CN103430100B - Photosensitive polymer combination, use its photoresist, the forming method of corrosion-resisting pattern and the forming method of conductive pattern - Google Patents

Photosensitive polymer combination, use its photoresist, the forming method of corrosion-resisting pattern and the forming method of conductive pattern Download PDF

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Publication number
CN103430100B
CN103430100B CN201280011581.8A CN201280011581A CN103430100B CN 103430100 B CN103430100 B CN 103430100B CN 201280011581 A CN201280011581 A CN 201280011581A CN 103430100 B CN103430100 B CN 103430100B
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photosensitive polymer
methyl
polymer combination
photoresist
corrosion
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CN103430100A (en
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丰田大贵
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Changxing Materials Industry Co.,Ltd.
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Nikko Materials Co Ltd
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    • 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
    • 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
    • G03F7/085—Photosensitive compositions characterised by adhesion-promoting non-macromolecular additives
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N

Abstract

The present invention relates to comprise binder polymer, have amino can the monomer of photopolymerization, Photoepolymerizationinitiater initiater and there is the photosensitive polymer combination of benzotriazole derivatives of carboxyl, and comprise the photosensitive polymer combination layer and the photoresist of supporting layer formed by this photosensitive polymer combination.Well, the foot of the solidification resist layer after development is minimum, fissility is the best for this photosensitive polymer combination and the resolution of photoresist and adaptation.

Description

Photosensitive polymer combination, use its photoresist, the forming method of corrosion-resisting pattern and conductor figure The forming method of case
Technical field
The photosensitive polymer combination that the present invention relates to can be developed by alkaline aqueous solution, comprise by this The photosensitive polymer combination layer of photosensitive polymer combination formation and the photoresist of supporting layer, use This photoresist forms the method for corrosion-resisting pattern on base material and uses the conductor of this photoresist The forming method of pattern.More specifically, the present invention relates to give be suitable for printed circuit board (PCB) manufacture, The manufacture of flexible print wiring board, the manufacture of lead frame (hereinafter referred to as lead frame) of IC chip carrying, The metal forming Precision Machining such as metal mask manufacture, BGA (BGA) and CSP (chip size packages, Chip size package) etc. semiconductor package body manufacture, TAB (Tape Automated Bonding, belt Automatically engage) and COF (Chip On Film: semiconducter IC is equipped on the fine circuits plate of film like Become chip) representated by the manufacture of belt substrate, the manufacture of quasiconductor projection, field of flat panel displays In corrosion-resisting pattern photosensitive of manufacture of ITO electrode, addressing electrode or electromagnetic wave shielding body component Property resin combination and correlation technique thereof.
Background technology
All the time, printed circuit board (PCB) uses photoetching process manufacture.Photoetching process refers to following method: will Photosensitive polymer combination is coated on substrate, carries out pattern exposure, and makes this photosensitive polymer combination Exposure portion polymerizing curable, by unexposed portion use developer solution remove, on substrate formed corrosion-resisting pattern, Implement etching or plating, after forming conductive pattern, by being shelled from this substrate by this corrosion-resisting pattern Leave away and remove, thus on substrate, form conductive pattern.
In above-mentioned photoetching process, following method can be optionally employed: be coated with by photosensitive polymer combination When cloth is on substrate, photoresist agent solution is coated on substrate the method being allowed to dry；Or use By supporting layer, the layer that formed by photosensitive polymer combination (hereinafter also referred to as " photosensitive polymer combination Layer ".) and the photoresist that stacks gradually of the protective layer that uses as required, it is photosensitive The method that property resin composition layer side is layered on substrate.In the manufacturing of printed circuit boards, it is used mostly The photoresist of the latter.
For the method using above-mentioned photoresist to manufacture printed circuit board (PCB), describe the most simply.
First, when photoresist has protective layer such as polyethylene film, from photosensitive polymer combination Layer is peeled off.Then, use laminating machine on substrate such as copper-clad laminated board, with this substrate, photosensitive Property resin composition layer, the order stacking photosensitive polymer combination layer of supporting layer and supporting layer.Then, Via having the mask of wiring pattern, to this photosensitive polymer combination layer, use and comprise ultrahigh pressure mercury lamp The ultraviolet isoreactivity energy-ray of the i ray (365nm) produced is exposed, and thus makes exposure portion segregation Close solidification.Then, supporting layer such as pet film is peeled off.Then, employing is aobvious Shadow liquid such as have weakly alkaline aqueous solution the unexposed portion of photosensitive polymer combination layer is dissolved or Person disperses to remove, and forms corrosion-resisting pattern on substrate.After corrosion-resisting pattern is formed, the technique forming circuit is big 2 kinds of methods it are divided on body.First method is to etch the copper face of the substrate not covered by corrosion-resisting pattern to go After removing, corrosion-resisting pattern part is used the method (etching method) that the alkaline aqueous solution more higher than developer solution is removed. Second method be use copper, scolding tin, nickel to carry out plating on the copper face of substrate after, remove anti- Corrosion figure case part, and then the method (plating method) that the copper face of the substrate exposed is etched.
On the other hand, the highdensity wiring homogeneous in order to make conductor shape, use semi-additive process. In semi-additive process, first, seed copper thin film is adopted form corrosion-resisting pattern with the aforedescribed process.Then, Between corrosion-resisting pattern, implement plating form copper facing wiring, after resist is peeled off, use and be referred to as dodging The method of erosion (flash etching), etches this copper facing wiring and seed copper thin film simultaneously.Semi-additive process with Above-mentioned plating method is different, and seed copper thin film is thin, almost without the impact produced by etching, it is possible to make Rectangle and highdensity wiring.
But, after development, the boundary member generation at solidification resist layer and substrate is referred to as foot (foot) The semi-solid preparation resist layer of (solidification resist layer foot) is (with reference to Fig. 1.).Particularly at highdensity corrosion-resisting pattern Between, due to foot, the surface area of the seed copper thin film exposed after development reduces, therefore passes through plating method The copper facing wiring formed and the contact area of Copper thin film reduce.Accordingly, it is possible to copper facing wiring can be caused to become The problem being easily peeled off.Connecting up following further, since foot is present in copper facing, resist also can when peeling off Become and stumbled, peel off bad reason.And then, in etching method, due to foot, expose after development The surface area of Copper thin film reduce, therefore there is etching and remove insufficient worry.Therefore, development is sought After the minimum photoresist of foot of solidification resist layer.
As the method solving these problems, such as patent documentation 1 proposes by using triazine chemical combination Thing prevents transmission light from producing halation, the method for the generation of suppression foot on substrate surface；It addition, specially Profit document 2 proposes and suppresses half admittedly by the photopolymerizable compound using intramolecular to have fluorene skeleton The method changing the generation of resist layer (foot).
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2007-114452 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2009-53388 publication
Summary of the invention
The problem that invention is to be solved
But, although the triaizine compounds described in above-mentioned patent documentation 1 is effective to reducing foot, but Still can not say fully；Intramolecular described in above-mentioned patent documentation 2 has the optical polymerism of fluorene skeleton The problem that resist fissility is significantly deteriorated is there is in compound because of its strong-hydrophobicity.
