[go: up one dir, main page]

CN103091985A - Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board - Google Patents

Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board Download PDF

Info

Publication number
CN103091985A
CN103091985A CN2012104274675A CN201210427467A CN103091985A CN 103091985 A CN103091985 A CN 103091985A CN 2012104274675 A CN2012104274675 A CN 2012104274675A CN 201210427467 A CN201210427467 A CN 201210427467A CN 103091985 A CN103091985 A CN 103091985A
Authority
CN
China
Prior art keywords
methyl
photosensitive polymer
acrylate
polymer combination
corrosion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2012104274675A
Other languages
Chinese (zh)
Inventor
村松有纪子
宫坂昌宏
冈出翔太
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2012237445A external-priority patent/JP6229256B2/en
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Publication of CN103091985A publication Critical patent/CN103091985A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—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

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Architecture (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Materials For Photolithography (AREA)

Abstract

The present invention provides a photosensitive resin composition, with resolution, adaptation and resist shapes of formed resist patterns being excellent. The photosensitive resin composition comprises: a binder polymer which has a structural unit derived from (meth) acrylic acid and structural units derived from at least one (meth) acrylate selected from the group of (EO)-modified dicyclopentenyl (meth) acrylate, (EO)-modified dicyclopentadiene (meth) acrylate, (EO)-modified isobornyl (meth) acrylate, (EO)-modified adamantyl (meth) acrylate and (EO)-modified cyclohexyl (meth) acrylate; photopolymerizable compounds; and a photopolymerization initiator.

