CN101925861A - Layered product of photosensitive resin - Google Patents

Layered product of photosensitive resin Download PDF

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Publication number
CN101925861A
CN101925861A CN2009801027051A CN200980102705A CN101925861A CN 101925861 A CN101925861 A CN 101925861A CN 2009801027051 A CN2009801027051 A CN 2009801027051A CN 200980102705 A CN200980102705 A CN 200980102705A CN 101925861 A CN101925861 A CN 101925861A
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integer
resin
photosensitive
layered product
formula
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CN101925861B (en
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五十岚勉
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Asahi Kasei Corp
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Asahi Chemical Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—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
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/161—Coating processes; Apparatus therefor using a previously coated surface, e.g. by stamping or by transfer lamination

Abstract

A layered product of a photosensitive resin is provided which has no problem concerning supporting-film removability and has satisfactory conformability in laminating. The layered product, after development, gives a satisfactory cured resist pattern in which the sidewalls are not rugged and the surface has no recesses. The foot after development spreads little. The photosensitive-resin layered product comprises a supporting film and, successively superposed thereon, a first layer having a thickness of 10-100 [mu]m, a second layer having a thickness of 0.1-10 [mu]m, and a photosensitive resin layer. The layered product is characterized in that the second layer comprises a mixture of a polyvinyl alcohol and one or more compounds selected from the group consisting of specific compounds.

Description

Photosensitive-resin layered product
Technical field
The present invention relates to photosensitive-resin layered product and uses thereof, more specifically, relate at printed-wiring board (PWB), flexible substrate, lead frame substrate, COF (chip on film, cover brilliant film) with substrate, semiconductor-sealing-purpose substrate, liquid crystal with transparency electrode, liquid crystal with TFT with the photosensitive-resin layered product that is suitable in the manufacturing of distribution, PDP (plasma display panel, plasma display) with the conductive pattern of electrode etc., and use the formation method of its corrosion-resisting pattern.
Background technology
In electronic equipments such as computer, mobile phone, use printed-wiring board (PWB) as being used for installing component, semi-conductive substrate.As the resist that is used to make printed-wiring board (PWB), use so-called dry film against corrosion (being designated hereinafter simply as DF) all the time, promptly at support membrane upper strata pressure sensitivity photosensitiveness resin bed, and then the photosensitive-resin layered product that the lamination protective seam forms on this photo-sensitive resin.
As employed photo-sensitive resin here, be generally the alkali developable photo-sensitive resin that uses weak alkaline aqueous solution as developer solution at present.
When using DF to make printed-wiring board (PWB) etc.; under the situation of matcoveredn, at first, peel off protective seam; use lamination DF on the permanent circuit of copper clad laminate, flexible substrate etc. is made with substrate such as laminating machine then, expose across Wiring pattern mask film (mask film) etc.Then, peel off support membrane as required, remove the photo-sensitive resin of unexposed portion, and on substrate, form the curing corrosion-resisting pattern by developing solution dissolution or dispersion.
After forming corrosion-resisting pattern, make its operation that forms circuit roughly be divided into two kinds of methods.
First method, etching use the alkaline aqueous solution stronger than developer solution to remove the method (etching method) of corrosion-resisting pattern part after removing the copper face of the copper clad laminate that do not covered by corrosion-resisting pattern etc.Second method after the plating that above-mentioned copper face is carried out copper, scolding tin, nickel and tin etc. is handled, is similarly removed the corrosion-resisting pattern part, and then the copper face of the copper clad laminate that manifests etc. is carried out etching method (plating method).Use cupric chloride, iron chloride, cupric ammine complex solution etc. during etching.
In addition, in recent years,, require the high-resolution of resist and tack (below, with reference to patent documentation 1) corresponding to the miniaturization that is installed in the printed-wiring board (PWB) on computer etc.As high resolving power, reach by the cross-linking density that improves photosensitive polymer combination usually, when cross-linking density was improved, the then curing corrosion-resisting pattern hardening after the exposure and crisp can produce the problems such as defective of carrying corrosion-resisting pattern in the operation.In addition, especially when photographic layer is film below about 10 μ m because transmitted light causes halation at substrate surface during exposure, thereby can sensitization to should unexposed photo-sensitive resin, and solidify in the corrosion-resisting pattern because it is reflected in, thereby also become the reason of short circuit.In addition, because halation can make the bottom surface of cured film produce the development residue that is referred to as flanging.When flanging produces according to the difference of its size, copper circuit can take place in etching work procedure produce and unfavorable condition such as rock.
In addition, the support membrane of DF, usually use mylar, because contained micro constitutents such as lubricant in the mylar, make when exposure an atomic little part by shading, the result: the face (surface) relative with substrate that can make the sidewall (sidewall) that solidifies corrosion-resisting pattern or solidify corrosion-resisting pattern produces and rocks or cave in.Especially during the fine distribution below being used to form 10 μ m, this influence can not be ignored.
In addition, during film below photographic layer is 10 μ m, because not servo-actuated fully of photographic layer during lamination on the small concavo-convex or scar of base material, thereby produce lamination bubble (air void), produce problems such as conductor opens circuit because of the infiltration of etching solution in this part.
Want to make no lamination bubble and high servo-actuated, the method for viscosity that reduces photographic layer is arranged, but exist photographic layer to ooze out, problems such as so-called excessive glue promptly take place from the tube end face.
In addition, when photographic layer is as thin as 10 μ m when following, the absolute magnitude deficiency of photographic layer, even at the concavo-convex or scar of base material and reduce the viscosity of photographic layer, its servo-actuated also can be insufficient.
For high resolving power and form good curing corrosion-resisting pattern shape and be not subjected to the influence of the lubricant in support membrane, the especially mylar, there is the method for peeling off support membrane and exposing, at this moment, because the curing that influences the resist surface that oxygen hinders is impaired, so film minimizing, the discoid problems such as shape of cured pattern of photographic layer take place.
As realizing high-resolution method, there is following method: by the middle layer that is formed by polyvinyl alcohol (PVA) is set between support membrane and photo-sensitive resin, before exposure process, peel off support membrane, on the middle layer, expose, thereby the realization high resolving power, and eliminating is by the influence to the resist shape of the generations such as lubricant of support membrane.But this method can not solve the problem of servo-actuated simultaneously.
Disclose following technology in the following patent documentation 2: the middle layer is formed by the polyvinyl alcohol resin that contains oxypropylene group, and photo-sensitive resin contains (methyl) acrylate moiety ester of polyvalent alcohol; And, following technology is disclosed in the following patent documentation 3: the polyvinyl alcohol (PVA) that the middle layer use is formed by olefin-copolymerization, the polyethylene oxide of the degree of polymerization more than 4000 etc.; But the flanging in these methods after all unresolved relevant high resolving power, high tack, the development, the problem of servo-actuated.
There is the relevant record that on interim supporter, is disposed with the photosensitive transfer printing material of thermoplastic resin, separating layer, photo-sensitive resin in the following patent documentation 4.Yet, when carrying out peeling off between thermoplastic resin and separating layer, have difficulties.
The COF that needs high-resolution in the miniaturization of printed-wiring board (PWB), as film is with in substrate manufacture, the semiconductor-sealing-purpose substrate manufacture etc., requirement has the photosensitive polymer combination and the photosensitive-resin layered product of following characteristic: the servo-actuated during lamination is good, demonstrate high-resolution, high tack, resist shape after the development well and not can produce rocking or depression in the surface of sidewall, and the flanging after developing is minimum.
Patent documentation 1: TOHKEMY 2001-159817 communique
Patent documentation 2: Japanese kokai publication hei 04-371957 communique
Patent documentation 3: Japanese kokai publication hei 06-242611 communique
Patent documentation 4: Japanese kokai publication hei 05-072724 communique
Summary of the invention
The problem that invention will solve
The objective of the invention is to, photosensitive-resin layered product with following characteristic is provided: the servo-actuated during lamination is good, demonstrate high-resolution and high tack, curing corrosion-resisting pattern after the development does not well have rocking or depression in the surface of sidewall, and the flanging after developing is minimum; And provide the formation method of the corrosion-resisting pattern that uses this layered product and the manufacture method of conductive pattern.