In this context, it is an object of the invention to provide resolution and adaptation good and And the solidification photosensitive polymer combination that foot is minimum, fissility is the best of resist layer, the bag after development Containing the photosensitive polymer combination layer formed by this photosensitive polymer combination and the photoresist of supporting layer Film, this photoresist is used to form the method for corrosion-resisting pattern on base material and use this photoresist The forming method of conductive pattern.
For solving the scheme of problem
The present inventor etc. conduct in-depth research to solve above-mentioned problem, it was found that by containing There is binder polymer as main component and containing can the monomer of photopolymerization, Photoepolymerizationinitiater initiater Photosensitive polymer combination in, containing have the monomer of amino as can photopolymerization monomer component, With there is the benzotriazole derivatives of carboxyl as giving the composition of fissility, can show high-resolution with And the foot of the solidification resist layer after high adhesion, and development is minimum, fissility is the best, it is possible to reach To above-mentioned purpose, thus complete the present invention.
That is, the purport of the present invention relates to a kind of photosensitive polymer combination, it is characterised in that it contains (A) What binder polymer, (B) had amino can the monomer of photopolymerization, (C) Photoepolymerizationinitiater initiater and (D) There is the benzotriazole derivatives of carboxyl.
Moreover, it relates to comprise the photonasty tree formed by the photosensitive polymer combination of the present invention Oil/fat composition layer and the photoresist of supporting layer.
And then, the invention still further relates to the forming method of corrosion-resisting pattern, it has the photic of the use present invention Etchant resist forms photosensitive polymer combination layer, and the operation being exposed, developing on base material.
Moreover, it relates to the forming method of conductive pattern, it has following operation: use this The photoresist of invention forms photosensitive polymer combination layer on circuit formation substrate, and exposes Light, development, form the operation of corrosion-resisting pattern；Formed with to the aforementioned circuit being formed with aforementioned corrosion-resisting pattern It is etched with substrate or plating, peels off the operation of aforementioned corrosion-resisting pattern.
The present invention comprises in the following manner.
[1] a kind of photosensitive polymer combination, it is characterised in that it contains (A) binder polymer, (B) Have amino the monomer of photopolymerization, (C) Photoepolymerizationinitiater initiater and (D) can have the benzo three of carboxyl Zole derivatives.
[2] according to photosensitive polymer combination described in [1], it is characterised in that what (B) had amino can The monomer of photopolymerization be represented by following logical formula (I) can the unsaturated compound of photopolymerization.
(wherein, the R in formula1For H or CH3。R2And R3Separately represent select free hydrogen atom, Group in the group that alkyl, alkoxyl and halogen group are formed, R2And R3Can be mutually bonded and Form the ring comprising N.X is the alkylidene of carbon number 1～10, or (C2H4O) m or (C3H6O) n represents , m, n be respectively 1～10 the polyoxy alkylidene of integer；Polyoxy alkylidene is atactic polymerization or embedding Duan Juhe.)
[3] according to the photosensitive polymer combination described in [1] or [2], it is characterised in that relative to 100 weights Amount part (A) binder polymer, containing 0.01～30 weight portions (B) there is amino can the list of photopolymerization Body.
[4] according to the photosensitive polymer combination described in any one of [1]～[3], it is characterised in that relatively In 100 weight portions (A) binder polymer, the benzotriazole containing 0.01～2 weight portions (D) with carboxyl is spread out Biological.
[5] according to the photosensitive polymer combination described in any one of [1]～[4], it is characterised in that (A) glues Knot agent polymer has carboxyl, and its acid number is 100～300mgKOH/g.
[6] a kind of photoresist, it is characterised in that it comprises the sense described in any one by [1]～[5] The photosensitive polymer combination layer of photosensitive resin composition formation and supporting layer.
[7] forming method of a kind of corrosion-resisting pattern, comprising: use the photoresist described in [6] at base Form photosensitive polymer combination layer on material, and be exposed, develop.
[8] forming method of a kind of conductive pattern, comprising: use the photoresist described in [6] at electricity Form photosensitive polymer combination floor on road formation substrate, and be exposed, develop, form resist pattern Case；And the aforementioned circuit formation substrate being formed with aforementioned corrosion-resisting pattern is etched or plating, Peel off aforementioned corrosion-resisting pattern.
The effect of invention
The photosensitive polymer combination of the present invention and photoresist have resolution and adaptation is good The effect that foot is minimum, fissility is the best of the solidification resist layer well and after development.Therefore, adopt With forming method and the formation side of conductive pattern of the corrosion-resisting pattern of the photoresist using the present invention Method, it is possible to obtain the effect that the stripping stripping bad, conductive pattern (wiring) of corrosion-resisting pattern reduces.
Accompanying drawing explanation
Fig. 1 is to be schematically illustrated in the conventional photoresist of use to form solidification on substrate (Copper thin film) Resist layer, produces foot's (solidification resist layer foot) when forming coating layer (thin copper film) and the problem that causes Sectional view.A represent development after sectional view, B represent plating after sectional view, C represent cutting after stripping Face figure.
Detailed description of the invention
Hereinafter, the present invention is specifically described.
It should be noted that in this specification, (methyl) acrylic acid refers to acrylic acid or corresponding thereto Methacrylic acid；(methyl) acrylate refers to acrylate or methacrylate corresponding thereto； (methyl) acryloyl refers to acryloyl or methacryl corresponding thereto.
[photosensitive polymer combination]
The photosensitive polymer combination of the present invention is characterised by, it contains (A) binder polymer, (B) Have amino the monomer of photopolymerization, (C) Photoepolymerizationinitiater initiater and (D) can have the benzo three of carboxyl Zole derivatives.
As (A) binder polymer, such as acrylic polymer, phenylethylene polymerization can be listed Thing, epoxide polymer, acylamide polymer, amide epoxy base polymer, alcohol acids polymer, phenol Base polymer etc., can be used alone the one in these polymer or be applied in combination therein two kinds with On.In these polymer, preferably carbonyl bearing polymer.
As carbonyl bearing polymer, can exemplary propylene acids polymers, polyester polymer, polyamide Base polymer, epoxide polymer etc.；Wherein, it is preferably used and makes (methyl) acrylate and ethylene not Saturated carboxylic acid and the acrylic polymer of other copolymerizable monomer copolymerizations as required.
((methyl) acrylate is complete with use for the content of construction unit based on above-mentioned (methyl) acrylate The ratio of portion's polymerizable monomer), seeing of alkali-developable, resolution and peel property is realized from well Solution is set out, and preferably comprises 10～70 mass parts, more preferably contains 20～60 mass parts, particularly preferably contains 30～50 mass parts.
It addition, the content of construction unit based on ethylene unsaturated carboxylic acid (ethylene unsaturated carboxylic acid with The ratio of whole polymerizable monomers used), the suppression that produces from resolution and adaptation, foot, From the viewpoint of fissility, preferably 12～50 mass parts, more preferably 15～40 mass parts, particularly preferably It is 18～30 mass parts.If the content of ethylene unsaturated carboxylic acid is very few, then there is alkali reaction poor, aobvious The tendency that shadow time, splitting time are elongated；If the content of ethylene unsaturated carboxylic acid is too much, then have aobvious The tendency that shadow liquid toleration reduces, adaptation reduces.
