CN109324480A - Photosensitive polymer combination, photosensitive element, the forming method of corrosion-resisting pattern, the manufacturing method of printed wiring board - Google Patents
Photosensitive polymer combination, photosensitive element, the forming method of corrosion-resisting pattern, the manufacturing method of printed wiring board Download PDFInfo
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- CN109324480A CN109324480A CN201811138918.7A CN201811138918A CN109324480A CN 109324480 A CN109324480 A CN 109324480A CN 201811138918 A CN201811138918 A CN 201811138918A CN 109324480 A CN109324480 A CN 109324480A
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- polymer combination
- photosensitive polymer
- methyl
- mass
- photosensitive
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- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002433 hydrophilic molecules Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- HJYKVGWOAOLIKY-UHFFFAOYSA-N methyl 2-methylidenenonanoate Chemical compound CCCCCCCC(=C)C(=O)OC HJYKVGWOAOLIKY-UHFFFAOYSA-N 0.000 description 1
- 229940086559 methyl benzoin Drugs 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 208000007578 phototoxic dermatitis Diseases 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
-
- 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
- G03F7/002—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor using materials containing microcapsules; Preparing or processing such materials, e.g. by pressure; Devices or apparatus specially designed therefor
- G03F7/0022—Devices or apparatus
- G03F7/003—Devices or apparatus characterised by storage means for the light sensitive material, e.g. cartridges
-
- 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
- G03F7/0035—Multiple processes, e.g. applying a further resist layer on an already in a previously step, processed pattern or textured surface
-
- 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
- G03F7/016—Diazonium salts or compounds
- G03F7/021—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders
- G03F7/0212—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders characterised by the polymeric binder or the macromolecular additives other than the diazo resins or the polymeric diazonium 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
- G03F7/0275—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with dithiol or polysulfide compounds
-
- 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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
- H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
- H05K3/184—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method using masks
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- Materials For Photolithography (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The present invention provides a kind of photosensitive polymer combination, photosensitive element, the forming method of corrosion-resisting pattern and the manufacturing method of printed wiring board, the photosensitive polymer combination contains (A) binder polymer, (B) photopolymerizable compound and (C) Photoepolymerizationinitiater initiater with ethylenic unsaturated bond, (A) (a1) that ingredient contains 50~80 mass % comes from the structural unit of (methyl) benzyl acrylate derivative, the structural unit of (a2) from styrene derivative of 5~40 mass %, (a3) of 1~20 mass % comes from the structural unit of (methyl) alkyl acrylate, and 5~30 mass % (a4) come from (methyl) acrylic acid structural unit.
Description
The application be the applying date be on May 9th, 2012, China application No. is 201210141658.5 patent application point
Case application.
Technical field
The present invention relates to photosensitive polymer combination and the photosensitive element, against corrosion of the photosensitive polymer combination is used
The forming method of pattern and the manufacturing method of printed wiring board.
Background technique
In recent years, it along with light and shortization of semiconductor element, the continuous development of a small amount of multi items, is used for IC core
Piece is equipped on the semiconductor packages such as the BGA (Ball Grid Array, ball array encapsulation) on substrate also continuous more pins, narrow
Smallization also requires densification to the printed wiring board for carrying them.
In the past, in the manufacturing field of printed wiring board, as anticorrosive additive material used in etching or plating etc., always
It is being widely used by support membrane, the photosensitive polymer combination being made of photosensitive polymer combination being laminated on the support membrane
Layer and the photosensitive element for being constituted the protective film that the photosensitive polymer combination layer covers.
Printed wiring board is manufactured by using photosensitive element and using method as shown below.Firstly, on one side will sense
The protection film stripping of photosensitiveness element, on one side by photosensitive polymer combination layer stackup (laminate) on substrate.Then, to sense
The prescribed portion irradiation active ray of photosensitive resin composition layer is so that exposed portion solidifies.It, will not after removing removes support membrane
Exposed portion removes (development) from substrate, thus formed on substrate be made of the solidfied material of photosensitive polymer combination it is anti-
Corrosion figure case.To the substrate for being formed with corrosion-resisting pattern, implement etching process or plating and after forming circuit on substrate, finally
Resist is removed and is removed, thus manufactures printed wiring board.
Especially in the manufacture of semiconductor packages mounted board, plating, against corrosion is carried out after forming corrosion-resisting pattern
Agent removing, soft etching half addition processing procedure (SAP) have become mainstream.
For photosensitive polymer combination used in above-mentioned half addition processing procedure (SAP), it is desirable that can be formed and previous sense
Photosensitive resin composition compares finer wiring.
Currently, largely having proposed the photosensitive resin composition that can form fine wiring (resolution and excellent adhesion)
Object (referring for example to Patent Documents 1 to 3).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2005-301101 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2006-234995 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2006-154740 bulletin
Summary of the invention
But even with photosensitive polymer combination described in above patent document 1 or 2, for institute in recent years
It is required that resolution, there is also rooms for improvement.In addition, distinguishing by the research of the inventors of the present invention: if using above-mentioned
Photosensitive polymer combination described in patent document 3, then in the plating process when forming corrosion-resisting pattern, resist is in end
The patience (hereinafter referred to as " resistance to plating ") of plating solution is reduced, coating infiltration (Japanese original text are as follows: め っ I も ぐ り) is generated,
There are rooms for improvement on this aspect.
As the method for improving resistance to plating, generally there is the method for adding hydrophobic compound in the resist, improves glass
The method of glass transition temperature.But the inventors of the present invention have found: having the following problems in these methods: because hydrophobicity improves
And generate development dross；Or the removing residue of attachment resist, or lead to resist because of the raising of glass transition temperature
Flexibility decline, coating infiltration are not improved.
In addition, the inventors of the present invention, which have also been attempted by adding hydrophilic compounds in the resist, improves resist softness
Property method, but there is the decline of the adaptation of resist and resistance to plating, it is difficult to which manufacture can form fine required by SAP
Wiring and the excellent photosensitive polymer combination of resistance to plating.
The present invention completes in view of the above problems, and its purpose is to provide resolution (also referred to as clarity) and adaptations
The good photosensitive polymer combination of excellent and resistance to plating and the photonasty member for having used the photosensitive polymer combination
The manufacturing method of part, the manufacturing method of corrosion-resisting pattern and printed wiring board.