The scheme that is used to deal with problems
Study in order to address the above problem, found that: by using specific photosensitive-resin layered product, photosensitive-resin layered product with following characteristic can be provided: the fissility of support membrane does not have problems, servo-actuated during lamination is good, curing corrosion-resisting pattern after the development does not well have rocking or depression in the surface of sidewall, and the flanging after the development is minimum.Thereby finished the present invention.
That is, the present invention is the invention of the manufacture method of following photosensitive-resin layered product, corrosion-resisting pattern formation method, conductive pattern.
(1) a kind of photosensitive-resin layered product, it is characterized in that, it is at lamination successively on the support membrane: bed thickness is more than the 10 μ m and the ground floor below the 100 μ m, bed thickness is more than the 0.1 μ m and the second layer below the 10 μ m, photosensitive-resin layered product that photo-sensitive resin forms, this ground floor contains thermoplastic resin, and this second layer contains polyvinyl alcohol (PVA): 75～99 quality % and be selected from least a kind of compound in the group of being made up of the compound shown in compound shown in the following general formula (I) and the following general formula (II): 1～25 quality % forms;
R 1-O-(CH 2CH 2O)n 1-R 2(I)
In the formula, R 1And R 2Be H or CH 3, they can be the same or different, and n 1It is 3～25 integer;
[Chemical formula 1]
Figure BPA00001185040100051
In the formula, R 3Be the alkyl of H or carbon number 1～6, and n 2It is 9～10,000 integer.
(2) according to (1) described photosensitive-resin layered product, wherein, described thermoplastic resin contains the compound shown in the following general formula (I);
R 1-O-(CH 2CH 2O)n 1-R 2(I)
In the formula, R 1And R 2Be H or CH 3, they can be the same or different, and n 1It is 3～25 integer.
(3) according to (1) or (2) described photosensitive-resin layered product, its further lamination protective seam on described photo-sensitive resin forms.
(4) according to each described photosensitive-resin layered product in (1)～(3), wherein, described photo-sensitive resin is served as reasons and is contained: (a) in the acid equivalent carboxyl-content be 100～600 and weight-average molecular weight be 5000～500000 binder resin: 20～90 quality %; (b) unsaturated compound of at least a photopolymerization: 3～70 quality %; Reach (c) Photoepolymerizationinitiater initiater: the layer that the photosensitive polymer combination of 0.1～20 quality % forms.
(5) according to (4) described photosensitive-resin layered product, wherein, the unsaturated compound of described (b) at least a photopolymerization is for being selected from the unsaturated compound of at least a photopolymerization in the group of being made up of the compound shown in the following general formula (III)～(VII);
[Chemical formula 2]
Figure BPA00001185040100061
In the formula, R 4And R 5Be H or CH 3, they can be the same or different, n 3, n 4And n 5, be respectively 3～20 integer independently;
[chemical formula 3]
Figure BPA00001185040100062
In the formula, R 6And R 7Be H or CH 3, they can be the same or different, and A is C 2H 4, B is CH 2CH (CH 3), n 6+ n 7Be 2～40 integer, n 8+ n 9Be 0～40 integer, n 6And n 7Be respectively 1～39 integer independently, n 8And n 9Be respectively 0～40 integer independently ,-(A-O)-and-(B-O)-the arrangement of repetitive, optionally be random or block, when be block ,-(A-O)-with-(B-O)-order be that any all can in the xenyl side;
[chemical formula 4]
Figure BPA00001185040100071
In the formula, R 8And R 9Be H or CH 3, they can be the same or different, and D is C 2H 4, E is CH 2CH (CH 3), m 1+ m 2Be 2～40 integer, m 3+ m 4Be 0～40 integer, m 1And m 2Be respectively 1～39 integer independently, m 3And m 4Be respectively 0～40 integer independently ,-(D-O)-and-(E-O)-the arrangement of repetitive, optionally be random or block, when be block ,-(D-O)-with-(E-O)-order be that any all can in the cyclohexyl side;
[chemical formula 5]
Figure BPA00001185040100072
In the formula, R 10Be the diisocyanate residue of carbon number 4～12, R 11And R 12Be H or CH 3, they can be the same or different, m 5And m 6It is 1～15 integer;
[chemical formula 6]
Figure BPA00001185040100081
In the formula, R 13Be H or CH 3, they can be the same or different, R 14Be the alkyl of carbon number 4～14, A ' is C 2H 4, B ' is CH 2CH (CH 3), m 7Be 1～12, m 8Be 0～12, m 9Be 0～3 integer ,-(A '-O)-and-(B '-O)-the arrangement of repetitive optionally be random or block, when be block ,-(A '-O)-with-(B '-O)-order be that any all can in the phenyl side.
(6) a kind of formation method of corrosion-resisting pattern, it is characterized in that, each described photosensitive-resin layered product in (1)～(5) is laminated on the surface of sheet metal or metallic cover insulcrete, peel off ground floor together with support membrane, after active light now exposes, remove unexposed portion by development.
(7) a kind of manufacture method of conductive pattern is characterized in that, the substrate that has formed corrosion-resisting pattern by (6) described method is carried out etching or plating.
The effect of invention
According to the present invention, photosensitive-resin layered product with following characteristic can be provided and use the formation method of corrosion-resisting pattern of this layered product and the manufacture method of conductive pattern: the fissility of support membrane does not have problems, servo-actuated during lamination is good, demonstrate high-resolution and high tack after the development, curing corrosion-resisting pattern after the development does not well have rocking or depression in the surface of sidewall, and the flanging after the development is minimum.
Embodiment
Below, the present invention is specifically described.
Photosensitive-resin layered product of the present invention, it is characterized in that, it is lamination successively on the support membrane: bed thickness is that 10 μ m ground floor, bed thickness above and that 100 μ m are following are the second layer that 0.1 μ m is above and 10 μ m are following, the photosensitive-resin layered product that photo-sensitive resin forms
This ground floor contains thermoplastic resin,
This second layer contains polyvinyl alcohol (PVA): 75～99 quality % and be selected from least a kind of compound of the group of being made up of the compound shown in compound shown in the following general formula (I) and the following general formula (II): 1～25 quality %;
R 1-O-(CH 2CH 2O)n 1-R 2 (I)
In the formula, R 1And R 2Be H or CH 3, they can be the same or different, and n 1It is 3～25 integer;
[chemical formula 7]
Figure BPA00001185040100091
In the formula, R 3Be the alkyl of H or carbon number 1～6, and n 2It is 9～10000 integer.
Behind lamination, the exposure before need from the second layer, to peel off ground floor together with support membrane.The application's formation particularly by the formation of the second layer, can be peeled off ground floor together with support membrane.In addition, as the thermoplastic resin that uses in the ground floor, the compound of the glass transition temperature that the roll temperature when preferably having lamination is following particularly preferably has the thermoplastic resin of the glass transition temperature below 120 ℃.More preferably glass transition temperature be below 100 ℃, preferred about below 80 ℃ especially.Its reason is: the thermoplastic resin of the glass transition temperature below the roll temperature during by the employing lamination, photographic layer is being transferred to (during lamination) when having on the concavo-convex substrate by heat and pressure, the absorptive substrate surface is concavo-convex fully, is not having to carry out lamination under the residual state of bubble fully.When having used the high resin of glass transition temperature, need at high temperature carry out lamination, unfavorable in practical operation.
In addition, when taking care of with tubular, from the viewpoint that prevents that thermoplastic resin from oozing out from the tube end face as photosensitive-resin layered product, the glass transition temperature of the thermoplastic resin that uses in the ground floor, be preferably more than 10 ℃, more preferably more than 20 ℃, more preferably more than 30 ℃.