Description

The formation method of photosensitive polymer combination, photosensitive element, corrosion-resisting pattern and the manufacture method of printing distributing board
Technical field
The present invention relates to the formation method of photosensitive polymer combination, photosensitive element, corrosion-resisting pattern and the manufacture method of printing distributing board.
Background technology
In the manufacture field of printing distributing board, the erosion resistant as using in etching processing or plating, be widely used photosensitive polymer combination.Photosensitive polymer combination is used mainly with the form of the photosensitive element (duplexer) of the layer that possesses support membrane and use photosensitive polymer combination to form on this support membrane (below be called " photosensitive polymer combination layer ").
Printing distributing board is for example manufactured as follows.At first, the photosensitive polymer combination of photosensitive element is folded to (lamination) on substrate (stacked operation) layer by layer.Then, after support membrane is peeled off and removed, the established part of photosensitive polymer combination layer is irradiated active ray and makes exposure section solidify (exposure process).Afterwards, by (development) removed to from substrate by unexposed section, thereby form the corrosion-resisting pattern (developing procedure) that the solidfied material by photosensitive polymer combination forms on substrate.The gained corrosion-resisting pattern is implemented etching processing or plating and form (circuit formation operation) after circuit on substrate, finally resist is peeled off and removed and manufacture printing distributing board (stripping process).
As the method for the exposure in exposure process, used in the past and usingd mercury lamp as the light source method that also Jie is exposed by photomask.And in recent years, using and be known as the processing of DLP(digital light, the numerical data of corrosion-resisting pattern directly is depicted in DigitalLight Processing) or the LDI(laser direct imaging, Laser Direct Imaging) directly described exposure method on the photosensitive polymer combination layer.This is directly described exposure method and is compared by the exposure method of photomask with Jie, and position alignment precision is more good, and can obtain the pattern of fine, thereby is imported into for making the high-density packages substrate.
In exposure process, in order to enhance productivity, be necessary to shorten the time shutter.But, directly describe exposure method above-mentioned, light source except using the monochromatic light such as laser, owing to wanting scan irradiation light on one side to substrate on one side, thus have with Jie in the past by the exposure method of photomask compare need to the more time shutter tendency.Therefore, in order to shorten the time shutter to enhance productivity, be necessary more in the past than the sensitivity that improved photosensitive polymer combination.
In stripping process, in order to enhance productivity, be necessary to shorten the corrosion-resisting pattern splitting time.In addition, for the stripping film that prevents resist is attached on circuit substrate again with the raising rate that manufactures a finished product, be necessary to reduce the size of stripping film.Like this, the excellent photosensitive polymer combination of peel property (splitting time, stripping film size) of the corrosion-resisting pattern after require solidifying.
In addition, along with the densification of printing distributing board in recent years, for the requirement of the photosensitive polymer combination of the exploring degree (resolving power) of formed corrosion-resisting pattern and adaptation excellence, increase.Particularly, when making base plate for packaging, it is wide that requirement can form L/S(live width/spacing) be 10/10(unit: the μ m) photosensitive polymer combination of following corrosion-resisting pattern.
And then, for the high-density packages substrate, due to the narrow width between circuit, thereby the shape of corrosion-resisting pattern (following also only be called " resist shape ") excellence also becomes very important.When the cross sectional shape of corrosion-resisting pattern is trapezoidal or inverted trapezoidal or when the crimping of corrosion-resisting pattern is arranged, likely by after etching processing or the circuit that forms of plating on generation short circuit or broken string.Therefore, require resist to be shaped as rectangle and there is no crimping.
In addition, expect covering and the bendability excellence of formed corrosion-resisting pattern.While lacking these characteristics, be easy in corrosion-resisting pattern to produce disappearance, after operation in become the short circuit reason of copper wiring pattern.
And then, expect the chemical reagent resistance excellence of formed corrosion-resisting pattern.While lacking this characteristic, be easy to the metal lining infiltration occurs in plating process, become the short circuit reason of copper wiring pattern.
For these requirements, various photosensitive polymer combinations (for example, with reference to patent documentation 1～8) had been inquired in the past.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2007-279381 communique
Patent documentation 2: No. 2007/004619 pamphlet of International Publication
Patent documentation 3: TOHKEMY 2009-003177 communique
Patent documentation 4: Japanese kokai publication hei 11-327137 communique
Patent documentation 5: TOHKEMY 2004-004294 communique
Patent documentation 6: TOHKEMY 2004-317874 communique
Patent documentation 7: TOHKEMY 2008-276194 communique
Patent documentation 8: TOHKEMY 2010-085605 communique
Summary of the invention
The technical matters that invention will solve
But existing photosensitive polymer combination is difficult to very abundant at exploring degree, adaptation or resist vpg connection sometimes.Particularly, wide owing to being difficult to form L/S(live width/spacing) be 10/10(unit: μ m) following corrosion-resisting pattern, thereby tight demand can be carried with 1 μ m unit the photosensitive polymer combination of high-resolution and adaptation.
In addition, while forming corrosion-resisting pattern on the thin plate substrate below 0.5mm, because the deflection of substrate etc. makes corrosion-resisting pattern when substrate is peeled off, after operation in can become the short circuit reason of copper wiring pattern.Therefore, formed corrosion-resisting pattern is required to good bendability.
The object of the present invention is to provide the photosensitive polymer combination that can form the corrosion-resisting pattern that exploring degree, adaptation, bendability and resist shape are excellent especially and used the photosensitive element of this photosensitive polymer combination, the formation method of corrosion-resisting pattern and the manufacture method of printing distributing board.
Means for the technical solution problem
The inventor etc. conduct in-depth research in order to solve above-mentioned problem, found that: by using, by specific copolymerization, form the binder polymer formed, can obtain and can form exploring degree, adaptation, bendability and the resist shape photosensitive polymer combination of excellent corrosion-resisting pattern especially, thereby complete the present invention.That is, the present invention is as described below.
<1 > a kind of photosensitive polymer combination, it contains: (A) binder polymer, it has: from (methyl) acrylic acid structural unit, with come since by (EO) modification dicyclopentenyl (dicyclopentenyl) (methyl) acrylate, (EO) modification two cyclopentyl (dicyclopentanyl) (methyl) acrylate, (EO) modification isobornyl (methyl) acrylate, (EO) structural unit of modification adamantyl (methyl) acrylate and at least a kind of (methyl) acrylate (EO) selecting in group that modification cyclohexyl (methyl) acrylate forms, (B) optical polymerism compound, and (C) Photoepolymerizationinitiater initiater.
Above-mentioned photosensitive polymer combination is by taking above-mentioned form, sensitivity excellence, particularly exploring degree, adaptation, bendability and resist shape excellence when corrosion-resisting pattern forms.According to above-mentioned photosensitive polymer combination, can form L/S(live width/spacing wide) be 10/10(unit: μ m) following corrosion-resisting pattern.
<2 > above-mentioned<1 > described photosensitive polymer combination, wherein, above-mentioned (A) binder polymer further has the structural unit of at least a kind of polymerizable monomer selecting in the group be comprised of styrene and styrene derivative.Thus, can further improve exploring degree and the adaptation of formed corrosion-resisting pattern.
<3 > above-mentioned<1 > or<2 > described photosensitive polymer combination, wherein, it is two (methyl) acrylate compounds that above-mentioned (B) optical polymerism compound contains bisphenol-A.Thus, the alkali-developable in the time of can further improving corrosion-resisting pattern formation, exploring degree and the peel property of formed corrosion-resisting pattern.
<4 > above-mentioned<1 >～<3 > any one described photosensitive polymer combinations, wherein, above-mentioned (C) Photoepolymerizationinitiater initiater contains 2,4,5-triarylimidazoles dipolymer.Thus, sensitivity excellence when corrosion-resisting pattern forms, can further improve exploring degree and the adaptation of formed corrosion-resisting pattern.
<5 > above-mentioned<1 >～<4 > any one described photosensitive polymer combinations, it also further contains (D) and has the sensitizing coloring matter of absorption maximum at 340nm～430nm.Thus, the sensitivity in the time of can further improving corrosion-resisting pattern formation.
<6 > a kind of photosensitive element, it possesses support membrane and is formed on above-mentioned support membrane as above-mentioned<1 >～the photosensitive polymer combination layer of filming of<5 > any one described photosensitive polymer combinations.By using this photosensitive element, can sensitivity well and efficiently form the excellent especially corrosion-resisting pattern of exploring degree, adaptation, resist shape and bendability.
<7 > a kind of formation method of corrosion-resisting pattern, it has following operation: will be as above-mentioned<1 >～the photosensitive polymer combination layer of filming or above-mentioned<6 of<5 > any one described photosensitive polymer combinations > photosensitive polymer combination of described photosensitive element is stacked in the stacked operation on substrate layer by layer; To at least a portion area illumination active ray of above-mentioned photosensitive polymer combination layer so that above-mentioned zone is solidified to form the exposure process of photocuring section; And thereby the developing procedure that forms the corrosion-resisting pattern that the photocured product by above-mentioned photosensitive polymer combination forms at aforesaid substrate is removed to from aforesaid substrate in the zone except photocuring section of above-mentioned photosensitive polymer combination layer.According to this formation method, can sensitivity well and efficiently form all good corrosion-resisting patterns of exploring degree, adaptation, resist shape and bendability.
<8 > a kind of manufacture method of printing distributing board, it has by above-mentioned<7 > the described formation method substrate that formed corrosion-resisting pattern carries out the operation that etching processing or plating form conductive pattern.According to this manufacture method, can precision well and efficiently manufacture high-density packages substrate etc. and there is the printing distributing board through the distribution of densification.
The invention effect
According to the present invention, the photosensitive polymer combination that can form the corrosion-resisting pattern that exploring degree, adaptation, bendability and resist shape are excellent especially can be provided and use the photosensitive element of this photosensitive polymer combination, the formation method of corrosion-resisting pattern and the manufacture method of printing distributing board.
The accompanying drawing explanation
Fig. 1 is the schematic section of an embodiment of expression photosensitive element of the present invention.
Fig. 2 for having produced an example of tortuous or crooked SEM photo in corrosion-resisting pattern.
Fig. 3 for having produced an example of tortuous or crooked SEM photo in corrosion-resisting pattern.
Fig. 4 is an example that has produced the SEM photo of disappearance or crackle in corrosion-resisting pattern.
The stereographic map of an example of the manufacturing process that Fig. 5 is the distributing board that schematically means to utilize semi-additive process.
Embodiment
Below at length describing for implementing mode of the present invention.But the present invention not is defined in following embodiment.In addition, in this instructions, (methyl) acrylic acid refers to that acrylic or methacrylic acid, (methyl) acrylate refer to that acrylate or methacrylate corresponding thereto, (methyl) acryloyl group refer to acryloyl group or methacryl.In addition, (gather) oxygen ethene (oxidation ethylidene) chain and refer to that oxyethylene group or polyoxyethylene groups, (gathering) oxypropylene (oxypropylene) chain refer to oxypropylene group or polyoxypropylene base.In addition, " (EO) modification " refer to that compound, " (PO) modification " with (gathering) oxygen ethylene chain refer to that compound, " (EO)-(PO) modification " with (gathering) oxypropylene chain refer to have the two compound of (gathering) oxygen ethylene chain and (gathering) oxypropylene chain.In addition, in this instructions, independently operation be not only in " operation " this term, even if, in the time of can't distinguishing clearly with other operations, as long as reach the purpose that this operation is expected, be also contained in this term.In addition, the numerical range of using "～" to mean means the scope that the numerical value put down in writing before and after "～" is included as minimum value and maximal value respectively.And, when there be a plurality of material suitable with each composition in the content of each composition in composition in composition, as long as no special instructions, refer to the total amount of the plurality of material existed in composition.
[photosensitive polymer combination]
The photosensitive polymer combination of present embodiment is to contain (A) binder polymer, (B) optical polymerism compound and (C) photosensitive polymer combination of Photoepolymerizationinitiater initiater, it is characterized in that, above-mentioned (A) binder polymer has: from (methyl) acrylic acid structural unit, with come since by (EO) modification dicyclopentenyl (methyl) acrylate, (EO) modification two cyclopentyl (methyl) acrylate, (EO) modification isobornyl (methyl) acrylate, (EO) modification adamantyl (methyl) acrylate, (EO) structural unit of at least a kind of (methyl) acrylate selecting in the group that modification cyclohexyl (methyl) acrylate forms.Thus, can form sensitivity while forming except corrosion-resisting pattern excellent, hide said many characteristics such as reliability (covering), fissility and anti-plating, exploring degree, adaptation, bendability and the excellent especially corrosion-resisting pattern of resist shape.And then, can form L/S(live width/spacing wide) be 10/10(unit: μ m) following corrosion-resisting pattern.
This for example can be as the consideration of getting off.Although the corrosion-resisting pattern formed by existing photosensitive polymer combination or bendability excellent (flexible height) but developer solution is easy to swelling, or developer solution is difficult to swelling but flexible little, thereby thinks and be difficult to meet exploring degree, adaptation, bendability and resist shape simultaneously.While even if formed corrosion-resisting pattern bendability is excellent, developer solution being easy to swelling, there is corrosion-resisting pattern that tortuous or crooked tendency (for example, with reference to Fig. 2, Fig. 3) occur.In addition, even if formed corrosion-resisting pattern is difficult to swelling but bendability hour to developer solution, there is corrosion-resisting pattern that the tendency (for example, with reference to Fig. 4) of disappearance or crackle occurs.Therefore, while particularly on the thin plate substrate below 0.5mm, forming corrosion-resisting pattern, need to form the photosensitive polymer combination that developer solution is difficult to the corrosion-resisting pattern of swelling and bendability excellence.In the present invention, binder polymer is by also containing the structural unit with oxygen ethylene chain and specific aliphatics ring on the basis from (methyl) acrylic acid structural unit, due to the balance excellence of the flexible and outspoken nature of binder polymer, thereby obtained and can form the photosensitive polymer combination that developer solution is difficult to the corrosion-resisting pattern of swelling and bendability excellence.In addition, binder polymer forms by also containing the structural unit with oxygen ethylene chain and specific aliphatics ring on the basis from (methyl) acrylic acid structural unit, the utilization ratio of the active ray irradiated improves, and can reach sensitivity excellence, good resist shape.
<(A) composition: binder polymer >
At first, binder polymer (following also referred to as " (A) composition " or " (A) binder polymer ") is described.
Above-mentioned photosensitive polymer combination contains at least a kind in binder polymer, this binder polymer has: from (methyl) acrylic acid structural unit, with come since by (EO) modification dicyclopentenyl (methyl) acrylate, (EO) modification two cyclopentyl (methyl) acrylate, (EO) modification isobornyl (methyl) acrylate, (EO) structural unit of modification adamantyl (methyl) acrylate and at least a kind of (methyl) acrylate (following also referred to as " (EO) modification ester ring type (methyl) acrylate ") of (EO) selecting in group that modification cyclohexyl (methyl) acrylate forms.