The 1st aspect of the present invention is a kind of photosensitive polymer combination, contains (A) binder polymer, (B) has
The photopolymerizable compound of ethylenic unsaturated bond and (C) Photoepolymerizationinitiater initiater, (a1) that (A) ingredient contains 50~80 mass % come
From the structure of (a2) from styrene derivative of the structural unit of (methyl) benzyl acrylate derivative, 5~40 mass %
(a3) (a4) from the structural unit of (methyl) alkyl acrylate and 5~30 mass % of unit, 1~20 mass %
Structural unit from (methyl) acrylic acid.
According to above-mentioned photosensitive polymer combination, resolution and excellent adhesion, and resistance to plating is good.The inventors of the present invention
Speculate, this is because: containing the specific copolymer composition of specific quantity by binder polymer, provides hydrophily and hydrophobicity
The excellent resist of balance.
The 2nd aspect of the present invention is a kind of photosensitive element, have support membrane and be formed on the support membrane by
The photosensitive polymer combination layer that above-mentioned photosensitive polymer combination is constituted.
The third mode of the invention is a kind of forming method of corrosion-resisting pattern, it includes: stacking is by above-mentioned on substrate
The lamination process for the photosensitive polymer combination layer that photosensitive polymer combination is constituted；On above-mentioned photosensitive polymer combination layer
Form the exposure process in photocuring portion；It is removed with by the above-mentioned photosensitive polymer combination layer other than above-mentioned photocuring portion
The developing procedure gone.Which is also possible to that the mode of photo-sensitive resin is laminated using photosensitive element.
4th kind of mode of the invention is a kind of manufacturing method of printed wiring board, to the shape by above-mentioned corrosion-resisting pattern
It is formed with the substrate of corrosion-resisting pattern at method, implements etching process or plating.
According to the present invention it is possible to provide resolution and excellent adhesion and excellent the resistance to plating on thin plate substrate
Photosensitive polymer combination and used the manufacturer of the photosensitive element of the photosensitive polymer combination, corrosion-resisting pattern
The manufacturing method of method and printed wiring board.
Detailed description of the invention
Fig. 1 is the schematic section for indicating an embodiment of photosensitive element of the invention.
Symbol description
1: photosensitive element, 10: support membrane, 20: photosensitive polymer combination layer
Specific embodiment
Hereinafter, being illustrated to an embodiment of the invention, however, the present invention is not limited thereto.In addition, in the present invention
(methyl) acrylic acid refers to acrylic acid and methacrylic acid, and (methyl) acrylate refers to acrylate and corresponding thereto
Methacrylate, (methyl) acryloyl group refer to acryloyl group and methylacryloyl.
(photosensitive polymer combination)
The photosensitive polymer combination of present embodiment contain (A) binder polymer (below also referred to as " (A) ingredient "),
(B) photopolymerizable compound (below also referred to as " (B) ingredient ") with ethylenic unsaturated bond and (C) Photoepolymerizationinitiater initiater (with
Down also referred to as " (C) ingredient ").In the following, (A)~(C) ingredient is described in detail.
Firstly, being illustrated to (A) binder polymer.Above-mentioned (A) binder polymer is used as in aftermentioned photonasty
The substrate of film shape is assigned on element and is played a role.
Above-mentioned (A) binder polymer contain (a1) from (methyl) benzyl acrylate derivative structural unit,
(a2) structural unit and (a4) from (methyl) alkyl acrylate of the structural unit from styrene derivative, (a3) come
From the structural unit of (methyl) acrylic acid.Binder polymer containing these structural units by make containing with each structural unit
Corresponding monomer, i.e. (methyl) benzyl acrylate derivative, styrene derivative, (methyl) alkyl acrylate and
The monomer composition of (methyl) acrylic acid is copolymerized to obtain.It, can be as so-called random in the obtained copolymer
Copolymer irregularly contains each structural unit in the copolymer like that, and one can also be locally present as block copolymer
Divide specific structural unit.Moreover, above structure unit can be respectively independent one kind be also possible to it is a variety of.
For (A) binder polymer by (a1) containing specific quantity from (methyl) benzyl acrylate derivative
Structural unit can not only maintain the flexibility of resin, and excellent adhesion.As (methyl) benzyl acrylate derivative
Specific example, such as (methyl) benzyl acrylate, (methyl) acrylic acid 4- methylbenzyl ester, (methyl) propylene can be enumerated
Sour 4- benzyl ethyl base ester, (methyl) acrylic acid 4- t-butylbenzyl, (methyl) acrylic acid 4- methoxybenzyl base ester, (methyl) third
Olefin(e) acid 4- ethoxy benzylidene base ester, (methyl) acrylic acid 4- hydroxybenzyl ester, (methyl) acrylic acid 4- benzyl chloride base ester.
(A) binder polymer passes through the structural unit of (a2) from styrene derivative containing specific quantity, thin thread part
Adaptation, resolution it is excellent.As the specific example of styrene derivative, such as styrene, vinyl first can be enumerated
Benzene, p-methylstyrene, p-chlorostyrene.
(A) binder polymer comes from the structural unit of (methyl) alkyl acrylate by (a3) containing specific quantity,
The flexibility and obdurability of binder polymer can excellently be taken into account.
As the alkyl in (methyl) alkyl acrylate, the preferably carbon atom number of straight-chain or branched is 1~12
Alkyl, further preferably the carbon atom number of straight-chain or branched be 1~8 alkyl, the carbon of more preferably straight-chain is former
The alkyl that subnumber is 1~4, particularly preferably methyl.
As the specific example of above-mentioned (methyl) alkyl acrylate, for example, can enumerate (methyl) methyl acrylate,
(methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl)
Tert-butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) acrylic acid
Monooctyl ester, (methyl) 2-EHA.
(A) binder polymer comes from the structural unit of (methyl) acrylic acid, alkali development by (a4) containing specific quantity
Property is excellent.
In addition, (A) binder polymer can also contain the structural unit other than above-mentioned (a1)~(a4).
(a1) of 50~80 mass % is contained from (methyl) benzyl acrylate derivative for (A) binder polymer
Structural unit preferably comprise 50~75 matter from the viewpoint of the flexibility for maintaining resin and keeping adaptation more excellent
Measure %, further preferably 50~70 mass %, further preferably 50~65 mass %.