As glass transition temperature is thermoplastic resin below 120 ℃, is preferably selected from least a kind in the following thermoplastic resin: tygon, polyolefin such as polypropylene, ethene and vinyl acetate or its saponified such ethylene copolymer, ethene and acrylate or its saponified such ethylene copolymer, Polyvinylchloride, vinyl chloride and vinyl acetate or its saponified such vinyl chloride copolymer, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene and (methyl) acrylate or its saponified such styrol copolymer, polyvinyl toluene, vinyltoluene and (methyl) acrylate or its saponified such vinyl toluene copolymer, poly-(methyl) acrylate, such (methyl) acrylate copolymers such as (methyl) butyl acrylate and vinyl acetate, vinyl acetate copolymer, nylon, copolymer nylon, N-r-o-methylation nylon, the polyamide that N-dimethylamino nylon is such etc.; In addition, can also use " プ ラ ス チ Star Network performance is list just " (Japanese プ ラ ス チ Star Network worker industry Even alliance, all Japan プ ラ ス チ Star Network shaping worker industry Even close Knitting work, worker's industry Tone look into can development capable, October 25 nineteen sixty-eight development capable) (" plastics performance brief guide " (Japan Plastics Industry Federation, all Japan plastics forming industrial combination can be write, the census of manufacturing can be issued, October 25 nineteen sixty-eight distribution)) in the glass transition temperature of record be below 120 ℃ and the thermoplastic resin more than 10 ℃.
The content of thermoplastic resin preferably contains 50～100 quality % in ground floor, especially preferably contain 65～100 quality %.
In the ground floor, except that above-mentioned thermoplastic resin, also can add the various plastifier that have compatibility with this thermoplastic resin, thereby actual glass transition temperature is reduced.In addition, in order to regulate the bonding force with the second layer, can not exceed under 120 ℃ the scope that the scope with 5～50 quality % adds adjuvant in the ground floor at them at the glass transition temperature of reality, for example, various polymkeric substance, supercooling material, adhere to modifying agent, surfactant or release agent.More preferably below the 35 quality %.
As plastifier, for example can list phthalate, o-toluene sulfonic acid acid amides, p-toluenesulfonic acid acid amides, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl tributyl citrate three n-propyls, ATBC, polypropylene glycol, polyglycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, phthalates such as diethyl phthalate.As phthalate dibutyl phthalate etc. is arranged.
In addition, also can add poly-alkyl diols such as polyglycol, polypropylene glycol, poly-alkyl diol methyl ether.Wherein, from improving the viewpoint of servo-actuated, preferably add the compound shown in the following general formula (I);
R 1-O-(CH 2CH 2O)n 1-R 2 (I)
In the formula, R 1And R 2Be H or CH 3, they can be the same or different, and n 1It is 3～25 integer.
More than the preferred 10 μ m of the thickness of thermoplastic resin.Its former because: when the thickness of thermoplastic resin is lower than 10 μ m, can not absorb the concavo-convex of the above substrate surface of 1 μ m fully.In addition, relevant its upper limit there is no special boundary on performance, from making applicability, below about 100 μ m, be preferably below about 50 μ m, more preferably below the 30 μ m.
In addition, the second layer need contain polyvinyl alcohol (PVA): 75～99 quality % and be selected from least a kind of compound in the group of being made up of the compound shown in compound shown in the following general formula (I) and the following general formula (II): 1～25 quality %;
R 1-O-(CH 2CH 2O)n 1-R 2 (I)
In the formula, R 1And R 2Be H or CH 3, they can be the same or different, and n 1It is 3～25 integer;
[chemical formula 8]
Figure BPA00001185040100121
In the formula, R 3Be the alkyl of H or carbon number 1～6, and n 2It is 9～10000 integer.Constitute by this, can make the interlayer bonding force of ground floor and the second layer be lower than support membrane and ground floor the interlayer bonding force, reach the interlayer bonding force of the second layer and photo-sensitive resin.
From the viewpoint of development and cost, the polyvinyl alcohol (PVA) of the second layer cooperates ratio, is preferably more than the 75 quality % and below the 99 quality %.More preferably more than the 85 quality % and below the 95 quality %.
The method for making of polyvinyl alcohol (PVA) is generally and makes polyvinyl acetate carry out alkali soapization to make.The weight-average molecular weight of employed polyvinyl alcohol (PVA) is preferably 1000～100000 among the present invention.From the viewpoint of oxygen barrier performance, development, more preferably weight-average molecular weight is 5000～50000.In addition, from the viewpoint of development, preferred 50 moles more than the % of saponification degree, more preferably 70 moles more than the %, more preferably 80 moles more than the %.
Gel permeation chromatograph (GPC) (pump: Gulliver, PU-1580 type that the weight-average molecular weight of polyvinyl alcohol (PVA) adopts Japanese beam split (strain) to make; Chromatographic column: clear and electrician's (strain) system Shodex (registered trademark) (HFIP-805, HFIP-803) 2 series connection; Mobile phase solvent: hexafluoroisopropanol; Use is by the calibration curve of polystyrene standard sample (based on clear and electrician (strain) system Shodex STANDARD SM-105)) obtain as weight-average molecular weight (polystyrene conversion).
Compound shown in the above-mentioned general formula (I) is from the aspect of foul smell, n 1Preferred more than 3, from the compatibility of polyvinyl alcohol (PVA) and the viewpoint of development, n 1Be preferably below 25.n 1More preferably more than 5 and below 20, more preferably more than 7 and below 15.As the concrete example of the compound shown in the above-mentioned general formula (I), it is 200 polyglycol (the system PEG200 of NOF Corp) that mean molecular weight is arranged, mean molecular weight is 300 polyglycol (the system PEG300 of NOF Corp), mean molecular weight is 400 polyglycol (the system PEG400 of NOF Corp), mean molecular weight is 600 polyglycol (the system PEG600 of NOF Corp), mean molecular weight is that 1000 polyglycol (the system PEG 1000 of NOF Corp) or mean molecular weight are 400 polyglycol monomethyl ether (the ユ ニ オ Star Network ス M-400 of NOF Corp's system), mean molecular weight is 550 polyglycol monomethyl ether (the system ユ ニ オ of NOF Corp Star Network ス M-550), mean molecular weight is 1000 a polyglycol monomethyl ether (the system ユ ニ オ of NOF Corp Star Network ス M-1000) etc.
Compound shown in the above-mentioned general formula (II) is from the fissility aspect of the ground floor and the second layer, n 2Preferred more than 9, from the viewpoint of development, n 2Preferred below 10000.n 2More preferably more than 20 and below 2000, more preferably more than 30 and below 1500.Concrete example as the compound shown in the above-mentioned general formula (II) has polyvinyl pyrrolidone.As concrete example, the weight-average molecular weight that has Nippon Shokubai Co., Ltd to make is that 40,000 K-15, weight-average molecular weight are that 100,000 K-30, weight-average molecular weight are that 900,000 K-85, weight-average molecular weight are 1,000,000 K-90 etc.
Viewpoint from the fissility of the second layer and ground floor, the content that is selected from least a kind of compound in the group of being made up of the compound shown in compound shown in the above-mentioned general formula (I) and the above-mentioned general formula (II) in the second layer is more than the 1 quality %, be preferably more than the 3 quality %, more preferably more than the 5 quality %.In addition, from the viewpoint of light sensitivity, be below the 25 quality %, more preferably below the 20 quality %, more preferably below the 15 quality %.
In addition, in the second layer, except that above-mentioned, also can contain known water-soluble polymers, for example, polyvinylether-maleic anhydride water soluble salt, carboxyalkyl starch water soluble salt, polyacrylamide, polyamide, polyacrylic acid water soluble salt, gelatin, polypropylene glycol etc.
From the viewpoint of resolution, tack, development, the bed thickness of the second layer is preferably below the 10 μ m, more preferably below the 5 μ m, more preferably below the 3 μ m.In addition, from the viewpoint of oxygen barrier performance, the bed thickness of the second layer is more than the 0.1 μ m, more than the preferred 0.5 μ m, more preferably more than the 1 μ m.