And then, content (other the copolymerizable list of the construction unit of copolymerizable monomers based on other The ratio of whole polymerizable monomers of body and use) preferably comprise 10～80 mass parts, more preferably contain 20～70 mass parts, particularly preferably containing 30～60 mass parts.
These polymer containing carboxyl may be used singly or two or more in combination.As two kinds The polymer containing carboxyl when combination of the above uses, can list such as: by different be copolymerized into fractal The two or more polymer containing carboxyl become, different weight average molecular weight two or more containing carboxylic The polymer of base, the two or more polymer etc. containing carboxyl of different dispersion.
Hereinafter, described acrylic polymer is illustrated.But the acrylic compounds used in the present invention Polymer is not limited to following acrylic polymer.
As above-mentioned (methyl) acrylate, can list such as: (methyl) acrylic acid methyl ester., (methyl) Ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Hexyl 2-propenoate, (first Base) carbon number of the alkyl such as 2-EHA, (methyl) cyclohexyl acrylate is 1～20, preferably It it is aliphatic (methyl) acrylate of 1～10；Aromatic series (methyl) acrylic acid such as (methyl) benzyl acrylate Ester；(methyl) diethylaminoethyl acrylate, (methyl) dimethylaminoethyl acrylate etc. are containing amino (methyl) Acrylate；Hydroxyl (methyl) acrylic acid such as (methyl) 2-(Acryloyloxy)ethanol, (methyl) Hydroxypropyl acrylate Ester；(methyl) glycidyl acrylates etc. are containing epoxy radicals (methyl) acrylate；(methyl) acrylic acid 2,2,2- Trifluoro ethyl ester, (methyl) acrylic acid tetrahydro furfuryl ester etc., these (methyl) acrylate can be used alone Or be used in combination.
As above-mentioned ethylene unsaturated carboxylic acid, for instance, it may be preferable to use acrylic acid, methacrylic acid, The monocarboxylic acids such as butenoic acid, it is possible to use the dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, they Anhydride, half ester, these ethylene unsaturated carboxylic acids may be used singly or in combination of two or more.Its In, particularly preferred acrylic acid, methacrylic acid.
As other copolymerizable monomers above-mentioned, (methyl) acrylamide, (methyl) third can be listed such as Olefin(e) acid 2,2,3,3-tetrafluoro propyl ester, acrylamide, diacetone acrylamide, styrene, α-methyl styrene, Vinyl naphthalene, vinyl cyclohexane, vinyltoluene, vinyl-acetic ester, alkyl vinyl ether, (first Base) acrylonitrile etc., these monomers may be used singly or in combination of two or more.
For described acrylic polymer, the suppression that produces from resolution and adaptation, foot, From the viewpoint of fissility, weight average molecular weight is preferably 0.5 ten thousand～200,000, and more preferably 10,000～100,000； Acid number is preferably 100～300mgKOH/g, more preferably 120～250mgKOH/g, particularly preferably It is 140～190mgKOH/g.It should be noted that weight average molecular weight (Mw) is for using GPC, (gel oozes Thoroughly chromatograph) device, with polystyrene benchmark measure dry polymer THF (oxolane) lysate and The value obtained.
Described acid number is the weight neutralizing the KOH (potassium hydroxide) required for 1g polymer；By to molten In the ketones such as alcohols, acetone, methyl ethyl ketone such as Xie Yu such as methanol or their mixed solvent Polymer is neutralized titration and measures.
If described weight average molecular weight is too low, then have what the photosensitive polymer combination after solidification became fragile to incline To；If the most excessive, then there is the tendency that resolution, resist layer fissility decline.It addition, it is above-mentioned If acid number is too small, then the tendency that the effect having suppression resolution, resist layer fissility to reduce dies down；Phase If instead excessive, then there is the tendency that the effect of the fine rule adaptation reduction of suppression solidification resist layer dies down.
The glass transition temperature (Tg) of aforesaid propylene acids polymers preferably the scope of 30～150 DEG C, enter One step is preferably the scope of 60～120 DEG C.If glass transition temperature is too low, then there is photoresist group Compound easily flows, and the tendency of edge-melting occurs when making web-like as photoresist；On the other hand, as Really glass transition temperature is too high, then have as concavo-convex tracing ability to substrate surface during photoresist The tendency declined.
Described glass transition temperature (Tg) can use DSC (Differential Scanning Calorimetry) measure, in the glass transition temperature of homopolymer of the comonomer of known binder polymer In the case of degree, it is possible to use Fox formula calculates.In the present invention, glass transition temperature is calculated by Fox formula Go out.
[mathematical expression 1]
FOX formula
1 Tg = Wa Ta + Wb Tb + . . .
(Tg represents the glass transition temperature of copolymer.Wa, Wb ... represent a composition, b composition ... Weight fraction.Ta, Tb ... represent that the vitrification of the homopolymer of a composition, b composition ... turns Temperature.)
As (B) have amino can the monomer of photopolymerization, such as, except N, N-dimethyl (methyl) Acrylamide, N, N-diethyl (methyl) acrylamide, dimethylamino-propyl (methyl) acrylamide, two Ethylaminopropyl (methyl) acrylamide, n-pro-pyl (methyl) acrylamide, isopropyl (methyl) acrylamide, Outside N-(methyl) acryloyl morpholine etc., also can list in the group represented by following logical formula I At least one can the unsaturated compound of photopolymerization.Wherein, from the viewpoint of the effect reducing foot, Be preferably used represented by following logical formula I can the unsaturated compound of photopolymerization.
(wherein, the R in formula1For H or CH3。R2And R3Separately represent select free hydrogen atom, Group in the group that alkyl, alkoxyl and halogen group are formed, R2And R3Shape can be mutually bonded Become to comprise the ring of N.X is the alkylidene of carbon number 1～10, or (C2H4O) m or (C3H6O) n institute table That show, m, n are respectively the polyoxy alkylidene of the integer of 1～10；Polyoxy alkylidene be atactic polymerization or Block polymerization.)
In above-mentioned logical formula I, the R in formula1For H or CH3。R2And R3Separately represent choosing Group in the group that free hydrogen atom, alkyl, alkoxyl and halogen group are formed, R2And R3 Can be mutually bonded and form the ring comprising N.The carbon number of alkyl and alkoxyl is usually 1～10, excellent Elect 1～6 as.X is carbon number 1～10, preferably 1～the alkylidene of 6, or (C2H4O) m or (C3H6O)n Represented, m, n are respectively the polyoxy alkylidene of the integer of 1～10.Polyoxy alkylidene both can be random Polymerization, it is also possible to block polymerization.
