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CN101802710A - Photosensitive resin composition and laminate thereof - Google Patents

Photosensitive resin composition and laminate thereof Download PDF

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Publication number
CN101802710A
CN101802710A CN200880107510A CN200880107510A CN101802710A CN 101802710 A CN101802710 A CN 101802710A CN 200880107510 A CN200880107510 A CN 200880107510A CN 200880107510 A CN200880107510 A CN 200880107510A CN 101802710 A CN101802710 A CN 101802710A
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photosensitive polymer
polymer combination
group
substrate
quality
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筒井大和
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Asahi Chemical Co Ltd
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Asahi Chemical Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1063—Esters of polycondensation macromers of alcohol terminated polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • H01L21/0274—Photolithographic processes

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  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Materials For Photolithography (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Graft Or Block Polymers (AREA)
  • Laminated Bodies (AREA)

Abstract

Disclosed is a photosensitive resin composition containing 20-90% by mass of a binder resin (a), 5-75% by mass of an addition polymerizable monomer (b) having at least one terminal ethylenically unsaturated group, and 0.01-30% by mass of a photopolymerization initiator (c). The binder resin (a) has an acid equivalent weight of the carboxyl group content of 100-600 and a weight average molecular weight of 5,000-500,000, while containing a specific compound as a copolymerization component. This photosensitive resin composition is characterized in that the addition polymerizable monomer (b) contains a specific addition polymerizable monomer.

Description

Photosensitive polymer combination with and layered product
Technical field
The photosensitive polymer combination that the present invention relates to develop by alkaline aqueous solution, this photosensitive polymer combination is laminated to photosensitive-resin layered product on the supporter, uses this photosensitive-resin layered product to form the method for corrosion-resisting pattern and the purposes of this corrosion-resisting pattern on substrate.In more detail, relate to a kind of photosensitive polymer combination, it provides the corrosion-resisting pattern that is applicable to following purposes: the manufacturing of printed-wiring board (PWB); The manufacturing of flexibility printed circuit board; The IC chip carries the manufacturing with lead frame (hereinafter referred to as lead frame); Metal forming Precision Machining, BGA (BGA Package) or CSP semiconductor package body manufacturings such as (chip size packages) with metal mask manufacturing etc.; (cover brilliant film: be the manufacturing of the belt base plate of representative the material that on the fine wiring board of film like, carries semiconducter IC) with TAB (carrier band bonding automatically) or COF; The manufacturing of semiconductor projection; The manufacturing of parts such as ITO electrode, addressing electrode or electromagnetic wave shield in the field of flat panel displays; And the protection mask parts during by blasting craft processing base material.
Background technology
At present, printed-wiring board (PWB) is by the photoetching process manufacturing.So-called photoetching process, be meant photosensitive resin coating composition on substrate, and make the exposed portion polymerizing curable of this photosensitive polymer combination by pattern exposure, remove unexposed portion and on substrate, form corrosion-resisting pattern by developer solution, carry out the processing of etching or plating and form conductive pattern, then, peel off from this substrate and to remove this corrosion-resisting pattern, thereby on substrate, form the method for conductive pattern.
In above-mentioned photoetching process, on substrate, during the photosensitive resin coating composition, can use any of following method: painting erosion resistant agent solution and make its dry method on substrate; Or will be successively lamination supporter, the layer that constitutes by photosensitive polymer combination (hereinafter referred to as " photo-sensitive resin ".) and the photosensitive-resin layered product that obtains of protective seam as required (hereinafter referred to as " dry film against corrosion ".) be laminated to the method on the substrate.And, in the manufacturing of printed-wiring board (PWB), use the latter's dry film against corrosion mostly.
Below simple the description use above-mentioned dry film against corrosion to make the method for printed-wiring board (PWB).
At first, have at dry film against corrosion under the situation of the protective seam of polyethylene film etc. for example, it is peeled off from photo-sensitive resin.Then, use laminating machine according to the order of substrate, photo-sensitive resin, supporter (usually by polyethylene terephthalate etc. form) photo-sensitive resin and support body layer to be pressed onto on the substrate such as copper clad laminate.Then, by having the photomask of line pattern, this photo-sensitive resin is exposed under the ultraviolet ray that contains i ray (365nm) that ultrahigh pressure mercury lamp sends, thereby make the exposed portion polymerizing curable.Peel off supporter then.Then, by having developer solution such as weakly alkaline aqueous solution, with the unexposed portion dissolving of photo-sensitive resin or disperse to remove, on substrate, form corrosion-resisting pattern.
Then, the technology of formation circuit roughly is divided into 2 kinds of methods after forming corrosion-resisting pattern.First method is that the copper face etching of the copper clad laminate that will do not covered by corrosion-resisting pattern etc. is removed, and uses the alkaline aqueous solution stronger than developer solution to remove the method for corrosion-resisting pattern part then.In this situation,, mostly adopt under the situation and cover through hole (through hole) with cured film for the simplification of operation, then etching method (Gai Kongfa, tenting).Second method is to handle carrying out the copper plating on the copper face same as described above, carries out the plating of solder, nickel and tin etc. as required again and handles, and removes the corrosion-resisting pattern part then equally, again the method (plating method) of the copper face of the copper clad laminate that exposes of etching etc.Use acidic etching liquids such as cupric chloride, iron protochloride, cupric ammine complex solution, sulfuric acid/aqueous hydrogen peroxide solution in the etching.
Be accompanied by the miniaturization of line segregation in the printed-wiring board (PWB) in recent years,, dry film against corrosion required high resolving power and high adhesion force in order to make the pattern of thin space with good yield rate.
And then, the semi-solid preparation resist of flanging (solidifying the resist root) (with reference to Fig. 1) appears being known as at the boundary member that solidifies resist and substrate after development sometimes, if it is big that this flanging becomes, then the flanging between the resist connects, resolution is insufficient, this with etching work procedure after the unsteady problem of conductive pattern to occur relevant.The very little dry film photoresist of flanging of the curing resist after therefore, requirement is developed.
In addition, recently, for the viewpoint of making the thin space pattern with good yield rate, it is important further that the plating method becomes.In the plating method, the anti-plating fluidity of resist is important, if anti-plating fluidity is insufficient, then treating fluid is infiltrated up between resist and the substrate when the plating pre-treatment, and undercutting appears in the resist after the curing, occurs the phenomenon of resist from substrate floating easily.This phenomenon occurs and can cause plating to be spread and sunk in oozing (plating overflow and to the phenomenon of the bottom of resist), so expect the photoresist of anti-plating fluidity excellence.
A kind of resolution, adhesion, anti-plating fluidity, peel property, scum silica frost generation property of photosensitive polymer combination are disclosed in patent documentation 1, but about the fully reply of can't saying so of resolution, adhesion, the present present situation of anti-plating fluidity, wherein said photosensitive polymer combination contains the quadripolymer and the tristane dimethanol dimethylacrylate of methacrylic acid/methyl methacrylate/butyl acrylate/2-EHA.
Patent documentation 1: TOHKEMY 2001-154348 communique
Summary of the invention
The problem that invention will solve
The objective of the invention is to, provide anticorrosive additive material as etching resist or plating resist etc. to have excellent especially high resolving power and high adhesion force and develop after the very little and then anti-plating fluidity excellence of flanging photosensitive polymer combination and use the photosensitive-resin layered product of this photosensitive polymer combination.