The structural unit of (a2) from styrene derivative for containing 5~40 mass % for (A) binder polymer, from
From the perspective of adaptation and resolution are more excellent, 5~35 mass % are preferably comprised.In addition, also containing 1~20 mass %'s
(a3) structural unit of (methyl) alkyl acrylate is come from, but is assigned by hydrophily and is dredged for resist better from harmonious
From the perspective of aqueous, 1~15 mass %, further preferably 1~10 mass %, further preferably 1~5 matter are preferably comprised
Measure %.In addition, (a4) also containing 5~30 mass % comes from the structural unit of (methyl) acrylic acid, but more excellent from alkali-developable
From the perspective of different, 5~25 mass %, further preferably 10~25 mass % are preferably comprised.
In addition, the weight average molecular weight (Mw) of (A) binder polymer is preferably 20000~150000, further preferably
30000~100000, more preferably 40000~80000, particularly preferably 40000~60000.It is reliable from covering (tenting)
From the perspective of property is more excellent, Mw is preferably 20000 or more, and further preferably 30000 or more, more preferably 40000 or more.
On the other hand, from the viewpoint of developability and clarity are more excellent, preferably 150000 hereinafter, further preferably 100000
Hereinafter, more preferably 80000 hereinafter, particularly preferably 60000 or less.In addition, in the present invention, Mw refers to by gel infiltration color
The weight average molecular weight for the standard polystyren conversion that spectrometry (GPC) measures.
In addition, the acid value (mgKOH/g) of (A) binder polymer is preferably 13~78, further preferably 39~65, more
Preferably 52~62.In addition, in the present specification, acid value refers to the potassium hydroxide relative to the 1g binder polymer in solution
Mg number, measuring method is identical as method documented in embodiment.
In addition, the photosensitive polymer combination of present embodiment is in addition to above-mentioned above-mentioned (a1)~(a4's) containing specified amount
Outside binder polymer, known binder polymer can also be used together.
There is the photopolymerizable compound of ethylenic unsaturated bond for (B), as long as can be carried out photo-crosslinking, so that it may without spy
It Xian Ding not ground use.It is sub as its concrete example, bisphenol-A system (methyl) acrylate compounds, hydrogenated bisphenol A system can be enumerated
(methyl) acrylate compounds, polyalkylene glycol (methyl) acrylate, carbamate monomer, pentaerythrite (methyl)
Acrylate, trimethylolpropane (methyl) acrylate.These can be used alone or combine two or more use.
Among above-mentioned, from the viewpoint of improving resolution and resistance to plating, bisphenol-A system two (methyl) propylene is preferably comprised
Ester compound.As bisphenol-A system two (methyl) acrylate compounds, such as the following general formula (1) expression can be enumerated
Compound.
In above-mentioned formula (1), R separately indicates hydrogen atom or methyl.EO, PO respectively indicate oxyethylene group, oxypropylene
Base.m1、m2、n1、n2Respectively indicate 0~40, m1+m2(average value) is 1~40, n1+n2It is 0~20.In addition, which in EO, PO
It is a to be located at phenolic hydroxyl group side.m1、m2、n1And n2Indicate the quantity of structural unit.Therefore, integer is indicated in single molecule
Value indicates the rational in terms of average value in the aggregate of different kinds of molecules.Hereinafter, the quantity of structural unit also with above-mentioned phase
Together.
From the viewpoint of resistance to plating is more excellent, preferably by (1-1) m in the compound of above-mentioned general formula (1) expression1+m2
(average value) is 5 compounds below and (1-2) m1+m2The compound combination that (average value) is 6~40 uses.
As (1-1) m1+m2(average value) is 5 compounds below, and m can be used for example1+m2(average value) be 4 it is new
The BPE-200 of middle village's Chemical Co., Ltd., as (1-2) m1+m2The compound that (average value) is 6~40, can be used for example
m1+m2The BPE-500 for the village the Xin Zhong Chemical Co., Ltd. that (average value) is 10.
In addition, (B) has the photopolymerizable compound of ethylenic unsaturated bond preferred: in addition to containing bisphenol-A system two (methyl)
Other than acrylate compounds, also contain the compound that following formula (2) indicate.
In above-mentioned formula (2), R14And R15Separately indicate that hydrogen atom or methyl, EO and PO are identical as above-mentioned meaning,
s1Indicate 1~30, r1And r2Respectively indicate 0~30, r1+r2(average value) is 1~30.
As the specific example for the compound that formula (2) indicate, R can be enumerated14And R15For methyl, r1+r2=4 is (average
Value), s1The vinyl compound (Hitachi's chemical conversion industry corporation, trade name FA-023M) of=12 (average values).
(C) Photoepolymerizationinitiater initiater can use without particular limitation, sub as its concrete example, can enumerate hexichol first
Ketone, N, N '-tetramethyl -4,4 '-diaminobenzophenone (michaelis ketone), N, N '-tetraethyl -4,4 '-diaminobenzophenone, 4-
Methoxyl group -4 '-dimethylamino benzophenone, 2- benzyl -2- dimethylamino -1- (4- morpholino phenyl)-butanone -1,2- first
The equal aromatic ketones of base -1- [4- (methylsulfany) phenyl] -2- morpholinyl-acetone -1；2- ethyl hydrazine, phenanthrenequione, 2- tert-butyl anthracene
Quinone, prestox anthraquinone, 1,2 benzae thracene quinone, 2,3- benzo anthraquinone, 2- phenyl anthraquinone, 2,3- diphenyl anthraquinone, 1- chloroanthraquinone, 2-
The quinones such as tectoquinone, 1,4- naphthoquinones, 9,10- phenanthrenequione, 2- methyl-1,4-naphthaquinone, 2,3- dimethyl anthraquinone；Benzoin methyl
The benzoin ethers compounds such as ether, benzoin ethyl ether, benzoin phenyl ether；The benzene such as benzoin, methylbenzoin, ethyl benzoin
Acyloin com；The benzyl derivatives such as benzil dimethyl ketal；2- (Chloro-O-Phenyl) -4,5- diphenyl-imidazole dimer, 2-
(Chloro-O-Phenyl) -4,5- two (methoxyphenyl) imidazole dimer, 2- (o-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；The acridine derivatives such as 9- phenylacridine, 1,7- bis- (9,9 '-acridinyl) heptane；N- phenyl is sweet
Propylhomoserin, N-phenylglycine derivative, coumarin series compounds.They can be used alone or combine two or more use.