As the compound represented by above-mentioned logical formula I, specifically, (methyl) third can be listed such as Olefin(e) acid N, N-dimethylamino methyl ester, (methyl) acrylic acid N, N-dimethylaminoethyl, (methyl) acrylic acid N, N-dimethylamino propyl ester, (methyl) acrylic acid N, N-dimethylamino butyl ester, (methyl) acrylic acid N, N-diformazan Amino pentyl ester, (methyl) acrylic acid N, the own ester of N-dimethylamino, (methyl) acrylic acid N, N-dimethylamino heptan Ester, (methyl) acrylic acid N, N-dimethylamino monooctyl ester, (methyl) acrylic acid N, N-dimethylamino nonyl ester, (first Base) acrylic acid N, N-dimethylamino ester in the last of the ten Heavenly stems, (methyl) acrylic acid N, N-lignocaine methyl ester, (methyl) propylene Acid N, N-lignocaine ethyl ester, (methyl) acrylic acid N, N-lignocaine propyl ester, (methyl) acrylic acid N, N- Lignocaine butyl ester, (methyl) acrylic acid N, N-lignocaine pentyl ester, (methyl) acrylic acid N, N-diethylamino The own ester of base, (methyl) acrylic acid N, N-lignocaine heptyl ester, (methyl) acrylic acid N, N-lignocaine monooctyl ester, (methyl) acrylic acid N, N-lignocaine nonyl ester, (methyl) acrylic acid N, N-lignocaine ester in the last of the ten Heavenly stems etc. (methyl) Acrylic acid dialkylaminoalkyl ester；(methyl) acrylic acid N-n-propylamine base ethyl ester, (methyl) acrylic acid N-is different Third amino ethyl ester, (methyl) acrylic acid N-tertiary fourth amino ethyl ester, (methyl) acrylic acid N-n-butyl amine base ethyl ester Deng (methyl) acrylic acid list alkyl amino alkyl ester；(methyl) acrylic acid N, N-dimethylamino macrogol ester, (first Base) acrylic acid N, N-lignocaine macrogol ester, (methyl) acrylic acid N, N-dimethylamino polypropylene glycol Ester, (methyl) acrylic acid N, dialkylamino polyethers (methyl) acrylate such as N-lignocaine polypropylene glycol ester； (methyl) acrylic acid cyclic aminoalkyl esters such as (methyl) acrylic acid morpholine ethyl ester.Wherein, preferably (methyl) Acrylic acid dialkylaminoalkyl ester, particularly preferably uses (methyl) acrylic acid lignocaine Arrcostab.
It should be noted that from the easness started with, the most above-mentioned formula R1For CH3、R2 And R3It is C2H5, X be C2H5Compound, i.e. methacrylic acid N, N-lignocaine ethyl ester is (such as, Common prosperity society chemistry (Zhu Shi commercial firm) manufactures, trade name: LIGHT ESTER DE).
Herein, the generation of foot of solidification resist layer be presumably due to, solidify weak semi-solid preparation against corrosion Acidic-group and the developer solution partial reaction of layer, is not removed and during after development dry, semi-solid preparation resists Erosion layer moves and is attached to resist layer bottom again.(B) can the amino of monomer of photopolymerization in photonasty Occurring to neutralize reaction with the acidic-group in (A) binder polymer in resin combination, (A) binding agent gathers The acidic-group of compound is protected, thus resistance to development fluidity improves, and the attachment again of semi-solid preparation resist layer reduces, Diminish i.e., it is possible to be thought of as foot.Further, since the monomer of (B) have can the structure of photopolymerization, Therefore curing degree raising, the raising of adaptation can be expected.Accordingly, as the monomer of (B), as long as There is amino and can the structure of photopolymerization, it is possible to expect same effect.
It should be noted that in view of occurring to pollute the bad of the acid solution such as plating bath, etching solution The worry of situation, in the photosensitive polymer combination of the purposes of photoresist, uses (B) never Have amino can the monomer of photopolymerization as can the monomer component of photopolymerization.But, in the present invention, The monomer with amino dare to be used, and the most not produce above-mentioned unfavorable condition, it is possible to Reach the purpose of the present invention.
In the present invention, above-mentioned (B) have amino can the content of monomer of photopolymerization relative to (A) Binder polymer 100 weight portion, preferably 0.01～30 weight portions, more preferably 0.1～25 weight portions, More preferably 0.5～20 weight portion, particularly preferably 1～15 weight portions.If described content is very few, The effect that Ze You foot reduces becomes insufficient tendency；If crossing the tendency having resolution to reduce at most.
Can also have with (B) amino can together with the monomer of photopolymerization, use following shown in can The monomer of photopolymerization.Such as, as having the monomer of 1 polymerism unsaturated group, can list: (first Base) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 2-hydroxy butyl ester, (methyl) Acrylic acid 2-phenoxy group-2-hydroxypropyl acrylate, phthalic acid 2-(methyl) acryloxy-2-hydroxypropyl acrylate, (methyl) Acrylic acid 3-chloro-2-hydroxypropyl acrylate, single (methyl) glycerol acrylate, 2-(methyl) acrylyl oxy-ethyl acid phosphorus Acid esters, half (methyl) acrylate etc. of phthalic acid derivatives, these monomers can be used alone or It is used in combination.
It addition, as having the monomer of 2 polymerism unsaturated groups, such as ethylene glycol bisthioglycolate can be listed (methyl) acrylate, diethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, Polyethylene Glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) Acrylate, Polyethylene Glycol polypropylene glycol two (methyl) acrylate, butanediol two (methyl) acrylate, Neopentyl glycol two (methyl) acrylate, bisphenol A-type two (methyl) acrylate of oxygen-containing ethylidene, oxygen-containing Bisphenol A-type two (methyl) acrylate of propylidene, the bisphenol A-type two (first of oxygen-containing ethylidene oxygen propylidene Base) acrylate, 1,6-HD two (methyl) acrylate, two (methyl) glycerol acrylate, Ji Wusi Alcohol two (methyl) acrylate, Ethylene glycol diglycidyl ether two (methyl) acrylate, diethylene glycol two Glycidyl ether two (methyl) acrylate, o-phthalic acid diglycidyl ester two (methyl) acrylate, Hydroxy new pentane acid modification neopentyl glycol two (methyl) acrylate etc., these monomers can be used alone or two Plant combination of the above to use.Wherein, bisphenol A-type two (methyl) propylene of oxygen-containing ethylidene is particularly preferably used Acid esters, Polyethylene Glycol polypropylene glycol two (methyl) acrylate.
And then, as having the monomer of more than 3 polymerism unsaturated groups, such as three hydroxyls can be listed Methylpropane three (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, dipentaerythritol five (first Base) acrylate, three (methyl) acryloyloxyethoxy trimethylolpropane, glycerol poly epihydric alcohol base Ether poly-(methyl) acrylate etc., these monomers may be used singly or in combination of two or more.
Additionally, it is possible to list urethane (methyl) acrylate.As urethane (methyl) acrylate, can Enumerate the such as diisocyanate such as hexamethylene diisocyanate, toluene di-isocyanate(TDI) and such as of sening as an envoy to Acrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-hydroxypropyl fat, monomethacrylate widow propylene glycol ester (oligopropylene Glycol monoacrylate) etc. a part has the hydroxyl (methyl) of hydroxyl and (methyl) acryloyl group Acrylate and polyol reaction as required and the compound that obtains.These compounds both can be single Solely use, it is also possible to be used in combination.
In the present invention, for (B) have amino can beyond the monomer of photopolymerization and (B) can light The total amount of the monomer of polymerization, relative to (A) binder polymer 100 weight portion, preferably 10～200 weight Part, particularly preferably 30～160 weight portions, more preferably 50～120 weight portion, particularly preferably 60～100 weight portions.If described content is very few, then has and solidify the tendency becoming insufficient；If too much Then there is the tendency easily producing cold deformation (cold flow).
