CN103282829A - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

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Publication number
CN103282829A
CN103282829A CN2011800625746A CN201180062574A CN103282829A CN 103282829 A CN103282829 A CN 103282829A CN 2011800625746 A CN2011800625746 A CN 2011800625746A CN 201180062574 A CN201180062574 A CN 201180062574A CN 103282829 A CN103282829 A CN 103282829A
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quality
polymer combination
compound
photosensitive polymer
integer
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CN103282829B (en
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国松真一
筒井大和
内藤一也
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular 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
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • H05K3/02—Apparatus 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
    • H05K3/06—Apparatus 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
    • H05K3/061—Etching masks
    • H05K3/064—Photoresists

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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)
  • Polymerisation Methods In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Manufacturing Of Printed Wiring (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

A photosensitive resin composition which comprises (A) an alkali-soluble polymer, (B) a photopolymerization initiator, and (C) a compound having an ethylenically unsaturated double bond, wherein the photopolymerization initiator (B) is a 2,4,5-triarylimidazole dimer or an acridine compound, while a compound represented by general formula (I) is contained as the compound (C). In general formula (I), R1, R2, A, B, n1, n2 and n3 are each as defined in the description. The photosensitive resin composition is excellently and stably dispersible in a developer to minimize the generation of an aggregate. Further, the resin composition exhibits proper developability and can provide a flexible cured resist with good etching resistance.

Description

Photosensitive polymer combination
Technical field
The present invention relates to photosensitive polymer combination etc.
Background technology
Precision Machining of printed circuit board (PCB) or metal etc. was made by photoetching process in the past.Photoetching process is a kind of like this method, that is, photosensitive polymer combination is coated on the substrate, passes through pattern exposure, make the exposed portion polymerizing curable of this photosensitive polymer combination, remove unexposed portion with developer solution, form corrosion-resisting pattern at substrate, implement etching or plating and handle, form conductive pattern, then, peel off this corrosion-resisting pattern of removal from this substrate, thereby form the method for conductive pattern at substrate.
In photoetching process; when being coated on photosensitive polymer combination on the substrate; can use following arbitrary method: with the photoresist solution coat on substrate and make it dry method; perhaps layer (hereinafter referred to as photo-sensitive resin) and the protective seam as required that forms with supporter, by photosensitive polymer combination lamination and the photosensitive-resin layered product that obtains is laminated to the method on the substrate successively, the use latter mostly in the manufacturing of printed circuit board (PCB).
Below the simple method of using above-mentioned photosensitive-resin layered product to make printed circuit board (PCB) of describing.
At first, peel off protective seams such as polyethylene film from photosensitive-resin layered product.Then, use laminating machine, on substrates such as copper clad laminate, according to the order of this substrate, photo-sensitive resin, supporter, with photo-sensitive resin and supporter lamination.Then, across the photomask with wiring pattern, with this photo-sensitive resin exposure, thereby make the exposed portion polymerizing curable.Then, will be peeled off by the supporter that polyethylene terephthalate etc. forms.Then, by having developer solution such as weakly alkaline aqueous solution, with the unexposed portion dissolving of photo-sensitive resin or disperse to remove, form corrosion-resisting pattern at substrate.The operation of removing the photo-sensitive resin of unexposed portion by this developing solution dissolution or dispersion is called as developing procedure, is used for making the photo-sensitive resin required shortest time of dissolving of unexposed portion to be known as minimum development time.
Photosensitive polymer combination is not all to dissolve in developer solution, developing procedure of every repetition, and the not solvent components of developer solution bad dispersibility increases, and produces aggregation.Aggregation is attached on the substrate, becomes the reason of short trouble.
Then, formed corrosion-resisting pattern carries out known etch processes or pattern plating and handles as the protection mask.At last, peel off this corrosion-resisting pattern from substrate, make substrate with conductive pattern, be printed circuit board (PCB).
In etch processes, the elching resistant of corrosion-resisting pattern is important.If elching resistant is poor, during etching, etching solution infiltrates from the gap between corrosion-resisting pattern and the substrate, and the part at circuit top is etched.The repeatability variation of the width of segment conductor pattern, rectilinearity difference and instability have been seen because of variable color, oxidation that infiltration causes from the appearance that top-direction is seen.In addition, during the elching resistant difference, breach or the broken string of conductive pattern takes place.Conductive pattern is more fine, and these defectives are more remarkable.Etched pattern with above-mentioned formation is called as etching work procedure as the operation that the protection mask carries out known etch processes.With above-mentioned developing procedure and etching work procedure interlock, dissolving does not need conductor partly owing to need fully, so the transporting velocity of substrate depends on etching work procedure mostly.At this moment, under the short situation of the minimum development time of photo-sensitive resin, have the situation of the adaptation that exceedingly is exposed to developer solution, infringement base material and formed corrosion-resisting pattern, this especially becomes remarkable under the situation of the photo-sensitive resin that used thickness is thin in order to improve image resolution ratio and etching efficiency.In addition, in developing procedure and etching work procedure, when solidifying resist layer and lacking flexibility, with conveying roller contact or the spraying of developer solution or etching solution will cause the part corrosion-resisting pattern damaged, breach or the broken string of conductive pattern takes place sometimes.
Under above-mentioned condition, in order to improve flexibility and the chemical-resistant that solidifies resist layer, report has the method for using polytetramethylene glycol two (methyl) acrylate or the method (with reference to patent documentation 1,2) of using carbamate compounds.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication sho 61-228007 communique
Patent documentation 2: No. 3859934 communique of Jap.P.
Summary of the invention
The problem that invention will solve
The chemical-resistant of record is object with aqueous alkali or plating liquid in the patent documentation 1 and 2, not have to disclose the patience to the acidic chemical that uses in the etching work procedure, also not openly development property or aggregation.Therefore, the necessity that still has the photosensitive polymer combination of generation, the development with appropriateness that developer solution dispersion stabilization excellence is provided, can suppresses aggregation, the flexibility of solidifying resist layer and good elching resistant.
In view of above-mentioned present situation, problem to be solved by this invention provides developer solution dispersion stabilization excellence, can suppress the generation of aggregation, has the photosensitive polymer combination of the development of appropriateness, the flexibility of solidifying resist layer and good elching resistant etc.
For the scheme of dealing with problems
The inventor found that in order to address the above problem further investigation, experiment repeatedly, can address the above problem by following technological means, has finished the present invention thus.
That is, the present invention is as described below.
[1] a kind of photosensitive polymer combination, it is the photosensitive polymer combination that contains (A) alkali solubility macromolecule, (B) Photoepolymerizationinitiater initiater and (C) have the compound of ethylenical unsaturated double bonds, should (B) Photoepolymerizationinitiater initiater be 2,4,5-triarylimidazoles dimer or acridine compound, and the compound that should (C) has an ethylenical unsaturated double bonds comprises the compound shown in the following general formula (I):
Figure BDA00003398455400041
In the formula (I), R 1And R 2Represent hydrogen atom or methyl independently of one another, A is C 2H 4Or C 3H 6,-(A-O) N1-and-(A-O) N3-in ,-C 2H 4-O-and-C 3H 6The arrangement of the repetitive of-O-is optional to be random or block, and this is arranged as under the situation of block ,-C 2H 4-O-and-C 3H 6Any one of-O-is in-B-O-group side, and B is the divalent alkyl chain of carbon number 4～8, n 1Be 0～10 integer, n 3Be 0～10 integer, n 1+ n 3Be 0～10 integer, and n 2It is 1～20 integer.