Among above-mentioned, from the viewpoint of adaptation and sensitivity, 2,4,5- triarylimidazoles dimers are preferably comprised, into one
Step preferably comprises 2- (Chloro-O-Phenyl) -4,5- diphenyl-imidazole dimer.
For the content of (A) binder polymer in photosensitive polymer combination, relative to (A) ingredient and (B) ingredient
100 mass parts of total amount, preferably 40~80 mass parts, further preferably 45~75 mass parts, more preferably 50~70 matter
Measure part.More than painting film property superior viewpoint when being used as photosensitive element, preferably 40 mass parts, further preferably
More than 45 mass parts, more than more preferably 50 mass parts.In addition, from the viewpoint of photo sensitivity is more excellent, preferably 80 mass
Part hereinafter, further preferably 75 below the mass, more preferably 70 below the mass.
It is excellent from photo sensitivity and internal curing for the content of (C) Photoepolymerizationinitiater initiater in photosensitive polymer combination
From the perspective of different, relative to 100 mass parts of total amount of (A) ingredient and (B) ingredient, preferably 0.01~5 mass parts, further
Preferably 0.1~4.5 mass parts, more preferably 1~4 mass parts.
In photosensitive polymer combination, can also add in the molecule there is at least one to be able to carry out sun as needed
Photopolymerizable compound, cationic polymerization initiators, sensitizer, the malachite green and other dyes, three of the cyclic ether group of ionic polymerization
Plasticizer, pigment, the fillings such as the light such as 2-bromomethylphenyl sulfone, colorless crystal violet color developing agent, heat colour developing preventing agent, para toluene sulfonamide
Agent, defoaming agent, fire retardant, stabilizer, adaptation imparting agent, levelling agent, removing promotor, antioxidant, fragrance, developer,
The additives such as thermal cross-linking agent.Content when these additives are added in photosensitive polymer combination is, relative to (A) ingredient
100 mass parts of total amount of (B) ingredient, can be respectively 0.01~20 mass parts or so.They can be used alone or group
Close two or more use.
For the total content of (A), (B) and (C) ingredient in photosensitive polymer combination, relative to photosensitive resin composition
The solid component total amount of object, preferably 90 mass % or more, further preferably 95 mass % or more.
For photosensitive polymer combination, it can be dissolved in the molten fibre of methanol, ethyl alcohol, acetone, methyl ethyl ketone, methyl as needed
The organic solvents such as agent, ethyl cellosolve, toluene, N,N-dimethylformamide, propylene glycol monomethyl ether or their mixed solvent
In, it is used in the form of solid component is calculated as the solution of 30~60 mass % or so.
Though photosensitive polymer combination is not particularly limited, it is preferably made liquid resist and is coated on copper, copper system conjunction
On the metal covering of gold, iron, iron-based alloy etc. and it is dry, then covering protection film comes using or with photonasty member as needed
The form of part uses.
(photosensitive element)
Hereinafter, being illustrated in conjunction with photosensitive element of the Fig. 1 to present embodiment.The photosensitive element 1 of present embodiment
The photosensitive polymer combination layer 20 for having support membrane 10 and being made of above-mentioned photosensitive polymer combination.Photosensitive resin composition
Nitride layer 20 is located on the 1st interarea 12 of support membrane 10.In addition, support membrane 10 has the 2nd interarea with the opposite side of the 1st interarea 12
14.In addition, protective film can also be equipped on the surface with 10 opposite side of support membrane of photosensitive polymer combination layer 20.Separately
Outside, above-mentioned photosensitive polymer combination layer is the photosensitive polymer combination that above-mentioned photosensitive polymer combination is uncured state
Layer.
The thickness of photosensitive polymer combination layer 20 is different depending on the application, it is preferably dry after with a thickness of 1~100 μm of left side
It is right.From the viewpoint of for half addition processing procedure (SAP), preferably 5~50 μm, further preferably 5~30 μm.
Support membrane 10 can be used for example by the polymerization of polyethylene terephthalate, polypropylene, polyethylene, polyester etc.
The film that object film is constituted.The thickness of these polymer films is preferably 1~100 μm.
Photosensitive polymer combination layer 20 can be by the way that above-mentioned photosensitive polymer combination to be coated on support membrane 10, simultaneously
Drying is to obtain.Above-mentioned coating can for example be applied using roller coating, comma scraper coating, intaglio plate coating, airblade coating, die coating, stick
It is carried out Deng well known method.In addition, drying can carry out 5~30 minutes or so at 70~150 DEG C.
In addition, photosensitive element 1 may be used also other than having photosensitive polymer combination layer 20, support membrane 10, protective film
To have the middle layers such as buffer layer, adhesive layer, light absorbing layer, gas-barrier layer or protective layer.
Photosensitive element 1 can for example be stored or the shape of said protection film has further been laminated with original state
State is wound in cylindric core and stores.At this point, it is preferred that being wound in such a way that support membrane 10 is located at outside.In above-mentioned roll
Photosensitive element roller end face on, from the viewpoint of protecting end face, end face spacer is preferably provided with, from the viewpoint of resistance to edge-melting
It sets out, is preferably provided with damp proof end face spacer.In addition, being preferably wrapped in the small sheet metal (black of penetrability as bundling method
Sheet, also referred to as black sheet) in and pack.
(forming method of corrosion-resisting pattern)
The method for forming corrosion-resisting pattern as above-mentioned photosensitive element 1 is used, such as the following method can be enumerated.
When there are protective film, after protective film is removed, photosensitive polymer combination layer 20 is heated to 70~130 on one side
DEG C or so, on one side with 0.1~1MPa or so (1~10kgf/cm2Left and right) pressure be crimped on substrate, thus stacking sense
Photosensitive resin composition layer.Furthermore it is also possible to be laminated under reduced pressure.The surface being stacked is usually metal covering, but without special
Limitation.
It can be by negative or positive mask pattern with image shape to the photosensitive polymer combination layer 20 for so completing stacking
Irradiate active ray.As the light source of above-mentioned active ray, can be used well known light source, for example, carbon arc lamp, mercury vapour arc lamp,
High-pressure sodium lamp, xenon lamp etc. effectively radiate the light sources such as ultraviolet light, visible light.