As (C) Photoepolymerizationinitiater initiater, can list such as: (C1) hexa-aryl bi-imidazole derivant, (C2) Alkylamino benzophenone derivates, N-aryl glycine derivant, acridine derivatives, diamino-anthraquinone etc. Anthraquinone derivative；N, N, N ', N '-tetra-aryl biphenyl amine derivative, triacetic acid riboflavin, benzophenone, Benzil dimethyl ketal, thioxanthone derivates, alkylamino benzoic acid Arrcostab, pyrrolotriazine derivatives, perfume (or spice) Legumin 6 coumarin derivative such as grade, triphenylphosphine, trimethylphenyl phosphine, three (xylyl) phosphine, terphenyl The triaryl phosphines etc. such as phosphine, three naphthyl phosphines, three anthryl phosphines, three phenanthryl phosphines, these Photoepolymerizationinitiater initiaters are permissible It is used alone or is used in combination.
As (C1) hexa-aryl bi-imidazole derivant, can list such as: 2,2 '-bis-(2,3-dichloro-benzenes Base)-4,4 ', 5,5 '-four (3-methoxyphenyl) double imidazoles, 2,2 '-bis-(2,3-Dichlorobenzene base)-4,4 ' and, 5,5 '-four (4- Methoxyphenyl) double imidazoles, 2,2 '-bis-(2,4 dichloro benzene bases)-4,4 ', 5,5 '-four (3-methoxyphenyl) phenyl is double Imidazoles, 2,2 '-bis-(2,5-Dichlorobenzene base)-4,4 ', 5,5 '-four (3-methoxyphenyl) double imidazoles, 2,2 '-bis-(2,6- Dichlorobenzene base)-4,4 ', 5,5 '-four (3-methoxyphenyl) double imidazoles, 2,2 ', 4,4 '-four (2-chlorphenyls)-5,5 '-bis- (3-methoxyphenyl) double imidazoles, 2,2 '-bis-(2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 ', 4,4 '- Four (2-chlorphenyls)-5,5 '-bis-(4-methoxyphenyl) double imidazoles, 2,2 ', 4,4 '-four (2-chlorphenyls)-5,5 '-bis- (2,3-Dimethoxyphenyl) double imidazoles, 2,2 ', 4,4 '-four (2-chlorphenyls)-5,5 '-bis-(3,4-Dimethoxyphenyls) Double imidazoles, 2,2 '-bis-(2-chlorphenyls)-4,4 ', 5,5 '-four (4-methoxyphenyl) double imidazoles, 2,2 '-bis-(2-chlorobenzenes Base)-4,4 ', 5,5 '-four (3,4-Dimethoxyphenyl) double imidazoles, 2,2 '-bis-(2-chlorphenyls)-4,4 ' and, 5,5 '-four Double (the 3-methoxyphenyl)-4 of (3,4,5-trimethoxyphenyl) double imidazoles, 2,2 '-bis-(2-chlorphenyl)-4,5-', 5 '- The double imidazoles of diphenyl, double (the 3,4-Dimethoxyphenyl)-4 of 2,2 '-bis-(2-chlorphenyl)-4,5-', the double miaow of 5 '-diphenyl Azoles, 2,2 '-bis-(2-chlorphenyl)-4-(3,4-Dimethoxyphenyl)-4 ', the double imidazoles of 5,5 '-triphenyl etc.；Wherein, Preferably 2,2 ', 4,4 '-four (2-chlorphenyls)-5,5 '-bis-(3-methoxyphenyl) double imidazoles, 2,2 ', 4,4 '-four (2-chlorobenzenes Base)-5,5 '-bis-(2,3-Dimethoxyphenyl) double imidazoles, 2,2 '-bis-(2-chlorphenyl)-4-(3,4-dimethoxy benzenes Base)-4 ', 5,5 '-triphenyl double imidazoles, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, these are six years old Aryl bi-imidazole derivant may be used singly or in combination of two or more.
As (C2) alkylamino benzophenone derivates, such as 4,4 '-bis-(lignocaine) hexichol can be listed Ketone, 3,3 '-dimethylamino-4-methoxy benzophenone, 4,4 '-bis-(dimethylamino) benzophenone etc.；Its In, particularly preferred 4,4 '-bis-(lignocaine) benzophenone, these alkylamino benzophenone can individually make With or be used in combination.
For the photosensitive polymer combination of the present invention, from the viewpoint of high-sensitivity, as Photoepolymerizationinitiater initiater (C), preferably at least contains (C1) hexa-aryl bi-imidazole derivant, particularly preferably containing (C1) Hexa-aryl bi-imidazole derivant and other Photoepolymerizationinitiater initiaters, further preferably containing the double miaow of (C1) six aryl Zole derivatives and (C2) alkylamino benzophenone derivates.
For the content of (C) Photoepolymerizationinitiater initiater, relative to (A) binder polymer 100 weight portion, excellent Elect 1～20 weight portions, particularly preferably 2～16 weight portions, more preferably 3～12 weight portion as.(C) light If the content of polymerization initiator is very few, then has and cannot obtain the sensitivity of necessity, resolution and closely sealed The tendency of property；If additionally too much, then there is the tendency producing insoluble matter in photosensitive polymer combination.
In the case of being applied in combination (C1) hexa-aryl bi-imidazole derivant and other Photoepolymerizationinitiater initiaters, example As, it is being applied in combination (C1) hexa-aryl bi-imidazole derivant and the feelings of (C2) alkylamino benzophenone derivates Under condition, relative to (A) binder polymer 100 weight portion, (C1) hexa-aryl bi-imidazole derivant is preferably 1～16 weight portions, particularly preferably 2～13 weight portions, more preferably 3～10 weight portion；(C2) alkane ammonia Base benzophenone derivates is preferably 0.01～4 weight portions, particularly preferably 0.02～3 weight portions, further It is preferably 0.06～2 weight portions.
There is the benzotriazole derivatives of carboxyl as (D), be preferably used such as 4-carboxyl benzotriazole, 5-carboxyl benzotriazole, 1-(1 ', 2 '-two carboxyethyl) benzotriazole, 1-(2 ', 3 '-dicarboxyl propyl group) benzotriazole, 1-((double (2-ethylhexyl) amino) methyl)-1H-benzotriazole carboxylic acid, they can be used alone or group Close two or more use.It should be noted that from the easness started with, particularly preferred 4-carboxyl benzene And triazole, 5-carboxyl benzotriazole.
Known benzotriazole derivatives is good with the affinity of copper metal, it is believed that on Copper base material upper strata After pressure photoresist, benzotriazole derivatives is coordinated in Copper base material.Understand the benzo three with carboxyl Strong alkali aqueous solution and this carboxyl when Zole derivatives is owing to peeling off occur to neutralize reaction, therefore can be easily By resist layer from the interface peel of Copper base material.
(D) is had to the content of the benzotriazole derivatives of carboxyl, relative to (A) binder polymer 100 weight portions, preferably 0.01～2 weight portions, particularly preferably 0.04～1.6 weight portions, further preferably It it is 0.08～1 weight portion.(D) if the content with the benzotriazole derivatives of carboxyl is very few, then there is stripping Property the tendency that reduces, if additionally too much, then have adaptation to reduce, foot also becomes big tendency.