Among the present invention, owing to peel off support membrane before ultraviolet exposure, therefore, support membrane need not to use and can see through ultraviolet transparent membrane.As support membrane of the present invention, it is the film of synthetic resin of the tygon of the above and 100 μ m of 10 μ m about following, polypropylene, polycarbonate, polyethylene terephthalate etc. that thickness is arranged, but can preferably use the polyethylene terephthalate that has the flexible and intensity of appropriateness usually.Be difficult for when making lamination fold takes place, or in order to prevent the breakage of support membrane, thickness is preferably more than the 10 μ m.
In the photosensitive-resin layered product of the present invention, by in the second layer, adopting above-mentioned formation, thereby do not have problems with the fissility of ground floor, promptly, when peeling off ground floor together with support membrane before exposure process, the interlayer bonding force that can obtain the ground floor and the second layer is lower than the fissility of the interlayer bonding force of support membrane and ground floor and the second layer and photographic layer.
In addition, as photosensitive-resin layered product of the present invention, on the support membrane successively on the basis of lamination ground floor, the second layer and photo-sensitive resin, further lamination protective seam.
As the characteristic of protective seam, the interlayer bonding force that the interlayer bonding force between photo-sensitive resin and protective seam is lower than between the ground floor and the second layer is important, thus, can easily peel off protective seam when lamination.
As protective seam, it is the film of synthetic resin of tygon, polypropylene, polycarbonate, polyethylene terephthalate etc. about 10～100 μ m that thickness is arranged, and can preferably use polyethylene film or polypropylene film.
The thickness of photo-sensitive resin of the present invention, according to the difference of purposes and difference, the upper limit of thickness is below the preferred 100 μ m, more preferably below the 50 μ m, further below the preferred 30 μ m, most preferably below the 10 μ m.In addition, lower limit is more than the preferred 0.5 μ m, further more than the preferred 1 μ m.
Photo-sensitive resin in the photosensitive-resin layered product of the present invention, be preferably by containing the layer that following composition photosensitive polymer combination forms: promptly (a) in the acid equivalent carboxyl-content be 100～600 and weight-average molecular weight be 5,000～500,000 binder resin: 20～90 quality %; (b) unsaturated compound of at least a photopolymerization: 3～70 quality %; Reach (c) Photoepolymerizationinitiater initiater: 0.1～20 quality %.Below, employed photosensitive polymer combination in the photosensitive-resin layered product of the present invention is elaborated.
(a) amount of contained carboxyl in the binder resin in acid equivalent, is preferably 100～600, and more preferably 250～450.Described acid equivalent is meant the quality of the binder resin of the carboxyl that has 1 equivalent in the binder resin.
In order to give development and the fissility of photo-sensitive resin to alkaline aqueous solution, the carboxyl in the binder resin is necessary.From the viewpoint of development patience, distinguishing and tack, acid equivalent is preferred more than 100, and is from the viewpoint of development and fissility, preferred below 600.
(a) weight-average molecular weight of binder resin is preferably 5000～500000.From the viewpoint of distinguishing, the weight-average molecular weight of binder resin is preferred below 500000, and is from the viewpoint of the glue that overflows, preferred more than 5000.In order further to bring into play effect of the present invention well, the weight-average molecular weight of binder resin more preferably 5000～200000, more preferably 5000～100000.Dispersion degree (also being called molecular weight distribution), with recently representing of the weight-average molecular weight of following formula and number mean molecular weight:
(dispersion degree)=(weight-average molecular weight)/(number mean molecular weight)
Dispersion degree can use the binder resin about 1～6, is preferably 1～4.In addition, use flat natural pond industry (strain) system flat natural pond automatic titration device (COM-555), adopt the sodium hydrate aqueous solution of 0.1mol/L, carry out the mensuration of acid equivalent by potential difference titration.
Molecular weight utilizes Japanese beam split (strain) system gel permeation chromatograph (GPC) (pump: Gulliver, PU-1580 type; Chromatographic column: clear and electrician's (strain) system Shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) 4 series connection, mobile phase solvent: tetrahydrofuran; Use is by the calibration curve of polystyrene standard sample (using clear and electrician's (strain) system Shodex STANDARD SM-105)) obtain as weight-average molecular weight (polystyrene conversion).
(a) binder resin can each monomer copolymerization a kind of or more than it obtains in two kinds of following monomers by making.
First monomer is carboxylic acid or the acid anhydrides that has a polymerism unsaturated group in the molecule.For example, can list (methyl) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester etc.
Second monomer is nonacid, has the compound of a polymerism unsaturated group in the molecule.This compound can be selected from the aspect of the various characteristics such as flexible of the patience the development, etching and the plating operation that keep photo-sensitive resin, cured film.As this compound, for example, can use (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) alkyl acrylates such as (methyl) 2-EHA, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) vinyl cyanide, (methyl) benzyl acrylate, (methyl) acrylic acid methoxy benzyl ester, (methyl) acrylic acid benzyl chloride ester, (methyl) acrylic acid chaff ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylic acid phenoxy ethyl, (methyl) phenyl acrylate, (methyl) CA, (methyl) acrylic acid aryl esters such as (methyl) acrylic acid naphthalene ester, has the vinyl compound (for example, styrene) of phenyl etc.From distinguishing, the coherent viewpoint of developer solution, preferred especially (methyl) benzyl acrylate.
(a) binder resin preferably synthesizes as follows: the potpourri that dilutes above-mentioned first monomer and second monomer with acetone, MEK or isopropyl alcohol equal solvent, in the solution of gained, add radical polymerization initiators such as an amount of benzoyl peroxide, azo isobutyronitrile, carried out thermal agitation and synthesize.Also can drip partially mixed thing on one side in reactant liquor synthesizes on one side.Also can after reaction finishes, further add solvent, be adjusted to desired concentration.As synthetic method, except that solution polymerization, also can adopt bulk polymerization, suspension polymerization or emulsion polymerization.
With respect to the photosensitive polymer combination total amount, (a) ratio of binder resin is preferably the scope of 20～90 quality %, more preferably 30～70 quality %.From make by exposure, the curing corrosion-resisting pattern forms of developing has the characteristic as resist, for example, in lid hole, etching and the various plating operation fully the viewpoint of patience etc. set out, be preferably more than the 20 quality % and below the 90 quality %.
Unsaturated compound as (b) at least a photopolymerization, from the viewpoint of high-resolution, preferred mode is for using the unsaturated compound that is selected from least a photopolymerization in the group of being made up of the compound shown in the following general formula (III)～(VII);
[chemical formula 9]
Figure BPA00001185040100171
In the formula, R 4And R 5Be H or CH 3, they can be the same or different, n 3, n 4And n 5Be respectively 3～20 integer independently;
[Chemical formula 1 0]
In the formula, R 6And R 7Be H or CH 3, they can be the same or different, and A is C 2H 4, B is CH 2CH (CH 3), n 6+ n 7Be 2～40 integer, n 8+ n 9Be 0～40 integer, n 6And n 7, be respectively 1～39 integer independently, n 8And n 9, be respectively 0～40 integer independently ,-(A-O)-and-(B-O)-the arrangement of repetitive, optionally be random or block, when be block ,-(A-O)-with-(B-O)-order be that any all can in the xenyl side;
[Chemical formula 1 1]
Figure BPA00001185040100182
In the formula, R 8And R 9Be H or CH 3, they can be the same or different, and D is C 2H 4, E is CH 2CH (CH 3), m 1+ m 2Be 2～40 integer, m 3+ m 4Be 0～40 integer, m 1And m 2Be respectively 1～39 integer independently, m 3And m 4Be respectively 0～40 integer independently ,-(D-O)-and-(E-O)-the arrangement of repetitive, optionally be random or block, when be block ,-(D-O)-with-(E-O)-order any one all can in the cyclohexyl side;
[Chemical formula 1 2]
Figure BPA00001185040100191
In the formula, R 10Be the diisocyanate residue of carbon number 4～12, R 11And R 12Be H or CH 3, they can be the same or different, m 5And m 6It is 1～15 integer;
[Chemical formula 1 3]
Figure BPA00001185040100192
In the formula, R 13Be H or CH 3, they can be the same or different, R 14Be the alkyl of carbon number 4～14, A ' is C 2H 4, B ' is CH 2CH (CH 3), m 7Be 1～12 integer, m 8Be 0～12 integer, m 9Be 0～3 integer ,-(A '-O)-and-(B '-O)-the arrangement of repetitive optionally be random or block, when be block ,-(A '-O)-with-(B '-O)-order any one all can in the phenyl side.