As exposure method, referred to as DLP (digital light processing, Digital Light Processing), LDI in recent years
(laser direct imaging, Laser Direct Imaging), the numerical data of pattern is directly painted into photoresist group
The direct description exposure method closed in nitride layer is being actually applied, but photosensitive polymer combination of the invention can be suitably used for
Directly describe exposure method.It is exposed that is, the photosensitive polymer combination of embodiments of the present invention can be suitably adapted to directly describe
Light method.That is, one of the preferred embodiment of the present invention is following photosensitive polymer combinations by directly describing
Exposure method forms the application in corrosion-resisting pattern, which contains (A) binder polymer, (B) has olefinic
The photopolymerizable compound of unsaturated bond and (C) Photoepolymerizationinitiater initiater, above-mentioned (A) ingredient contain (a1) of 50~80 mass %
The knot of (a2) from styrene derivative of structural unit, 5~40 mass % from (methyl) benzyl acrylate derivative
Structure unit, 1~20 mass % (a3) from the structural unit of (methyl) alkyl acrylate and 5~30 mass %
(a4) structural unit of (methyl) acrylic acid is come from.
There are when support membrane 10 on photosensitive polymer combination layer after exposure, after support membrane 10 is removed, Ke Yitong
It crosses wet developing, dry process development carried out using developer solutions such as alkaline aqueous solution, water system developer solution, organic solvents etc. and will not expose
Light part removes to develop, and corrosion-resisting pattern is consequently formed.
As above-mentioned alkaline aqueous solution, such as the weak solution of 0.1~5 weight % sodium carbonate, 0.1~5 weight can be enumerated
Measure weak solution, the weak solution of 0.1~5 weight % sodium hydroxide etc. of % potassium carbonate.The pH of above-mentioned alkaline aqueous solution is preferably 9~
11 range, temperature are adjusted according to the developability of photosensitive polymer combination layer.In addition, can also be in alkaline aqueous solution
It is mixed into surfactant, defoaming agent, organic solvent etc..As the mode of above-mentioned development, such as impregnation method, spray can be enumerated
Mist mode, brushing, slap etc..
As the processing after development, as needed can by carry out 60~250 DEG C or so heating or 0.2~10J/
cm2The exposure of left and right and use after further solidifying corrosion-resisting pattern.It is manufactured when using the photosensitive element of present embodiment
When printed wiring board, handled using the corrosion-resisting pattern after development as mask and by copper facing.
Then, aqueous solution more stronger than the alkalinity of the alkaline aqueous solution used in development can be used for example in corrosion-resisting pattern
It is removed.As the aqueous solution of above-mentioned strong basicity, such as the sodium hydrate aqueous solution of 1~10 weight %, 1~10 can be used
The potassium hydroxide aqueous solution etc. of weight %.As above-mentioned removing mode, such as impregnation method, spray pattern can be enumerated etc..
(manufacturing method of printed wiring board)
The manufacturing method of the printed wiring board of present embodiment is carried out by following: to the shape by above-mentioned corrosion-resisting pattern
It is formed with the substrate of corrosion-resisting pattern at method, implements etching process or plating.Wherein, the etching process or plating of substrate
Processing by using the corrosion-resisting pattern after development as mask and using well known method by the surface of substrate etch or plating come into
Row.
Photosensitive polymer combination of the invention can be in the encapsulation substrate or flexible printing line for especially requiring slimming
On the plate copper-clad laminated board of road formed circuit when it is preferable to use.
As etching solution used in etching, copper chloride solution, ferric chloride solution, alkaline etching etching solution can be used for example.
As plating, such as copper facing, plating scolding tin, nickel plating, gold-plated can be enumerated.
Be etched or plating after, corrosion-resisting pattern can for example pass through the alkalinity than the alkaline aqueous solution used in development
Stronger aqueous solution is removed.As the aqueous solution of the strong basicity, the sodium hydroxide of 1~10 mass % can be used for example
Aqueous solution, potassium hydroxide aqueous solution of 1~10 mass % etc..As removing mode, such as impregnation method can be enumerated, be sprayed
Mode etc..In addition, the printed wiring board for foring corrosion-resisting pattern can be multilayer printed circuit board, it is possible to have path is logical
Hole.
In addition, when the circuit formation to the conductor layer for having insulating layer and being formed on insulating layer has carried out plating with substrate
When, it is necessary to the conductor layer in addition to removing pattern.As the removing method, such as following methods can be enumerated: by resist pattern
The method being slightly etched after case removing；Plating scolding tin etc. is carried out in then above-mentioned plating, then by removing corrosion-resisting pattern
And sheltered wiring portion with scolding tin, then using the method for being only capable of handling conductor layer etching solution for etching.
The photosensitive polymer combination of present embodiment is as described above, is preferably suitable for the system of printed wiring board
It makes.That is, one of the preferred embodiments of the present invention is following photosensitive polymer combinations in the manufacture of printed wiring board
Using the photosensitive polymer combination contains (A) binder polymer, (B) has the optical polymerism chemical combination of ethylenic unsaturated bond
Object and (C) Photoepolymerizationinitiater initiater, above-mentioned (A) ingredient contain (a1) of 50~80 mass % from (methyl) benzyl acrylate
The structural unit of derivative, (a2) structural unit from styrene derivative of 5~40 mass %, 1~20 mass %
(a3) (a4) of the structural unit from (methyl) alkyl acrylate and 5~30 mass % are from (methyl) acrylic acid
Structural unit.
Embodiment
Hereinafter, based on embodiment, the present invention will be described in more detail, but the present invention is not by embodiment below
Any restriction.
(Examples 1 to 5 and comparative example 1~4)
(preparation of photosensitive polymer combination solution)
(A) ingredient, (B) ingredient shown in cooperation table 1, (C) ingredient, additive and solvent, obtain photoresist group
Polymer solution.In addition, the binder polymer in (A) ingredient is obtained by following methods.
[synthesis of binder polymer]
It will have been dissolved obtained from 0.6g azodiisobutyronitrile in the polymerizable monomer of (a1)~(a4) shown in table 2
Mixed liquor is used as " solution a ".
In the flask for having blender, reflux cooler, thermometer, dropping funel and nitrogen ingress pipe, methyl is added
Mixed liquor (mass ratio 3:2) 100g of cellosolve 60g and toluene 40g, adds while stirring while nitrogen is blown into flask
Heat is allowed to warm to 80 DEG C.