The scheme that is used to deal with problems
Above-mentioned purpose can realize by following scheme of the present invention.Be that the present invention thes contents are as follows.
1. photosensitive polymer combination, it contains:
(a) bonding agent resin of 20～90 quality %, its carboxyl-content counts 100～600 with acid equivalent, as copolymer composition contain be selected from following general formula (I) and (II) shown in the compound group at least a compound unit, and weight-average molecular weight is 5000～500000;
(b) of 5～75 quality % has the addition polymerization monomer of at least one terminal ethylenically unsaturated group; And,
0.01 (c) Photoepolymerizationinitiater initiater of～30 quality %,
Should contain at least a kind of addition polymerization monomer that is selected from the compound group shown in the following general formula (III) by (b) addition polymerization monomer,
[Chemical formula 1]
Figure GPA00001061356300041
In the formula, R 1Expression hydrogen atom or methyl, R 2Expression is selected from a kind of group in the group of being made up of alkoxy, carboxyl and the haloalkyl of the alkyl of hydrogen atom, halogen atom, hydroxyl, carbon number 1～12, carbon number 1～12,
[Chemical formula 2]
Figure GPA00001061356300042
In the formula, R 3Expression hydrogen atom or methyl, R 4Expression is selected from a kind of group in the group of being made up of alkoxy, carboxyl and the haloalkyl of the alkyl of hydrogen atom, halogen atom, hydroxyl, carbon number 1～12, carbon number 1～12,
[chemical formula 3]
Figure GPA00001061356300051
R 5And R 6Represent hydrogen atom or methyl independently of one another; A and B represent the alkylidene of carbon number 2～6, and they can be the same or different, not simultaneously ,-(A-O)-and-(B-O)-repetitive can be block structure, also can be disordered structure; M1, m2, m3 and m4 are 0 or positive integer, and their summation is 0～40; R 7Be that halogen atom or carbon number are 1～3 alkyl, n is 0～14 integer.
2. according to aforementioned 1. described photosensitive polymer combinations, wherein, the containing ratio of at least a addition polymerization monomer shown in the above-mentioned general formula (III) is 5～35 quality % with respect to overall photosensitive polymer combination.
3. according to aforementioned 1. or 2. described photosensitive polymer combinations, described Photoepolymerizationinitiater initiater (c) contains and is selected from least a 2,4 in the compound group shown in the following general formula (IV), 5-triarylimidazoles dipolymer,
[chemical formula 4]
Figure GPA00001061356300061
In the formula, it is a kind of group in the group formed of 1～5 alkyl and alkoxy and halogen radical that X, Y and Z represent to be selected from by hydrogen, carbon number independently of one another, and p, q and r are 1～5 integer independently of one another.
4. according to aforementioned 1.～3. each described photosensitive polymer combinations, wherein, described addition polymerization monomer (b) contains and is selected from least a kind of addition polymerization monomer in the compound group shown in the following general formula (V),
[chemical formula 5]
Figure GPA00001061356300062
In the formula, R 8And R 9Represent hydrogen atom or methyl independently of one another, t1 and t3 are 0～4 integer, and t2 is 4～20 integer.
5. according to aforementioned 1.～4. each described photosensitive polymer combinations, the terminal ethylenically unsaturated group of the described addition polymerization monomer (b) that every 100g photosensitive polymer combination is contained is 0.10～0.40 mole.
6. photosensitive-resin layered product, it comprises supporter and aforementioned 1.～5. each described photosensitive polymer combinations of lamination thereon.
7. corrosion-resisting pattern formation method, it comprises lamination, exposure process and the developing procedure that uses aforementioned 6. described photosensitive-resin layered products to form photo-sensitive resin on substrate.
8. according to aforementioned 7. described corrosion-resisting pattern formation methods, wherein, in aforementioned exposure process, directly draw.
9. the manufacture method of a printed-wiring board (PWB), it comprises the operation of the substrate that utilizes aforementioned 7. or 8. described methods to form corrosion-resisting pattern being carried out etching or plating.
10. the manufacture method of a lead frame, it comprises that the substrate to utilizing aforementioned 7. or 8. described methods to form corrosion-resisting pattern carries out etched operation.
11. the manufacture method of a semiconductor package body, it comprises the operation of the substrate that utilizes aforementioned 7. or 8. described methods to form corrosion-resisting pattern being carried out etching or plating.
12. the manufacture method of a projection, it comprises the operation of the substrate that utilizes aforementioned 7. or 8. described methods to form corrosion-resisting pattern being carried out etching or plating.
13. the manufacture method with base material of relief pattern, it comprises the operation of the substrate that utilizes aforementioned 7. or 8. described methods to form corrosion-resisting pattern being processed by sandblast.
The effect of invention
Photosensitive polymer combination of the present invention, photosensitive-resin layered product and use their to form method, printed-wiring board (PWB), lead frame, packaging body, the projection of corrosion-resisting pattern and manufacture method with base material of relief pattern can be brought into play following effect: particularly have excellent high resolving power and high adhesion force, and the flanging after developing is very little, and then anti-plating fluidity excellence.
Description of drawings
Fig. 1 is the explanation sketch of the flanging (solidifying the resist root) of the boundary member of curing resist and substrate.
Description of reference numerals
1 solidifies corrosion-resisting pattern
2 substrates
3 flangings
Embodiment
Below, the present invention is carried out specific description.
(a) bonding agent resin
The used bonding agent of the present invention with resin (a) is: carboxyl-content counts 100～600 with acid equivalent, as copolymer composition contain be selected from following general formula (I) and (II) shown in the compound group at least a compound, and weight-average molecular weight is 5000～500000 bonding agent resin.
[chemical formula 6]
Figure GPA00001061356300081
(in the formula, R 1Expression hydrogen atom or methyl, R 2Expression is selected from a kind of group in the group of being made up of alkoxy, carboxyl and the haloalkyl of hydrogen atom, halogen atom, hydroxyl, carbon number 1～12 alkyl, carbon number 1～12.)
[chemical formula 7]
Figure GPA00001061356300082
(in the formula, R 3Expression hydrogen atom or methyl, R 4Expression is selected from a kind of group in the group of being made up of alkoxy, carboxyl and the haloalkyl of hydrogen atom, halogen atom, hydroxyl, carbon number 1～12 alkyl, carbon number 1～12.)
Bonding agent is preferably counted more than 100 below 600 with acid equivalent with the amount of the contained carboxyl of resin (a), more preferably more than 250 below 450.So-called acid equivalent is meant the bonding agent that wherein the has 1 equivalent carboxyl quality of resin.
In order to give the development of photo-sensitive resin for alkaline aqueous solution, fissility, the carboxyl in the bonding agent is necessary.From improving anti-development and improving resolution and the viewpoint of adhesion, preferably this acid equivalent is more than 100, and from improving the viewpoint of development and fissility, preferably this acid equivalent is below 600.The flat natural pond automatic titration device (COM-555) that the mensuration of acid equivalent uses flat natural pond Industry Co., Ltd to make uses the NaOH of 0.1mol/L to be undertaken by potential difference titration.