As above-mentioned (EO) modification ester ring type (methyl) acrylate, so long as contain (gathering) oxygen ethylene chain and there is (methyl) acrylate of specific aliphatics cyclic group, can be not particularly limited to use.Particularly preferably specific aliphatics cyclic group at least is situated between by the structure of (gathering) oxygen ethylene chain and (methyl) acrylic acid generation ester linkage.Now, except (gathering) oxygen ethylene chain, also can further be situated between by (gathering) oxypropylene chain.As specific aliphatics cyclic group, can enumerate dicyclopentenyl, two cyclopentyl, isobornyl, adamantyl and cyclohexyl.Wherein, from the viewpoint of exploring degree, preferably from the group formed by dicyclopentenyl, two cyclopentyl, isobornyl and adamantyl, select at least a kind, more preferably dicyclopentenyl or two cyclopentyl, further preferred dicyclopentenyl.
The quantity that contains of above-mentioned oxyethylene group is suitably selected according to purpose.The quantity that contains of oxyethylene group is preferably 1～10, more preferably 1～5, more preferably 1～3, is particularly preferably 1.And then the quantity of the oxypropylene group contained as required is preferably 0～10, more preferably 0～5, more preferably 0～3, is particularly preferably 0.
In addition, above-mentioned binder polymer so long as contain the multipolymer from (methyl) acrylic acid structural unit on the basis of the structural unit from above-mentioned (EO) modification ester ring type (methyl) acrylate, is not particularly limited.Specifically, can enumerate the binder polymer with the structural unit shown in the structural unit shown in following general formula (I) and following general formula (II).
Figure BDA00002337350700071
Here, R 1mean independently of one another hydrogen atom or methyl.X means any in dicyclopentenyl, two cyclopentyl, isobornyl, adamantyl and cyclohexyl.A means 0～10, b means 1～10.In addition, oxyethylene group (OC 2h 4) and oxypropylene group (OC 3h 6) put in order can be from above-mentioned different, in addition when them when forming more than 3, a+b is 3 when above, but oxyethylene group and oxypropylene group can randomly be arranged, also block ground is arranged.Wherein, a and b mean the structural unit number of structural unit.Therefore, mean round values in single molecule; Mean the rational number as mean value during as the aggregate of different kinds of molecules.Below the structural unit number of structural unit is similarly defined.
In structural unit shown in above-mentioned general formula (I), from the viewpoint of exploring degree excellence, a is preferably 0～10, more preferably 0～5, more preferably 0～3, is particularly preferably 0.
In addition, b is preferably 1～10, more preferably 1～5, more preferably 1～3, is particularly preferably 1.B is 1 when above, the tendency that has developability to become more good.In addition, when being 10 when following, the tendency that is easy to obtain sufficient exploring degree is arranged.
As the polymerizable monomer that can form the structural unit shown in above-mentioned general formula (I), can enumerate (methyl) acrylic acid dicyclopentenyl oxygen base ethyl ester, (methyl) acrylic acid two cyclopentyloxy ethyl esters, (methyl) acrylic acid isobornyl oxygen base ethyl ester, (methyl) acrylic acid cyclohexyl oxygen base ethyl ester, (methyl) acrylic acid adamantyl oxygen base ethyl ester, (methyl) acrylic acid dicyclopentenyl two (oxygen base ethyl) ester, (methyl) acrylic acid two cyclopentyl two (oxygen base ethyl) ester, (methyl) acrylic acid isobornyl two (oxygen base ethyl) ester, (methyl) acrylic acid cyclohexyl two (oxygen base ethyl) ester, (methyl) acrylic acid adamantyl two (oxygen base ethyl) ester, (methyl) acrylic acid dicyclopentenyl oxygen base propoxyl group ethyl ester, (methyl) acrylic acid two cyclopentyloxy propoxyl group ethyl esters, (methyl) acrylic acid two cyclopentyloxy propoxyl group ethyl esters, (methyl) acrylic acid adamantyl oxygen base propoxyl group ethyl ester etc.
(A) containing ratio of structural unit shown in the general formula in binder polymer (I) take the molecule gross mass as benchmark be preferably 3 quality %～85 quality %, more preferably 4 quality %～83 quality %, more preferably 5 quality %～80 quality～, be particularly preferably 10 quality %～80 quality %, the utmost point is preferably 20～80 quality %.Its containing ratio is 3 quality % when above, and adaptation, bendability and flexible more excellent tendency are arranged.In addition, its containing ratio is 85 quality % when following, and the more excellent tendency of exploring degree is arranged.
As the polymerizable monomer that can form structural unit shown in above-mentioned general formula (II), can enumerate acrylic acid and methacrylic acid.(A) containing ratio of structural unit shown in the general formula in binder polymer (II) be take the molecule gross mass and is preferably 10 quality %～60 quality %, more preferably 15 quality %～50 quality %, 20 quality %～35 quality % more preferably as benchmark.Its containing ratio is 10 quality % when above, and the tendency that the alkali dissolubility further improves, splitting time further shortens is arranged.In addition, its containing ratio is 60 quality % when following, and the more excellent tendency of exploring degree is arranged.
In addition, (A) binder polymer also can further contain other structural units except the structural unit shown in the structural unit shown in general formula (I) and general formula (II).As the polymerizable monomer that can form other structural units, can enumerate (methyl) alkyl acrylate, (methyl) acrylic acid cycloalkyl ester, (methyl) benzyl acrylate, (methyl) benzyl acrylate derivant, (methyl) acrylic acid chaff ester, (methyl) acrylic acid hydroxyalkyl acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid adamantane esters, (methyl) acrylic acid two cyclopentyl esters, (methyl) acrylic acid dimethylamino ethyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) glycidyl acrylate, (methyl) acrylic acid 2, 2, the 2-trifluoro ethyl ester, (methyl) acrylic acid 2, 2, 3, (methyl) acrylate such as 3-tetrafluoro propyl ester, alpha-brominated acrylic acid, α-chloro-acrylicacid, (methyl) propenoic acid beta-furans ester, (methyl) propenoic acid beta-(methyl) acrylic acid derivatives such as styryl ester, styrene, vinyltoluene, α-methyl styrene etc. are at alpha-position or the substituted polymerisable styrene derivative of aromatic ring, the acrylamides such as diacetone acrylamide, vinyl cyanide, the ester class of the vinyl alcohol such as vinyl-n-butyl ether, maleic acid, maleic anhydride, the maleic acid monoesters such as monomethyl maleate, ethyl maleate, maleic acid list isopropyl ester, the unsaturated carboxylic acids such as fumaric acid, cinnamic acid, alpha-cyano cinnamic acid, itaconic acid, crotonic acid, propiolic acid etc.These materials can be used alone a kind, also can at random be used in combination two or more.
(A) viewpoint of binder polymer from making exploring degree and adaptation become good, the preferred structural unit that further there is at least a kind of polymerizable monomer selecting in the group formed by styrene and styrene derivative.; (A) binder polymer be preferably by make (methyl) acrylic acid at least one, at least a kind of (EO) modification ester ring type (methyl) acrylate and at least a kind of polymerizable monomer generation free radical polymerization selecting from the group be comprised of styrene and styrene derivative obtains, and preferably has the structural unit from these polymerizable monomers.
(A), when binder polymer has the structural unit from the styrene or derivatives thereof, its containing ratio be take the molecule gross mass and is preferably 10～70 quality %, more preferably 15～60 quality %, 20 quality %～50 quality % more preferably as benchmark.Its containing ratio is 10 quality % when above, and the tendency that is easy to obtain sufficient adaptation is arranged.In addition, its containing ratio is 70 quality % when following, has and suppresses the stripping film tendency excessive, that splitting time shortens that becomes.
In addition, (A) binder polymer, from improving the viewpoint of alkali-developable and peel property, preferably further has the structural unit of at least a kind of polymerizable monomer selecting in the group be comprised of (methyl) alkyl acrylate and (methyl) benzyl acrylate.
As the alkyl in (methyl) alkyl acrylate, from improving the viewpoint of alkali-developable and peel property, the alkyl that the alkyl that preferably carbon number is 1～20, the alkyl that more preferably carbon number is 1～15, further preferred carbon number are 1～12.As (methyl) alkyl acrylate, can enumerate particularly (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) 2-EHA etc.These materials can be used alone a kind or at random be used in combination two or more.
(A) binder polymer is when having the structural unit of at least a kind of polymerizable monomer selecting in the group by (methyl) alkyl acrylate and (methyl) benzyl acrylate form, and its containing ratio be take the molecule gross mass and is preferably 1 quality %～50 quality %, more preferably 2 quality %～40 quality %, 3 quality %～30 quality % more preferably as benchmark.This containing ratio is 1 quality % when above, has and suppresses the stripping film tendency excessive, that splitting time shortens that becomes.In addition, this containing ratio is 50 quality % when following, and the tendency that is easy to obtain sufficient exploring degree and adaptation is arranged.
(A) acid number of binder polymer be preferably 90mgKOH/g～250mgKOH/g, more preferably 100mgKOH/g～230mgKOH/g, more preferably 110mgKOH/g～210mgKOH/g, be particularly preferably 120mgKOH/g～200mgKOH/g.This acid number is 90mgKOH/g when above, and the tendency that has development time to shorten for 250mgKOH/g when following, has the tendency of the anti-development fluidity (adaptation) of the solidfied material that is easy to obtain fully photosensitive polymer combination.In addition, while in developing procedure described later, carrying out solvent develop, preferably marginally prepare from (methyl) acrylic acid etc. and there is the structural unit of the polymerizable monomer of carboxyl.
(A), when the weight-average molecular weight of binder polymer (Mw) utilizes gel permeation chromatography (GPC) to be measured (being converted by the typical curve that has used polystyrene standard), be preferably 10000～200000, more preferably 20000～150000, more preferably 25000～120000.Weight-average molecular weight (Mw) is 10000 when above, and the tendency of the anti-development fluidity (adaptation) of the solidfied material that is easy to obtain fully photosensitive polymer combination is arranged; Be 200000 when following, the tendency that has development time to shorten.
In addition, (A) light that binder polymer also can have having the wavelength in 340nm～430nm scope as required in its molecule has photosensitive characteristic group.In addition, as (A) composition, the a kind of binder polymer that can be used alone, also can at random be used in combination binder polymer of more than two kinds.
(A) content of composition makes (A) composition and (B) when the total amount of composition is 100 mass parts, be preferably 30 mass parts～70 mass parts, more preferably 35 mass parts～65 mass parts, be particularly preferably 40 mass parts～60 mass parts.This content is 30 mass parts when above, and the tendency that is easy to form film (photosensitive polymer combination layer) is arranged, and is 70 mass parts when following, and the tendency that is easy to obtain fully sensitivity and exploring degree is arranged.
<(B) composition: optical polymerism compound >
Then, (B) optical polymerism compound (following also referred to as " (B) composition ") is described.
As (B) composition, be not particularly limited so long as can carry out photopolymerisable material, but preferably use the compound with ethylenic unsaturated link.As the compound with ethylenic unsaturated link, can enumerate compound, the compound with 2 ethylenic unsaturated links with 1 ethylenic unsaturated link, there is the compound of 3 above ethylenic unsaturated links etc.Wherein, (B) composition, from the viewpoint of adaptation and developability, preferably contains the compound with the unsaturated bonding of ethylenic and (gathering) oxygen ethylene chain.
And then (B) composition preferably contains at least a kind in the compound with 2 ethylenic unsaturated links.(B) when composition contains the compound with 2 ethylenic unsaturated links, its containing ratio makes (A) composition and (B) when the total amount of composition is 100 mass parts, is preferably 10 mass parts～80 mass parts, 30 mass parts～70 mass parts more preferably.
As the compound that there are 2 ethylenic unsaturated links in molecule, such as enumerating bisphenol-A, be that two (methyl) acrylate compounds, hydrogenated bisphenol A are to have the two poly alkylene glycol two (methyl) acrylate compounds, trimethylolpropane two (methyl) acrylate compounds etc. of (gathering) oxygen ethylene chain and (gathering) oxypropylene chain in two (methyl) acrylate compounds (following also referred to as " urethane monomer ") of having ammonia ester bond in two (methyl) acrylate compounds, molecule, molecule.Wherein, from anti-plating, the viewpoint of adaptation is set out, it is two (methyl) acrylate compounds that compound with 2 ethylenic unsaturated links is preferably bisphenol-A, hydrogenated bisphenol A is to have the two poly alkylene glycol two (methyl) acrylate compounds of (gathering) oxygen ethylene chain and (gathering) oxypropylene chain in two (methyl) acrylate compounds or molecule, more preferably (EO) modified bisphenol A is two (methyl) acrylate compounds, (EO) modified hydrogenated bisphenol-A is two (methyl) acrylate compounds or has the two poly alkylene glycol two (methyl) acrylate compounds of (gathering) oxygen ethylene chain and (gathering) oxypropylene chain.
In above-mentioned, (B) composition is in two (methyl) acrylate compounds at least a kind from improving the viewpoint of sensitivity and exploring degree, preferably containing bisphenol-A, more preferably to contain (EO) modified bisphenol A be at least a kind in two (methyl) acrylate compounds.Be at least a kind of conduct (B) composition in two (methyl) acrylate compounds by combination (EO) modified bisphenol A in above-mentioned binder polymer, can form exploring degree, adaptation and the more excellent corrosion-resisting pattern of resist shape.
Be two (methyl) acrylate compounds as bisphenol-A, can enumerate the compound shown in following general formula (2).
In above-mentioned general formula (2), R 3and R 4mean independently of one another hydrogen atom or methyl.XO and YO mean oxyethylene group or oxypropylene group independently of one another, and they are different.(XO) m 1, (XO) m 2, (YO) n 1reach (YO) n 2mean independently of one another (gathering) oxygen ethylene chain or (gathering) oxypropylene chain.M 1, m 2, n 1and n 2mean independently of one another 0～40.XO is oxyethylene group, YO while being oxypropylene group, m 1+ m 2be 1～40, n 1+ n 2be that 0～20, XO is oxypropylene group, YO while being oxyethylene group, m 1+ m 2be 0～20, n 1+ n 2be 1～40.
In the compound shown in above-mentioned general formula (2), two (the 4-(methacryloxy five ethoxys) phenyl of 2,2-) propane can be used as BPE-500(Xin Zhong village chemical industry Co., Ltd. system, trade name) or FA-321M(Hitachi Chemical Co., Ltd. system, trade name) obtain from commercial channels.In addition, 2, two (the 4-(methacryloxy 15 ethoxys) phenyl of 2-) propane can be used as BPE-1300(Xin Zhong village chemical industry Co., Ltd. system, trade name) obtain from commercial channels, two (the 4-(methacryloxy diethoxy) phenyl of 2,2-) propane can be used as BPE-200(Xin Zhong village chemical industry Co., Ltd. system, trade name) obtain from commercial channels.These materials can be used alone a kind or at random be used in combination two or more.
(B) when composition contains the compound shown in general formula (2), from improving the viewpoint of sensitivity and exploring degree, its content makes (A) composition and (B) when the total amount of composition is 100 mass parts, be preferably 3 mass parts～60 mass parts, more preferably 10 mass parts～50 mass parts, more preferably 15 mass parts～45 mass parts, be particularly preferably 15 mass parts～30 mass parts.
In addition, (B) composition, from the flexible viewpoint of the solidfied material (cured film) of raising photosensitive polymer combination, preferably contains at least a kind in poly alkylene glycol two (methyl) acrylate compounds.(B) when composition contains poly alkylene glycol two (methyl) acrylate compounds, as its containing ratio, make (A) composition and (B) when the total amount of composition is 100 mass parts, be preferably 3 mass parts～50 mass parts, 5 mass parts～40 mass parts more preferably.
As poly alkylene glycol two (methyl) acrylate compounds, preferably there is the two poly alkylene glycol two (methyl) acrylate compounds of (gathering) oxygen ethylene chain and (gathering) oxypropylene chain.In the molecule of poly alkylene glycol two (methyl) acrylate compounds, (gathering) oxygen ethylene chain and (gathering) oxypropylene chain can be distinguished block ground continuously and exist, and also can randomly exist.Wherein, (gathering) oxypropylene group in the oxypropylene chain can be any of oxygen base-positive propenyl and oxygen base isopropenyl.In addition, in (gathering) oxygen isopropyl alkene chain, can be the secondary bond with carbon of isopropenyl on oxygen atom, can be also that primary carbon is bonded on oxygen atom.
Poly alkylene glycol two (methyl) acrylate compounds also can further have (gathering) oxygen base-n-butene chain, (gathering) oxygen base isobutylene chain, (gathering) oxygen base-positive amylene chain, (gathering) oxygen base hexene chain or (gathering) oxygen base alkylidene chain that is 4～6 left and right as their carbon number of constitutional isomer etc.