[2] according to [1] described photosensitive polymer combination, wherein, the compound that described (C) has ethylenical unsaturated double bonds also comprises the compound shown in the following general formula (II):
Figure BDA00003398455400042
In the formula (II), R 3And R 4Be hydrogen atom or methyl independently of one another, n 4And n 7Be 0～20 integer independently of one another, n 4+ n 7Be 0～40 integer, n 5And n 6Be 1～20 integer independently of one another, n 5+ n 6Be 2～40 integer, and-(C 2H 4-O)-and-(C 3H 6-O)-the arrangement of repetitive optional be random or block, this is arranged as under the situation of block ,-(C 2H 4-O)-and-(C 3H 6-O)-any one in the bisphenol group side.
[3] according to [2] described photosensitive polymer combination, wherein, in described general formula (II), n 4And n 7Be 1～20 integer independently of one another, and n 4+ n 7It is 2～40 integer.
[4] according to each described photosensitive polymer combination of [1]～[3], wherein, described (A) alkali solubility macromolecule is selected from and contains styrene and/or (methyl) benzyl acrylate as the alkali solubility macromolecule of multipolymer composition.
[5] according to each described photosensitive polymer combination of [1]～[4], wherein, in described general formula (I), n 2Be 1～10 integer, and n 1+ n 3Be 0.
[6] according to each described photosensitive polymer combination of [1]～[5], wherein, the compound that described (C) has ethylenical unsaturated double bonds also comprises the compound that has at least one amino-formate bond in the molecule.
[7] according to each described photosensitive polymer combination of [1]～[6], wherein, the compound that described (C) has ethylenical unsaturated double bonds also comprises the compound shown in the following general formula (III):
Figure BDA00003398455400051
In the formula (III), R 5And R 6Be hydrogen atom or methyl independently of one another, n 8And n 9Be 3～40 integer independently of one another, and-(C 2H 4-O)-and-(C 3H 6-O)-the arrangement of repetitive optional be random or block.
[8] according to each described photosensitive polymer combination of [1]～[7], wherein, the compound that described (C) has an ethylenical unsaturated double bonds also comprise following general formula (IV) and/or (V) shown in compound:
Figure BDA00003398455400052
In the formula (IV), R 5And R 6Be hydrogen atom or methyl independently of one another, n 10～n 12Be 1～30 integer independently of one another;
Figure BDA00003398455400053
In the formula (V), R 5And R 6Be hydrogen atom or methyl independently of one another, n 10～n 12Be 1～30 integer independently of one another.
[9] according to each described photosensitive polymer combination of [1]～[8], wherein, the compound that described (C) has ethylenical unsaturated double bonds also comprises the compound that has the isocyanuric acid ester group in the molecule.
[10] according to each described photosensitive polymer combination of [1]～[9], wherein, be 100 quality % in the solid shape branch gross mass of photosensitive polymer combination, the high molecular use level of described (A) alkali solubility is 40 quality %～80 quality %; Solid shape branch gross mass in photosensitive polymer combination is 100 quality %, and the use level of described (B) Photoepolymerizationinitiater initiater is 0.1 quality %～20 quality %; Solid shape branch gross mass in photosensitive polymer combination is 100 quality %, and the use level that described (C) has the compound of ethylenical unsaturated double bonds is 5 quality %～50 quality %.
[11] a kind of photosensitive-resin layered product, it is the photosensitive-resin layered product that is pressed with the photo-sensitive resin that is formed by each described photosensitive polymer combination of [1]～[10] on the support film upper strata.
[12] a kind of manufacture method that is formed with the substrate of corrosion-resisting pattern, it is included in the lamination operation of [11] described photosensitive-resin layered product of lamination on the substrate; Across the exposure process of mask with this photosensitive-resin layered product exposure; And the developing procedure of removing unexposed portion.
[13] a kind of method that forms circuit substrate, substrate by [12] described method manufacturing is carried out etching for it or plating forms circuit substrate.
The effect of invention
By the present invention, developer solution dispersion stabilization excellence can be provided, can suppress the generation of aggregation, the development with appropriateness, the flexibility of solidifying resist layer and good elching resistant, the photosensitive-resin layered product etc. that is applicable to the photosensitive polymer combination that forms good conductive pattern and has the photo-sensitive resin that is formed by said composition.
Embodiment
Below, describe the enforcement mode of the present invention (being designated hereinafter simply as embodiment) that is used in detail.Wherein, the present invention is not limited to following embodiment, can carry out various distortion in the scope of its main idea and implement.
＜photosensitive polymer combination 〉
In the present embodiment, photosensitive polymer combination contains (A) alkali solubility macromolecule, (B) Photoepolymerizationinitiater initiater and the compound that (C) has ethylenical unsaturated double bonds.
＜(A) alkali solubility macromolecule 〉
(A) the alkali solubility macromolecule refers to contain the vinyl resin of carboxyl, for example, is the multipolymer of (methyl) acrylic acid, (methyl) acrylate, (methyl) vinyl cyanide, (methyl) acrylamide etc.(A) the alkali solubility macromolecule contains carboxyl, and acid equivalent is preferably 100～600.From the viewpoint consideration that improves anti-development, improves image resolution ratio and adaptation, acid equivalent is preferably more than 100, considers from the viewpoint that improves development and fissility, is preferably below 600.Acid equivalent more preferably 250～450.
(A) the high molecular weight-average molecular weight of alkali solubility is preferably more than 5,000 and below 500,000.Consider from the proterties of development aggregation, the viewpoint of proterties of unexposed films such as edge-melting (edge fuse), smear metal when forming photosensitive-resin layered product, (A) the high molecular weight-average molecular weight of alkali solubility is preferably 5, more than 000, consider from the viewpoint that improves development, be preferably below 500,000.Herein, edge-melting is when coiling into drum as photosensitive-resin layered product, the phenomenon that the photosensitive polymer combination layer overflows from the end face of reel.Smear metal is the phenomenon that fragment splashes when with cutter unexposed film being cut off, and when fragment is attached to the upper surface of photosensitive-resin layered product etc., in post-exposure process etc., is transferred on the mask, constitutes the reason of substandard products.(A) the high molecular weight-average molecular weight of alkali solubility is more preferably more than 5,000 and below 300,000, more preferably more than 10,000 and below 200,000.
(A) the alkali solubility macromolecule for example can be by being selected from one or more the incompatible acquisition of monomer copolymerization separately in the following two class monomers.
First monomer is carboxylic acid or the acid anhydrides that has a polymerism unsaturated group in the molecule.For example, can list (methyl) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester etc.Especially preferred (methyl) acrylic acid.Wherein, (methyl) acrylic acid refers to acrylic or methacrylic acid.
Second monomer be nonacid and molecule in have the monomer of at least one polymerism unsaturated group.For example, can list (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) 2-EHA, (methyl) benzyl acrylate; The ester class of vinyl alcohol, for example, vinyl acetate; (methyl) vinyl cyanide; Styrene, styrene derivative etc.Especially preferred (methyl) methyl acrylate, (methyl) n-butyl acrylate, styrene, styrene derivative and (methyl) benzyl acrylate.
As the multipolymer composition in (A) alkali solubility macromolecule, optimization styrene or styrene derivative, its copolymerization ratio is preferably 20 quality %～60 quality %.Consider that from the viewpoint with sufficient aggregation and elching resistant etc. this copolymerization ratio is preferably more than the 20 quality %, consider from the viewpoint with appropriate development and cured film flexibility, be preferably below the 60 quality %.This copolymerization ratio is 20 quality %～50 quality % more preferably, more preferably 20 quality %～30 quality %.In addition, as the multipolymer composition, preferably with styrene or styrene derivative, (methyl) methyl acrylate and (methyl) acrylic acid copolymer and the multipolymer that obtains.In addition, except above-mentioned, in order to obtain excellent image resolution ratio, the copolymerization ratio of styrene or styrene derivative is preferably 40 quality %～60 quality %, in addition, as the multipolymer composition, preferably with styrene or styrene derivative, (methyl) methyl acrylate and (methyl) acrylic acid copolymer and the multipolymer that obtains.