The bonding agent that the present invention uses is 5000～500000 with the weight-average molecular weight of resin (a).From improving the viewpoint of development and resolution, this weight-average molecular weight is below 500000, from suppressing that photosensitive-resin layered product is wound into the phenomenon that photosensitive polymer combination oozes out from the tube end face under the situation of tubular is the viewpoint of edge-melting, and this weight-average molecular weight is more than 5000.。In order to bring into play effect of the present invention better, bonding agent is with the weight-average molecular weight of resin more preferably 5000～100000, and more preferably 5000～60000.
Weight-average molecular weight is gel permeation chromatography (GPC) (pump: Gulliver, the PU-1580 type of making by Japanese beam split Co., Ltd.; Post: 4 series connection of Shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) that clear and electrician's (strain) makes; Fluidized bed solvent: tetrahydrofuran; The typical curve that utilizes polystyrene standard sample (the Shodex STANDARD SM-105 that uses Showa Denko K. K to make) to draw) tries to achieve with polystyrene conversion.
The bonding agent that the present invention uses can be by respectively selecting one or more monomer and its copolymerization obtained from following 2 kinds of monomers with resin (a).
First monomer is carboxylic acid or the acid anhydrides that has a polymerism unsaturated group in the molecule.Can list for example (methyl) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester.
Second monomer is the compound that has a polymerism unsaturated group in nonacid, the molecule.This compound is selected with the development that keeps photo-sensitive resin, the mode of various characteristicses such as pliability of patience, cured film in etching and plating operation, and contain be selected from above-mentioned general formula (I) and (II) shown in the compound group at least a compound as necessary composition.
Compound as shown in the above-mentioned general formula (I) can list styrene and styrene derivative, for example α-Jia Jibenyixi, para hydroxybenzene ethene, p-methylstyrene, to methoxy styrene, to chlorostyrene.
As the compound shown in the above-mentioned general formula (II), for example can enumerate (methyl) benzyl acrylate, (methyl) acrylic acid 4-hydroxyl benzyl ester, (methyl) acrylic acid 4-methoxy benzyl ester, (methyl) acrylic acid 4-methyl benzyl ester, (methyl) acrylic acid 4-benzyl chloride ester.
Particularly, as be selected from above-mentioned general formula (I) and (II) shown in the compound group at least a compound, flanging after develop produces the viewpoint of property low (not having flanging or very little), the preferred styrene that uses, in addition, from the productive viewpoint of resolution, adhesion and flanging, more preferably use (methyl) acrylic acid benzyl ester.
1 molecule bonding agent with resin (a) in copolymerization, be selected from above-mentioned general formula (I) and (II) shown in the compound group in the consumption of at least a compound, be preferably below the above 95 quality % of 10 quality % with resin (a) with respect to bonding agent.This consumption is preferably more than the 10 quality % from resolution and adhesion, anti-plating bath, the productive viewpoint of flanging, is preferably below the 95 quality % from the viewpoint of development.More preferably below the above 90 quality % of 20 quality %, more preferably below the above 80 quality % of 25 quality %.
As bonding agent used in the present invention with resin (a), as second monomer, except as must the above-mentioned general formula (I) and/or compound (II) of composition, also can and with the known monomer beyond their as copolymer composition.Can list for example (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) cyclohexyl acrylate, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxyl butyl ester, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, (methyl) acrylamide, N hydroxymethyl acrylamide, N-butoxymethyl acrylamide, (methyl) vinyl cyanide, glycidyl methacrylate, these can use separately also and can be used in combination more than 2 kinds.
The used bonding agent of the present invention is preferably as follows with resin (a) and synthesizes: above-mentioned first monomer and second monomer are mixed, with solvent for example acetone, MEK, isopropanol, an amount of radical polymerization initiator for example benzoyl peroxide, the azoisobutyronitrile of adding in gained solution, and carry out heated and stirred, synthesize thus.Also have in reactant liquor, to drip a part of potpourri on one side, Yi Bian the situation of synthesizing.Also have after reaction finishes, also will add the situation that solvent is adjusted to required concentration.As synthetic method, except that solution polymerization, also can use bulk polymerization, suspension polymerization and emulsion polymerization.
The used bonding agent of the present invention with resin (a) with respect to the ratio of the summation of photosensitive polymer combination (solid constituent, also identical below) scope at 20～90 quality %, be preferably 30～70 quality %.From have the characteristic as resist through exposure, the corrosion-resisting pattern that develop to form, for example the viewpoint of the abundant patience in lid hole, etching and various plating operation etc. is set out, and this ratio is preferably below the above 90 quality % of 20 quality %.
(b) addition polymerization monomer
The used addition polymerization monomer (b) of the present invention is the addition polymerization monomer with at least one terminal ethylenically unsaturated group.Addition polymerization monomer (b) comprises at least a kind of addition polymerization monomer being selected from shown in the following general formula (III) in the compound group as must composition.
[chemical formula 8]
Figure GPA00001061356300121
(R 5And R 6Represent hydrogen atom or methyl independently of one another.A and B represent the alkylidene of carbon number 2～6, and they are optional identical or different, not simultaneously ,-(A-O)-and-(B-O)-repetitive optional be block structure, or disordered structure.Ml, m2, m3 and m4 are 0 or positive integer, and their summation is 0～40.R 7Be that halogen atom or carbon number are 1～3 alkyl, n is 0～14 integer.)
The A and the B that are selected from least a kind addition polymerization monomer in the compound group shown in the above-mentioned general formula (III) are preferably ethylidene or propylidene.In addition, from the viewpoint of resolution and adhesion, preferred m1+m2+m3+m4 is below 40, more preferably below 20, more preferably below 10.N is preferably 0.
As the concrete example of at least a addition polymerization monomer shown in the above-mentioned general formula (III), tristane dimethanol diacrylate (the system NK エ ス テ of Xin Zhong village chemical industry Co., Ltd. Le A-DCP) and tristane dimethanol dimethylacrylate (the system NK エ ス テ of Xin Zhong village chemical industry Co., Ltd. Le DCP) are arranged
In the present invention, being selected from the content of at least a kind of addition polymerization monomer in the compound group shown in the above-mentioned general formula (III), preferably is the embodiment of 5～40 quality % with respect to overall photosensitive polymer combination.From obtaining the viewpoint of resolution, adhesion and anti-plating fluidity, this content is preferably more than the 5 quality %, is preferably below the 40 quality % from the viewpoint of development.More preferably the scope of content is 7～35 quality %, and further preferred range is 9～30 quality %.
As the employed addition polymerization monomer of photosensitive polymer combination of the present invention (b), except above-claimed cpd, can also use known compound with at least one terminal ethylenically unsaturated group.