As poly alkylene glycol two (methyl) acrylate compounds, at least one in the compound shown in any of following general formula (3), (4) or general formula (5) particularly preferably.These materials can be used alone a kind or be used in combination two or more.
Figure BDA00002337350700131
In above-mentioned general formula (3), (4) and (5), R 5～R 10mean independently of one another hydrogen atom or methyl, EO means oxyethylene group, and PO means oxypropylene group.R 1, r 2, r 3and r 4the structural unit number of the structural unit that expression consists of oxyethylene group, s 1, s 2, s 3and s 4the structural unit number of the structural unit that expression consists of oxypropylene group, the structural unit sum r of oxyethylene group 1+ r 2, r 3and r 4(mean value) means 1～30 independently of one another, the structural unit sum s of oxypropylene group 1, s 2+ s 3and s 4(mean value) means 1～30 independently of one another.
In the compound shown in above-mentioned general formula (3), (4) or (5), the structural unit of oxyethylene group sum r 1+ r 2, r 3and r 4be 1～30, from exploring degree, adaptation and the more excellent viewpoint of resist shape, more preferably 1～10, more preferably 4～9, be particularly preferably 5～8.
In addition, the structural unit of oxypropylene group sum s 1, s 2+ s 3and s 4be 1～30, from further carrying high-resolution, further suppress the viewpoint of the generation of sludge, be preferably 5～20, more preferably 8～16, more preferably 10～14.
As the compound shown in above-mentioned general formula (3), can enumerate R 5and R 6=methyl, r 1+ r 2=6(mean value), s 1=12(mean value) vinyl compound (Hitachi Chemical Co., Ltd.'s system, trade name: FA-023M) etc.As the compound shown in above-mentioned general formula (4), can enumerate R 7and R 8=methyl, r 3=6(mean value), s 2+ s 3=12(mean value) vinyl compound (Hitachi Chemical Co., Ltd.'s system, trade name: FA-024M) etc.As the compound shown in above-mentioned general formula (5), can enumerate R 9and R 10=hydrogen atom, r 4=1(mean value), s 4=9(mean value) vinyl compound (Xin Zhong village chemical industry Co., Ltd. system, sample name: NK Ester HEMA-9P) etc.These materials can be used alone a kind or be used in combination two or more.
In addition, (B) composition is from the viewpoint of peel property and exploring degree, and preferably containing hydrogenated bisphenol A is at least a kind in two (methyl) acrylate compounds.(B) when composition contains hydrogenated bisphenol A and is two (methyl) acrylate compounds, its content makes (A) composition and (B) when the total amount of composition is 100 mass parts, is preferably 3 mass parts～50 mass parts, 5 mass parts～45 mass parts more preferably.
Be two (methyl) acrylate compounds as hydrogenated bisphenol A, can enumerate particularly two (the 4-(methacryloxy five ethoxys) cyclohexyl of 2,2-) propane etc.
(B) composition preferably contains at least a kind in the compound with 1 ethylenic unsaturated link.(B) when composition contains the compound with 1 ethylenic unsaturated link, its containing ratio is put forward the viewpoint of high-resolution, adaptation, resist shape and peel property well from balance, make (A) composition and (B) when the total amount of composition is 100 mass parts, be preferably 1 mass parts～30 mass parts, more preferably 3 mass parts～25 mass parts, more preferably 5 mass parts～20 mass parts, be particularly preferably 5 mass parts～10 mass parts.
As the compound that there is 1 ethylenic unsaturated link in molecule, can enumerate Nonylphenoxy polyethyleneoxy acrylate, phthalic acid based compound and (methyl) alkyl acrylate etc.
In above-mentioned, from balance, put forward well the viewpoint of high-resolution, adaptation, resist shape and peel property, preferably contain Nonylphenoxy polyethyleneoxy acrylate or phthalic acid based compound.
As above-mentioned Nonylphenoxy polyethyleneoxy acrylate, can enumerate Nonylphenoxy triethylene oxygen base acrylate, Nonylphenoxy four ethyleneoxy acrylate, Nonylphenoxy five ethyleneoxy acrylate, Nonylphenoxy six ethyleneoxy acrylate, Nonylphenoxy seven ethyleneoxy acrylate, Nonylphenoxy eight ethyleneoxy acrylate, Nonylphenoxy nine ethyleneoxy acrylate, Nonylphenoxy ten ethyleneoxy acrylate, Nonylphenoxy 11 ethyleneoxy acrylate etc.These materials can be used alone or at random are used in combination two or more.In addition, " Nonylphenoxy polyethyleneoxy acrylate " also is known as " Nonylphenoxy polyethylene glycol acrylate ".
Wherein, Nonylphenoxy eight ethyleneoxy acrylate for example can be used as M-114(Toagosei Co., Ltd system, trade name, 4-n-nonyl phenoxy group eight ethyleneoxy acrylate) obtain from commercial channels.In addition, " 4-n-nonyl phenoxy group eight ethyleneoxy acrylate " also are known as " 4-n-nonyl phenoxy group eight EDIAs ".
As above-mentioned phthalic acid based compound, can enumerate γ-chloro-beta-hydroxy propyl group-β '-(methyl) acryloxy ethyl-phthalic ester, beta-hydroxy ethyl-β '-(methyl) acryloxy ethyl-phthalic ester, beta-hydroxy propyl group-β '-(methyl) acryloxy ethyl-phthalic ester etc.Preferred γ-chloro-beta-hydroxy propyl group-β '-(methyl) acryloxy ethyl-phthalic ester wherein.γ-chloro-beta-hydroxy propyl group-β '-methacryloxyethyl-phthalic ester can be used as FA-MECH(Hitachi Chemical Co., Ltd. system, trade name) obtain from commercial channels.These materials can be used alone a kind or be used in combination two or more.
(B) composition also preferably contains the optical polymerism compound with 3 above ethylenic unsaturated links.(B) when composition contains the optical polymerism compound with 3 above ethylenic unsaturated links, put forward well the viewpoint of high-resolution, adaptation, resist shape and peel property from balance, its content makes (A) composition and (B) is being preferably 3 mass parts～30 mass parts, 5 mass parts～20 mass parts more preferably when the total amount of composition is 100 mass parts.
As the compound with 3 above ethylenic unsaturated links, can enumerate trimethylolpropane tris (methyl) acrylate, EO modification trimethylolpropane tris (methyl) acrylate (the structural unit number of oxyethylene group is 1～5), (PO) modification trimethylolpropane tris (methyl) acrylate, (EO) modification trimethylolpropane tris (methyl) acrylate-(PO), tetramethylol methane three (methyl) acrylate, tetramethylol methane four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc.These materials can be used alone or are used in combination two or more.Wherein, as obtainable material, can enumerate A-TMM-3(Xin Zhong village chemical industry Co., Ltd. system, trade name, tetramethylol methane triacrylate), TMPT21E, TMPT30E(Hitachi Chemical Co., Ltd. system, sample name, (EO) modification trimethylol-propane trimethacrylate) etc.
Above-mentioned photosensitive polymer combination, by being in two (methyl) acrylate compounds at least a kind and from by having at least a kind of combination that the two poly alkylene glycol two (methyl) acrylate compounds of (gathering) oxygen ethylene chain and (gather) oxypropylene chain selects in reaching (EO) group that modification trimethylolpropane tris (methyl) acrylate forms in molecule, being used as (B) composition by (EO) modified bisphenol A in above-mentioned binder polymer, can form exploring degree, adaptation, bendability and the more excellent corrosion-resisting pattern of resist shape.
(B) content of composition integral body makes (A) composition and (B) when the total amount of composition is 100 mass parts, be preferably 30 mass parts～70 mass parts, more preferably 35 mass parts～60 mass parts, be particularly preferably 35 mass parts～50 mass parts.This content is 30 mass parts when above, and the tendency that is easy to obtain sufficient sensitivity and exploring degree is arranged.In addition, be 70 mass parts when following, the tendency that has the formative of film to improve, the tendency that is easy to obtain in addition good resist shape.
<(C) composition: Photoepolymerizationinitiater initiater >
Then, Photoepolymerizationinitiater initiater (following also referred to as " (C) composition ") is described.
Photoepolymerizationinitiater initiater as (C) composition is not particularly limited.As Photoepolymerizationinitiater initiater, can enumerate benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1,2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-the aromatic ketone compounds such as 2-morpholino-acetone-1; The naphtoquinone compounds such as alkyl-anthraquinone; The benzoin ether compounds such as benzoin alkylether; The benzoin compounds such as benzoin, alkyl benzene acyloin; The benzyl derivatives such as benzyl dimethyl ketal; The 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dipolymer, the adjacent fluorophenyl of 2-()-4,5-diphenyl-imidazole dipolymer etc. 2,4,5-triarylimidazoles dipolymer; 9-phenylacridine, 1,7-(9,9 '-acridinyl) acridine derivatives such as heptane etc.These materials can be used alone a kind or be used in combination two or more.
(C) viewpoint of sensitivity when composition forms from improving corrosion-resisting pattern and the adaptation of formed corrosion-resisting pattern, preferably contain 2,4,5-triarylimidazoles dipolymer, more preferably contain the 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dipolymer.The structure of 2,4,5-triarylimidazoles dipolymer can be symmetrical, also can be asymmetrical.
(C) content of composition makes (A) composition and (B) when the total amount of composition is 100 mass parts, be preferably 0.1 mass parts～10 mass parts, more preferably 1 mass parts～7 mass parts, more preferably 2 mass parts～6 mass parts, be particularly preferably 3 mass parts～5 mass parts.This content is 0.1 mass parts when above, and the tendency that is easy to obtain good sensitivity, exploring degree or adaptation is arranged.In addition, be 10 mass parts when following, the tendency that is easy to obtain good resist shape is arranged.
<(D) composition: sensitizing coloring matter >
Above-mentioned photosensitive polymer combination preferably further contains at least a kind in sensitizing coloring matter (following also referred to as " (D) composition "), more preferably contains at wavelength 340nm～430nm and has at least a kind in the sensitizing coloring matter of absorption maximum.Below to describing as the sensitizing coloring matter of (D) composition.
As the sensitizing coloring matter of (D) composition, can enumerate dialkyl amido benzophenone cpd, pyrazoline compounds, anthracene compound, coumarin compound, xanthone compound, thioxanthones compound, oxazole compounds, benzoazole compounds, thiazolium compounds, benzothiazole compound, triazole compounds, diphenyl ethene compounds, triaizine compounds, thiophene compound, naphthalimide compound, triarylamine compound, aminacrine compound etc.These materials can be used alone a kind or be used in combination two or more.
When the active ray that is particularly 340nm～430nm at the use wavelength carries out the exposure of photosensitive polymer combination layer, viewpoint from sensitivity and adaptation, (D) to be preferably at wavelength be the sensitizing coloring matter that 340nm～430nm has absorption maximum to composition, more preferably contain from by the dialkyl amido benzophenone cpd, pyrazoline compounds, anthracene compound, coumarin compound, triarylamine compound, at least a kind of sensitizing coloring matter selecting in the group that thioxanthones compound and aminacrine compound form, wherein further preferably contain from by pyrazoline compounds, in the group that anthracene compound and triarylamine compound form, select at least a kind.
(D) content of composition makes (A) composition and (B) when the total amount of composition is 100 mass parts, is preferably 0.01 mass parts～10 mass parts, more preferably 0.05 mass parts～5 mass parts, 0.1 mass parts～3 mass parts more preferably.This content is 0.01 mass parts when above, has and is easy to obtain better sensitivity and the tendency of exploring degree.In addition, be 10 mass parts when following, the tendency that is easy to obtain fully good resist shape is arranged.
As above-mentioned pyrazoline compounds, in the group preferably formed from the compound shown in the compound by shown in following general formula (6) and general formula (7), select at least a kind.
Figure BDA00002337350700181
In above-mentioned general formula (6), R 11～R 13mean independently of one another the alkyl of straight chain shape that carbon number is 1～12 or a chain, straight chain shape that carbon number is 1～10 or alkoxy or the halogen atom of a chain.In addition, a, b and c mean 0～5 integer independently of one another, and the summation of a, b and c is 1～6.When the summation of a, b and c is 2 when above, the R of a plurality of existence 11～R 13can be mutually identical also can be different.
In above-mentioned general formula (6), R 11～R 13in at least 1 straight chain shape that preferably carbon number is 1～12 or the alkyl of a chain or straight chain shape that carbon number is 1～10 or the alkoxy of a chain, the alkoxy of the alkyl of the straight chain shape that to be more preferably carbon number be 1～3 or a chain or the straight chain shape that carbon number is 1～3 or a chain, more preferably isopropyl, methoxy or ethoxy.
As the pyrazoline compounds shown in above-mentioned general formula (6), be not particularly limited.Can enumerate particularly 1-phenyl-3-(4-cumene vinyl)-the 5-(4-isopropyl phenyl)-pyrazoline, 1-phenyl-3-(4-the tert-butyl group-styryl)-5-(4-tert-butyl group)-pyrazoline, 1-phenyl-3-(4-methoxyl-styrene)-5-(4-methoxyphenyl)-pyrazoline, 1-phenyl-3-(3, the 5-dimethoxy-styryl)-5-(3, the 5-Dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(3, the 4-dimethoxy-styryl)-5-(3, the 4-Dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2, the 6-dimethoxy-styryl)-5-(2, the 6-Dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2, the 5-dimethoxy-styryl)-5-(2, the 5-Dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2, the 3-dimethoxy-styryl)-5-(2, the 3-Dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2, the 4-dimethoxy-styryl)-5-(2, the 4-Dimethoxyphenyl)-pyrazoline etc. is equivalent to the pyrazoline compounds of the a=0 in above-mentioned general formula (6).
Figure BDA00002337350700191
In above-mentioned general formula (7), R 14～R 16mean independently of one another the alkyl of straight chain shape that carbon number is 1～12 or a chain, straight chain shape that carbon number is 1～10 or alkoxy, halogen atom or the phenyl of a chain.In addition, d, e and f mean 0～5 integer independently of one another, and the summation of d, e and f is 1～6.The summation of d, e and f is 2 when above, the R of a plurality of existence 14～R 16can be mutually identical also can be different.
In above-mentioned general formula (7), R 14～R 16in at least 1 straight chain shape that preferably carbon number is 1～12 or the alkyl of a chain, straight chain shape that carbon number is 1～10 or alkoxy or the phenyl of a chain, alkoxy or the phenyl of the alkyl of the straight chain shape that to be more preferably carbon number be 1～4 or a chain, the straight chain shape that carbon number is 1～4 or a chain, the more preferably tert-butyl group, isopropyl, methoxyl, ethoxy or phenyl.
In addition, as the pyrazoline compounds shown in above-mentioned general formula (7), be not particularly limited, can enumerate 1-phenyl-3, two (4-the tert-butyl-phenyl)-pyrazolines of 5-, 1-phenyl-3, two (4-the methoxyphenyl)-pyrazolines of 5-, 1-phenyl-3-(4-methoxyphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-tert-butyl-phenyl)-5-(4-methoxyphenyl)-pyrazoline, 1-phenyl-3-(4-isopropyl phenyl)-5-(4-the tert-butyl group-phenyl)-pyrazoline, 1-phenyl-3-(4-tert-butyl-phenyl)-5-(4-isopropyl phenyl)-pyrazoline, 1-phenyl-3-(4-methoxyphenyl)-5-(4-isopropyl phenyl)-pyrazoline, 1-phenyl-3-(4-isopropyl phenyl)-5-(4-methoxyphenyl)-pyrazoline, 1,5-diphenyl-3-(4-tert-butyl-phenyl)-pyrazoline, 1,3-diphenyl-5-(4-tert-butyl-phenyl)-pyrazoline, 1,5-diphenyl-3-(4-isopropyl phenyl)-pyrazoline, 1,3-diphenyl-5-(4-isopropyl phenyl)-pyrazoline, 1,5-diphenyl-3-(4-methoxyl-phenyl)-pyrazoline, 1,3-diphenyl-5-(4-methoxyphenyl)-pyrazoline, 1-phenyl-3, two (4-the tert-butyl-phenyl)-pyrazolines of 5-, 1,5-diphenyl-3-(4-tert-butyl-phenyl)-pyrazoline etc. is equivalent to the pyrazoline compounds of the d=0 in above-mentioned general formula (7), 1-phenyl-3-(4-xenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-xenyl)-the tertiary octyl phenyl of 5-(4-)-pyrazoline etc. is equivalent to e=1, R in above-mentioned general formula (7) 15the pyrazoline compounds of=phenyl etc.
As above-mentioned anthracene compound, preferably contain at least a kind in the compound shown in following general formula (8).
Figure BDA00002337350700201
In above-mentioned general formula (8), R 17and R 18mean independently of one another the alkyl that carbon number is 1～20, naphthenic base, phenyl or the benzyl that carbon number is 5～12.Wherein, the aromatic rings in above-mentioned general formula (8) only otherwise damaging effect of the present invention can have substituting group.
In above-mentioned general formula (8), as R 17and R 18, can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl etc.As R 17and R 18combination, the combination of combination, butyl and butyl that for example can enumerate combination, propyl group and the propyl group of ethyl and ethyl.
Preferred above-mentioned R 17and R 18mean independently of one another the alkyl that carbon number is 1～4.
As the compound shown in above-mentioned general formula (8), can enumerate particularly 9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 9,10-dibutoxy anthracene etc.
As above-mentioned triarylamine compound, preferably contain at least a kind in the compound shown in following general formula (9).
Figure BDA00002337350700202