Solid shape branch gross mass with photosensitive polymer combination is 100 quality % timing, and the high molecular use level of (A) alkali solubility in the photosensitive polymer combination is preferably the scope of 40 quality %～80 quality %, more preferably 50 quality %～70 quality %.Consider that from the viewpoint of edge-melting this use level is preferably more than the 40 quality %, consider from the viewpoint of development time, be preferably below the 80 quality %.
＜(B) Photoepolymerizationinitiater initiater 〉
Above-mentioned photosensitive polymer combination contains the essential composition of 2,4,5-triarylimidazoles dimer or acridine compound conduct (B) Photoepolymerizationinitiater initiater.As their object lesson, for example, 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-diphenyl-imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenyl-imidazole dimer etc. 2,4,5-triarylimidazoles dimer, 9-phenylacridine, 1, acridine derivatives such as two (9, the 9-acridinyl) heptane of 7-etc.
Except 2,4, beyond 5-triarylimidazoles dimer or the acridine compound, as the Photoepolymerizationinitiater initiater that can further contain in the photosensitive polymer combination, for example, can list benzophenone, N, N '-tetramethyl-4,4 '-dimethylamino benzophenone (Michler's keton), N, N '-tetraethyl-4,4 '-diaminobenzophenone, 4-methoxyl-4 '-dimethylamino benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl-aromatic ketones such as 1-acetone; 2-EAQ, phenanthrenequione, 2-tert-butyl group anthraquinone, prestox anthraquinone, 1,2-benzo anthraquinone, 2,3-benzo anthraquinone, 2-phenyl anthraquinone, 2,3-diphenyl anthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinones, 9,10-phenanthrenequione, 2-methyl isophthalic acid, 4-naphthoquinones, 2, quinones such as 3-dimethyl anthraquinone; Benzoin ether compounds such as benzoin methylether, benzoin ethyl ether, benzoin phenylate; Benzil derivants such as benzil methyl ketal; The N-phenylglycine derivant; Coumarin series compounds; 4,4 '-two (lignocaine) benzophenone etc.These Photoepolymerizationinitiater initiaters can use separately, also can be used in combination of two or more.
Solid shape branch gross mass with photosensitive polymer combination is 100 quality % timing, and the use level of (B) Photoepolymerizationinitiater initiater in the photosensitive polymer combination is preferably 0.1 quality～20 quality %.From obtaining the viewpoint of sufficient light sensitivity, this use level is preferably more than the 0.1 quality %, from making light fully be transmitted to the resist layer bottom surface, obtaining the viewpoint of good high image resolution, is preferably below the 20 quality %.The preferred scope of this use level is 0.5 quality %～10 quality %.
＜(C) have a compound of ethylenical unsaturated double bonds 〉
(C) compound with ethylenical unsaturated double bonds is as referring to have the compound of ethylenical unsaturated double bonds as described in literal.Have the compound of ethylenical unsaturated double bonds as (C), for example, can list two (methyl) esters of acrylic acid.Wherein, (methyl) acrylate refers to acrylate or methacrylate.
Photosensitive polymer combination contains the compound shown in the following general formula (I) has ethylenical unsaturated double bonds as (C) compound.
Figure BDA00003398455400101
In the formula (I), R 1And R 2Represent hydrogen atom or methyl independently of one another, A is C 2H 4Or C 3H 6,-(A-O) N1-and-(A-O) N3-in ,-C 2H 4-O-and-C 3H 6The arrangement of the repetitive of-O-is optional to be random or block, and this is arranged as under the situation of block ,-C 2H 4-O-and-C 3H 6Any one of-O-is in-B-O-group side, and B is the divalent alkyl chain of carbon number 4～8, n 1Be 0～10 integer, n 3Be 0～10 integer, n 1+ n 3Be 0～10 integer, and n 2It is 1～20 integer.
Wherein, when two (methyl) acrylate shown in the above-mentioned general formula (I) and other technical scheme are combined as photosensitive polymer combination, developer solution dispersion stabilization excellence can be provided, can suppress aggregation generation, have appropriateness development, solidify the flexibility of resist layer and the photosensitive polymer combination of good elching resistant, though the detail of its mechanism is also indeterminate, is speculated as following effect.
Namely be speculated as, two (methyl) acrylate shown in the general formula (I) has-group shown in the B-O-, compare with normally used oxidation ethylidene or oxypropylene, strand is longer and do not have side chain, so the flexibility of the degree of freedom height of main chain, chemical constitution (being sometimes referred to as protuberance property (tenting)) excellence.
In addition, ehter bond generally has because acid causes the carbon with the oxygen adjacency and stands the tendency that nucleophilic substitution ftractures, two (methyl) acrylate shown in the general formula (I) has-(B-O)-shown in group in, the ratio at the cleacvage reaction position that acid produces is less than oxidation ethylidene or oxypropylene, thinks acid resistance (being sometimes referred to as elching resistant) excellence.
In addition, think two (methyl) acrylate shown in the general formula (I) have-(B-O)-shown in group have high lipophilicity, form the dispersion stabilization excellence that contains the phenyl initiating agent (can suppress the generation of aggregation) of development aggregation easily.
Wherein, about the development of appropriateness, infer the lipophilicity be derived from the appropriateness that two (methyl) acrylate shown in the general formula (I) has.
In the compound shown in the above-mentioned general formula (I), n 1And n 30 integer preferably.That is n, 1+ n 30 integer preferably.More specifically, consider that from viewpoints such as edge-melting, property easy to manufacture the compound preference shown in the above-mentioned general formula (I) is polytetramethylene glycol two (methyl) acrylate shown in the following general formula (VI) in this way.
Figure BDA00003398455400111
In the formula (VI), R 1And R 2Represent hydrogen atom or methyl independently of one another, and n 2Preferably 1～20 integer is more preferably 1～15 integer, special preferably 1～10 integer.
More specifically, for example, can list butylene glycol two (methyl) acrylate, dibutylene glycol two (methyl) acrylate, three butylene glycol two (methyl) acrylate, four butylene glycol two (methyl) acrylate, five butylene glycol two (methyl) acrylate, six butylene glycol two (methyl) acrylate, seven butylene glycol two (methyl) acrylate, eight butylene glycol two (methyl) acrylate, nine butylene glycol two (methyl) acrylate, ten butylene glycol two (methyl) acrylate, 11 butylene glycol two (methyl) acrylate, ten dibutylene glycol two (methyl) acrylate, thirteen kinds of furuncles glycol two (methyl) acrylate, 14 butylene glycol two (methyl) acrylate, 15 butylene glycol two (methyl) acrylate etc.
At above-mentioned general formula (I) with in the compound (VI), n 2Preferably 1～20 integer is more preferably 1～15 integer, special preferably 1～10 integer.Consider n from the viewpoint of cured film flexibility 2Be preferably more than 1, on the other hand, consider n from the viewpoint of elching resistant 2Be preferably below 20.More preferably, n 2It is 5～10 integer.
Solid shape branch gross mass with photosensitive polymer combination is 100 quality % timing, the above-mentioned general formula (I) in the photosensitive polymer combination or (VI) shown in the use level of compound be preferably 1 quality %～15 quality %.Consider that from the viewpoint that obtains the cured film flexibility this use level is preferably more than the 1 quality %, consider from the viewpoint of elching resistant, be preferably below the 15 quality %.The preferred scope of this use level is 1 quality %～10 quality %, and further preferred range is 3 quality %～10 quality %.