From the viewpoint of boiling point, foul smell, the preferred n of compound shown in the above-mentioned general formula (III) 3, n 4And n 5Be more than 3.From the viewpoint by the caused light sensitivity of concentration at the photolytic activity position of per unit mass, n 3, n 4And n 5Be preferably below 20.Concrete example as the compound shown in the above-mentioned general formula (III) that uses among the present invention, for example, can list preferred in addition in the polypropylene glycol of average 12 moles epoxypropane, the compound of the dimethylacrylate of the glycol of average 3 moles of ethylene oxide of further addition at two ends respectively.
In the compound shown in the above-mentioned general formula (IV), n 6+ n 7And n 8+ n 9Need be for below 40, from the viewpoint of light sensitivity, not preferred when surpassing 40.Be preferably below 30.
As the concrete example of the compound shown in the above-mentioned general formula (IV) that uses among the present invention, the dimethylacrylate of the poly-alkyl diol of average 2 moles epoxypropane of addition respectively and average 6 moles oxirane is arranged at the two ends of bisphenol-A, the dimethylacrylate of the poly-alkyl diol of average 2 moles epoxypropane of addition and average 15 moles oxirane respectively at the two ends of bisphenol-A, distinguish the dimethylacrylate (Xin Zhong village chemical industry (strain) system NK ESTER BPE-500) of the polyglycol of the average 5 moles oxirane of addition at the two ends of bisphenol-A, distinguish the dimethylacrylate (Xin Zhong village chemical industry (strain) system NK ESTER BPE-200) of the polyglycol of the average 2 moles oxirane of addition at the two ends of bisphenol-A.
In the compound shown in the above-mentioned general formula (V), m 1+ m 2And m 3+ m 4Need be for below 40, from the viewpoint of light sensitivity, not preferred when surpassing 40.Be preferably below 30.As the concrete example of the compound shown in the above-mentioned general formula (V), the two ends that the bisphenol-A behind hydrogenation arranged are the dimethylacrylate of the polyglycol of the average 5 moles oxirane of addition respectively.
Work as m 5And m 6Surpass at 15 o'clock, the compound shown in the above-mentioned general formula (VI) can not obtain sufficient light sensitivity.Concrete example as the compound shown in the above-mentioned general formula (VI), for example, can list hexamethylene diisocyanate, toluene diisocyanate or 2,2, have the urethane compound etc. of the compound (acrylic acid 2-hydroxypropyl acrylate, oligomeric propylene glycol monomethyl acrylate etc.) of hydroxyl and (methyl) acrylic in diisocyanate cpd such as 4-trimethyl hexamethylene diisocyanate and a part.The reactant that hexamethylene diisocyanate and oligomeric propylene glycol monomethyl acrylate (Japanese grease (strain) system, BLEMMER PP1000) particularly, arranged.
Work as m 7And m 8Surpass at 12 o'clock, the compound shown in the above-mentioned general formula (VII) can not obtain sufficient light sensitivity.Even m 9Surpass 3, can not obtain sufficient light sensitivity.
Concrete example as the compound shown in the above-mentioned general formula (VII), for example, can listing on nonylphenol addition, the acrylate of the compound of polypropylene glycol and polyglycol is arranged is 4-n-nonyl phenoxy group seven ethylene glycol bisthioglycolate propylene glycol acrylate, wherein, the polypropylene glycol addition has average 2 moles epoxypropane, and the polyglycol addition has average 7 moles oxirane.Also can be set forth in addition on the nonylphenol acrylate of compound of polyglycol be that (East Asia synthetic (strain) system, M-114), wherein, the polyglycol addition has average 8 moles oxirane to 4-n-nonyl phenoxy group eight EDIAs.
As the unsaturated compound of (b) at least a photopolymerization, above-mentioned general formula (III), (IV), (V), (VI) and (VII) shown in the compound group beyond compound, the unsaturated compound of the photopolymerization shown in following is arranged.For example, can list 1,6-hexanediol two (methyl) acrylate, 1,4-cyclohexanediol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, polyglycol two (methyl) acrylate, 2-two (to hydroxyphenyl) propane two (methyl) acrylate, glycerine three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, polyoxyethyl propyl trimethylolpropane tris (methyl) acrylate, polyoxy ethyl trimethylolpropane triacrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, trihydroxymethylpropanyltri diglycidyl ether three (methyl) acrylate, bisphenol A diglycidyl ether two (methyl) acrylate, β-hydroxy propyl-Beta '-(acryloxy) propyl group phthalic ester, phenoxy group polyglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate etc.
From the viewpoint of light sensitivity, with respect to the photosensitive polymer combination total amount, (b) ratio of the unsaturated compound total amount of at least a photopolymerization is preferably more than the 3 quality %, and the viewpoint from the glue that overflows is preferably below the 70 quality %.More preferably 10～60 quality %, more preferably 15～55 quality %.
In addition, with respect to the photosensitive polymer combination total amount, the ratio that is selected from the unsaturated compound of at least a photopolymerization in the group of being made up of the compound shown in the above-mentioned general formula (III)～(VII) is the scope of 3～70 quality %.From the viewpoint of resolution, be more than the 3 quality %, from the flexible viewpoint of corrosion-resisting pattern, be below the 70 quality %.More preferably below 3～30 quality %.
As (c) Photoepolymerizationinitiater initiater, so long as by various active rays, the compound of for example ultraviolet isoreactivityization and initiated polymerization gets final product, from high-resolution viewpoint, contain be selected from by the compound shown in the following general formula (VIII), and following general formula (IX) shown in the group formed of compound at least a 2,4, the Photoepolymerizationinitiater initiater of 5-triarylimidazoles quinoline dipolymer is for preferred embodiment.
[Chemical formula 1 4]
Figure BPA00001185040100221
In the formula, X, Y, and Z represent any of alkyl, alkoxy or halogen base of hydrogen, carbon number 1～5 respectively independently, and p, q, and r be respectively 1～5 integer independently.
[Chemical formula 1 5]
Figure BPA00001185040100231
In the formula, X, Y, and Z represent any of alkyl, alkoxy or halogen base of hydrogen, carbon number 1～5 respectively independently, and p, q, and r are respectively 1～5 integer independently.
As 2,4,5-triarylimidazoles dipolymer, for example, 2-(Chloro-O-Phenyl)-4 is arranged, 5-diphenyl-imidazole dipolymer, 2-(Chloro-O-Phenyl)-4,5-couple-(m-methoxyphenyl) imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenyl-imidazole dipolymer etc., preferred especially 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dipolymer.
As (c) Photoepolymerizationinitiater initiater that uses among the present invention, preferred and with being selected from least a 2 in the group of forming by the compound shown in compound shown in the above-mentioned general formula (VIII) and the above-mentioned general formula (IX), 4, the system of 5-triarylimidazoles dipolymer and p-aminophenyl ketone.As the p-aminophenyl ketone, for example, can list to aminobenzophenone, to the fourth aminoacetophenone, to the dimethylamino acetophenone, to dimethylamino benzophenone, p, p '-two (ethylamino) benzophenone, p, p '-two (dimethylamino) benzophenone [rice is sneered ketone], p, p '-two (lignocaine) benzophenone, p, p '-two (dibutylamino) benzophenone.
In addition, as the Photoepolymerizationinitiater initiater beyond the aforesaid compound, for example, quinones such as 2-EAQ, 2-tert-butyl group anthraquinone are arranged, acridine compound, benzil dimethyl ketal, benzil diethyl ketal, pyrazolines such as benzoin ethers such as aromatic series ketones such as benzophenone, benzoin, benzoin methyl ether, benzoin ethylether, 9-phenylacridine, for example, 1-phenyl-3-(the 4-tert-butyl group-styryl)-5-(the 4-tert-butyl group-phenyl)-pyrazoline.In addition, for example, thioxanthones, 2 is arranged also, the combination of tertiary amine compound such as thioxanthene ketone such as 4-diethyl thioxanthone, 2-clopenthixal ketone and dimethylamino benzoic acid alkyl ester compound.