It addition, in the present invention, from the viewpoint of the minimizing of foot and fissility are all taken into account, It is applied in combination aforementioned (B) composition and aforementioned (D) composition is important, the most aforementioned (B) composition and aforementioned (D) Weight rate (B)/(D) of composition is more than 1 and the scope of less than 500.Particularly preferably weight rate (B)/(D) More than 3 and the scope of less than 200, further preferred weight rate (B)/(D) is more than 5 and less than 50 Scope.If described ratio fruit is the most too low, then has and can be easily peeled off but foot becomes big tendency；If crossed Height, then have and can suppress producing but the tendency of stripping change difficulty of foot.
In the photosensitive polymer combination of the present invention, on the basis of the compound of above-mentioned (A)～(D), excellent Choosing contain dyestuff further, and then, as described dyestuff, can list such as crystal violet, malachite green oxalate, Malachite green oxalate color lake, viride nitens, diamond green, patent blue, crystal violet, Victoria blue, Victoria are pure The illuminating colours such as indigo plant, solvent blue, alkali blue 20, rosaniline, paramagenta, ethyl violet；Three (4-diformazans Amino-2-tolyl) methane ［ leuco crystal violet ］, three (4-dimethylamino-2-aminomethyl phenyl) methane ［ procrypsis Malachite green oxalate ］, the leuco dye etc. such as fluoran based dyes (FluoranDye).
It addition, the photosensitive polymer combination of the present invention can also contain halogenide.As halogenide, Such as amyl bromide, isoamyl bromide, brominated isobutylene, glycol dibromide, benzhydryl can be listed Bromide, benzyl bromide a-bromotoluene, methylene bromide, trisbromomethyl phenyl sulfone, carbon tetrabromide, three (2,3-dibromopropyls) Double (rubigan) ethane of phosphate ester, trichloroacetamide, amyl iodide, isobutyl iodide, the chloro-2,2-of 1,1,1-tri-, Chloro triaizine compounds etc..
And then, in the photosensitive polymer combination of the present invention, as required can also be containing plasticizer etc. Additive.As such additive, such as Polyethylene Glycol, polypropylene glycol, polyoxy Asia can be listed Propyl group polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxy Asia second Base polyoxypropylene monomethyl ether, polyoxyethylene list ethylether, polyoxypropylene list ethylether, polyoxy The phthalic acids such as diol-lipid, diethyl phthalate such as ethylidene polyoxypropylene list ethylether Esters, orthotoluene sulfonamide, para toluene sulfonamide, tributyl citrate, triethyl citrate, acetyl Base triethyl citrate, acetyl citrate three n-propyl, acetyl tributyl citrate etc..
In order to improve the heat stability of the photosensitive polymer combination of the present invention, storage stability, photosensitive Property resin combination can also contain radical polymerization inhibitor.As radical polymerization inhibitor, can list Such as p methoxy phenol, hydroquinone, 1,2,3,-thrihydroxy-benzene, naphthylamines, tert-butyl catechol, Cu-lyt., 2,6-di-t-butyl-paracresol, 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), 2,2 '-di-2-ethylhexylphosphine oxide (4- Ethyl-6-tert-butyl phenol), nitrosophenylhydroxylamine aluminium salt and diphenyl nitrosamine etc..
The photosensitive polymer combination of the present invention can be dissolved in as required methanol, ethanol, acetone, Methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, propylene glycol Monomethyl ether equal solvent or the mixed solvent of these solvents and make about solid constituent 30～60 weight % Solution.This solution can be used as the photosensitive polymer combination for forming photoresist described later The coating fluid of layer.It should be noted that this cloth liquid can also be coated on the bases such as circuit formation substrate On plate so that it is be dried, form photosensitive polymer combination layer, but from viewpoints such as working performances, excellent It is selected to be formed the photosensitive polymer combination layer of photoresist described later.
And then, in the photosensitive polymer combination of the present invention, it is also possible to contain adaptation aptly and give Agent, antioxidant, thermal polymerization inhibitor, surface tension modifier, stabilizer, chain-transferring agent, froth breaking The additive such as agent, fire retardant, during containing these additives, the content of described additive is relative to (A)～(D) Solid constituent total amount 100 mass parts of composition, contains 0.01～20 mass parts, further preferably the most respectively Containing 0.02～15 mass parts, particularly preferably containing 0.03～10 mass parts.These additives can individually make With or be used in combination.
[photoresist]
The photoresist of the present invention contains the photosensitive resin composition formed by photosensitive polymer combination Nitride layer and supporting layer.As supporting layer used herein, preferably saturating through the light radiated by exposure light source Bright supporting layer.
As such supporting layer, such as pet film can be listed, gather Alcohol film, polyvinyl chloride film, vinyl chloride copolymer thin film, Vingon thin film, inclined chloroethene Alkene copolymerization thin film, polymethyl methacrylate copolymer thin film, polystyrene film, polyacrylonitrile thin film, Styrol copolymer thin film, polyamide film, cellulose derivative film etc.；Wherein, preferably poly-to benzene Naphthalate thin film.These thin film can use stretched thin film as required.
The preferably mist degree of supporting layer is less than 5.When the thickness of supporting layer is thin, from image formative and warp Ji property from the standpoint of be favourable, from maintain intensity need consider, be preferably used 10～30 μm Support layer.The thickness of the photosensitive polymer combination layer in photoresist is different according to purposes, is preferably 5～100 μm, more preferably 7～60 μm, particularly preferably 10～50 μm.If photosensitive polymer combination Layer is the thinnest, then have film-strength to become too low tendency；If blocked up, then there be adaptation, sensitivity, divide The tendency that resolution reduces.
The photoresist of the present invention as required can also be at the supporting layer of photosensitive polymer combination layer On the surface of the opposition side of side, there is protective layer.In photoresist use protective layer key property it One is: can be easily peeled off from photosensitive polymer combination layer in use；Therefore, for photosensitive Closing force between property resin composition layer, it is desirable to compared to supporting layer, side is sufficiently small for protective layer one.Make For protective layer, it may be preferred to use such as polyethylene film, polypropylene film.The thickness of protective layer is preferred It is 10～100 μm, more preferably 10～50 μm.
The photoresist of the present invention can be such as manufacture of getting off, i.e. by the photonasty tree containing the present invention The coating liquid of oil/fat composition, at the one side of supporting layer, is dried, and then uses protective layer as required Cover its coated side.More specifically, can be such as manufacture of getting off, i.e. at the one side of supporting layer, use roller The even spread such as coating, stick coating method contains the coating fluid of the photosensitive polymer combination of the present invention, The baking oven that 50～120 DEG C or temperature raise successively is dried, forms photosensitive polymer combination layer, Then, at the upper surface pressurization stacking protective layer of this layer.
[forming method of corrosion-resisting pattern]
To the photoresist for using the present invention, each operation forming corrosion-resisting pattern on base material is carried out Explanation.
The corrosion-resisting pattern using the photoresist of the present invention can be formed by comprising following operation: layer Folded operation, exposure process and developing procedure.One example of concrete grammar expressed below.