In addition, consider from the viewpoint of further raising flexibility that preferably, photosensitive polymer combination also contains the compound shown in the following general formula (II) has ethylenical unsaturated double bonds as (C) compound.
Figure BDA00003398455400121
In the formula (II), R 3And R 4Be hydrogen atom or methyl independently of one another, n 4And n 7Be 0～20 integer independently of one another, n 4+ n 7Be 0～40 integer, n 5And n 6Be 1～20 integer independently of one another, n 5+ n 6Be 2～40 integer, and-(C 2H 4-O)-and-(C 3H 6-O)-the arrangement of repetitive optional be random or block, this is arranged as under the situation of block ,-(C 2H 4-O)-and-(C 3H 6-O)-any one in the bisphenol group side.
Wherein, with above-mentioned general formula (I) or the compound shown in the compound (VI) and the above-mentioned general formula (II) when being used in combination, realize the photosensitive polymer combination that flexibility further improves, though the detail of its mechanism and indeterminate is speculated as the effect of the following stated.
That is, with above-mentioned general formula (I) or the compound shown in the compound (VI) and the above-mentioned general formula (II) when being used in combination, infer and improved photopolymerisable reactivity.And, infer that thus the cured film after the exposure becomes more tough, has showed good toughness.
In the above-mentioned general formula (II), n 4And n 7Be 0～20 integer independently of one another, n 4+ n 7Be 0～40 integer, n 5And n 6Be 1～20 integer independently of one another, n 5+ n 6It is 2～40 integer.In addition, n 4+ n 5+ n 6+ n 7Lower limit be preferably more than 2, on the other hand, its upper limit is preferably below 40.Consider n from the viewpoint of the flexibility of cured film 4+ n 5+ n 6+ n 7Be preferably more than 2, on the other hand, consider from the viewpoint of image resolution ratio, be preferably below 40.In addition, consider n from the viewpoint of elching resistant 4+ n 5+ n 6+ n 7Preferred scope following be limited to more than 4, on be limited to below 20, further preferred range following be limited to more than 6, on be limited to below 12.In addition, consider n from the viewpoint of protuberance property 4+ n 5+ n 6+ n 7Preferred scope following be limited to more than 16, on be limited to below 40, further preferred range following be limited to more than 30, on be limited to below 40.In addition, n 4And n 7Preferred is 1～10 integer independently of one another, n 4+ n 7Be more preferably 1～20 integer, on the other hand, n 5+ n 6Be more preferably 2～20 integer.
As the object lesson of the compound shown in the above-mentioned general formula (II), can list at the two ends of bisphenol-A addition respectively average 2 moles oxirane ethylene glycol dimethylacrylate or at the two ends of bisphenol-A respectively addition the dimethylacrylate of ethylene glycol of average 5 moles oxirane, at the two ends of bisphenol-A respectively addition the dimethylacrylate of aklylene glycol of average 6 moles oxirane and average 2 moles epoxypropane, in the addition of the two ends of bisphenol-A addition the dimethylacrylate etc. of aklylene glycol of dimethylacrylate of aklylene glycol of average 15 moles oxirane and average 2 moles epoxypropane.
Solid shape branch gross mass with photosensitive polymer combination is 100 quality % timing, and the use level of the compound shown in the above-mentioned general formula (II) in the photosensitive polymer combination is preferably 5 quality %～20 quality %.Consider that from the viewpoint that obtains elching resistant this use level is preferably more than the 5 quality %, consider from the viewpoint of cured film flexibility, be preferably below the 20 quality %.The preferred scope of this use level is 5 quality %～15 quality %, and further preferred range is 7 quality %～15 quality %.
Consider that from the viewpoint that improves the cured film flexibility photosensitive polymer combination preferably also contains the compound shown in the following general formula (III) has ethylenical unsaturated double bonds as (C) compound.
In the formula (III), R 5And R 6Be hydrogen atom or methyl independently of one another, n 8And n 9Be 3～40 integer independently of one another, and-(C 2H 4-O)-and-(C 3H 6-O)-the arrangement of repetitive optional be random or block.
In the compound shown in the above-mentioned general formula (III), consider n from the viewpoint that improves the cured film flexibility 8And n 9Preferably be the integer more than 3 independently of one another, be more preferably the integer more than 5.
As the object lesson of the compound shown in the above-mentioned general formula (III), for example, can list in addition on the polypropylene glycol of average 9 moles epoxypropane further the dimethylacrylate of the poly alkylene glycol of average 1 moles of ethylene oxide of addition etc.
Solid shape branch gross mass with photosensitive polymer combination is 100 quality % timing, and the use level of the compound shown in the above-mentioned general formula (III) in the photosensitive polymer combination is preferably 1 quality %～20 quality %.Consider that from the viewpoint that obtains the cured film flexibility this use level is preferably more than the 1 quality %, consider from the viewpoint of elching resistant, be preferably below the 20 quality %.The preferred scope of this use level is 3 quality %～15 quality %, and further preferred range is 5 quality %～10 quality %.
Consider from the viewpoint that improves the cured film flexibility, photosensitive polymer combination preferably also contain following general formula (IV) and/or (V) shown in compound have the compound of ethylenical unsaturated double bonds as (C).
Figure BDA00003398455400141
In the formula, R 5And R 6Be hydrogen atom or methyl independently of one another, n 10～n 12Be 1～30 integer independently of one another;
Figure BDA00003398455400142
In the formula, R 5And R 6Be hydrogen atom or methyl independently of one another, n 10～n 12Be 1～30 integer independently of one another.
At above-mentioned general formula (IV) or in the compound (V), consider n from the viewpoint that improves the cured film flexibility 10～n 12Preferably be the integer more than 1, the more preferably integer more than 3 independently of one another.
As above-mentioned general formula (IV) or the object lesson of the compound (V), for example, can list in addition on the polypropylene glycol of average 18 moles epoxypropane further at two ends the dimethylacrylate of the poly alkylene glycol of each average 7 moles of ethylene oxide of addition respectively, in addition the further dimethylacrylate of the poly alkylene glycol of each average 3 moles of ethylene oxide of addition respectively at two ends on the polypropylene glycol of average 18 moles epoxypropane, in addition the further dimethylacrylate of the poly alkylene glycol of each average 3 moles of ethylene oxide of addition respectively at two ends on the polypropylene glycol of average 12 moles epoxypropane, in addition the further dimethylacrylate of the poly alkylene glycol of each average 6 moles of epoxypropane of addition etc. respectively at two ends on the polyglycol of average 6 moles oxirane.
Solid shape branch gross mass with photosensitive polymer combination is 100 quality % timing, the above-mentioned general formula (IV) in the photosensitive polymer combination or (V) shown in the use level of compound be preferably 1 quality %～30 quality %.Consider that from the viewpoint that obtains elching resistant this use level is preferably more than the 1 quality %, consider from the viewpoint of cured film flexibility, be preferably below the 30 quality %.The preferred scope of this use level is 5 quality %～25 quality %, and further preferred range is 5 quality %～23 quality %.