In above-mentioned general formula (9), R 27, R 28and R 29mean independently of one another the alkoxy that alkyl that carbon number is 1～10 or carbon number are 1～4,0～5 the integer that g, h and i mean that the value according to g+h+i reaches that mode more than 1 selects.Wherein, when g is 2 when above, the R of a plurality of existence 27can be identical also can be different; When h is 2 when above, the R of a plurality of existence 28can be identical also can be different; When i is 2 when above, the R of a plurality of existence 29can be identical also can be different.
<other compositions >
That above-mentioned photosensitive polymer combination preferably contains is two [4-(dimethylamino) phenyl] methane, two [4-(diethylamino) phenyl] methane or leuco crystal violet.These materials can be used alone a kind or be used in combination two or more.When photosensitive polymer combination contains these compounds, its content makes (A) composition and (B) when the total amount of composition is 100 mass parts, be preferably 0.01 mass parts～10 mass parts, more preferably 0.05 mass parts～5 mass parts, be particularly preferably 0.1 mass parts～2 mass parts.This content is 0.01 mass parts when above, and having becomes is easy to obtain the tendency of abundant sensitivity.In addition, be 10 mass parts when following, have and further effectively be suppressed at the tendency that above-claimed cpd that film forms rear surplus is separated out as foreign matter.
The photosensitive polymer combination of present embodiment also can contain the optical polymerism compound (oxetane compound etc.) of the ring-type ether that has at least 1 cationically polymerizable in molecule as required, cationic polymerization initiators, the dyestuffs such as peacock green, trisbromomethyl phenyl sulfone, hot color development preventing agent, the plastifier such as para toluene sulfonamide, pigment, filling agent, defoamer, fire retardant, stabilizing agent, the adaptation imparting agent, levelling agent, peel off promoter, antioxidant, spices, preparation, thermal cross-linking agent etc.These materials can be used alone or are used in combination two or more.Their content makes (A) composition (binder polymer) and (B) when the total amount of composition (optical polymerism compound) is 100 mass parts, preferably is being respectively 0.01 mass parts～20 mass parts left and right.
<organic solvent >
The photosensitive polymer combination of present embodiment can contain at least a kind in organic solvent as required.The containing ratio of the organic solvent in photosensitive polymer combination is not particularly limited, and can suitably select according to purpose.Photosensitive polymer combination for example can be made into the solution (following also referred to as " coating fluid ") that solid constituent is 30 quality %～60 quality % left and right and uses.Here solid constituent refers to and remove remaining composition after volatile ingredient from photosensitive polymer combination.
As organic solvent, can enumerate the alcoholic solvents such as methyl alcohol, ethanol; The ketone solvent such as acetone, MEK; The glycol ether solvents such as methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether; The hydrocarbon solvents such as toluene; The non-proton property such as DMF polar solvent; And their mixed solvent.
Above-mentioned coating fluid for example can be as follows for the formation of photosensitive polymer combination layer.Go up and be dried by above-mentioned coating fluid being coated on to the surfaces such as sheet metal, can form the photosensitive polymer combination layer that the photosensitive polymer combination by present embodiment forms.As the metal of sheet metal, can enumerate the iron-based alloys such as copper, copper series alloy, nickel, chromium, iron, stainless steel etc., preferably copper, copper series alloy, iron-based alloy etc.
The thickness of photosensitive polymer combination layer according to its purposes and difference, is preferably 1 μ m～100 μ m left and right with dried thickness gauge.Can also be with diaphragm by the photosensitive polymer combination layer and the surface coverage sheet metal opposition side.As diaphragm, can enumerate the polymer films such as tygon, polypropylene etc.
[photosensitive element]
Photosensitive element 1 of the present invention possesses as shown in Figure 1 support membrane 2 and is formed on the photosensitive polymer combination layer 3 that the above-mentioned photosensitive polymer combination of conduct on above-mentioned support membrane 2 is filmed, and also possesses as required other inscapes (for example diaphragm 4).By possessing the photosensitive polymer combination layer formed by above-mentioned photosensitive polymer combination, can form the corrosion-resisting pattern that exploring degree, adaptation, bendability and resist shape are excellent especially.
Photosensitive element can obtain as follows: above-mentioned coating fluid is coated on support membrane and is dried, form the photosensitive polymer combination layer of filming as above-mentioned photosensitive polymer combination on support membrane, thereby obtain.
Be not particularly limited as support membrane, can suitably select from normally used polymer film.As support membrane, can use polyethylene terephthalate, polypropylene, tygon, polyester etc. to there is the polymer film of thermotolerance and solvent resistance.
In addition, the thickness of support membrane (polymer film) is preferably 1 μ m～100 μ m, more preferably 5 μ m～50 μ m, 5 μ m～30 μ m more preferably.This thickness is 1 μ m when above, can suppress support membrane and break when peeling off support membrane.In addition, be 100 μ m when following, the tendency that is easy to obtain fully the exploring degree is arranged.
Photosensitive element 1 as shown in Figure 1, also can possess as required by photosensitive polymer combination layer 3 and diaphragms 4 surface coverage support membrane 2 opposition sides.
As diaphragm, preferably the bonding force of photosensitive polymer combination layer is less than to the bonding force of support membrane to the photosensitive polymer combination layer, preferably hang down in addition the film of flake.
Specifically, as diaphragm, can use polyethylene terephthalate, polypropylene, tygon, polyester etc. to there is the polymer film of thermotolerance and solvent resistance.In addition, diaphragm can be identical with support membrane.
The thickness of diaphragm be preferably 1 μ m～100 μ m, more preferably 5 μ m～50 μ m, more preferably 5 μ m～30 μ m, be particularly preferably 15 μ m～30 μ m.This thickness is 1 μ m when above, by photosensitive polymer combination layer and diaphragm stacked (lamination) on substrate the time, and the tendency that has diaphragm to be difficult to break.In addition, be 100 μ m when following, the tendency that has throughput rate to improve.
The coating of coating fluid on support membrane can utilize the known methods such as roller coat, comma coating, intaglio plate coating, airblade coating, mould are coated with, rod painting to carry out.
The drying that coating fluid is coated with to formed coating layer is preferably carried out about 5 minutes～30 minutes under 70 ℃～150 ℃.After drying, the viewpoint of the diffusion of the organic solvent operation after preventing of the remaining organic solvent amount in the photosensitive polymer combination layer, be preferably below 2 quality %.
The thickness of the photosensitive polymer combination layer in photosensitive element is according to purposes and difference, with dried thickness gauge, is preferably 1 μ m～100 μ m, more preferably 1 μ m～50 μ m, 5 μ m～40 μ m more preferably.This thickness is 1 μ m when above, and the tendency that industrial coating becomes easily, throughput rate further improves is arranged.In addition, be 100 μ m when following, the tendency that is easy to obtain fully adaptation and exploring degree is arranged.
The photosensitive element of gained can or be wound into the roller shape with sheet and take care of on the volume core.While being wound into the roller shape, preferably according to support membrane, in the mode in the outside, reeled.
[the formation method of corrosion-resisting pattern]
The formation method of corrosion-resisting pattern of the present invention possesses following operation: the photosensitive polymer combination layer that (i) will film as above-mentioned photosensitive polymer combination or the photosensitive polymer combination of above-mentioned photosensitive element are layered in the stacked operation on substrate; (ii) at least a portion area illumination active ray of above-mentioned photosensitive polymer combination layer so that above-mentioned zone photocuring and form the exposure process of photocuring section; Thereby (iii) by the zone except photocuring section by above-mentioned photosensitive polymer combination layer, from aforesaid substrate, remove the developing procedure that forms the corrosion-resisting pattern that the photocured product by above-mentioned photosensitive polymer combination forms at aforesaid substrate, also there are as required other operations.The formation method of above-mentioned corrosion-resisting pattern preferably above-mentioned stacked operation is that the heating of the photosensitive polymer combination layer of above-mentioned photosensitive element is crimped on substrate and carries out stacked operation.
(i) stacked operation
At first, the photosensitive polymer combination that uses photosensitive polymer combination to form is stacked on substrate layer by layer.As substrate, can use the substrate (circuit forms and uses substrate) that possesses insulation course and be formed at the conductor layer on this insulation course.
Stacked on substrate of photosensitive polymer combination layer heat one side to the photosensitive polymer combination layer of photosensitive element on one side after for example removing by the diaphragm by above-mentioned photosensitive element and is crimped on aforesaid substrate and carries out.Thus, can obtain the duplexer that forms and they are laminated in order by substrate and photosensitive polymer combination layer and support membrane.
This lamination operation, from the position of adaptation and servo-actuated property, is preferably under reduced pressure carried out.Photosensitive polymer combination layer during crimping and/or the heating of substrate preferably carry out at the temperature of 70 ℃～130 ℃, preferably with 0.1MPa～1.0MPa left and right (1kgf/cm 2～10kgf/cm 2left and right) pressure carries out crimping, but these conditions are not particularly limited.In addition, when the photosensitive polymer combination layer is heated to 70 ℃～130 ℃, there is no need in advance substrate to be carried out to thermal pretreatment, but, in order further to improve stackability, also can carry out the thermal pretreatment of substrate.
(ii) exposure process
Then, at least a portion area illumination active ray of being layered in the photosensitive polymer combination layer on substrate so that this regional exposure, photocuring occur and form photocuring section.Now, when the support membrane on being present in the photosensitive polymer combination layer is permeability to active ray, can sees through support membrane and irradiate active ray.On the other hand, when support membrane is light-proofness to active ray, after support membrane is removed, the photosensitive polymer combination layer is irradiated to active ray and get final product.
As exposure method, the negative or positive mask pattern that can enumerate by being called as former figure irradiates into active ray the method (mask exposure method) of image shape.In addition, also can adopt and utilize the LDI(laser direct imaging, Laser Direct Imaging) exposure method or DLP(digital light process, Digital LightProcessing) exposure method etc. directly describes exposure method and active ray irradiated into to the method for image shape.
Photosensitive polymer combination of the present invention can be preferably used for directly describing exposure method., one of the preferred embodiment of the present invention is the application of photosensitive polymer combination in directly describing exposure method, described photosensitive polymer combination contains: (A) binder polymer, it has: from (methyl) acrylic acid structural unit, with come since by (EO) modification dicyclopentenyl (methyl) acrylate, (EO) modification two cyclopentyl (methyl) acrylate, (EO) modification isobornyl (methyl) acrylate, (EO) structural unit of modification adamantyl (methyl) acrylate and at least a kind of (methyl) acrylate (EO) selecting in group that modification cyclohexyl (methyl) acrylate forms, (B) optical polymerism compound, and (C) Photoepolymerizationinitiater initiater.
Light source as active ray, known light source can be used, the light source of the effectively radiation ultraviolet ray of solid state laser, the semiconductor lasers etc. such as the gas lasers such as carbon arc lamp, mercuryvapour arc lamp, high-pressure sodium lamp, xenon lamp, argon laser, YAG laser instrument, visible ray etc. can be used.
As the wavelength (exposure wavelength) of active ray, from more positively obtaining the viewpoint of effect of the present invention, be preferably in the scope scope interior, more preferably 350nm～420nm of 340nm～430nm.
(iii) developing procedure
And then, by the zone except photocuring section by above-mentioned photosensitive polymer combination layer, from aforesaid substrate, remove, form the corrosion-resisting pattern that the photocured product by above-mentioned photosensitive polymer combination forms on aforesaid substrate.When on the photosensitive polymer combination layer, having support membrane, the removing of the part (unexposed portion) after support membrane is removed except above-mentioned photocuring section (exposed portion) (development).Wet developing and dry process development are arranged in developing method, but be widely used wet developing.
When utilizing wet developing, use the developer solution corresponding to the formation of photosensitive polymer combination, utilize known developing method to be developed.As developing method, can enumerate the method for using impregnation method, revolving the submergence mode of covering, spray pattern, hairbrush, beating, nog plate, swing impregnating, from putting forward the viewpoint of high-resolution, the high-pressure fog mode is best suited for.In addition, developing method can carry out the Combination of Methods of more than two kinds of selecting from said method.
The formation of developer solution is suitably selected according to the formation of above-mentioned photosensitive polymer combination.Can enumerate particularly alkaline aqueous solution, water system developer solution, organic solvent is developer solution etc.
After unexposed portion is removed, carry out as required heating or the 0.2～10J/cm of 60～250 ℃ of left and right 2the exposure of left and right, thus corrosion-resisting pattern further can be solidified.
[manufacture method of printing distributing board]
The manufacture method of printing distributing board of the present invention has the substrate that the formation method by above-mentioned corrosion-resisting pattern has been formed to corrosion-resisting pattern and carries out the operation that etching processing or plating form conductive pattern, has as required other operations.The etching processing of substrate or plating be take formed corrosion-resisting pattern as mask, conductor layer of substrate etc. is carried out.
Etching liquid when carrying out etching processing, can enumerate copper chloride solution, ferric chloride solution, alkaline etching solution, hydrogen peroxide etching liquid.Wherein the good aspect from the etching factor, preferably used ferric chloride solution.
Coating method when carrying out plating, bathe the nickel plating such as (nickelous sulfate-nickel chloride) plating, nickel sulfamic acid, the hard gold of plating, plate the golden plating such as soft gold etc. such as enumerating the scolding tin plating such as the copper plating such as copper sulphate plating, cupric pyrophosphate plating, High Throw scolding tin plating, Watts.
After etching processing or plating end, corrosion-resisting pattern for example can utilize than the stronger aqueous solution of alkalescence of the alkaline aqueous solution used that develops and be peeled off.As this alkaline aqueous solution, such as using 1 quality %～10 quality % sodium hydrate aqueous solutions, 1 quality %～10 quality % potassium hydroxide aqueous solutions etc.Wherein, preferably use 1 quality %～10 quality % sodium hydrate aqueous solutions or potassium hydroxide aqueous solution, more preferably use 1 quality %～5 quality % sodium hydrate aqueous solution or potassium hydroxide aqueous solutions.
As the mode of peeling off of corrosion-resisting pattern, can enumerate impregnation method, spray pattern etc., these modes can be used alone and also can and use.In addition, the printing distributing board that has formed corrosion-resisting pattern can be multi-layer printed circuit board, also can have the path through hole.
The photosensitive polymer combination of present embodiment can be preferred for the manufacture of printing distributing board., one of the preferred embodiment of the present invention is the application of photosensitive polymer combination in the manufacture of printing distributing board, described photosensitive polymer combination contains: (A) binder polymer, it has: from (methyl) acrylic acid structural unit, with come since by (EO) modification dicyclopentenyl (methyl) acrylate, (EO) modification two cyclopentyl (methyl) acrylate, (EO) modification isobornyl (methyl) acrylate, (EO) structural unit of modification adamantyl (methyl) acrylate and at least a kind of (methyl) acrylate (EO) selecting in group that modification cyclohexyl (methyl) acrylate forms, (B) optical polymerism compound, and (C) Photoepolymerizationinitiater initiater.In addition, preferred embodiment is application, the above-mentioned photosensitive polymer combination application in semi-additive process of above-mentioned photosensitive polymer combination in the manufacture of high-density packages substrate.In addition, will utilize the example of manufacturing process of the distributing board of semi-additive process to be shown in Fig. 5.