As processed base material, in the case of manufacturing for the purpose of printed circuit board (PCB), copper clad layers can be listed Lamination；It addition, (such as, in the case of manufacturing for the purpose of concavo-convex base material, glass baseplate can be listed Plasmia indicating panel base material, surface electrolysis display base material), be formed with Silicon Wafer and the pottery of through hole Porcelain base material etc..Plasmia indicating panel base material is following base material: after forming electrode on the glass substrate, Form dielectric layer, then coating partition glass paste, partition glass paste part is implemented sandblasting Processing, forms partition.
First, laminating machine is used to carry out lamination process.In the case of photoresist has protective layer, After being peeled off by protective layer, laminating machine is used photosensitive polymer combination layer to be added thermo-compressed and is layered in and is added On work substrate surface.Now, photosensitive polymer combination layer both can only be layered in the one side of substrate surface On, it is also possible to it is layered on two-sided.Heating-up temperature now is usually 40～160 DEG C.
Then, exposure machine is used to be exposed operation.If desired, supporting layer is peeled off, covers through light Mould uses activity light to be exposed.Light exposure is determined by light illumination and time of exposure, it is possible to use Quantometer measures.
It addition, in exposure process, it is possible to use directly describe exposure method.Directly describe exposure method For not using photomask directly to describe the mode being exposed on base material.As light source, it is possible to use The such as semiconductor laser of wavelength 350～410nm, ultrahigh pressure mercury lamp.Depicting pattern by computer control, Light exposure now is determined by the translational speed of light illumination and substrate.
Then, develop after peeling off removal supporting layer as required.Photonasty tree due to the present invention Oil/fat composition is diluted alkaline developable, therefore, during development, uses and comprises sodium carbonate, potassium carbonate, tetramethyl The alkaline aqueous solution of 0.1～5 weight % of the alkali cpds such as ammonium hydroxide is carried out.Above-mentioned alkaline aqueous solution PH preferably 9～11 scope, its temperature can regulate according to the developability of photosensitive polymer combination layer. By this development, unexposed portion (removing the region of target pattern image) quilt in photosensitive polymer combination layer Remove, form corrosion-resisting pattern.It should be noted that in above-mentioned alkaline aqueous solution, surface can be mixed into Activating agent, defoamer, for promote development a small amount of organic solvent etc..
Corrosion-resisting pattern can be obtained by above-mentioned operation, but difference according to circumstances, it is also possible to further Carry out heating process or the UV curing process of 100～300 DEG C.By implementing these operations, it is possible to more Improve chemical reagent resistance further.
[forming method of conductive pattern]
The forming method of the conductive pattern of the present invention uses the circuit such as copper-clad laminated board, flexible substrate to be formed and uses Substrate, as base material, carries out after above-mentioned corrosion-resisting pattern formed, carrying out through following operation.First, The face of the substrate exposed by development use the known method such as plating method or etching method formed Conductive pattern.
As coating method when carrying out plating, such as, can enumerate: copper sulfate plating, Copper pyrophosphate. plate The solder plating such as copper plating, high homogeneity (high throw) solder plating, the watt bath (nickel sulfate-chlorine such as cover Change nickel) the nickel plating such as plating, nickel sulfamic acid, firmly the gold plating such as gold plating, soft gold plating etc..Entering During row plating, the plating pretreating agent such as degreasing agent, soft etchant is preferably used and carries out pretreatment.It addition, Etching generally uses the acidic etching liquid such as copper chloride-hydrochloric acid aqueous solution, iron chloride-aqueous hydrochloric acid solution according to often Carry out by method.The most also Ammonia alkali etching liquid is used.
After plating or etching terminate, with comprise containing the alkali cpd such as sodium hydroxide, potassium hydroxide, Concentration is the alkali stripper of the aqueous alkali about 0.1～10 weight %；Or 3～15 the having of weight % aqueous solution Machine amine system's stripper (the particularly liquid with monoethanolamine as main component), carries out the stripping of corrosion-resisting pattern Remove.
During it should be noted that fill plating etc. in through hole with corrosion-resisting pattern, the most also do not remove anti- In the case of corrosion figure case on corrosion-resisting pattern stacking electrically conductive film.In the case of plating, then carry out dodging erosion. Through above operation, the conductive pattern on the circuit substrates such as printed circuit board (PCB) can be formed.
Embodiment
Below, enumerate embodiment and specifically describe the present invention further, but the present invention is without departing from it Purport is just not limited to the following examples.It should be noted that following " % " " part " refers to weight basis.
1) making of sample for evaluation
The photoresist of embodiment and comparative example makes as follows.It is 55 weight % with solid constituent amount Mode prepares the solution of the photosensitive polymer combination shown in table 1, is sufficiently stirred for and mixes, and use is smeared Device, is coated in the way of becoming 25 μm using dried coating thickness as 16 μ m-thick supporting thin film On polyethylene terephthalate (PET) thin film.Respectively 60 DEG C, the baking oven of 90 DEG C carries out 2 minutes It is dried, and then from the top of described photosensitive polymer combination layer, with the polyethylene film of thickness 21 μm Cover, obtain photoresist.For the photoresist obtained, evaluation following items as described below.
[table 1]
Symbol in table 1 represents following material.
((A) binder polymer)
P-1: make methacrylic acid/methyl methacrylate/styrene (weight ratio 22/38/40) polymerization obtain 40% methyl ethyl ketone solution that arrive, weight average molecular weight 42,000.Solid constituent acid number= 143.4mgKOH/g.Glass transition temperature=113.9 DEG C.
P-2: make methacrylic acid/methyl methacrylate/styrene (weight ratio 28/32/40) polymerization obtain 40% methyl ethyl ketone solution that arrive, weight average molecular weight 34,000.Solid constituent acid number= 182.5mgKOH/g.Glass transition temperature=118.1 DEG C.
The monomer of photopolymerization (can)
M-1: methacrylic acid N, N-lignocaine ethyl ester CH2=CH (CH3)COOC2H5N(C2H5)2 (manufacture of chemistry society of common prosperity society, trade name: LIGHT ESTER DE)
M-2: methacrylic acid N-tertiary fourth amino ethyl ester CH2=CH (CH3)COOC2H5NH(t-C4H9)
M-3: the oxygen-containing Asia obtained at the oxygen ethylidene of average 5 moles of the both sides of bisphenol-A addition respectively The bisphenol A-type dimethylacrylate (chemical industry society of Xin Zhong village manufactures, trade name: BPE-500) of ethyl
M-4: nine ethylene glycol dimethacrylates (chemical industry society of Xin Zhong village manufactures, trade name: 9G〕
(Photoepolymerizationinitiater initiater)
I-1:2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole
I-2:4,4 '-bis-(lignocaine) benzophenone
(dyestuff)
D-1: malachite green oxalate
D-2: leuco crystal violet
(benzotriazole derivatives)
T-1:4-carboxyl benzotriazole
T-2:1-(1 ', 2 '-two carboxyethyl) benzotriazole
T-3:1-((double (2-ethylhexyl) amino) methyl)-1H-benzotriazole carboxylic acid
T-4: benzotriazole
(solvent)
F-1: methyl ethyl ketone
2) evaluation methodology
After peeling off the polyethylene film of above-mentioned photoresist, with photosensitive polymer combination aspect with cover copper The mode that substrate connects, in laminating roll temperature 100 DEG C, laminating roll pressure 0.3MPa, laminate speed It is laminated under 1.2m/min.Thereafter, the negative film (Si Tuo made in the way of light transmission capacity gradually reduces is used 21 sections of stage actinometers of husband (stouffer 21 step tablet)), utilize there is the parallel of ultrahigh pressure mercury lamp Exposure machine (ORC MANUFACTURING CO., LTD. manufacture, trade name: EXM-1201)) to this Torr 21 sections of whole faces of stage actinometer of husband carry out uniform exposure.After exposure, after 15 minutes, peel off PET Thin film, with development point 2 times of (break point) (time that unexposed portion is completely dissolved) at 27 DEG C Developing time sprays 0.7 weight % aqueous sodium carbonate, thus dissolves and removes unexposed portion and solidified Resist layer image.By the hop count of residual after each light exposure and development, study 21 sections of stage exposures of Si Tuofu Light exposure (the mJ/cm that residual classification hop count is 6 sections after table development2)。
(resolution)
As glass chrome mask during exposure, use the line of a width of 1:1 ratio in exposure portion and unexposed portion Bar pattern mask (Line pattern mask), is carried out with the light exposure that hop count is 6 sections of stage actinometer Expose and develop.The minimum mask width (μm) solidifying corrosion-resisting pattern will be normally formed as the value of resolution.