In addition, 1-phenyl-1 is arranged, 2-propanedione-2-O-benzoyl oxime (benzoyloxime), 1-phenyl-1, oxime ester classes such as 2-propanedione-2-(O-ethoxy carbonyl) oxime etc.In addition, also can use N-aryl-alpha-amino acid compound, wherein, preferred especially N-phenylglycine.
Photosensitive polymer combination in the photosensitive-resin layered product of the present invention preferably contains (c) Photoepolymerizationinitiater initiater with respect to 0.1～20 quality % of photosensitive polymer combination total amount.From obtaining the viewpoint of sufficient light sensitivity, more than the preferred 0.1 quality %, the viewpoint of the halation of the light by photomask when preventing to expose is below the preferred 20 quality %.
As photosensitive polymer combination, can use basic-dyeable fibre.Concrete example as basic-dyeable fibre, can list magenta, phthalocyanine green, auramine alkali, the green S of alkoxide, paramagenta, crystal violet, methyl orange, Nile blue 2B, malachite green (protecting native ケ paddy chemistry (strain) system ア イ ゼ Application (registered trademark) MALACHITE GREEN), alkali blue 20, diamond green (protecting native ケ paddy chemistry (strain) system ア イ ゼ Application (registered trademark) DIAMOND GREEN GH), Victoria blue (protecting native ケ paddy chemistry (strain) system ア イ ゼ Application (registered trademark) VICTORIA PURE BLUE) etc.
In the photosensitive polymer combination, also can contain the color development based dye of color development by illumination.
As the color development based dye that is used, for example, the combination of leuco dye or fluoran dyes and halogen compounds is arranged.As leuco dye, for example, can list three (4-dimethylamino-2-aminomethyl phenyl) methane [leuco crystal violet], three (4-dimethylamino-2-aminomethyl phenyl) methane [procrypsis malachite green] etc.
As halogen compounds, can list bromo pentane, bromo isopentane, bromo isobutylene, bromoethylene, bromo diphenyl-methane, benzal bromide, methylene bromide, trisbromomethyl benzene sulfone, carbon tetrabromide, three (2, the 3-dibromopropyl) phosphate, trichloroacetamide, iodo-pentane, iodo isobutane, 1,1,1-three chloro-2, two (rubigan) ethane of 2-, carbon trichloride, halo triaizine compounds etc.As this halo triaizine compounds, can list 2,4,6-three (trichloromethyl) s-triazine, 2-(4-methoxyphenyl)-4, two (trichloromethyl) s-triazine of 6-.
In this type of color development based dye, the combination of the combination of trisbromomethyl benzene sulfone and leuco dye, halo triaizine compounds and leuco dye is comparatively useful.
For thermal stability, the storage stability that improves photosensitive polymer combination of the present invention, preferably make photosensitive polymer combination contain radical polymerization inhibitor.As this type of radical polymerization inhibitor, for example, can list p methoxy phenol, quinhydrones, pyrogallol, naphthylamines, tert-butyl catechol, stannous chloride, 2,6-two-tert-butyl group-paracresol, 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), diphenyl nitrosamine etc.
In addition, in the photosensitive polymer combination, can contain plastifier as required.As this type of plastifier, for example, can list phthalate, o-toluene sulfonic acid acid amides, p-toluenesulfonic acid acid amides, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl tributyl citrate three n-propyls, ATBC, polypropylene glycol, polyglycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, phthalates such as diethyl phthalate.As phthalate, dibutyl phthalate etc. is arranged.
Below to lamination support membrane, ground floor, the second layer, photo-sensitive resin and protective seam successively and the method for making photosensitive-resin layered product describe.
At first, use rod to be coated with machine or roll coater coating thermoplastic resin on support membrane, for example, the methyl ethyl ketone solution of the polymethylmethacrylate that obtains by solution polymerization (weight-average molecular weight 60,000, solid component concentration 40 quality %, 105 ℃ of glass transition temperatures), and carry out drying.Thus, can be on support membrane the lamination ground floor.The viscosity of the methyl ethyl ketone solution of polymethylmethacrylate preferably is adjusted to 10～2000mPas.
Secondly, with polyvinyl alcohol (PVA), for example, PVAC polyvinylalcohol-205 resin of the Network ラ レ of Co., Ltd. system and be selected from above-mentioned general formula (I) or (II) shown in the group of compound in more than one compounds, for example, polyglycol or polyoxyethylene monomethyl ether or polyvinyl pyrrolidone, with the solid constituent ratio is amount about 10 quality %, slowly join in the water that is heated to 85 ℃, stirred about 1 hour, make its uniform dissolution.Then, as described above like that at lamination on the support membrane on the ground floor of ground floor, use rod to be coated with machine or the roll coater coating contains the aqueous solution of polyvinyl alcohol (PVA), and carry out drying.The viscosity that contains the aqueous solution of polyvinyl alcohol (PVA) preferably is adjusted to 10～500mPas.Have at the lamination of gained on the second layer of support membrane of the ground floor and the second layer, with the coating of the second layer similarly, use rod to be coated with the photo-sensitive resin that machine or roll coater coating are made up of photosensitive polymer combination, and carry out drying.Then, lamination protective seam on photo-sensitive resin, thus can produce photosensitive-resin layered product.
Below, an example that uses photosensitive-resin layered product of the present invention to make the method for printed-wiring board (PWB) is described.
Printed-wiring board (PWB) can be made through following each operation.
(1) lamination
On photosensitive-resin layered product during matcoveredn, when peeling off protective seam, the operation of using the hot-roll lamination machine on substrates such as copper clad laminate or flexible substrate, to adhere to this photosensitive-resin layered product.
(2) exposure process
From photosensitive-resin layered product, between the ground floor and the second layer, peel off, and peel off with the bonding state of support membrane with ground floor, on the second layer, adhere to mask film, use the active ray source to implement the operation of exposure with desired Wiring pattern.
(3) developing procedure
Use alkaline-based developer, the unexposed portion of the second layer and photo-sensitive resin is removed in dissolving or dispersion, forms the operation of solidifying corrosion-resisting pattern on substrate.
(4) etching work procedure or plating operation
To formed corrosion-resisting pattern spraying etching solution, the copper face that is not covered by corrosion-resisting pattern is carried out etched operation or the copper face that is not covered by corrosion-resisting pattern carried out the operation that platings such as copper, scolding tin, nickel, tin are handled.
(5) stripping process
Use alkaline stripper to remove the operation of corrosion-resisting pattern from substrate.
Active ray source as using in above-mentioned (2) exposure process can list high-pressure sodium lamp, ultrahigh pressure mercury lamp, ultraviolet fluorescent lamp, carbon arc lamp, xenon lamp etc.In addition, in order to obtain finer corrosion-resisting pattern, more preferably use parallel light source.When wanting to do one's utmost to reduce the influencing of dirt, foreign matter, also can be with photomask with from floating more than tens of μ m on the second layer and the state below hundreds of μ m expose (proximity printing).
In addition, as the alkaline-based developer that uses in above-mentioned (3) developing procedure, can list the aqueous solution of sodium carbonate, sal tartari etc.These alkaline aqueous solutions can be selected according to the characteristic of photo-sensitive resin, use the aqueous sodium carbonate that 0.5 quality % is above and 3 quality % are following usually.
Above-mentioned (4) etching work procedure carries out according to acid etching, alkali etching etc., method suitable in the DF that uses.
As the alkaline stripper that uses in above-mentioned (5) stripping process, can enumerate than the stronger aqueous solution of using in the common development of alkaline aqueous solution alkalescence, for example the NaOH that 1 quality % is above and 5 quality % are following, the aqueous solution of potassium hydroxide.