In Fig. 5 (a), prepare to be formed with the substrate (circuit forms and uses substrate) of conductor layer 10 on insulation course 15.Conductor layer 10 is for example metal copper layer.In Fig. 5 (b), utilize above-mentioned stacked operation stacked photosensitive polymer combination layer 32 on the conductor layer 10 of substrate.In Fig. 5 (c), laminated mask 20 irradiate active ray 50 on photosensitive polymer combination layer 32, exposed the zone be laminated with beyond the zone of mask 20, forms photocuring section.In Fig. 5 (d), by the zone beyond the photocuring section that utilizes developing procedure to form by above-mentioned exposure process, from substrate, remove, form the corrosion-resisting pattern 30 as photocuring section on substrate.In Fig. 5 (e), utilize and to using the plating as mask as the corrosion-resisting pattern 30 of photocuring section, form coating layer 42 on conductor layer 10.In Fig. 5 (f), after utilizing the aqueous solution of highly basic to peel off as the corrosion-resisting pattern 30 of photocuring section, lose (Flash Etching) by sudden strain of a muscle and process the part of coating layer 42 and the conductor layer 10 covered by corrosion-resisting pattern 30 are removed, form circuit pattern 40.
[embodiment]
Specifically describe by the following examples the present invention, but the present invention not is defined in these embodiment.
(preparation of photosensitive polymer combination)
By the use level with shown in table 2 and table 3, (unit: the mass parts) composition shown in mixture table 2 and table 3 has prepared respectively the solution of the photosensitive polymer combination of embodiment 1～13 and comparative example 1～12.Wherein, the use level of (A) composition shown in table 2 and table 3 is quality (solid constituent amount), the cooperation of "-" expression of nonvolatile component.In addition, the details of each composition shown in table 2 and table 3 is as described below.
<(A) binder polymer >
For binder polymer (A-1)～(A-10), the mass ratio of polymerizable monomer (monomer) (%), acid number and weight-average molecular weight are shown in to table 1.Wherein, "-" means not coordinate.
[synthesizing of binder polymer (A-1)]
To be 26/25/5/44 as methacrylic acid 78g, methacrylic acid dicyclopentenyl oxygen base ethyl ester 75g, methyl methacrylate 15g and the styrene 132g(mass ratio of polymerizable monomer (monomer)) and azoisobutyronitrile 2.5g mixing, using the solution of gained as " solution a ".
Dissolve azoisobutyronitrile 1.2g in mixed liquor (mass ratio the is 3:2) 150g of methyl cellosolve 100g and toluene 50g, using the solution of gained as " solution b ".
Drop into mixed liquor (mass ratio the is 3:2) 300g of methyl cellosolve 180g and toluene 120g in the flask that possesses stirrer, reflux cooler, thermometer, tap funnel and nitrogen ingress pipe, be blown into nitrogen and stir on one side and heated in flask on one side, being warming up to 80 ℃.
After dripping above-mentioned solution a with time of 4 hours in the above-mentioned mixed liquor in flask, while stir under 80 ℃ insulation 2 hours.Then, after dripping above-mentioned solution b with time of 10 minutes in the solution in flask, on one side the insulation 3 hours under 80 ℃ on one side of solution in stirred flask.And then, be warming up to 90 ℃ with the time solution in the chien shih flask of 30 minutes, under 90 ℃ insulation cooling after 2 hours, obtain the solution of binder polymer (A-1).
The nonvolatile component (solid constituent) of binder polymer (A-1) is that 42.8 quality %, weight-average molecular weight are 43000, acid number is 170mgKOH/g.
Wherein, weight-average molecular weight utilizes gel permeation chromatography (GPC) to measure, and the typical curve by the Application standard polystyrene is converted derives.The condition of GPC below is shown.
The GPC condition
Pump: the L-6000 of Hitachi type (Hitachi Co., Ltd's system)
Chromatographic column: following amounts to 3
Gelpack?GL-R420
Gelpack?GL-R430
The above Hitachi Chemical Co., Ltd. of Gelpack GL-R440(system, trade name)
Eluent: tetrahydrofuran
Measure temperature: 40 ℃
Flow: 2.05mL/ minute
Detecting device: the L-3300 of Hitachi type RI(Hitachi Co., Ltd system)
[synthesizing of binder polymer (A-2)]
As polymerizable monomer (monomer), use makes the material identical with binder polymer (A-1) to be the equal in quality ratio and to mix the solution that azoisobutyronitrile 0.25g obtains, in addition, similarly operate with the solution that obtains binder polymer (A-1), obtain the solution of binder polymer (A-2).
[synthesizing of binder polymer (A-3)～(A-10)]
As polymerizable monomer (monomer), use the material shown in table 1 with the mass ratio shown in table 1, in addition, with the solution that obtains binder polymer (A-1), similarly operate, obtain the solution of binder polymer (A-3)～(A-10).
Table 1
Figure BDA00002337350700281
<(B) optical polymerism compound >
TMPT21E(Hitachi Chemical Co., Ltd. system, sample name): (EO) modification trimethylol-propane trimethacrylate (the average 21mol addition product of oxirane)
FA-321M(Hitachi Chemical Co., Ltd. system, trade name): two (the 4-(methacryloxy five ethoxys) phenyl of 2,2-) propane
BPE-200(Xin Zhong village chemical industry Co., Ltd. system, trade name): two (the 4-(methacryloxy diethoxy) phenyl of 2,2-) propane
Crosslinking chemical 1:2, two (the 4-(methacryloxy diethoxy dipropoxy) phenyl of 2-) propane
Crosslinking chemical 2:2, two (the 4-(methacryloxy five ethoxys) cyclohexyl of 2-) propane
Crosslinking chemical 3:(EO)-(PO) modification tetramethylol methane tetraacrylate (the average 8mol addition product of the average 8mol of oxirane and epoxypropane)
FA-024M(Hitachi Chemical Co., Ltd. system, trade name): R in above-mentioned general formula (4) 7and R 8=methyl, r 3=6(mean value), s 2+ s 3=12(mean value) vinyl compound
FA-023M(Hitachi Chemical Co., Ltd. system, trade name): R in above-mentioned general formula (3) 5and R 6=methyl, r 1+ r 2=6(mean value), s 1=12(mean value) vinyl compound
M-114(Toagosei Co., Ltd system, trade name): 4-n-nonyl phenoxy group eight EDIAs
<(C) Photoepolymerizationinitiater initiater >
B-CIM(Hampford company system, trade name): 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole
<(D) sensitizing coloring matter >
PYR-1(Nippon Chemical Works Co. Ltd. system): 1-phenyl-3-(4-methoxyl-styrene)-5-(4-methoxyphenyl) pyrazoline
DBA(Kawasaki Kasei Chemicals Ltd. system, trade name): 9,10-dibutoxy anthracene
J205(Japan distillating industries Co., Ltd. system, trade name): the triphenylamine derivant shown in following formula (10)
Figure BDA00002337350700291
EAB(soil conservation ケ paddy chemical industry Co., Ltd. system, trade name): 4,4 '-bis-(diethylamino) benzophenone
<(E) amine compound >
LCV(hillside plot chemical industry Co., Ltd. system, trade name): leuco crystal violet
<dyestuff >
MKG(Osaka Organic Chemical Industry Co., Ltd. system, trade name): peacock green
Table 2
Figure BDA00002337350700301
Table 3
(photosensitive element)
The photosensitive polymer combination of above-mentioned acquisition is coated on respectively on the polyethylene terephthalate film that thickness is 16 μ m (Teijin Ltd's system, trade name " HTF-01 ") equably, dry successively with the hot wind convection type exsiccator of 70 ℃ and 110 ℃, forming dried thickness is the photosensitive polymer combination layer of 25 μ m.Sticky note diaphragm (Tamapoly Co., Ltd. system, trade name " NF-15 ") on this photosensitive polymer combination layer; make and stack gradually the photosensitive element that polyethylene terephthalate film (support membrane), photosensitive polymer combination layer and diaphragm form, obtained respectively the photosensitive element of embodiment 1～13 and comparative example 1～12.
(multilayer board)
Copper Foil to core (Hitachi Chemical Co., Ltd.'s system, trade name " E-679-F ") carries out the roughening processing, after lamination laminated material (build up materials) (Hitachi Chemical Co., Ltd.'s system, trade name " AS-Z3 "), carry out remove photoresist slag and the processing of electroless plating copper of Atotech company system.The surface roughness Ra of this copper base (following only be called " substrate ") is that 0.2 μ m, thickness are 0.5mm.After making it be warming up to 80 ℃ to aforesaid substrate heating, by the photosensitive element lamination (stacked) of embodiment 1～13 and comparative example 1～12 on the copper surface of substrate.Lamination carries out as follows: Yi Bian remove diaphragm, Yi Bian, according to the lip-deep mode of the closely sealed copper at substrate of the photosensitive polymer combination layer of each photosensitive element, be that 120 ℃, lamination pressure are 3.9 * 10 in temperature 5pa(4kgf/cm 2) condition under carry out.
So, obtained the multilayer board of stacked thoughts photosensitive resin composition layer and polyethylene terephthalate film on the copper surface of substrate.
(evaluation of sensitivity)
The multilayer board of gained is let cool, at the time point that reaches 23 ℃, closely sealed following smooth tool on the polyethylene terephthalate film of multilayer board, 41 sections stage metraster that this light tool has that concentration range is 0.00～2.00, the concentration step is 0.05, the metraster size is 3mm * 12mm for 20mm * 187mm, the size in each stage.What Hitachi Via Mechanics Co., Ltd. system that the bluish-violet color laser diode of wavelength 405nm is light source was take in use directly describes exposure machine " DE-1UH " (trade name), with 80mJ/cm 2energy (exposure) across light tool and polyethylene terephthalate film, the photosensitive polymer combination layer is exposed.In addition, the mensuration of illumination is to use the ultraviolet illuminometer (Ushio Electric Co., Ltd system, trade name " UIT-150 ") of having applied the corresponding probe of 405nm to carry out.
After exposure, the polyethylene terephthalate film is peeled off from multilayer board, expose the photosensitive polymer combination layer, under 30 ℃, spraying 1 quality % aqueous sodium carbonate is 50 seconds, thereby unexposed portion is removed.So, form the cured film that the solidfied material by photosensitive polymer combination forms on the copper surface of substrate.Make the remaining hop count (stage hop count) of the stage metraster of cured film acquisition by mensuration, estimate the sensitivity of photosensitive polymer combination.For sensitivity, by above-mentioned stage hop count, meaned, this hop count is higher shows that sensitivity is better.Show the result in table 5 and table 6.
(evaluation of exploring degree and adaptation)
Using live width (L)/spacing wide (S) (below be designated as " L/S ") is 3/3～30/30(unit: μ m) describe pattern, the energy fluence that the remaining hop count of 41 sections stage metraster of take is 16 sections is to the photosensitive polymer combination layer of above-mentioned multilayer board exposed (describing).After exposure, carry out the development treatment identical with the evaluation of above-mentioned sensitivity.
After development, utilization in the situation that spacing part (unexposed portion) is not removed with thering is no residue and line part (exposed portion) does not occur tortuous and lack the wide value of the live width/spacing of the corrosion-resisting pattern formed in minimum value, evaluation exploring degree and adaptation.This numerical value is less, shows that exploring degree and adaptation are all better.Show the result in table 5 and table 6.
(evaluation of resist shape)
Use the scanning electron microscope S-500A of Hitachi to be observed the resist shape (cross sectional shape of corrosion-resisting pattern) of gained in the evaluation of above-mentioned exploring degree and adaptation.When resist is shaped as trapezoidal or inverted trapezoidal or while thering is the crimping of resist or crackle, has in the circuit of etching processing after utilizing or plating formation and be easy to the tendency that is short-circuited or breaks.Therefore, the resist shape is preferably rectangle (rectangle) and there is no crimping or the crackle of resist.Wherein, " crackle " refers to line part (exposed portion) upper cracking or be full of cracks of corrosion-resisting pattern or follows this situation and online part is upper that disappearance or fracture occur.Resist is shaped as to rectangle and there is no the crimping of resist or the average evaluation of crackle for " A ", will the visible resist of part the average evaluation of crimping for " B ", the average evaluation of the crimping of visible resist is " C " on the whole.Show the result in table 5 and table 6.
(evaluation of peel property)
Each photosensitive element is layered in to above-mentioned copper plate lamination (substrate) upper, is exposed under the conditions shown in Table 4 and develop, thereby having made the test film (40mm * 50mm) that is formed with cured film (corrosion-resisting pattern) on substrate.After this test film is at room temperature placed to diel, peeled off under the conditions shown in Table 4.The time till removing of being peeled off fully from substrate to cured film from stir starting is as splitting time (second).In addition, the shape and size of the stripping film after visualization is peeled off, estimated by following standard.Splitting time is shorter, the stripping film size is less, shows that peel property is better.Show the result in table 5 and table 6.
The stripping film size
L: sheet
M:30mm is square～and 40mm is square
S: be less than 30mm square
Table 4
(hiding the evaluation of reliability)
At 1.6mm, on thick copper plate lamination, have in vain on the base material that continuous 3 diameters are the 4mm hole, with above-mentioned, similarly at upper strata, two sides pressure sensitivity photosensitiveness element, the remaining stage hop count of take after developing is exposed as the exposure of 15.0 sections, carries out the development of 2 times 50 seconds.After development, 3 parts that connect φ 4mm hole that amount to 18 are measured to the holes number, hide destructive rate (following formula) as abnormity and estimated, using it as hiding reliability.
Abnormity hides destructive rate (%)=(holes number (individual)/18()) * 100
(evaluation of bendability)
FPC substrate (trade name: F-30VC1, substrate are thick: 25 μ m, copper are thick: 18 μ m, Nikkan Industrial Co., Ltd system) is heated to 80 ℃; photosensitive polymer combination layer and the support membrane of the photosensitive element of lamination embodiment 1～13 and comparative example 1～12 in the following manner on its copper surface: make photosensitive polymer combination layer and FPC substrate-side in opposite directions, while peel off diaphragm, use the hot-rolling of 110 ℃ to carry out lamination with the speed of 1.5m/ minute.Using the FPC substrate that is laminated with this photosensitive polymer combination layer and supporter as for estimating the test film of bendability.Use be take the Hitachi Via Mechanics company system that the bluish-violet color laser diode of 405nm is light source and is directly described exposure machine DE-1UH, the energy fluence that reaches 11 sections with the remaining stage hop count after the development of 41 sections stage metraster is exposed to above-mentioned test film, makes photosensitive polymer combination layer generation photocuring.Afterwards, support membrane is peeled off, developed, thereby obtain the bendability evaluation substrate that is laminated with corrosion-resisting pattern on the FPC substrate.
Bendability utilizes axle test (mandrel test) to be estimated, and the bendability evaluation is cut into to the strip of wide 2cm, long 10cm with substrate, with 180 °, with rod cylindraceous, rubs mutually 5 back and forth.Then, obtain the diameter (mm) of the cylinder of the minimum of not peeling off between FPC substrate and corrosion-resisting pattern.The diameter of cylinder is less, and bendability is more excellent.
(evaluation of anti-plating)
The evaluation of anti-plating is carried out as follows.
Use the multilayer board of above-mentioned acquisition, under the process conditions shown in table 4, by the exposure of regulation, exposed, then, according in degreaser (Meltex Co., Ltd. system, ProductName " PC-455 ", 25 quality %) in, dipping is 5 minutes, washing, in soft etching liquid (ammonium persulfate 150g/L), dipping is 2 minutes, washing, in 10 quality % sulfuric acid, the dipping order of 1 minute is carried out pre-treatment, put into the copper sulphate plating and bathe (copper sulphate 75g/L, sulfuric acid 190g/L, chlorion 50ppm, Meltex Co., Ltd. system, ProductName " カ パ mono-ゲ リ mono-system PCM " 5mL/L) in, in room temperature, 2.0A/dm 2under carry out the copper sulphate plating 40 minutes, washed afterwards.
After washing, drying, in order to study anti-plating, paste immediately the Cellotape(registered trademark on corrosion-resisting pattern), it is vertically peeled off to (90 ° of disbonded tests), observe and have or not peeling off of corrosion-resisting pattern.In addition, after corrosion-resisting pattern is peeled off, from top with observation by light microscope, have or not copper-plated metal penetration.When copper-plated metal penetration has occurred when, can be at the regional observation hidden by corrosion-resisting pattern to the metallic copper of separating out by plating.
Table 5
Table 6
From table 5 and table 6, the sensitivity of the photosensitive polymer combination of embodiment 1～13, exploring degree, adaptation, bendability, covering reliability, anti-plating, resist shape and peel property are all good.On the other hand, the exploring degree of the photosensitive polymer combination of comparative example 1～12, adaptation, bendability, flexible, hide reliability, anti-plating and resist shape any is all poor than embodiment.Wherein, for comparative example 11, because photosensitive polymer combination layer when the lamination is not closely sealed on substrate, thereby can't estimate.