(adaptation)
As mask film during exposure, use the line image mask of only exposure portion, with stage exposure The hop count of light table is that the light exposure of 6 sections is exposed and develops.Solidification corrosion-resisting pattern will be normally formed Little mask width (μm) is as the value of adaptation.
(foot of the solidification resist layer after development)
To the photoresist being laminated on substrate, through chromium glass mask with the hop count of stage actinometer It is that the light exposure of 6 sections is exposed and develops.Live width/line-spacing=10/10 μm to the corrosion-resisting pattern obtained Foot's following labelling grade of line.Foot length (foot length) employing SEM (NEC society manufactures, Trade name: JSM-6390) measure foot's width of foot (foot section) of solidification corrosion-resisting pattern.
◎: the foot at solidification corrosion-resisting pattern confirms the foot length having below 1 μm.
Zero: the foot at solidification corrosion-resisting pattern confirms to have more than 1 μm and is the foot length of below 3 μm.
×: the foot at solidification corrosion-resisting pattern confirms to have more than the foot length of 3 μm.
(fissility)
To the photoresist being laminated on substrate, become the exposure of 6 sections with the hop count of stage actinometer Amount exposure 4cm × 4cm square pattern.After the developing time development of 2 times of minimum developing time, Carry out copper sulfate plating.And then use the caustic soda aqueous solution of 3 weight % to spray at 50 DEG C, survey Surely the splitting time of resist layer is solidified, by the fissility labelling grade as described below of solidification resist layer.
◎: resist layer splitting time is less than 50 seconds.
Zero: resist layer splitting time was more than 50 seconds and be less than 60 seconds.
×: resist layer splitting time was more than 60 seconds.
3) evaluation result
The evaluation result of embodiment and comparative example is shown in table 2.
[table 2]
As shown in table 2, the resolution of photosensitive polymer combination of embodiment 1～7, excellent adhesion. And then, owing to the foot of solidification resist layer is little, when the etching of subsequent handling, plating, it is not likely to produce obstacle. Further, since fissility is the best, it can be ensured that stable productivity ratio.
On the other hand, the resolution of photosensitive polymer combination of comparative example 1～4, adaptation are all deteriorated. It addition, the photosensitive polymer combination of comparative example 1,3,4 is big due to the foot of solidification resist layer, follow-up The worry producing obstacle is there is when the etching of operation, plating.And then, due to the photonasty of comparative example 1,2 The fissility of resin combination is the poorest, it is difficult to obtain stable volume of production.
In detail and describe the present invention with reference to specific embodiment, but the technology of art Personnel understand, without departing from the spirit and scope of the present invention can various changes or repair in addition Change.
The application based on Japanese patent application (Japanese Patent Application 2011-046373) filed in 3 days March in 2011, Its content is as with reference to introducing in the application.
Industrial applicability
The photosensitive polymer combination of the present invention and photoresist have resolution and adaptation is good The effect that foot is minimum, fissility is the best of the solidification resist layer well and after development.Therefore, originally The photosensitive polymer combination of invention and photoresist are at printed circuit board (PCB), lead frame, semiconductor package The manufacture of dress body etc., metal the field such as Precision Machining in, it is possible to be used as etching resist, plating aptly The anticorrosive additive materials such as resist.
Description of reference numerals
1 solidification resist layer
2 substrates (Copper thin film)
3 foots
4 coating layers (thin copper film)

Claims (8)

1. a photosensitive polymer combination, it is characterised in that it contains (A) binder polymer, (B) Have amino the monomer of photopolymerization, (C) Photoepolymerizationinitiater initiater and (D) can have the benzo three of carboxyl Zole derivatives, described (A) binder polymer has carboxyl, and the acid number of described binder polymer is 100～300mgKOH/g.
Photosensitive polymer combination the most according to claim 1, it is characterised in that (B) has amino Can the monomer of photopolymerization be following logical formula (I) represent can the unsaturated compound of photopolymerization,
Wherein, the R in formula (I)1For H or CH3；R2And R3Separately represent and select free hydrogen former Group in the group that son, alkyl, alkoxyl and halogen group are formed, R2And R3Can mutual key Close and form the ring comprising N；X is the alkylidene of carbon number 1～10, or (C2H4O) m or (C3H6O) n institute That represent, m, n are respectively the polyoxy alkylidene of the integer of 1～10；Polyoxy alkylidene be atactic polymerization or Person's block polymerization.
Photosensitive polymer combination the most according to claim 1 and 2, it is characterised in that relative to 100 Weight portion (A) binder polymer, containing 0.01～30 weight portions (B) there is amino can the list of photopolymerization Body.
Photosensitive polymer combination the most according to claim 1 and 2, it is characterised in that relative to 100 Weight portion (A) binder polymer, has the benzotriazole derivatives of carboxyl containing 0.01～2 weight portions (D).
Photosensitive polymer combination the most according to claim 3, it is characterised in that relative to 100 Weight portion (A) binder polymer, has the benzotriazole derivatives of carboxyl containing 0.01～2 weight portions (D).
6. a photoresist, it is characterised in that it comprises by described in any one of Claims 1 to 5 Photosensitive polymer combination formed photosensitive polymer combination layer and supporting layer.
7. a forming method for corrosion-resisting pattern, comprising: use the photoresist described in claim 6 Film forms photosensitive polymer combination layer on base material, and is exposed, develops.
8. a forming method for conductive pattern, comprising: use the photoresist described in claim 6 Film forms photosensitive polymer combination layer on circuit formation substrate, and is exposed, develops, and is formed Corrosion-resisting pattern；And
The described circuit formation substrate being formed with described corrosion-resisting pattern is etched or plating, peels off Described corrosion-resisting pattern.
CN201280011581.8A 2011-03-03 2012-02-27 Photosensitive polymer combination, use its photoresist, the forming method of corrosion-resisting pattern and the forming method of conductive pattern Active CN103430100B (en)

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