After above-mentioned solution a was added dropwise with 4 hours in above-mentioned mixed liquor into flask, methyl cellosolve 6g and toluene 4g are used
Mixed liquor (mass ratio 3:2) be added dropwise while washing dropping funel with 10 minutes, protected at 80 DEG C while stirring
Temperature 2 hours.Then, in the solution in flask, with 10 minutes be added dropwise methyl cellosolve 6g and toluene 4g mixed liquor (quality
After to have dissolved the obtained solution of 0.2g azodiisobutyronitrile in 3:2), with 10 minutes dropwise addition methyl cellosolve 18g and first
Solution in flask is existed while stirring and keeps the temperature 3 hours at 80 DEG C by the mixed liquor (mass ratio 3:2) of benzene 12g.Then,
The solution in flask is warming up to 90 DEG C with 30 minutes, after keeping the temperature 2 hours at 90 DEG C, cooling obtains each binder polymer
Solution.
In addition, weight average molecular weight is measured by gel permeation chromatography (GPC), and according to the correction of standard polystyren song
Line converts and exports.The condition of GPC is as follows.
GPC condition
Pump: Hitachi's L-6000 type (Hitachi Co., Ltd's system)
Chromatographic column: below 3 total
Gelpack GL-R420
Gelpack GL-R430
Gelpack GL-R440 (the above are Hitachi Chemical Co., Ltd.'s systems, trade name)
Eluent: tetrahydrofuran
Measuring temperature: 40 DEG C
Flow: 2.05mL/ minutes
Detector: Hitachi L-3300 type RI (Hitachi Co., Ltd's system)
(acid value measuring)
The solution 0.5g of synthesized binder polymer is weighed in conical flask, and mixed solvent (mass ratio: first is added
Benzene/methanol=70/30) after 30ml dissolved, add the phenolphthalein solution as indicator, with N/10 alcoholic caustic potash into
Row titration, measures acid value.
[table 1]
(unit: g)
BPE-500: there is average 10 moles of the polyoxyethylated bisphenol-A system dimethylacrylate (village Xin Zhong chemistry strain
Formula commercial firm system, trade name)
BPE-200: there is average 4 moles of the polyoxyethylated bisphenol-A system dimethylacrylate (village Xin Zhong chemistry strain formula
Commercial firm's system, trade name)
FA-023M: obtained from average 3 moles of the polyoxyethylene of both ends addition of average 12 moles of polyoxypropylene
Dimethylacrylate (Hitachi Chemical Co., Ltd.'s system, trade name)
(production of photosensitive element)
Then, obtained photosensitive polymer combination solution is uniformly coated to the poly terephthalic acid second two of 16 μ m-thicks
It is 10 minutes dry using 100 DEG C of hot wind convection type drying machines on alcohol ester film (Teijin Ltd's system, trade name " G2-16 ")
Afterwards, it is protected with the polyethylene film of 28 μ m-thicks (Tamapoly Co. Ltd. system, trade name " NF-15A "), to obtain
Photosensitive element.Film thickness after the drying of photosensitive polymer combination layer is 15 μm.
(formation of corrosion-resisting pattern)
Then, to printed wiring board copper-clad laminated board (Hitachi Chemical Co., Ltd.'s system, trade name " MCL-E679 ")
Copper surface implement roughening, alkali degreasing, acid elution, after washing, be dried using air stream, obtained substrate is heated up to
80℃.Use 100 DEG C of heating roller with 1m/ minutes speed while removing polyethylene film, by above-mentioned photoresist group
It closes nitride layer to be laminated on the copper surface, to obtain evaluation laminated body.
<evaluation of photo sensitivity>
On above-mentioned evaluation laminated body, the 21 step segmentation exposure meter (Stouffer 21 of Stouffer of minus is sticked
Step tablet), it is exposed using the exposure machine (Oak Co. Ltd. system, trade name " EXM-1201 ") with high-pressure sodium lamp
Light.Then, polyethylene terephthalate film is removed, spraying 1 weight % aqueous sodium carbonate is (spraying (aobvious at 30 DEG C
Shadow) time: 2 times of minimum developing time), remove unexposed portion.Then, the photocuring being formed on copper-clad laminated board is measured
The step number (X/21) of the stage exposure meter of film will show the light exposure (mJ/cm of ST=5/212) value as photo sensitivity.It should
Numerical value is smaller, indicates that photo sensitivity is higher.
<evaluation of adaptation>
On above-mentioned evaluation laminated body, the glass with the wiring pattern that line width is 1~30 (unit: μm) of minus is sticked
Glass photomask (phototool) carries out pattern exposure using the energy that the residual stage step number after development is ST=5/21.It connects
, polyethylene terephthalate film is removed, spraying 1 weight % aqueous sodium carbonate is (when spraying (development) at 30 DEG C
Between: 2 times of minimum developing time), remove unexposed portion.Then, it is observed using optical microscopy, evaluates adaptation.
The value of adaptation with by development treatment in the case where unstripped the smallest value in remaining line width (μm) indicate, should
Numerical value is smaller, indicates that adaptation is higher.
<evaluation of clarity>
On above-mentioned evaluation laminated body, the line width/interval width that has for sticking minus is 1/1~30/30 (unit: μm)
Wiring pattern glass system photomask, use after development residual stage step number be ST=5/21 energy carry out pattern exposure
Light.Then, polyethylene terephthalate film is removed, spraying 1 weight % aqueous sodium carbonate is (spraying (aobvious at 30 DEG C
Shadow) time: 2 times of minimum developing time), remove unexposed portion.Then, it is observed using optical microscopy, evaluation is clear
Clear degree.The smallest value table in interval width (μm) of the value of clarity to completely remove unexposed portion by development treatment
Show, the numerical value is smaller, indicates that clarity is higher.