Photosensitive polymer combination preferably also contains the compound that has at least one amino-formate bond in the molecule has ethylenical unsaturated double bonds as (C) compound.Particularly, can list hexamethylene diisocyanate, toluene diisocyanate, 2, diisocyanate cpds such as 2,4-trimethyl hexamethylene diisocyanate react and the carbamate compounds of acquisition with hydroxyl (methyl) acrylate compounds such as (methyl) acrylic acid 2-hydroxypropyl acrylate, the low macrogol ester of (methyl) acrylic acid, the oligomeric propylene glycol esters of (methyl) acrylic acid.Consider from the viewpoint of elching resistant, preferably, the compound that has at least one amino-formate bond in the molecule for example is hexamethylene diisocyanate, toluene diisocyanate, 2, diisocyanate cpds such as 2,4-trimethyl hexamethylene diisocyanate react the carbamate compounds that obtains with the oligomeric propylene glycol ester of (methyl) acrylic acid.
Solid shape branch gross mass with photosensitive polymer combination is 100 quality % timing, and the use level that has the compound of at least one amino-formate bond in the above-mentioned molecule in the photosensitive polymer combination is preferably 5 quality %～20 quality %.Consider that from the viewpoint that obtains elching resistant this use level is preferably more than the 5 quality %, consider from the viewpoint of aggregation, be preferably below the 20 quality %.The preferred scope of this use level is 8 quality %～20 quality %, and further preferred range is 8 quality %～17 quality %.
Photosensitive polymer combination preferably also contains the compound that has the isocyanuric acid ester group in the molecule has ethylenical unsaturated double bonds as (C) compound.Particularly, as the compound that has the isocyanuric acid ester group in the molecule, for example, can list ethoxylation isocyanuric acid triacrylate, single (the 2-acryloxy ethyl) isocyanuric acid ester of 6-caprolactone modification, two (the 2-acryloxy ethyl) isocyanuric acid esters of 6-caprolactone modification, 6-caprolactone modification three (2-acryloxy ethyl) isocyanuric acid ester, isocyanuric acid oxirane modification acrylate, isocyanuric acid oxirane modification diacrylate, isocyanuric acid oxirane modification triacrylate, isocyanuric acid epoxy pronane modification acrylate, isocyanuric acid epoxy pronane modification diacrylate, isocyanuric acid epoxy pronane modification triacrylate etc.
Solid shape branch gross mass with photosensitive polymer combination is 100 quality % timing, and the use level that has the compound of isocyanuric acid ester group in the molecule in the photosensitive polymer combination is preferably 1 quality %～20 quality %.Consider that from the viewpoint that obtains elching resistant this use level is preferably more than the 1 quality %, consider from the viewpoint of cured film flexibility, be preferably below the 20 quality %.The preferred scope of this use level is 1 quality %～15 quality %, and further preferred range is 2 quality %～10 quality %.
The compound that has ethylenical unsaturated double bonds as (C), photosensitive polymer combination also can contain the alefinically unsaturated compounds of the photopolymerization shown in following except containing the compound that is selected from the group of being made of the compound that has the isocyanuric acid base in the compound that has at least one amino-formate bond in the compound shown in the above-mentioned general formula (I)～(VI), the molecule, the molecule.
Particularly, as the alefinically unsaturated compounds of photopolymerization, can list polypropylene glycol two (methyl) acrylate, polyglycol (methyl) acrylate, 2-two (p-hydroxybenzene) propane (methyl) acrylate, glycerine three (methyl) acrylate, trihydroxy methyl three (methyl) acrylate, polyoxyethyl propyl trimethylolpropane tris (methyl) acrylate, polyoxy ethyl trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, trimethyl propane triglycidyl ether three (methyl) acrylate, phenoxy group polyglycol (methyl) acrylate, Nonylphenoxy polyglycol (methyl) acrylate etc.These can use separately, also can be used in combination of two or more.
Solid shape branch gross mass with photosensitive polymer combination is 100 quality % timing, and the use level that (C) in the photosensitive polymer combination has the compound of ethylenical unsaturated double bonds is preferably 5 quality %～50 quality %.Consider that from the viewpoint of light sensitivity, image resolution ratio, adaptation this use level is preferably more than the 5 quality %, the viewpoint consideration of peeling off delay from suppressing cold flow and solidifying resist layer is preferably below the 50 quality %.This use level is 25 quality %～45 quality % more preferably.
＜leuco dye, fluoran dyes, coloring material 〉
Photosensitive polymer combination can also contain leuco dye, fluoran dyes or coloring material.By containing these dyestuffs, the exposed portion colour developing, therefore the viewpoint from visuality is preferred, in addition, when checkout facility etc. read for the alignment mark of exposure, the contrast of exposed portion and unexposed portion was big, then identified easily but favourable.
As leuco dye, can list three (4-dimethylamino phenyl) methane [leuco crystal violet], two (4-dimethylamino phenyl) phenylmethane [procrypsis malachite green].Especially, from the good viewpoint of contrast, as leuco dye, preferably use leuco crystal violet.
As fluoran dyes, can list 2-(dibenzyl amino) fluorane, 2-anilino--3-methyl-6-lignocaine fluorane, 2-anilino--3-methyl-6-dibutylamino fluorane, the amino fluorane of 2-anilino--3-methyl-6-N-ethyl-N-isopentyl, the amino fluorane of 2-anilino--3-methyl-6-N-methyl-N-cyclohexyl, 2-anilino--3-chloro-6-lignocaine fluorane, 2-anilino--3-methyl-6-N-ethyl-N-isobutylamino fluorane, 2-anilino--6-dibutylamino fluorane, the amino fluorane of 2-anilino--3-methyl-6-N-ethyl-N-tetrahydrofurfuryl, 2-anilino--3-methyl-6-piperidyl amino fluorane, 2-(o-chloraniline base)-6-lignocaine fluorane, 2-(3,4-dichloro-benzenes amido)-6-lignocaine fluorane etc.
Solid shape branch gross mass with photosensitive polymer combination is 100 quality % timing, and the leuco dye in the photosensitive polymer combination or the content of fluoran dyes are preferably 0.1 quality %～10 quality %.Consider that from the viewpoint of the contrast of exposed portion and unexposed portion this content is preferably more than the 0.1 quality %, consider from the viewpoint of keeping storage stability, be preferably below the 10 quality %.
As coloring material, for example, can list magenta, phthalocyanine green, alkali Chinese scholartree Huang, paramagenta (para magenta), crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (hodogaya chemical (strain) Aizen(registered trademark processed), MALACHITE GREEN), alkali blue 20, Viride Nitens (hodogaya chemical (strain) Aizen(registered trademark processed) DIAMOND GREEN GH).Solid shape branch gross mass with photosensitive polymer combination is 100 quality % timing, and the content of the coloring material in the photosensitive polymer combination is preferably 0.001 quality %～1 quality %.Consider that from the viewpoint that improves the property handled this content is preferably more than the 0.001 quality %, consider that from the viewpoint of keeping storage stability this content is preferably below the 1 quality %.
＜halogen compounds 〉
In embodiments of the present invention, from the viewpoint of adaptation and contrast, preferably, in photosensitive polymer combination, leuco dye and following halogen compounds are used in combination.
As halogen compounds, for example, can list amyl bromide, isoamyl bromide, bromination isobutylene, ethylene bromide, diphenyl methyl bromine, benzyl bromide a-bromotoluene, methylene bromide, trisbromomethyl phenyl sulfone, carbon tetrabromide, three (2, the 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide,, 1,1,1-three chloro-2, two (rubigan) ethane of 2-, chlorination triaizine compounds etc., especially preferred trisbromomethyl phenyl sulfone.Solid shape branch gross mass with photosensitive polymer combination is 100 quality % timing, the content of the halogen compounds in the photosensitive polymer combination is preferably 0.01 quality %～3 quality %, consider from the viewpoint that obtains adaptation and contrast, this use level is preferably more than 0.01%, consider from the viewpoint of storage stability, be preferably below the 3 quality %.