Can enumerate for example 4-nonyl phenyl seven ethylene glycol bisthioglycolate propylene glycol acrylate, 2-hydroxyl-3-phenoxy propyl acrylate, phenoxy group six EDIAs, (Japanese catalyst chemistry is made for the half ester compound of phthalic anhydride and acrylic acid 2-hydroxy propyl ester and the reactant of epoxypropane, trade name OE-A200), 4-n-octyl phenoxy group five propylene glycol acrylate, 2, two [{ 4-(methyl) the acryloyl-oxy Quito ethoxy } phenyl] propane of 2-, 2, two { (the 4-acryloyl-oxy Quito ethoxy) cyclohexyl } propane of 2-, 2, two { (the 4-methacrylic acid oxygen Quito ethoxy) cyclohexyl } propane of 2-, 1,6-hexanediol (methyl) acrylate, 1,4-cyclohexanediol two (methyl) acrylate, polyoxy is for alkane glycol two (methyl) acrylate polypropylene glycol two (methyl) acrylate for example, polyglycol two (methyl) acrylate, the polyoxyethylene polyoxy is for propylene glycol two (methyl) acrylate etc., 2-two (p-hydroxybenzene) propane two (methyl) acrylate, glycerine three (methyl) acrylate, polyfunctional group (methyl) acrylate (for example urine alkide of hexamethylene diisocyanate and five propylene glycol monomethyl acrylate) that contains urethane groups, and multifunctional (methyl) acrylate of isocyanurate compound.These can use separately also and can be used in combination more than 2 kinds.
Wherein, from the viewpoint of development, addition polymerization monomer (b) contains and is selected from that at least a kind of addition polymerization monomer in the compound group is the preferred embodiments of the invention shown in the following general formula (V).
[chemical formula 9]
(in the formula, R 8And R 9Represent hydrogen atom or methyl independently of one another.T1 and t3 are 0～4 integer, and t2 is 4～20 integer.)
As being selected from least a kind of addition polymerization monomer in the compound group shown in the above-mentioned general formula (V), for example can list four propylene glycol two (methyl) acrylate, seven propylene glycol two (methyl) acrylate, nine propylene glycol two (methyl) acrylate, 15 propylene glycol two (methyl) acrylate, two (methyl) acrylate that forms at the two ends of six propylene glycol addition diglycol, two (methyl) acrylate that forms at the two ends of ten dipropylene glycol addition diglycol.In the present invention, being selected from the consumption of at least a kind addition polymerization monomer in the compound group shown in the above-mentioned general formula (V), is that 5～30 quality % are preferred embodiment with respect to overall photosensitive polymer combination.The consumption of addition polymerization monomer is preferably more than the 5 quality % from the viewpoint of resolution, adhesion, development, is preferably below the 30 quality % from the viewpoint of development.Preferred scope is 5～25 quality %, and further preferred range is 5～20 quality %.
The consumption of contained addition polymerization monomer (b) is with respect to the scope of overall photosensitive polymer combination at 5～75 quality % in the photosensitive polymer combination of the present invention, and preferred scope is 15～70 quality %.From suppressing to solidify viewpoint bad and that development time postpones, this amount is more than the 5 quality %, and in addition, from the viewpoint of peeling off delay that suppresses cold flow and solidify resist, this amount is below the 75 quality %.
In photosensitive polymer combination of the present invention, the molal quantity of the terminal ethylenically unsaturated group of the addition polymerization monomer (b) that every 100g photosensitive polymer combination is contained is 0.10～0.40, and this viewpoint from resolution and corrosion liquid resistance is an embodiment preferred.
The terminal ethylenically unsaturated group here is meant and can causes photopolymerisable reactive group by the poly-property initiating agent of light in the structure of addition polymerization monomer, is meant acrylic and methacrylic acid group.
For keep after the higher exposure cross-linking density, when suppressing to develop swelling, keep resolution and adhesion, etching solution can not take place when the etching contaminate from line against corrosion bottom surface and make copper cash wait problem built on the sand, this value is preferably more than 0.10, in order to keep the high cross-linking density of appropriateness, not reduce the flexibility of cured film, this value is preferably below 0.40.The more preferably scope of above-mentioned value is 0.12～0.35, and further preferred range is 0.15～0.30.
(c) Photoepolymerizationinitiater initiater
As the Photoepolymerizationinitiater initiater that uses among the present invention (c), from high-resolution viewpoint, contain at least a 2,4 shown in the following general formula (IV), 5-triarylimidazoles dipolymer is an embodiment preferred.
[Chemical formula 1 0]
Figure GPA00001061356300151
(in the formula, X, Y and Z represent independently of one another to be selected from by hydrogen, carbon number be 1～5 alkyl and alkoxy, and the group formed of halogen group at least a group, p, q and r are 1～5 integer independently of one another.)
Compound shown in the above-mentioned general formula (IV) is connected 1 with 2 lophines (Lophine) base key covalent bond altogether, 1 '-, 1,2 '-, 1,4 '-, 2,2 '-, 2,4 '-or 4,4 '-position, but preferably be connected in the compound of 1,2 '-position.2,4,5-triarylimidazoles dipolymer has for example 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dipolymer, 2-(Chloro-O-Phenyl)-4,5-two (m-methoxyphenyl) imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenyl-imidazole dipolymer etc., preferred especially 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dipolymer.
In photosensitive polymer combination of the present invention, containing at least a 2,4 shown in the above-mentioned general formula (IV), the ratio during 5-triarylimidazoles dipolymer is preferably 0.1～20 quality %.From the viewpoint of resolution and adhesion is more than the 0.1 quality %, is below the 20 quality % from the coherent viewpoint of developing.Preferred scope is 0.5～15 quality %, and further preferred range is 1～10 quality %.
As the Photoepolymerizationinitiater initiater that uses among the present invention (c), preferred also with 2,4 shown in the above-mentioned general formula (IV), 5-triarylimidazoles dipolymer and p-aminophenyl ketone.As p-aminophenyl ketone for example can list aminobenzophenone, to the fourth aminoacetophenone, to the dimethylamino acetophenone, to dimethylamino benzophenone, P, P '-two (ethylamino) benzophenone, P, Michler's keton), P P '-two (dimethylamino) benzophenone (has another name called:, P '-two (lignocaine) benzophenone, P, P '-two (dibutylamino) benzophenone.
In addition, with pyrazoline compounds 1-phenyl-3-(4-t-butyl styrene base)-5-(4-tert-butyl-phenyl)-pyrazoline and with also being embodiment preferred for example.
In addition, except the Photoepolymerizationinitiater initiater of the compound shown in above-mentioned, can also and with other Photoepolymerizationinitiater initiater.Here the Photoepolymerizationinitiater initiater of indication is can be by various active rays for example activation such as ultraviolet ray and the compound of initiated polymerization.
As other Photoepolymerizationinitiater initiater, quinones is arranged, for example 2-EAQ, 2-tert-butyl group anthraquinone, the aromatic series ketone is benzophenone, benzoin for example, benzoin ethers is benzoin methylether, benzoin ethyl ether for example, the acridine compound for example, 9-phenylacridine, benzil dimethyl ketal, benzil diethyl ketal.
In addition, can also be thioxanthones, 2 for example, thioxanthene ketones such as 4-diethyl thioxanthone, 2-clopenthixal ketone are with the combination of tertiary amine compounds such as dimethylamino benzoic acid alkyl ester compound.
In addition, also has for example 1-phenyl-1 of oxime ester class, 2-propanedione-2-O-benzoyl oximes, 1-phenyl-1,2-propanedione-2-(O-carbethoxyl group) oxime.Also can use N-aryl-alpha-amino acid compound in addition, wherein preferred especially N-phenylglycine.