<evaluation of resistance to plating>
By the way that photosensitive polymer combination to be pressed on to copper-clad laminated board used for flexible printed circuit board (Nikkan industry layer by layer
Co. Ltd. system, trade name " F30VC1 ") on and make evaluation laminated body on, stick minus have 1/1~30/30
The glass system photomask of the wiring pattern of (unit: μm), using the residual stage step number after development be ST=5/21 energy into
Row pattern exposure.Then, polyethylene terephthalate film is removed, the spraying 1 weight % aqueous sodium carbonate at 30 DEG C
(spraying (development) time: 2 times of minimum developing time), unexposed portion is removed, evaluation substrate is obtained.Above-mentioned evaluation is used
Substrate successively implements sour degreasing, washing, sulfuric acid dipping, using copper sulfate bath, in 1A/dm2Under conditions of carry out copper plating treatment
Until thickness of coating reaches 12 μm.After washing, drying, resist is removed, is seeped from top using optical microscopy measurement coating
Saturating width.The value of resistance to plating permeates width using coating to evaluate, and numerical value is smaller, indicates that resistance to plating is better.
<bendability>
By the way that photosensitive polymer combination to be pressed on to copper-clad laminated board used for flexible printed circuit board (Nikkan industry strain layer by layer
Formula commercial firm system, trade name " F30VC1 ") and evaluation laminated body is made, which is cut into 30mm × 150mm with laminated body and is seen
The size of side carries out blanket exposure using the energy that the residual stage step number after development is ST=5/21.Then, by poly- to benzene two
Formic acid glycol ester film stripping, spraying 1 weight % aqueous sodium carbonate (spraying (development) time: when minimum development at 30 DEG C
Between 2 times).It is straight that obtained sample Gardner formula bent spindle testing machine is measured to the maximum not being cracked on resist
Diameter.Diameter is smaller, indicates that bendability is better.
Table 3 shows: having used the bendability of the Examples 1 to 5 of photosensitive polymer combination of the invention, resistance to plating excellent
It is different, and show sufficient photo sensitivity, adaptation and clarity.
Claims (36)
1. a kind of photosensitive polymer combination contains (A) binder polymer, (B) has the photopolymerization of ethylenic unsaturated bond
Property compound and (C) Photoepolymerizationinitiater initiater,
(A) ingredient contains the structural unit of (a1) from (methyl) benzyl acrylate derivative of 50~80 mass %, 5
Structural unit of (a2) of~40 mass % from styrene derivative, 1~20 mass % (a3) come from (methyl) acrylic acid
(a4) of the structural unit of Arrcostab and 5~30 mass % come from the structural unit of (methyl) acrylic acid,
The acid value of (A) ingredient is 13~78mgKOH/g.
2. photosensitive polymer combination according to claim 1, the acid value of (A) ingredient is 39~65mgKOH/g.
3. photosensitive polymer combination according to claim 1, the acid value of (A) ingredient is 52~62mgKOH/g.
4. photosensitive polymer combination described in any one of claim 1 to 3, in (methyl) alkyl acrylate
Alkyl be straight-chain or branched carbon atom number be 1~12 alkyl.
5. photosensitive polymer combination described in any one of claim 1 to 3, in (methyl) alkyl acrylate
Alkyl be straight-chain or branched carbon atom number be 1~8 alkyl.
6. photosensitive polymer combination described in any one of claim 1 to 3, in (methyl) alkyl acrylate
Alkyl be straight-chain carbon atom number be 1~4 alkyl.
7. photosensitive polymer combination described in any one of claim 1 to 3, in (methyl) alkyl acrylate
Alkyl be methyl.
8. photosensitive polymer combination described in any one of claim 1 to 3, described adhesive polymer contains 50~
(a1) of 75 mass % comes from the structural unit of (methyl) benzyl acrylate derivative.
9. photosensitive polymer combination described in any one of claim 1 to 3, described adhesive polymer contains 50~
(a1) of 70 mass % comes from the structural unit of (methyl) benzyl acrylate derivative.
10. photosensitive polymer combination described in any one of claim 1 to 3, described adhesive polymer contains 50
(a1) of~65 mass % comes from the structural unit of (methyl) benzyl acrylate derivative.
11. photosensitive polymer combination described in any one of claim 1 to 3, described adhesive polymer contains 5~
The structural unit of (a2) from styrene derivative of 35 mass %.
12. photosensitive polymer combination described in any one of claim 1 to 3, described adhesive polymer contains 1~
(a3) of 15 mass % comes from the structural unit of (methyl) alkyl acrylate.
13. photosensitive polymer combination described in any one of claim 1 to 3, described adhesive polymer contains 1~
(a3) of 10 mass % comes from the structural unit of (methyl) alkyl acrylate.
14. photosensitive polymer combination described in any one of claim 1 to 3, described adhesive polymer contains 1~
(a3) of 5 mass % comes from the structural unit of (methyl) alkyl acrylate.
15. photosensitive polymer combination described in any one of claim 1 to 3, described adhesive polymer contains 5~
(a4) of 25 mass % comes from the structural unit of (methyl) acrylic acid.
16. photosensitive polymer combination described in any one of claim 1 to 3, described adhesive polymer contains 10
(a4) of~25 mass % comes from the structural unit of (methyl) acrylic acid.
17. photosensitive polymer combination described in any one of claim 1 to 3, the weight of (A) binder polymer
Average molecular weight is 20000~150000.
18. photosensitive polymer combination described in any one of claim 1 to 3, the weight of (A) binder polymer
Average molecular weight is 30000~100000.
19. photosensitive polymer combination described in any one of claim 1 to 3, the weight of (A) binder polymer
Average molecular weight is 40000~80000.
20. photosensitive polymer combination described in any one of claim 1 to 3, the weight of (A) binder polymer
Average molecular weight is 40000~60000.
21. photosensitive polymer combination described in any one of claim 1 to 3 has olefinic insatiable hunger as (B)
With the photopolymerizable compound of key, include bisphenol-A system two (methyl) acrylate compounds.
22. photosensitive polymer combination according to claim 21, bisphenol-A system two (methyl) acrylate compounds
It is the compound that the following general formula (1) indicates,
In general formula (1), R separately indicates hydrogen atom or methyl；EO, PO respectively indicate oxyethylene group, oxypropylene group；m1、
m2、n1、n2Respectively indicate 0~40, m1+m2Average value be 1~40, n1+n2It is 0~20；m1、m2、n1And n2Indicate structural unit
Quantity.
23. photosensitive polymer combination according to claim 22, in the compound that the general formula (1) indicates, by (1-1)
m1+m2Average value be 5 compounds below and (1-2) m1+m2Average value be 6~40 compound combination use.