In addition, when plating operations such as semi-additive process are set, after peeling off corrosion-resisting pattern, also can carry out etching to the copper face that exposes under the corrosion-resisting pattern.
Below, by embodiment the example of embodiments of the present invention is further elaborated.
Embodiment
Below, the evaluation of embodiment and comparative example is described with the method for making of sample and to the evaluation method and the evaluation result of gained sample.
(embodiment 1～15, comparative example 1～4)
1. estimate making with sample
Photosensitive-resin layered product in embodiment and the comparative example is made as follows.
The making of＜photosensitive-resin layered product 〉
Use rod to be coated with machine in the thick pet film (East レ system 16QS48 standard 3 of 16 μ m) the even methyl ethyl ketone solution of the ground floor shown in the coating table 1 in surface, drying is 2 minutes in 95 ℃ dryer, forms uniform ground floor on support membrane.The thickness of ground floor is 20 μ m.Then, the aqueous solution of the composition of the second layer shown in abundant stirring, the mixture table 1, use rod to be coated with machine to have on the surface of ground floor of support membrane of aforementioned ground floor the evenly aqueous solution of the composition of the coating second layer at lamination, drying is 3 minutes in 100 ℃ dryer, forms the uniform second layer on ground floor.The thickness of the second layer is 2 μ m.And then, use rod to be coated with machine and be laminated to the photosensitive polymer combination shown in the even coating table 1 on the second layer of support membrane, drying is 3 minutes in 95 ℃ dryer, forms uniform photo-sensitive resin.The thickness of photo-sensitive resin is 2 μ m.
Then, on the surface on the photo-sensitive resin, the thick polyethylene film of the 25 μ m that fit obtains photosensitive-resin layered product as protective seam.
＜substrate 〉
Use on insulating resin lamination Sumitomo Metal Industries' (strain) systems S ' PERFLEX of 8 μ m Copper Foils, the rocking and surface state of sidewall of having estimated flanging after resolution, tack, the development, having solidified corrosion-resisting pattern.In addition, the evaluation of the lamination bubble behind the relevant lamination uses the flexible substrate about Ra=0.2 to estimate.
＜lamination 〉
Peel off the protective seam of photosensitive-resin layered product of the present invention, (エ of Asahi Chemical Industry Application ジ ニ ア リ Application グ (strain) society system AL-70), has been carried out lamination under 105 ℃ of roll temperatures to adopt the hot-roll lamination machine simultaneously.Air pressure is made as 0.35MPa, and laminate speed is made as 1.0m/min.The lamination bubble is estimated in (servo-actuated evaluation), and air pressure is made as 0.2MPa, and laminate speed is made as 2.0m/min.
＜exposure 〉
Peel off after the pet film upper strata is pressed with the support membrane of ground floor, required mask film places on the second layer in the evaluation with photo-sensitive resin, and (オ one Network is made made, HMW-801) with 140mJ/cm by ultrahigh pressure mercury lamp 2Exposure expose.
＜develop
30 ℃ 0.5 quality %Na at the appointed time sprays 2CO 3Aqueous solution, the unexposed portion of photo-sensitive resin is removed in dissolving.At this moment, dissolving the required minimum time fully with the photo-sensitive resin of unexposed portion is minimum development time.Be to develop under 2 times of minimum development time at the development time of reality, obtain solidifying corrosion-resisting pattern.
2. evaluation method
(1) servo-actuated evaluation
Behind the lamination, expose with 100mJ subject to the foregoing, with the scope of observation by light microscope 10cm * 10cm, computation layer is pressed bubble quantity and bubble, estimates by following grade:
◎: do not produce the lamination bubble fully;
Zero: can see to produce several left and right sides lamination bubbles;
△: can see to produce dozens of left and right sides lamination bubble;
*: can see to produce the infinite layers bubble of calming the anger.
(2) the film fissility is estimated
Before exposure, peel off when being pressed with the support membrane of ground floor on the pet film upper strata, relevant fissility, estimate by following grade:
Zero: but between the ground floor and the second layer, peel off no problem;
*: between the ground floor and the second layer, can't peel off, support membrane be between polyethylene terephthalate and ground floor or the second layer and photoresist interlayer peelable.
(3) light sensitivity evaluation
Use lightness from transparent to black 21 sections stage metraster of ス ト one Off ア, one system of totally 21 phase change, light sensitivity, the resolution evaluation through 15 minutes behind the lamination exposed with substrate.After the exposure, develop with 2 times development time of minimum development time, by make resist film fully residual stage metraster hop count be 4 exposure, as following, carry out classification:
Zero: exposure is 140mJ/cm 2Below;
△: exposure surpasses 140mJ/cm 2, and 150mJ/cm 2Below;
*: exposure surpasses 150mJ/cm 2
(4) distinguishing evaluation
The mask film of the line pattern mask of 1: 1 ratio of width that uses exposure portion and unexposed portion during as exposure as described above, exposes, develops the substrate through 15 minutes behind the lamination.Normally to form the minimum mask width that solidifies corrosion-resisting pattern is the value of resolution, classification distinguishing as following:
◎: the value of resolution is below the 5 μ m;
Zero: the value of resolution surpasses 5 μ m, and below the 10 μ m;
△: the value of resolution surpasses 10 μ m, and below the 15 μ m;
*: the value of resolution surpasses 15 μ m.
(5) tack evaluation
Mask film when using exposure portion independently the line pattern mask is as exposure as described above, exposes, develops the substrate through 15 minutes behind the lamination.Normally to form the minimum mask width that solidifies corrosion-resisting pattern is the value of tack, presses following such classification tack:
◎: the value of tack is below the 5 μ m;
Zero: the value of tack surpasses 5 μ m, and below the 10 μ m;
△: the value of tack surpasses 10 μ m, and below the 15 μ m;
*: the value of tack surpasses 15 μ m.
(6) development back flanging evaluation
Mask film when using the chromium glass photomask as exposure as described above, exposes, develops.Shape by 10 μ m lines of the cured pattern of following classification gained:
◎: it is good and do not have a flanging flange to solidify the cutting of root of resist;
Zero: the cutting of the root of curing resist is good and the flanging flange is minimum;
△: the root that solidifies resist can be seen the flanging flange that 3 μ m are following;
*: the root that solidifies resist can be seen the flanging flange that surpasses 3 μ m.
(7) the resist sidewall after developing rocks evaluation
Use the chromium glass photomask, as described above, the layered product that is laminated on the substrate is exposed, develops.Resist sidewall shape by 10 μ m lines of the cured pattern of following classification gained:
Zero: on formed resist sidewall, almost do not have and rock;
△: on formed resist sidewall, have atomic little rocking;
*: rock in all existing everywhere of formed resist sidewall.
(8) the curing resist surface state after the development is estimated
Use the chromium glass photomask, as described above, the layered product that is laminated on the substrate is exposed, develops.Resist surface state by 10 μ m lines of the cured pattern of following classification gained:
Zero: on formed resist surface, almost do not have depression;
△: on formed resist surface, have atomic little depression;
*: on formed resist surface, all there is depression everywhere.
3. evaluation result
The evaluation result of embodiment and comparative example is shown in following table 1.P-1～P-2 in the table 1, the mass parts of Q-2～Q-4 is the amount as methyl ethyl ketone solution.In the table 1, comparative example 1 no ground floor, the comparative example 2 no second layers, comparative example 3 are short of the compound shown in above-mentioned general formula (I) or the general formula (II) in the second layer.The above-mentioned general formula (I) of comparative example 4 or the content of the compound shown in the general formula (II) shortcoming the application constitute.