Claims (8)

1. a photosensitive polymer combination, it contains:
(A) binder polymer, it has: from the structural unit of (methyl) acrylic acid structural unit and at least a kind of (methyl) acrylate selecting in the group that by (EO) modification dicyclopentenyl (methyl) acrylate, (EO) modification two cyclopentyl (methyl) acrylate, (EO) modification isobornyl (methyl) acrylate, (EO) modification adamantyl (methyl) acrylate and (EO) modification cyclohexyl (methyl) acrylate forms;
(B) optical polymerism compound; And
(C) Photoepolymerizationinitiater initiater.
2. photosensitive polymer combination according to claim 1, wherein, described (A) binder polymer further has the structural unit of at least a kind of polymerizable monomer selecting in the group be comprised of styrene and styrene derivative.
3. photosensitive polymer combination according to claim 1 and 2, wherein, it is two (methyl) acrylate compounds that described (B) optical polymerism compound contains bisphenol-A.
4. according to the described photosensitive polymer combination of claim 1 ~ 3 any one, wherein, described (C) Photoepolymerizationinitiater initiater contains 2,4,5-triarylimidazoles dipolymer.
5. according to the described photosensitive polymer combination of claim 1 ~ 4 any one, it also further contains (D) and has the sensitizing coloring matter of absorption maximum at 340nm ~ 430nm.
6. a photosensitive element, it possesses support membrane and is formed on described support membrane the photosensitive polymer combination layer of filming as the described photosensitive polymer combination of claim 1 ~ 5 any one.
7. the formation method of a corrosion-resisting pattern, it has following operation:
To be stacked in layer by layer the stacked operation on substrate as the photosensitive polymer combination layer of filming of the described photosensitive polymer combination of claim 1 ~ 5 any one or the photosensitive polymer combination of photosensitive element claimed in claim 6;
To at least a portion area illumination active ray of described photosensitive polymer combination layer so that described zone is solidified to form the exposure process of photocuring section; And
Thereby the developing procedure that forms the corrosion-resisting pattern that the photocured product by described photosensitive polymer combination forms at described substrate is removed to from described substrate in the zone except photocuring section of described photosensitive polymer combination layer.
8. the manufacture method of a printing distributing board, it has the substrate that will form corrosion-resisting pattern by formation method claimed in claim 7 and carries out the operation that etching processing or plating form conductive pattern.
CN2012104274675A 2011-10-31 2012-10-31 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board Pending CN103091985A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2011239700 2011-10-31
JP2011-239700 2011-10-31
JP2012-237445 2012-10-29
JP2012237445A JP6229256B2 (en) 2011-10-31 2012-10-29 Photosensitive element, resist pattern forming method, and printed wiring board manufacturing method