＜radical polymerization inhibitor, benzotriazole, carboxyl benzotriazole class 〉
In addition, for thermal stability, the storage stability that improves photosensitive polymer combination, photosensitive polymer combination can further contain at least a above compound that is selected from the group of being made up of radical polymerization inhibitor, benzotriazole and carboxyl benzotriazole class.
As radical polymerization inhibitor, for example, can list p methoxy phenol, quinhydrones, pyrogallol, naphthylamines, tert-butyl catechol, stannous chloride, 2,6-di-t-butyl-paracresol, 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), nitroso-phenyl azanol aluminium salt, diphenyl nitroso-amines etc.
As benzotriazole, for example, can list 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, two (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, two (N-2-ethylhexyl) aminomethylene-1,2,3-tolytriazole, two (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole etc.
As the carboxyl benzotriazole class, for example, can list 4-carboxyl-1,2,3-benzotriazole, 5-carboxyl-1,2,3-benzotriazole, N-(N, N-two-2-ethylhexyl) aminomethylene carboxyl benzotriazole, N-(N, N-two-2-hydroxyethyl) aminomethylene carboxyl benzotriazole, the amino ethylidene carboxyl benzotriazole of N-(N, N-two-2-ethylhexyl) etc.
The total content of radical polymerization inhibitor, benzotriazole and carboxyl benzotriazole class is preferably 0.01 quality %～3 quality % with respect to whole photosensitive polymer combination, more preferably 0.05 quality %～1 quality %.Consider that with the viewpoint of storage stability this content is preferably more than the 0.01 quality % from giving photosensitive polymer combination, from keeping light sensitivity, suppressing dye decolored viewpoint consideration, be preferably below the 3 quality %.
＜plastifier 〉
Photosensitive polymer combination can also contain plastifier as required.As this plastifier, for example, can list phthalic acid ester classes such as diethyl phthalate; Orthotoluene sulfonamide, para toluene sulfonamide, tributyl citrate, triethyl citrate, CitroflexA-2, acetyl group citric acid three n-propyls, acetyl group tri-n-butyl citrate, polyglycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether etc.
Solid shape branch gross mass with photosensitive polymer combination is 100 quality % timing, and the content of the plastifier in the photosensitive polymer combination is preferably 1 quality %～50 quality %, more preferably 1～30 quality %.Postpone, give the viewpoint consideration of cured film with flexibility from suppressing development time, this content is preferably more than the 1 quality %, considers from suppressing curing viewpoint insufficient or cold flow, is preferably below the 50 quality %.
＜solvent 〉
As the solvent that is used for the dissolving photosensitive polymer combination, can list with MEK (MEK) is the ketone of representative, is the alcohols etc. of representative with methyl alcohol, ethanol or isopropyl alcohol.This solvent preferably adds in the photosensitive polymer combination, and feasible viscosity for the solution that is applied to the photosensitive polymer combination on the support film is 500mPas～4000mPas down at 25 ℃.
＜photosensitive-resin layered product 〉
In the present embodiment, photosensitive-resin layered product comprises photo-sensitive resin and the support film that is formed by photosensitive polymer combination.In addition, photo-sensitive resin preferably is laminated on the support film.As required, on the surface of the opposite side with the support film side of photo-sensitive resin, can have protective seam.
As support film, it is desirable to, see through from the transparent support film of the light of exposure light source emission.As this support film, for example, can list ethylene glycol terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, plasticon, polyacrylonitrile film, styrol copolymer film, polyamide film, cellulose derivative film etc.These films can use the film that stretched as required, the preferred film of mist degree below 5.The thin thickness of film is being favourable aspect image formation property and the economy, but in order to keep intensity, preferably uses the film of 10 μ m～30 μ m.
The key property of the protective seam that uses in the photosensitive-resin layered product for the closing force of itself and photo-sensitive resin fully less than the closing force of support film and photo-sensitive resin, can easily peel off.For example, polyethylene film, polypropylene film etc. preferably use as protective seam.In addition, can also use the film of the fissility excellence shown in the Japanese kokai publication sho 59-202457 communique.The thickness of protective seam is preferably 10 μ m～100 μ m, more preferably 10 μ m～50 μ m.The thickness of the photo-sensitive resin in the photosensitive-resin layered product is according to purposes and difference is preferably 5 μ m～100 μ m, more preferably 7 μ m～60 μ m, and more thin image resolution ratio is more high, and more thick film intensity is more high.In addition, in the etching purposes that does not need high protuberance property, the thickness of the photo-sensitive resin in the photosensitive-resin layered product is preferably 10 μ m～20 μ m.Consider that from the viewpoint of elching resistant the thickness of photo-sensitive resin is more than the 10 μ m, consider that from the viewpoint of image resolution ratio this thickness is below the 20 μ m.
The method for making of＜photosensitive-resin layered product 〉
Method as support film, photo-sensitive resin and protective seam as required lamination are successively made photosensitive-resin layered product can adopt known method.For example, will be for the photosensitive polymer combination of photo-sensitive resin and the solvent of dissolving it, form the solution of homogeneous, at first, use rod to be coated with machine or roll coater coating in support film, then dry, thus photo-sensitive resin that can lamination is formed by photosensitive polymer combination on support film.Then, lamination protective seam on photo-sensitive resin as required, thus can make photosensitive-resin layered product.
＜have a manufacture method of the substrate of corrosion-resisting pattern 〉
Below explanation uses photosensitive-resin layered product to make an example of the method for the substrate that is formed with corrosion-resisting pattern.As required, by substrate etching or the plating that will make like this, can make circuit substrate or printed circuit board (PCB).
Use photosensitive-resin layered product to make the substrate that is formed with corrosion-resisting pattern and used the circuit substrate of this substrate or the method for printed circuit board (PCB) to comprise following operation.Wherein, operation (4) and (4 ') can be used any one in them, perhaps can utilize them the two.
(1) lamination operation
The protective seam of photosensitive-resin layered product is peeled off on the limit, and the limit uses the hot-roll lamination machine to make the operation of photosensitive-resin layered product driving fit on substrates such as copper clad laminate, flexible base, board.
(2) exposure process
Make the mask film driving fit with required wiring pattern on supporter (for example support film etc.), utilize active light source to expose, perhaps the operation of implementing to expose by the required wiring pattern of direct drafting.
(3) developing procedure
After the exposure, the supporter on the photo-sensitive resin is peeled off, then used the developer solution of aqueous alkali, develop and remove unexposed portion, form the operation of corrosion-resisting pattern at substrate.
As aqueous alkali, for example, can use Na 2CO 3Or K 2CO 3Aqueous solution.Aqueous alkali is suitably selected according to the characteristic of photo-sensitive resin, and normally concentration is about 0.2 quality %～2 quality %, about 20 ℃～40 ℃ Na 2CO 3Aqueous solution.
Through above-mentioned each operation, can obtain corrosion-resisting pattern, according to circumstances can also further carry out about 100 ℃～300 ℃ heating process.By implementing this heating process, can further improve chemical-resistant.Heating can be used the heating furnace of hot blast, infrared ray, far infrared mode.
(4) etching work procedure
From formed corrosion-resisting pattern top spraying etching solution, the etched operation of copper face that will do not covered by corrosion-resisting pattern.
The method that etching work procedure adopts acid etching, alkali etching etc. to be suitable for used photosensitive-resin layered product is carried out.
(4 ') plating process
Adopt copper facing, plating weldering (solder plating) etc., the substrate that is formed with corrosion-resisting pattern is carried out the operation of plating.
Method as plating is handled can list with substrate and carry out electric plating method etc. as electrode.