Figure BPA00001185040100321
＜symbol description 〉
The methyl ethyl ketone solution of the bipolymer of the benzyl methacrylate of P-1:80 quality %, the methacrylic acid of 20 quality % (solid component concentration 50 quality %, weight-average molecular weight 2.5 ten thousand, acid equivalent 430, dispersion degree 2.7)
The methyl ethyl ketone solution of the cinnamic terpolymer of the methyl methacrylate of P-2:50 quality %, the methacrylic acid of 25 quality %, 25 quality % (solid component concentration 35 quality %, weight-average molecular weight 50,000, acid equivalent 344, dispersion degree 3.1)
M-1: in addition average 12 moles epoxypropane polypropylene glycol two ends further respectively addition the dimethylacrylate of poly-alkyl diol of average 3 moles oxirane
M-2: at the two ends of bisphenol-A respectively addition the dimethylacrylate of poly-alkyl diol of average 2 moles epoxypropane and average 6 moles oxirane
M-3: at the two ends of bisphenol-A respectively addition the dimethylacrylate (Xin Zhong village chemical industry (strain) system NK ESTER BPE-200) of polyglycol of average 2 moles oxirane
M-4: at the two ends of bisphenol-A respectively addition dimethylacrylate (Xin Zhong village chemical industry (strain) the system NK ESTER BPE-500 of polyglycol of average 5 moles oxirane
M-5:2, two { 4-(the methacryloxy five ethoxys) cyclohexyl } propane of 2-
M-6: (Japanese grease (strain) system, reactant BLEMMERPP1000) is the urethane polypropylene glycol dimethacrylate for hexamethylene diisocyanate and oligomeric propylene glycol monomethyl acrylate
M-7: trimethylol-propane trimethacrylate
M-8: three oxygen ethyl trimethylolpropane triacrylates (Xin Zhong village chemical industry (strain) system NK ESTER A-TMPT-3EO)
M-9: nine glycol diacrylates
G-1:4,4 '-two (lignocaine) benzophenone
G-2:2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dipolymer
J-1: diamond green (protecting native ケ paddy chemistry (strain) system ア イ ゼ Application (registered trademark) DIAMOND GREEN GH)
J-2: leuco crystal violet
1: 1 potpourri of L-1:1-(2-two-n-butyl amine ylmethyl)-5-carboxyl benzotriazole and 1-(2-di-n-butyl amino methyl)-6-carboxyl benzotriazole
L-2: 3 of pentaerythrite, 5-two-tert-butyl group-4-hydroxyphenylpropionic acid four esters (チ バ ス ペ シ ヤ リ テ イ ケ ミ カ Le ズ (strain) makes IRGANOX245)
Q-1: polyoxyethylene monomethyl ether (Japanese grease (strain) system ユ オ Star Network ス M-550, weight-average molecular weight 550)
Q-2: the methyl ethyl ketone solution of polymethylmethacrylate (solid component concentration 40 quality %, weight-average molecular weight 60,000)
The methyl ethyl ketone solution of the bipolymer of the methyl methacrylate of Q-3:80 quality %, the methyl acrylate of 20 quality % (solid component concentration 40 quality %, weight-average molecular weight 60,000)
The methyl ethyl ketone solution of the methyl methacrylate of Q-4:80 quality %, the cinnamic bipolymer of 20 quality % (solid component concentration 40 quality %, weight-average molecular weight 50,000)
Q-5: dibutyl phthalate
Q-6: polyvinyl alcohol (PVA) ((strain) Network ラ レ makes PVA-205)
Q-7: polyglycol (weight-average molecular weight 400)
Q-8: polyvinyl pyrrolidone (weight-average molecular weight 40,000) ((strain) Japanese catalyst system, K-15 (production code member))
Utilizability on the industry
According to the present invention, printed substrate, flex circuit application, COF (covering brilliant film) with substrate, lead frame, base plate for encapsulating semiconductor, liquid crystal with transparency electrode, liquid crystal with TFT with in distribution, PDP (plasma display) field with the manufacturing of the conductive pattern of electrode etc., be suitable for and do anti-etching dose or anti-plating agent.

Claims (7)

1. photosensitive-resin layered product, it is characterized in that, it is at lamination successively on the support membrane: bed thickness is more than the 10 μ m and the ground floor below the 100 μ m, bed thickness is more than the 0.1 μ m and the second layer below the 10 μ m, photosensitive-resin layered product that photo-sensitive resin forms, this ground floor contains thermoplastic resin, and this second layer contains polyvinyl alcohol (PVA): 75～99 quality % and be selected from least a kind of compound in the group of being made up of the compound shown in compound shown in the following general formula (I) and the following general formula (II): 1～25 quality % forms;
R 1-O-(CH 2CH 2O)n 1-R 2(I)
In the formula, R 1And R 2Be H or CH 3, they can be the same or different, and n 1It is 3～25 integer;
Figure FPA00001185040000011
In the formula, R 3Be the alkyl of H or carbon number 1～6, and n 2It is 9～10000 integer.
2. photosensitive-resin layered product according to claim 1, wherein, described thermoplastic resin contains the compound shown in the following general formula (I);
R 1-O-(CH 2CH 2O)n 1-R 2 (I)
In the formula, R 1And R 2Be H or CH 3, they can be the same or different, and n 1It is 3～25 integer.
3. photosensitive-resin layered product according to claim 1 and 2, its further lamination protective seam on described photo-sensitive resin forms.
4. photosensitive-resin layered product according to claim 1 and 2, wherein, described photo-sensitive resin is served as reasons and is contained: (a) in the acid equivalent carboxyl-content be 100～600 and weight-average molecular weight be 5000～500000 binder resin: 20～90 quality %; (b) unsaturated compound of at least a photopolymerization: 3～70 quality %; Reach (c) Photoepolymerizationinitiater initiater: the layer that the photosensitive polymer combination of 0.1～20 quality % forms.
5. photosensitive-resin layered product according to claim 4, wherein, the unsaturated compound of described (b) at least a photopolymerization is for being selected from the unsaturated compound of at least a kind of photopolymerization in the group of being made up of the compound shown in the following general formula (III)～(VII);
Figure FPA00001185040000021
In the formula, R 4And R 5Be H or CH 3, they can be the same or different, n 3, n 4And n 5Be respectively 3～20 integer independently;
Figure FPA00001185040000022
In the formula, R 6And R 7Be H or CH 3, they can be the same or different, and A is C 2H 4, B is CH 2CH (CH 3), n 6+ n 7Be 2～40 integer, n 8+ n 9Be 0～40 integer, n 6And n 7Be respectively 1～39 integer independently, n 8And n 9Be respectively 0～40 integer independently ,-(A-O)-and-(B-O)-the arrangement of repetitive can also can be block for random, when be block ,-(A-O)-with-(B-O)-order be that any all can in the xenyl side;
Figure FPA00001185040000031
In the formula, R 8And R 9Be H or CH 3, they can be the same or different, and D is C 2H 4, E is CH 2CH (CH 3), m 1+ m 2Be 2～40 integer, m 3+ m 4Be 0～40 integer, m 1And m 2Be respectively 1～39 integer independently, m 3And m 4Be respectively 0～40 integer independently ,-(D-O)-and-(E-O)-the arrangement of repetitive can also can be block for random, when be block ,-(D-O)-with-(E-O)-order be that any all can in the cyclohexyl side;
Figure FPA00001185040000032
In the formula, R 10Be the diisocyanate residue of carbon number 4～12, R 11And R 12Be H or CH 3, they can be the same or different, m 5And m 6It is 1～15 integer;
Figure FPA00001185040000033
In the formula, R 13Be H or CH 3, they can be the same or different, R 14Be the alkyl of carbon number 4～14, A ' is C 2H 4, B ' is CH 2CH (CH 3), m 7Be 1～12, m 8Be 0～12, m 9Be 0～3 integer ,-(A '-O)-and-(B '-O)-the arrangement of repetitive can also can be block for random, when be block ,-(A '-O)-with-(B '-O)-order be that any all can in the phenyl side.
6. the formation method of a corrosion-resisting pattern, it is characterized in that, claim 1 or 2 described photosensitive-resin layered products are laminated on the surface of sheet metal or metallic cover insulcrete, peel off ground floor together with support membrane, after the active ray exposure, remove unexposed portion by development.
7. the manufacture method of a conductive pattern is characterized in that, the substrate that has formed corrosion-resisting pattern by the described method of claim 6 is carried out etching or plating.
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