24. photosensitive polymer combination described in any one of claim 1 to 3 has olefinic insatiable hunger as (B)
With the photopolymerizable compound of key, the compound further indicated containing the following general formula (2),
In general formula (2), R14And R15Separately indicate that hydrogen atom or methyl, EO and PO respectively indicate oxyethylene group, oxypropylene
Base, s1Indicate 1~30, r1And r2Respectively indicate 0~30, r1+r2Average value be 1~30.
25. photosensitive polymer combination described in any one of claim 1 to 3 causes as (C) photopolymerization
Agent contains 2,4,5- triarylimidazoles dimers.
26. photosensitive polymer combination described in any one of claim 1 to 3 causes as (C) photopolymerization
Agent contains 2- (Chloro-O-Phenyl) -4,5- diphenyl-imidazole dimer.
27. photosensitive polymer combination described in any one of claim 1 to 3, (A) binder polymer contains
Measuring relative to 100 mass parts of total amount of (A) ingredient and (B) ingredient is 40~80 mass parts.
28. photosensitive polymer combination described in any one of claim 1 to 3, (A) binder polymer contains
Measuring relative to 100 mass parts of total amount of (A) ingredient and (B) ingredient is 45~75 mass parts.
29. photosensitive polymer combination described in any one of claim 1 to 3, (A) binder polymer contains
Measuring relative to 100 mass parts of total amount of (A) ingredient and (B) ingredient is 50~70 mass parts.
30. photosensitive polymer combination described in any one of claim 1 to 3, (C) Photoepolymerizationinitiater initiater contains
Measuring relative to 100 mass parts of total amount of (A) ingredient and (B) ingredient is 0.01~5 mass parts.
31. photosensitive polymer combination described in any one of claim 1 to 3, (C) Photoepolymerizationinitiater initiater contains
Measuring relative to 100 mass parts of total amount of (A) ingredient and (B) ingredient is 0.1~4.5 mass parts.
32. photosensitive polymer combination described in any one of claim 1 to 3, (C) Photoepolymerizationinitiater initiater contains
Measuring relative to 100 mass parts of total amount of (A) ingredient and (B) ingredient is 1~4 mass parts.
33. a kind of photosensitive element, have support membrane and be formed on the support membrane by described in claim 1 photosensitive
Property resin combination constitute photosensitive polymer combination layer.
34. a kind of forming method of corrosion-resisting pattern, it includes:
The photoresist that the photosensitive polymer combination described in any one of claim of right1~32 is constituted is laminated on substrate
The lamination process of composition layer；
The exposure process in photocuring portion is formed on the photosensitive polymer combination layer；With
The developing procedure that the photosensitive polymer combination layer other than the photocuring portion is removed.
35. a kind of forming method of corrosion-resisting pattern, it includes:
By photosensitive element described in claim 33 according to the sequential layer of the photosensitive polymer combination layer, the support membrane
The lamination process being laminated on substrate；
The exposure process in photocuring portion is formed on the photosensitive polymer combination layer；With
The developing procedure that the photosensitive polymer combination layer other than the photocuring portion is removed.
36. a kind of manufacturing method of printed wiring board, to the formation side by corrosion-resisting pattern described in claim 34 or 35
Method and the substrate for being formed with corrosion-resisting pattern implement etching process or plating.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011105441 | 2011-05-10 | ||
| JP2011-105441 | 2011-05-10 | ||
| CN2012101416585A CN102778815A (en) | 2011-05-10 | 2012-05-09 | Photosensitive resin composition, photosensitive element, method of forming anti-corrosion pattern and method of manufacturing pcb |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2012101416585A Division CN102778815A (en) | 2011-05-10 | 2012-05-09 | Photosensitive resin composition, photosensitive element, method of forming anti-corrosion pattern and method of manufacturing pcb |
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|---|---|
| CN109324480A true CN109324480A (en) | 2019-02-12 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2012101416585A Pending CN102778815A (en) | 2011-05-10 | 2012-05-09 | Photosensitive resin composition, photosensitive element, method of forming anti-corrosion pattern and method of manufacturing pcb |
| CN201811138918.7A Pending CN109324480A (en) | 2011-05-10 | 2012-05-09 | Photosensitive polymer combination, photosensitive element, the forming method of corrosion-resisting pattern, the manufacturing method of printed wiring board |
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| CN2012101416585A Pending CN102778815A (en) | 2011-05-10 | 2012-05-09 | Photosensitive resin composition, photosensitive element, method of forming anti-corrosion pattern and method of manufacturing pcb |
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| JP (2) | JP5935462B2 (en) |
| KR (1) | KR101935609B1 (en) |
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| CN110531583A (en) * | 2019-09-14 | 2019-12-03 | 浙江福斯特新材料研究院有限公司 | Photosensitive polymer combination, dry film resist layer |
| CN110632825A (en) * | 2019-09-14 | 2019-12-31 | 浙江福斯特新材料研究院有限公司 | Photosensitive resin composition and dry film resist |
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| JP6023010B2 (en) * | 2013-06-26 | 2016-11-09 | 東京エレクトロン株式会社 | Substrate processing method, program, computer storage medium, and substrate processing system |
| JP6318484B2 (en) * | 2013-07-09 | 2018-05-09 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, resist pattern forming method and printed wiring board manufacturing method |
| KR102582910B1 (en) * | 2014-05-13 | 2023-09-26 | 가부시끼가이샤 레조낙 | Photosensitive resin composition, photosensitive element, method for forming resist pattern, and process for producing printed wiring board |
| KR20220084015A (en) * | 2019-10-16 | 2022-06-21 | 쇼와덴코머티리얼즈가부시끼가이샤 | Photosensitive resin film, resist pattern formation method, and wiring pattern formation method |
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI644171B (en) | 2018-12-11 |
| JP5935462B2 (en) | 2016-06-15 |
| KR101935609B1 (en) | 2019-01-04 |
| TWI670568B (en) | 2019-09-01 |
| CN102778815A (en) | 2012-11-14 |
| JP2012252320A (en) | 2012-12-20 |
| JP2016118793A (en) | 2016-06-30 |
| TW201303493A (en) | 2013-01-16 |
| KR20120126013A (en) | 2012-11-20 |
| JP6052440B2 (en) | 2016-12-27 |
| TW201839511A (en) | 2018-11-01 |
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