(5) peel off
The aqueous solution of using alkalescence to be better than developer solution is peeled off corrosion-resisting pattern from substrate afterwards.The aqueous alkali of peeling off usefulness is not particularly limited the aqueous solution of NaOH, KOH etc. that the general about 2 quality % of working concentration～5 quality %, temperature are about 40 ℃～70 ℃.Stripper can also add a spot of water-soluble solvent.
As mentioned above, present embodiment relate to the photosensitive polymer combination that can develop by alkaline aqueous solution, with this photosensitive polymer combination photosensitive-resin layered product that lamination forms on supporter, use this photosensitive-resin layered product to form the method for corrosion-resisting pattern and the purposes of this corrosion-resisting pattern etc. at substrate.These photosensitive polymer combinations etc. can provide the corrosion-resisting pattern that is suitable for following manufacturing: the manufacturing of printed circuit board (PCB), the manufacturing of flexible printed circuit board, the IC chip is installed the manufacturing with lead frame (hereinafter referred to as lead frame), metal forming Precision Machining such as metal mask manufacturing, the BGA(ball grid array) or the CSP(chip size packages) etc. the semiconductor packages manufacturing, with TAB(Tape Automated Bonding, the automatic combination of winding) or COF(Chip On Film: the fine wiring plate at the film shape is installed semiconducter IC) be the manufacturing of the winding substrate of representative (tape substrate), the manufacturing of semiconductor projection, ITO electrode in the field of flat panel displays, addressing electrode, the manufacturing of parts such as electromagnetic wave shield.
Embodiment
By the following examples 1～14 and comparative example 1 and 2 further specifically describe.
At first, the method for making of the evaluation usefulness sample of embodiment and comparative example is described, then shows evaluation method and the evaluation result thereof of gained sample.
(1) estimates the method for making of using sample
The evaluation of embodiment and the comparative example following making of sample.
The making of＜photonasty lamination body 〉
Photosensitive polymer combination and the solvent of the composition shown in the following table 1 (wherein the numeral of each composition is in the use level (mass parts) of solid shape branch) are fully stirred, mix, form the photosensitive polymer combination blending liquid, using rod to be coated with machine is coated on equably as the thick pet film of 16 μ m of supporter (Mitsubishi Polyester Film GmbH system, R130-16) surface, drying is 1.5 minutes in 95 ℃ dryer, forms the photoresist combination layer.The thickness of photoresist combination layer is 15 μ m.
Then, on the surface that does not have the lamination pet film of photoresist combination layer, fitting, (TAMAPOLY CO., LTD. system GF-818), obtain photosensitive-resin layered product as the thick polyethylene film of 19 μ m of protective seam.The title of the material composition in the photosensitive polymer combination blending liquid of representing with shorthand notation in the table 1 has been shown in the following table 2.
＜substrate leveling 〉
As the evaluation substrate of development, elching resistant, the thick copper clad laminate of 1.6mm of 35 μ m rolled copper foils that used lamination.Substrate surface is carried out the wet type polishing roll grind (3M corporate system, Scotch Brite(registered trademark) HD#600, by 2 times).
＜lamination 〉
The polyethylene film of photosensitive-resin layered product is peeled off on the limit, and the hot-roll lamination machine is used on the limit, and (Asahi Chemical Industry's (strain) system AL-700) is pressed onto on the copper clad laminate that flattens and be preheated to 60 ℃ in 105 ℃ of lower floors of roll temperature.Air pressure is set at 0.35MPa, and laminate speed is set at 2.0m/ minute.
＜exposure 〉
The necessary mask film of the evaluation of photoresist combination layer is placed on the pet film as supporter, in embodiment 1～6, embodiment 9～14 and comparative example 1 and 2, use ultrahigh pressure mercury lamp (ORC MANUFACTURING CO., LTD. make, HMW-801) with 70mJ/cm 2Exposure expose.In embodiment 7 and 8, use direct drafting formula exposure device (Hitachi Via Mechanics, the Ltd. system, DI exposure machine DE-1DH, light source: GaN royal purple diode, predominant wavelength 405 ± 5nm) is with 15mJ/cm 2Exposure expose.
Assess sample for the cured film flexibility, the pet film as supporter at the photosensitive-resin layered product of making is as mentioned above placed the necessary mask film of evaluation, in embodiment 1～6, embodiment 9～14 and comparative example 1 and 2, use ultrahigh pressure mercury lamp (ORC MANUFACTURING CO., LTD. make, HMW-801) with 70mJ/cm 2Exposure expose.In embodiment 7 and 8, use direct drafting formula exposure device (Hitachi Via Mechanics, the Ltd. system, DI exposure machine DE-1DH, light source: GaN royal purple diode, predominant wavelength 405 ± 5nm) is with 15mJ/cm 2Exposure expose.
＜develop
About the evaluation substrate of development and elching resistant, after pet film peeled off, use alkali developing machine (FUJI KIKO., Co.Ltd. system, dry film developing machine), 30 ℃ the 1 quality %Na of the stipulated time of spraying 2CO 3Aqueous solution, the unexposed portion of photo-sensitive resin is removed in dissolving.At this moment, develop making curing corrosion-resisting pattern with 2 times time of minimum development time.Wherein, minimum development time refers to the required shortest time of photo-sensitive resin for the dissolving unexposed portion as mentioned above.
About the assess sample of cured film flexibility, after polyethylene film peeled off, with developing under 2 times of times of minimum development time, the same terms, obtain to solidify resist layer.
＜etching 〉
On the evaluation substrate that has formed corrosion-resisting pattern by development, use mantoquita Etaching device (Tokyo chemical industry machine (strain) system, the mantoquita Etaching device), 50 ℃ of cupric chloride etching solutions of spraying stipulated time cupric chloride concentration 250g/L, concentration of hydrochloric acid 3mol/L, dissolving are removed the Copper Foil of the part that is not covered by corrosion-resisting pattern on the copper clad laminate.
＜peel off
On the evaluation substrate after the etching, spraying is heated to 50 ℃ 3 quality % sodium hydrate aqueous solutions, and the resist layer that solidifies is peeled off.
(2) evaluation method of sample
Then, the evaluation method of interpret sample.
(i) development
Estimate the method for making of using sample according to above-mentioned (1), make substrate, lamination develops, and obtains corrosion-resisting pattern.According to minimum development time, classification as described below:
A: minimum development time is more than 14 seconds.
B: minimum development time is more than 10 seconds and less than 14 seconds.
C: minimum development time was less than 10 seconds.
(ii) elching resistant
Estimate method for making with sample according to above-mentioned (1), the width by exposed portion and unexposed portion is than being the line style pattern mask of 1:1, with behind the lamination through 15 minutes elching resistant evaluation base plate exposure.Further, develop by 2 times of times of minimum development time, will remove the required time of Copper Foil by etching and be made as minimum etching period, carry out etching with 1.4 times of times of minimum etching period.Peel off the curing resist layer with sodium hydrate aqueous solution, use the observation by light microscope conductive pattern, according to relevant observations, as described belowly carry out classification:
A: conductive pattern forms linearity, does not see the infiltration of etching solution.
B: conductive pattern forms linearity, but has seen the infiltration of etching solution.
C: conductive pattern does not form linearity, has seen concavo-convex.
The (iii) flexibility of cured film
Estimate method for making with sample according to above-mentioned (1), the rectangular mask by 5mm * 40mm is with the photosensitive-resin layered product exposure of made.Further, develop acquisition curing resist layer with 2 times of times of minimum development time.With cupping machine (ORIENTEC Co., LTD. system RTM-500) stretch with 100mm/ minute the speed curing resist layer with the 5mm * 40mm of made, according to the elongation of the curing resist layer of this moment, as described belowly carry out classification:
A +: the elongation of solidifying resist layer is more than the 45mm.