The ratio of Photoepolymerizationinitiater initiater of the present invention (c) is 0.01～30 quality %.If this ratio then can not get sufficient light sensitivity less than 0.01 quality %.In addition, if this ratio greater than 30 quality %, blushing takes place in diffraction of light by photomask when then exposing easily, the result worsens resolution.This content is 0.1～15 quality % more preferably, more preferably 0.1～10 quality %.
(d) other compositions
In photosensitive polymer combination of the present invention,, can contain leuco dye in order to bring into play the contrast (distinguishing of exposed portion and unexposed portion) after the exposure.Content when containing leuco dye is preferably 0.1～10 quality %.Leuco crystal violet), three (4-dimethylamino-2-aminomethyl phenyl) methane (has another name called: concealed malachite green), fluoran dyes can list three (4-dimethylamino-2-aminomethyl phenyl) methane as such leuco dye (has another name called:.Wherein, when using leuco crystal violet, so contrast is good preferred.
Being used in combination above-mentioned leuco dye and halogen compounds in photosensitive polymer combination, is the preferred embodiments of the invention from the viewpoint of adhesion and contrast.
For example can list as halogen compounds, bromo pentane, bromo isopentane, bromo isobutylene, bromoethylene, bromo diphenyl methane, benzal bromide, methylene bromide, trisbromomethyl phenyl sulfone, carbon tetrabromide, three (2, the 3-dibromo phenyl) phosphate, trichloroacetamide, iodo-pentane, iodo isobutane, 1,1,1-three chloro-2, two (rubigan) ethane of 2-, carbon trichloride, halogenation triaizine compounds.Can list 2,4 as this halogenation triaizine compounds, 6-three (trichloromethyl) s-triazine, 2-(4-methoxyphenyl)-4, two (trichloromethyl) s-triazine of 6-.
When containing halogen compounds, the content of the halogen compounds in the photosensitive polymer combination is preferably 0.01～10 quality %.
In order to improve the operability of photosensitive polymer combination, can also add above-mentioned leuco dye other coloring materials in addition.For example can list as this type of coloring material, magenta, phthalocyanine green, auramine, paramagenta, crystal violet, methyl orange, Nile blue (Nile blue)-2B, Victoria blue, malachite green (are protected native ケ paddy chemistry (strain) system, ア イ ゼ Application (registered trademark) MALACHITE GREEN), alkali blue 20, diamond green (are protected native ケ paddy chemistry (strain) system, ア イ ゼ Application (registered trademark), DIAMOND GREEN GH).
Addition when containing above-mentioned coloring material preferably is 0.001～1 quality % in photosensitive polymer combination.0.001 the above content of quality % has the effect that improves operability, the following content of 1 quality % has the effect of keeping storage stability.
Wherein, the combination of the combination of trisbromomethyl phenyl sulfone and leuco dye, triaizine compounds and leuco dye is useful.
And then thermal stability, storage stability in order to improve photosensitive polymer combination of the present invention, preferably in photosensitive polymer combination, contain more than one the compound that is selected from the group that radical polymerization inhibitor, benzotriazole and carboxyl benzotriazole class formed.
For example can list as this type of radical polymerization inhibitor, p methoxy phenol, quinhydrones, 1,2,3,-thrihydroxy-benzene, naphthylamines, tert-butyl catechol, protochloride ketone, 2,6-di-t-butyl-paracresol, 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), nitroso-phenyl azanol aluminium salt and diphenyl nitrosamine.
In addition, for example can list 1 as benzotriazole, 2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, two (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, two (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole and two (N-2-hydroxyethyl) aminomethylene-1,2, the 3-benzotriazole.
In addition, for example can list as the carboxyl benzotriazole class, 4-carboxyl-1,2,3-benzotriazole, 5-carboxyl-1,2,3-benzotriazole, N-(N, N-two-2-ethylhexyl) aminomethylene carboxyl benzotriazole, N-(N, N-two-2-hydroxyethyl) aminomethylene carboxyl benzotriazole and N-(N, N-two-2-ethylhexyl) aminomethylene carboxyl benzotriazole.
The summation addition of radical polymerization inhibitor, benzotriazole and carboxyl benzotriazole class is preferably 0.01～3 quality %, more preferably 0.05～1 quality %.From giving the viewpoint of photosensitive polymer combination storage stability, this amount is preferably more than the 0.01 quality %, in addition, and from the viewpoint of maintenance light sensitivity, more preferably below the 3 quality %.
In photosensitive polymer combination of the present invention, can contain plastifier as required.For example can list as this type of plastifier; polyglycol; polypropylene glycol; PPOX polyoxyethylene ether; the polyoxyethylene monomethyl ether; the PPOX monomethyl ether; polyoxyethylene polyoxypropylene monomethyl ether; polyoxyethylene list ether; PPOX list ether; two pure and mild ester classes such as polyoxyethylene PPOX list ether; phthalates such as diethyl phthalate, the o-methyl-benzene sulfonamide; to methyl benzenesulfonamide; tributyl citrate; triethyl citrate; CitroflexA-2; acetyl group citric acid three n-propyls; the acetyl group tri-n-butyl citrate.
Amount when containing plastifier preferably is 5～50 quality %, more preferably 5～30 quality % in photosensitive polymer combination.Viewpoint from suppressing to develop and postpone or give the cured film flexibility is preferably more than the 5 quality %, from suppressing to solidify the viewpoint of not enough and cold flow, is preferably below the 50 quality % in addition.
＜photosensitive polymer combination modulating liquid 〉
Photosensitive polymer combination of the present invention can also be made the photosensitive polymer combination modulating liquid that adds solvent.As the solvent that is fit to, can enumerate with MEK (MEK) is the ketone and the alcohols of representative, for example methyl alcohol, ethanol and isopropyl alcohol.Preferably in photosensitive polymer combination, add solvent, make that the viscosity of photosensitive polymer combination modulating liquid is 500～4000mPasec under 25 ℃.
＜photosensitive-resin layered product 〉
Photosensitive-resin layered product of the present invention comprises photo-sensitive resin and supports the supporter of this layer, can also be as required has protective seam with the surface of the opposite side of supporter of photo-sensitive resin.
As use therein supporter, the transparent supporting body that it is desirable to make the light that radiates by exposure light source to see through.As such supporter, can enumerate polyethylene terephthalate thin film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, Vingon film, vinylidene chloride copolymerization film, polymethyl methacrylate copolymer film, plasticon, polyacrylonitrile film, styrol copolymer film, polyamide film and cellulose derivative film etc.These films can also use the film of drawn as required.Preferred turbidity is below 5.About the thickness of film, the film of thin thickness owing to must keep intensity, preferably uses the thickness of 10～30 μ m being favourable aspect image formation property and the economy.
In addition, as the key property of protective seam used in photosensitive-resin layered product, with regard to regard to the adhesion of photo-sensitive resin, compared to supporter, the adhesion of protective seam aspect is enough little and can easily peel off.For example, can preferably use polyethylene film and polypropylene film etc. as protective seam.In addition, can use the film of the fissility excellence shown in the Japanese kokai publication sho 59-202457 communique.The thickness of protective seam is preferably 10～100 μ m, more preferably 10～50 μ m.
The thickness of the photo-sensitive resin in the photosensitive-resin layered product of the present invention is preferably 5～100 μ m, more preferably 5～50 μ m.Thickness is thin more, and resolution is high more, and in addition, thickness is thick more, and film strength is strong more, therefore can suitably select according to purposes.