Publications (1)

Publication Number Publication Date
CN103091985A true CN103091985A (en) 2013-05-08

Family

ID=48204732

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2012104274675A Pending CN103091985A (en) 2011-10-31 2012-10-31 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board

Country Status (2)

Country Link
KR (1) KR20130047656A (en)
CN (1) CN103091985A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107407880A (en) * 2015-04-08 2017-11-28 旭化成株式会社 Photosensitive resin composition
CN113412289A (en) * 2019-02-05 2021-09-17 昭和电工材料株式会社 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board
CN116209571A (en) * 2020-08-07 2023-06-02 株式会社力森诺科 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board
TWI829181B (en) * 2014-04-25 2024-01-11 日商力森諾科股份有限公司 Photosensitive element, laminated body, permanent resist mask and manufacturing method thereof, and semiconductor package manufacturing method

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6584105B2 (en) 2015-03-19 2019-10-02 株式会社日立製作所 Microbe-immobilized carrier and method for producing microorganism-immobilized carrier

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07140650A (en) * 1993-06-16 1995-06-02 Hitachi Chem Co Ltd Photosensitive resin composition and photosensitive film using the same
WO2007004619A1 (en) * 2005-07-05 2007-01-11 Hitachi Chemical Company, Ltd. Photosensitive resin composition, and, photosensitive element, method for forming resist pattern, method for manufacturing printed wiring board and method for manufacturing partition wall for plasma display panel using the composition
JP2007279381A (en) * 2006-04-06 2007-10-25 Hitachi Chem Co Ltd Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board
JP2009003177A (en) * 2007-06-21 2009-01-08 Hitachi Chem Co Ltd Photosensitive resin composition, and photosensitive element, forming method of resist pattern and production method of printed wiring board using the same
CN101855597A (en) * 2007-11-16 2010-10-06 富士胶片株式会社 Radiation-sensitive resin composition for forming spacer, spacer, method for forming spacer, and liquid crystal display device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07140650A (en) * 1993-06-16 1995-06-02 Hitachi Chem Co Ltd Photosensitive resin composition and photosensitive film using the same
WO2007004619A1 (en) * 2005-07-05 2007-01-11 Hitachi Chemical Company, Ltd. Photosensitive resin composition, and, photosensitive element, method for forming resist pattern, method for manufacturing printed wiring board and method for manufacturing partition wall for plasma display panel using the composition
JP2007279381A (en) * 2006-04-06 2007-10-25 Hitachi Chem Co Ltd Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board
JP2009003177A (en) * 2007-06-21 2009-01-08 Hitachi Chem Co Ltd Photosensitive resin composition, and photosensitive element, forming method of resist pattern and production method of printed wiring board using the same
CN101855597A (en) * 2007-11-16 2010-10-06 富士胶片株式会社 Radiation-sensitive resin composition for forming spacer, spacer, method for forming spacer, and liquid crystal display device

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI829181B (en) * 2014-04-25 2024-01-11 日商力森諾科股份有限公司 Photosensitive element, laminated body, permanent resist mask and manufacturing method thereof, and semiconductor package manufacturing method
CN107407880A (en) * 2015-04-08 2017-11-28 旭化成株式会社 Photosensitive resin composition
CN107407880B (en) * 2015-04-08 2022-02-08 旭化成株式会社 Photosensitive resin composition
CN113412289A (en) * 2019-02-05 2021-09-17 昭和电工材料株式会社 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board
CN113412289B (en) * 2019-02-05 2024-04-05 株式会社力森诺科 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board
CN116209571A (en) * 2020-08-07 2023-06-02 株式会社力森诺科 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board

Also Published As

Publication number Publication date
KR20130047656A (en) 2013-05-08

Similar Documents

Publication Publication Date Title
CN103339568A (en) Photosensitive resin composition, photosensitive element, method for producing resist pattern, and method for manufacturing printed wiring board
JP5029617B2 (en) Photosensitive resin composition, photosensitive element, resist pattern forming method and printed wiring board manufacturing method
TWI689783B (en) Photosensitive resin composition, photosensitive element, method of forming resist pattern and method of producing printed circuit board
CN102272676B (en) Photosensitive resin composition, and photosensitive element, resist pattern formation method and printed circuit board production method each utilizing same
JP6229256B2 (en) Photosensitive element, resist pattern forming method, and printed wiring board manufacturing method
KR102171606B1 (en) Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board
CN103543608A (en) Photosensitive resin composition, and photosensitive element, resist pattern formation method and printed circuit board production method each utilizing same
CN103792788A (en) Photosensitive resin composition, photosensitive element, method for forming resist pattern and method for manufacturing printed wiring board
CN103091985A (en) Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board
JP5151446B2 (en) Photosensitive resin composition, photosensitive element, resist pattern forming method and printed wiring board manufacturing method
CN106233204A (en) Photosensitive polymer combination, photosensitive element, the forming method of corrosion-resisting pattern and the manufacture method of printing distributing board
CN103064250A (en) Photosensitive resin composition, photosensitive element wherein same is used, method for forming a resist-pattern, and method for producing a printed wiring board
KR102756112B1 (en) Photosensitive resin composition, photosensitive element, method for forming resist pattern, and process for producing printed wiring board
CN103064254B (en) Photosensitive polymer combination, photosensitive element, the manufacture method of the forming method of resist pattern and printed circuit board (PCB)
JP2012215787A (en) Photosensitive resin composition, photosensitive element, method for manufacturing resist pattern, and printed wiring board and method for manufacturing the same
CN102754032A (en) Photosensitive resin composition and photosensitive element using same, resist pattern formation method and printed circuit board manufacturing method
CN101980082B (en) Photosensitive resin composition, photosensitive element, resist pattern forming method and process for manufacturing printed circuit board
WO2016017596A1 (en) Photosensitive resin composition, photosensitive element, method for producing resist pattern and method for manufacturing printed wiring board
JP5532551B2 (en) Photosensitive resin composition, photosensitive element, resist pattern forming method and printed wiring board manufacturing method
CN103076719A (en) Photosensitive resin composition, photosensitive component, forming method of corrosion-resistant pattern and manufacturing method of printed wiring board
KR102458633B1 (en) Photosensitive resin composition, photosensitive element, method for producing substrate with resist pattern and method for producing printed wiring board
CN103076717A (en) Photosensitive resin composition, photosensitive component, forming method of corrosion-resistant pattern and manufacturing method of printed wiring board
CN108780276A (en) The manufacturing method of photosensitive polymer combination, photosensitive element, the manufacturing method of substrate with resist pattern and printing distributing board
JP6724445B2 (en) Photosensitive resin composition, photosensitive element, method for producing substrate with resist pattern, and method for producing printed wiring board
CN102981357A (en) Photosensitive resin composition, and photosensitive element, and resist pattern formation method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20130508