A: the elongation of solidifying resist layer is more than the 40mm and less than 45mm.
B: the elongation of solidifying resist layer is more than the 15mm and less than 40mm.
C: solidify the elongation of resist layer less than 15mm.
(iv) aggregation
Make thickness 15 μ m, area 2.0m in the photosensitive-resin layered product 2Photographic layer be dissolved in the 1 quality %Na of 200ml 2CO 3In the aqueous solution, use circulating spraying plant, under atomisation pressure 0.1MPa, sprayed continuously 3 hours.After this, developer solution was left standstill 1 hour, observe the generation of aggregation.When producing a large amount of aggregation, on the bottom surface and side of spraying plant, observe the aggregation of powdery or the aggregation of oily.The combination that the developer solution aggregation is good does not produce these aggregations fully.According to the generation state of aggregation, as described below aggregation is carried out classification:
A: do not produce aggregation fully.
B: seen aggregation in the bottom of spraying plant or the part of side.
C: in whole spraying plant, seen aggregation.
(the v) high molecular acid equivalent of alkali solubility
Acid equivalent refers to wherein to have the high molecular quality of alkali solubility of the carboxyl of 1 equivalent.The mensuration of acid equivalent is used flat natural pond industry (strain) system flat natural pond automatic titration device (COM-555), adopt 0.1mol/L NaOH, undertaken by potential difference titration.
(vi) weight-average molecular weight
Weight-average molecular weight is used Japanese light splitting (strain) gel permeation chromatograph processed (GPC) (pump: Gulliver, PU-1580 type; Post: clear and electrician's (strain) Shodex(registered trademark processed) (KF-807, KF-806M, KF-806M, KF-802.5) 4 series connection; Fluidized bed solvent: tetrahydrofuran; The calibration curve that uses polystyrene standard sample (clear and electrician's (strain) Shodex STANDARD processed SM-105) to obtain), obtain according to polystyrene conversion.
(3) evaluation result
The evaluation result of embodiment and comparative example has been shown in the table 1.
[table 1]
Figure BDA00003398455400291
[table 2]
Utilizability on the industry
Above-mentioned photosensitive polymer combination and layered product can be suitable for metal forming Precision Machining such as the manufacturing of printed circuit board (PCB), flexible printed circuit board, lead frame or metal mask manufacturing, the manufacturing of semiconductor packages such as BGA or CSP, the manufacturing of winding such as TAB or COF substrate, the manufacturing of semiconductor projection, the manufacturing of ITO electrode or addressing electrode, electromagnetic wave shield etc.

Claims (13)

1. photosensitive polymer combination, it is the photosensitive polymer combination that contains (A) alkali solubility macromolecule, (B) Photoepolymerizationinitiater initiater and (C) have the compound of ethylenical unsaturated double bonds, should (B) Photoepolymerizationinitiater initiater be 2,4,5-triarylimidazoles dimer or acridine compound, and the compound that should (C) has an ethylenical unsaturated double bonds comprises the compound shown in the following general formula (I):
Figure FDA00003398455300011
In the formula (I), R 1And R 2Represent hydrogen atom or methyl independently of one another, A is C 2H 4Or C 3H 6,-(A-O) N1-and-(A-O) N3-in ,-C 2H 4-O-and-C 3H 6The arrangement of the repetitive of-O-is optional to be random or block, and this is arranged as under the situation of block ,-C 2H 4-O-and-C 3H 6Any one of-O-is in-B-O-group side, and B is the divalent alkyl chain of carbon number 4～8, n 1Be 0～10 integer, n 3Be 0～10 integer, n 1+ n 3Be 0～10 integer, and n 2It is 1～20 integer.
2. photosensitive polymer combination according to claim 1, wherein, the compound that described (C) has ethylenical unsaturated double bonds also comprises the compound shown in the following general formula (II):
Figure FDA00003398455300012
In the formula (II), R 3And R 4Be hydrogen atom or methyl independently of one another, n 4And n 7Be 0～20 integer independently of one another, n 4+ n 7Be 0～40 integer, n 5And n 6Be 1～20 integer independently of one another, n 5+ n 6Be 2～40 integer, and-(C 2H 4-O)-and-(C 3H 6-O)-the arrangement of repetitive optional be random or block, this is arranged as under the situation of block ,-(C 2H 4-O)-and-(C 3H 6-O)-any one in the bisphenol group side.
3. photosensitive polymer combination according to claim 2, wherein, in described general formula (II), n 4And n 7Be 1～20 integer independently of one another, and n 4+ n 7It is 2～40 integer.
4. according to each described photosensitive polymer combination of claim 1～3, wherein, described (A) alkali solubility macromolecule is selected from and contains styrene and/or (methyl) benzyl acrylate as the alkali solubility macromolecule of multipolymer composition.
5. according to each described photosensitive polymer combination of claim 1～4, wherein, in described general formula (I), n 2Be 1～10 integer, and n 1+ n 3Be 0.
6. according to each described photosensitive polymer combination of claim 1～5, wherein, the compound that described (C) has ethylenical unsaturated double bonds also is included in the compound that has at least one amino-formate bond in the molecule.
7. according to each described photosensitive polymer combination of claim 1～6, wherein, the compound that has ethylenical unsaturated double bonds as described (C) also comprises the compound shown in the following general formula (III):
Figure FDA00003398455300021
In the formula (III), R 5And R 6Be hydrogen atom or methyl independently of one another, n 8And n 9Be 3～40 integer independently of one another, and-(C 2H 4-O)-and-(C 3H 6-O)-the arrangement of repetitive optional be random or block.
8. according to each described photosensitive polymer combination of claim 1～7, wherein, the compound that described (C) has an ethylenical unsaturated double bonds also comprise following general formula (IV) and/or (V) shown in compound:
Figure FDA00003398455300022
In the formula (IV), R 5And R 6Be hydrogen atom or methyl independently of one another, n 10～n 12Be 1～30 integer independently of one another;
In the formula (V), R 5And R 6Be hydrogen atom or methyl independently of one another, n 10～n 12Be 1～30 integer independently of one another.
9. according to each described photosensitive polymer combination of claim 1～8, wherein, the compound that described (C) has ethylenical unsaturated double bonds also comprises the compound that has the isocyanuric acid ester group in the molecule.
10. according to each described photosensitive polymer combination of claim 1～9, wherein, be 100 quality % in the solid shape branch gross mass of photosensitive polymer combination, the high molecular use level of described (A) alkali solubility is 40 quality %～80 quality %,
Solid shape branch gross mass in photosensitive polymer combination is 100 quality %, and the use level of described (B) Photoepolymerizationinitiater initiater is 0.1 quality %～20 quality %,
Solid shape branch gross mass in photosensitive polymer combination is 100 quality %, and the use level that described (C) has the compound of ethylenical unsaturated double bonds is 5 quality %～50 quality %.
11. a photosensitive-resin layered product, it is pressed with the photo-sensitive resin that each the described photosensitive polymer combination by claim 1～10 forms on the support film upper strata.
12. a manufacture method that is formed with the substrate of corrosion-resisting pattern, it comprises: the lamination operation of the described photosensitive-resin layered product of lamination claim 11 on substrate; Across the exposure process of mask with this photosensitive-resin layered product exposure; And the developing procedure of removing unexposed portion.
13. a method that forms circuit substrate, substrate by the described method manufacturing of claim 12 is carried out etching for it or plating forms circuit substrate.
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