Lamination supporter, photo-sensitive resin and the protective seam that is provided with as required and prepare the method for photosensitive-resin layered product of the present invention can adopt known method at present successively.For example, the photosensitive polymer combination that will be used for photo-sensitive resin is in advance made aforementioned photosensitive polymer combination modulating liquid, elder generation uses rod to be coated with machine or roll coater is applied to it on supporter, drying, the photo-sensitive resin that lamination is made of this photosensitive polymer combination on supporter.Then, as required,, thereby can prepare photosensitive-resin layered product by lamination protective seam on this photo-sensitive resin.
＜corrosion-resisting pattern formation method 〉
Use the corrosion-resisting pattern of photosensitive-resin layered product of the present invention to form by the operation that comprises lamination, exposure process and developing procedure.An example of concrete grammar is shown.
At first, use laminating machine to carry out lamination.Have at photosensitive-resin layered product under the situation of protective seam and peel off protective seam, then, use laminating machine that photo-sensitive resin is added thermo-compressed and be laminated on the substrate surface.At this moment, photo-sensitive resin can only be laminated on the single face of substrate surface, also can be laminated on the two sides as required.The heating-up temperature of this moment is generally 40～160 ℃.In addition, add thermo-compressed, can improve the adhesion of gained corrosion-resisting pattern substrate by carrying out more than the secondary this.At this moment, crimping can be used the two-period form laminating machine with two company's rollers, also can repeated multiple times carry out crimping by roller.
Then, use exposure machine to carry out exposure process.When needing, peel off supporter, and use active light to expose by photomask.Exposure is by light illumination and time shutter decision.Can also use quantometer to measure.
In exposure process, can also use maskless exposure method.Maskless exposure need not to use photomask, exposes by direct drawing apparatus on substrate.As light source, using wavelength is the semiconductor laser of 350～410nm or ultrahigh pressure mercury lamp etc.Describe pattern and controlled by computer, the exposure under this situation is decided by the illumination of exposure light source and the translational speed of substrate.
Then, use developing apparatus to carry out developing procedure.After exposure, have on the photo-sensitive resin under the situation of supporter this supporter is removed.Then, use the developer solution that constitutes by alkaline aqueous solution, unexposed portion is developed remove, obtain corrosion-resisting pattern.As alkaline aqueous solution, preferred Na 2CO 3Or K 2CO 3Aqueous solution.These can suitably be selected according to the characteristic of photo-sensitive resin, normally the Na of 0.2～2 quality % concentration 2CO 3Aqueous solution.Can also in this alkaline aqueous solution, sneak into surfactant, defoamer, be used to promote a small amount of organic solvent that develops etc.In addition, the temperature of this developer solution in the developing procedure preferably keeps steady temperature in 20～40 ℃ scope.
Obtain corrosion-resisting pattern by above-mentioned operation, but can also according to circumstances carry out this corrosion-resisting pattern is heated to 100～300 ℃ heating process.By carrying out this heating process, can further improve chemical reagent resistance.Heating can be used the heating furnace of the mode of hot blast, infrared ray or far infrared.
The manufacture method of＜printed-wiring board (PWB) 〉
The manufacture method of printed-wiring board (PWB) of the present invention is after forming corrosion-resisting pattern by above-mentioned corrosion-resisting pattern formation method on as the copper clad laminate of substrate or flexible substrate, carries out through following operation.
At first, carry out following operation: on the copper face of the substrate that exposes by development, for example etching method or plating method form the operation of conductive pattern to use known method.
Then, use aqueous solution, thereby obtain the printed-wiring board (PWB) of expectation the stripping process of corrosion-resisting pattern from strippable substrate with alkalescence stronger than developer solution.For the alkaline aqueous solution of peeling off usefulness (below be also referred to as " stripper ".) have no particular limits, use the NaOH of 2～5 quality % concentration or the aqueous solution of KOH usually.In stripper, also can add a spot of water-soluble solvent.In addition, the temperature of this stripper in the stripping process is preferably 40～70 ℃ scope.
The manufacture method of＜lead frame 〉
Lead frame manufacture method of the present invention is after forming corrosion-resisting pattern by aforementioned corrosion-resisting pattern formation method on as the sheet metal of copper, aldary or the iron-based alloy etc. of substrate, to carry out through following operation.
At first, thus carry out the substrate that exposes by development is carried out the operation that etching forms conductive pattern.Then, carry out by peeling off the stripping process of corrosion-resisting pattern, thereby obtain the lead frame of expectation with the same method of the manufacture method of above-mentioned printed-wiring board (PWB).
The manufacture method of＜semiconductor package body 〉
The manufacture method of semiconductor package body of the present invention can be by encapsulating by following operation and make semiconductor package body having finished circuit-formed chip as LSI.
At first, for the metal part of having exposed base material in the base material that adheres to corrosion-resisting pattern that obtains by development, implement the copper sulphate plating, thereby form conductive pattern.Then, the stripping process that the same method of the manufacture method of utilization and above-mentioned printed-wiring board (PWB) is peeled off corrosion-resisting pattern carries out etching again, so that remove the thin metal level of the part beyond the column plating, encapsulation said chip, thereby the semiconductor package body of acquisition expectation.
The manufacture method of＜projection 〉
For the circuit-formed chip of having finished as LSI is encapsulated, the manufacture method of projection of the present invention is according to following operation manufacturing.
At first, for the metal part of having exposed base material in the base material that adheres to corrosion-resisting pattern that obtains by development, implement the copper sulphate plating, thereby form conductive pattern.Then, the same method of the manufacture method of utilization and above-mentioned printed-wiring board (PWB) is peeled off the stripping process of corrosion-resisting pattern, carry out again removing the column plating operation of the thin metal level of part in addition by etching, thus the projection that acquisition is expected.
＜have a manufacture method of the base material of relief pattern 〉
The corrosion-resisting pattern that forms by aforementioned corrosion-resisting pattern formation method can be used as and utilizes sand-blast that the protection mask parts that substrate adds man-hour is used.
As substrate, can enumerate for example glass, Silicon Wafer, amorphous silicon, polysilicon, pottery, sapphire, metal material etc.On substrates such as these glass, form corrosion-resisting pattern by the method identical with aforementioned corrosion-resisting pattern formation method.Then, be formed in the base material that has the micro concavo-convex pattern on the substrate through following operation: from formed corrosion-resisting pattern be cut to the degree of depth that is used to spray sand-blast material the blasting treatment operation, remove the corrosion-resisting pattern stripping process partly that residues on the substrate from substrate with alkaline stripper.The sand-blast material that uses in the above-mentioned blasting treatment operation can use known material, for example, uses SiC, SiO 2, Al 2O 3, CaCO 3, ZrO, glass, stainless steel etc. particle diameter be particulate about 2～100 μ m.
The method of utilizing above-mentioned sand-blast manufacturing to have the base material of relief pattern can be used in: the perforation processing of the manufacturing in the next door of flat-panel monitor, the processing of the glass cover of organic EL, Silicon Wafer and the contact pin processing of pottery.Can be used in strong dielectric film and the manufacturing that is selected from the electrode of the metal material layer in the group of forming by noble metal, precious metal alloys, refractory metal and high melting point metal compound in addition.
