substrate, it is to by the method manufacture described in claim 12 Substrate be etched or plating and form circuit substrate.
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