Embodiment
Below, the example of embodiment of the present invention is elaborated.
(embodiment 1～8, comparative example 1～3)
The evaluation method of sample preparation of embodiment and comparative example at first is described, then, the evaluation method and the evaluation result thereof of gained sample is shown.
1. estimate preparation with sample
Evaluation in embodiment and the comparative example is prepared as follows with sample.
The preparation of＜photosensitive-resin layered product 〉
(wherein the numeral of each composition is as the use level (mass parts) of solid constituent fully to stir the composition shown in the table 1.) photosensitive polymer combination and solvent, mix and formation photosensitive polymer combination modulating liquid, use rod to be coated with machine it evenly is applied to surface as the polyethylene terephthalate thin film of 16 μ m thickness of supporter, drying is 2.5 minutes in 95 ℃ dryer, thereby forms photo-sensitive resin.The thickness of photo-sensitive resin is 25 μ m.
Then, on the surface that does not have the lamination polyethylene terephthalate thin film of photo-sensitive resin, fit, thereby obtain photosensitive-resin layered product as the thick polyethylene film of 21 μ m of protective seam.
The title of material composition B-1～D-2 in the photosensitive polymer combination modulating liquid of the symbolic representation in table 1 shown in the following table 2.
The whole face of＜substrate 〉
Use lamination that the thick copper clad laminate of 0.4mm of 35 μ m rolled copper foils is arranged as resolution, adhesion, flanging generation property and the evaluation of anti-plating fluidity with substrate, under injection pressure 0.20MPa, this laminate surface is carried out jet cleaning and grind (Japanese カ one リ Star ト (strain) makes, サ Network ラ Application ダ system R (registered trademark) #220).
＜lamination 〉
The polyethylene film of photosensitive-resin layered product is peeled off on the limit, and (Asahi Kasei Electronics Components Co., Ltd makes, and AL-70) is preheated to 60 ℃ copper clad laminate upper strata pressure sensitivity photosensitiveness resinite at whole face under 105 ℃ of roll temperatures by the hot-roll lamination machine on the limit.Air pressure is 0.35MPa, and laminate speed is 1.5m/min.
＜exposure 〉
Use the chromium glass photomask, at ultrahigh pressure mercury lamp (manufacturing of ウ シ オ Electric Co., Ltd, projection aligner UX2003SM-MS04), with 120mJ/cm 2Exposure carry out i ray monochromatic exposure.
＜develop
After peeling off polyethylene terephthalate thin film, 30 ℃ the 1 quality %Na of spray stipulated time 2CO 3Aqueous solution, the unexposed portion of photo-sensitive resin is removed in dissolving.At this moment, dissolving the needed minimum time fully with the photo-sensitive resin of unexposed portion is minimum development time.
＜plating pre-treatment 〉
Anti-plating evaluation substrate after developing is immersed in acid degreasing FRX (10% aqueous solution, ア ト テ Star Network ヅ ヤ パ Application (strain) is made) body lotion 40 ℃ under 4 minutes.At room temperature be immersed in 10% the aqueous sulfuric acid 2 minutes after the washing.
＜copper sulphate plating 〉
Concentrated sulphuric acid copper (Copper Sulfate Conc) (メ Le テ Star Network ス (strain) system) with the Dilution of sulphuric acid to 3.6 of 19 weight % times, is added concentrated hydrochloric acid to 200ppm.Add then as the カ パ ラ シ Star De HL of the 0.4ml/l of polishing material and the カ パ ラ シ Star De GS of 20ml/l.The copper sulphate plating solution of use utilizes the even plating apparatus of Haring cell (society of Yamamoto Gold Plating Tester Co., Ltd. system), under the impressed current 0.4A to the (plating of 6cm * 12.5cm) 65 minutes of the anti-plating evaluation substrate after the plating pre-treatment.The thickness of the copper plating film of this moment is 21 μ m.
＜peel off
Evaluation substrate after plating is handled sprays the sodium hydrate aqueous solution of 50 ℃ 3 weight %, peels off and removes resist film.
2. evaluation method
Each evaluation method below is shown.
(1) resolution
To behind the lamination through 15 minutes resolution evaluation substrate, the width by exposed portion and unexposed portion is that the line pattern mask (chromium glass photomask) of 1: 1 ratio exposes.Develop with 2 times of minimum development time development times, will normally form the minimum mask line width that solidifies the corrosion-resisting pattern line value as resolution, resolution is carried out classification according to following.
◎ (excellent): the value of resolution is below the 7.5 μ m.
Zero (very): the value of resolution surpasses 7.5 μ m, and is below the 8.5 μ m.
* (bad): the value of resolution surpasses 8.5 μ m.
(2) adhesion
To behind the lamination through 15 minutes adhesion evaluation substrate, the width by exposed portion and unexposed portion is that the line pattern mask (chromium glass photomask) of 1: 100 ratio exposes.Develop with 2 times of minimum development time development times, will normally form the minimum mask line width that solidifies the corrosion-resisting pattern line value as adhesion, adhesion carries out classification according to following.
◎ (excellent): the value of adhesion is below the 13 μ m.
Zero (very): the value of adhesion surpasses 13 μ m, and is below the 14 μ m.
* (bad): the value of adhesion surpasses 14 μ m.
(3) flanging generation property
To producing property evaluation substrate through 15 minutes flanging behind the lamination, the width by exposed portion and unexposed portion is that the line pattern mask (chromium glass photomask) of 1: 100 ratio exposes.Develop with 2 times of minimum development time development times, the flanging that the root of the resist line of the 15 μ m that observe at gained occurs, flanging produce property and carry out classification according to following.
◎ (excellent): do not have flanging to occur fully.
Zero (very): the width that the online side of flanging occurs is less than 1 μ m.
* (bad): the width that the online side of flanging occurs is more than the 1 μ m.
(4) anti-plating fluidity
To behind the lamination through 15 minutes anti-plating evaluation substrate, the width by exposed portion and unexposed portion is that the line pattern mask (chromium glass photomask) of 1: 100 ratio exposes.2 times development time with minimum development time develops, and carries out the copper sulphate plating then, peels off the curing resist again.The copper sulphate plating line of 15 μ m part behind the resist is peeled off in observation, and anti-plating fluidity is carried out classification according to following.
Zero (very): do not have spreading and sinking in of copper sulphate plating to ooze fully.
△ (generally): the online side of width that the spreading and sinking in of copper sulphate plating oozed is less than 1 μ m.
* (bad): the online side of width of oozing of spreading and sinking in of copper sulphate plating is more than the 1 μ m.
3. evaluation result
The evaluation result of embodiment 1～8 and comparative example 1～3 is as shown in table 1.
Figure GPA00001061356300281
Table 2
Symbol Composition
??B-1 The methyl ethyl ketone solution of the 43 quality % (solid constituent) that composition, acid equivalent with methacrylic acid/methyl methacrylate/styrene (mass ratio 25/50/25) is 344, weight-average molecular weight is 50,000 multipolymer
??B-2 The methyl ethyl ketone solution of the 41 quality % (solid constituent) that composition, acid equivalent with methacrylic acid/styrene/methacrylic acid benzyl ester (mass ratio 30/20/50) is 290, weight-average molecular weight is 5.5 ten thousand multipolymer
??B-3 The methyl ethyl ketone solution of the 50 quality % (solid constituent) that composition, acid equivalent with methacrylic acid/benzyl methacrylate (mass ratio 20/80) is 430, weight-average molecular weight is 2.5 ten thousand multipolymer
??B-4 The methyl ethyl ketone solution of the 34 quality % (solid constituent) that composition, acid equivalent with methacrylic acid/methyl methacrylate/n-butyl acrylate (mass ratio 25/65/10) is 374, weight-average molecular weight is 80,000 multipolymer
??M-1 Tristane dimethanol dimethylacrylate (the system NK エ ス テ of Xin Zhong village KCC Le DCP, ProductName)
??M-2 Tristane dimethanol diacrylate (the system NK エ ス テ of Xin Zhong village KCC Le A-DCP, ProductName)
??M-3 Seven propylene glycol dimethylacrylates
??M-4 7: 3 potpourri of pentaerythritol triacrylate and tetramethylol methane tetraacrylate (East Asia synthetic (strain) system, M-306)
??M-5 (2, two [4-(methacryloxy five ethoxys) phenyl] propane of 2-(Xin Zhong village chemistry (strain) system, BPE-500, ProductName)
??1-1 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,1 '-bisglyoxaline
??1-2 4,4 '-two (lignocaine) benzophenone
??D-1 Diamond green (hodogaya chemical (strain) system, ア イ ゼ Application (registered trademark) DIAMOND GREENGH)
Symbol Composition
??D-2 Leuco crystal violet
As shown in table 1, embodiment 1～8 is by adopting formation of the present invention, resolution, adhesion, flanging generation property and the equal balance excellence of anti-plating fluidity.
In the comparative example 1, bonding agent with resin do not contain be selected from above-mentioned general formula (I) and (II) shown in the compound group at least a compound as copolymer composition, comparative example 2 and comparative example 3 do not contain at least a addition polymerization monomer that is selected from the compound group shown in the above-mentioned general formula (III) as addition polymerization monomer (b).Therefore as can be known, resolution, adhesion, flanging generation property and the equal balance of anti-plating fluidity are unexcellent.
Industrial utilizability
The present invention can be in the manufacturing of printed substrate, and the IC chip carrying is with the manufacturing in the next door of the flat-panel monitors such as the manufacturing of the Production Example of the manufacturing of the metal forming Precision Machining such as the manufacturing of lead frame, metal mask manufacturing, semiconductor package body such as BGA or CSP, belt base plate such as COF or TAB, semiconductor projection, ITO electrode, addressing electrode, electromagnetic wave shield and have by the blasting craft manufacturing in the method for base material of relief pattern and use.

Claims (13)

1. photosensitive polymer combination, it contains:
(a) bonding agent resin of 20～90 quality %, its carboxyl-content counts 100～600 with acid equivalent, as copolymer composition contain be selected from following general formula (I) and (II) shown in the compound group at least a compound unit, and weight-average molecular weight is 5000～500000;
(b) of 5～75 quality % has the addition polymerization monomer of at least one terminal ethylenically unsaturated group; And,
0.01 (c) Photoepolymerizationinitiater initiater of～30 quality %,
Should contain at least a kind of addition polymerization monomer that is selected from the compound group shown in the following general formula (III) by (b) addition polymerization monomer,
[Chemical formula 1]
Figure FPA00001061356200011
In the formula, R 1Expression hydrogen atom or methyl, R 2Expression is selected from a kind of group in the group of being made up of alkoxy, carboxyl and the haloalkyl of the alkyl of hydrogen atom, halogen atom, hydroxyl, carbon number 1～12, carbon number 1～12,
[Chemical formula 2]
Figure FPA00001061356200012
In the formula, R 3Expression hydrogen atom or methyl, R 4Expression is selected from a kind of group in the group of being made up of alkoxy, carboxyl and the haloalkyl of the alkyl of hydrogen atom, halogen atom, hydroxyl, carbon number 1～12, carbon number 1～12,
[chemical formula 3]
R 5And R 6Represent hydrogen atom or methyl independently of one another; A and B represent the alkylidene of carbon number 2～6, and they can be the same or different, not simultaneously ,-(A-O)-and-(B-O)-repetitive can be block structure, also can be disordered structure; M1, m2, m3 and m4 are 0 or positive integer, and their summation is 0～40; R 7Be that halogen atom or carbon number are 1～3 alkyl, n is 0～14 integer.
2. photosensitive polymer combination according to claim 1, wherein, the containing ratio of at least a addition polymerization monomer shown in the above-mentioned general formula (III) is 5～35 quality % with respect to overall photosensitive polymer combination.
3. photosensitive polymer combination according to claim 1 and 2, described Photoepolymerizationinitiater initiater (c) contain and are selected from least a 2,4 in the compound group shown in the following general formula (IV), 5-triarylimidazoles dipolymer,
[chemical formula 4]
Figure FPA00001061356200031
In the formula, it is a kind of group in the group formed of 1～5 alkyl and alkoxy and halogen radical that X, Y and Z represent to be selected from by hydrogen, carbon number independently of one another, and p, q and r are 1～5 integer independently of one another.
4. according to each described photosensitive polymer combination of claim 1～3, wherein, described addition polymerization monomer (b) contains and is selected from least a kind of addition polymerization monomer in the compound group shown in the following general formula (V),
[chemical formula 5]
Figure FPA00001061356200032
In the formula, R 8And R 9Represent hydrogen atom or methyl independently of one another, t1 and t3 are 0～4 integer, and t2 is 4～20 integer.
5. according to each described photosensitive polymer combination of claim 1～4, the terminal ethylenically unsaturated group of the described addition polymerization monomer (b) that every 100g photosensitive polymer combination is contained is 0.10～0.40 mole.
6. photosensitive-resin layered product, it comprises supporter and each described photosensitive polymer combination of claim 1～5 of lamination thereon.
7. corrosion-resisting pattern formation method, it comprises lamination, exposure process and the developing procedure that uses the described photosensitive-resin layered product of claim 6 to form photo-sensitive resin on substrate.
8. corrosion-resisting pattern formation method according to claim 7 wherein, in aforementioned exposure process, is directly drawn.
9. the manufacture method of a printed-wiring board (PWB), it comprises the operation of the substrate that utilizes claim 7 or 8 described methods to form corrosion-resisting pattern being carried out etching or plating.
10. the manufacture method of a lead frame, it comprises that the substrate to utilizing claim 7 or 8 described methods to form corrosion-resisting pattern carries out etched operation.
11. the manufacture method of a semiconductor package body, it comprises the operation of the substrate that utilizes claim 7 or 8 described methods to form corrosion-resisting pattern being carried out etching or plating.
12. the manufacture method of a projection, it comprises the operation of the substrate that utilizes claim 7 or 8 described methods to form corrosion-resisting pattern being carried out etching or plating.
13. the manufacture method with base material of relief pattern, it comprises the operation of the substrate that utilizes claim 7 or 8 described methods to form corrosion-resisting pattern being processed by sandblast.
CN200880107510A 2007-09-18 2008-09-17 Photosensitive resin composition and laminate thereof Pending CN101802710A (en)

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